A method for adsorbing phenolic substances in an acrylic monomer solution and applications thereof

Abstract

The application relates to application of a MOFs material loaded on iron wire in adsorption of a solution containing phenolic substances, the material is that MOF-808-S6 is loaded on the iron wire through polyamide acid, according to the technical scheme of the application, a method for adsorbing phenolic substances in an acrylic monomer solution is further provided, and the adsorption method is simple. The MOFs material is loaded on the iron wire mesh sintering, the adsorption capacity of the MOFs material on the phenolic substances is improved, a subsequent separation and purification procedure of acrylic acid and the adsorption material is further simplified, and after adsorption, the adsorption material only needs to be directly taken out simply. The MOFs material has very high adsorption capacity on trace inhibitors in the acrylic acid. The application has the advantages of low equipment requirement, no need of various expensive reaction devices, low reaction condition, easy large-scale production and the like, and good social and economic benefits can be expected.

Description

Technical Field

[0001] This invention belongs to the field of new applications of metal-organic frameworks, and relates to a method for adsorbing phenolic substances in an acrylic monomer solution. Background Technology

[0002] Acrylic acid monomer is a widely used chemical raw material, playing an important role in organic synthesis, polymer production, coatings, adhesives, and resins. A significant characteristic of acrylic acid is its tendency to self-polymerize; under certain conditions, it readily aggregates to form solids, making its industrial production, storage, and transportation challenging. To address this issue in industrial production, effective methods are needed to inhibit the polymerization reaction of acrylic acid. Polymerization inhibitors are compounds that can suppress or delay the polymerization reaction. Commonly used types of polymerization inhibitors include phenolic inhibitors, quinone inhibitors, inorganic compound inhibitors, and aromatic nitro compound inhibitors. However, these acrylic acid polymerization inhibitors tend to coexist with acrylic acid, and even after separation and purification, trace amounts of the inhibitor remain difficult to remove.

[0003] Polyphenols and their substituted phenols are a widely used and effective class of polymerization inhibitors. Common phenolic polymerization inhibitors include p-methoxyphenol (MEHQ), hydroquinone (HQ), p-tert-butylcatechol (TBS), di-tert-butyl-p-cresol (DBPC), 2,6-di-tert-butyl-p-methylphenol (BHT), and bisphenol A. These inhibitors can consume free radicals in the monomer (which are oxidized to the corresponding quinones) in the early stages of the acrylic acid self-polymerization reaction, thereby preventing the monomer self-polymerization reaction from occurring. From the perspective of the polymerization inhibition mechanism, some phenolic derivatives can also act as acrylic acid monomer polymerization inhibitors, such as o-methoxyphenol and 4-methylguaiacol.

[0004] Currently, most methods for removing these substances include alkaline washing (NaOH reacts with phenols to form soluble sodium salts, followed by extraction and separation to obtain monomers), column chromatography (the adsorbent, alkaline ion exchange resin, binds to the phenols and inhibits their polymerization on the column, while the monomers are carried away by the eluent), extraction (based on the difference in solubility / polarity between monomers and inhibitors, another solvent is added to separate monomers / inhibitors), vacuum distillation / rectification (generally, inhibitors are less volatile than monomers, and separation is achieved by utilizing the difference in volatility), recrystallization (separation is achieved by utilizing the difference in boiling points between inhibitors and monomers), activated carbon adsorption (direct adsorption of small inhibitor particles), and membrane separation (inhibitors and monomers have differences in particle size at the molecular level, and monomers are separated using semi-permeable membranes / separation membranes). Although these methods can remove most inhibitors, they introduce other impurities in the process, increasing the cost by adding separation and purification procedures for acrylic acid monomers and impurities. Summary of the Invention

[0005] In view of this, the object of the present invention is to provide a simple method for adsorbing phenolic substances in an acrylic monomer solution, and a metal-organic framework complex for adsorbing phenolic substances.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] 1. The application of a MOF material loaded on an iron wire in the adsorption of a solution containing phenolic substances, wherein the MOF is MOF-808.

[0008] Furthermore, in the aforementioned application, the MOF-808 is loaded onto the iron wire using polyamic acid.

[0009] Furthermore, in the aforementioned application, the MOF-808 is MOF-808-S6.

[0010] Furthermore, in the aforementioned application, the preparation method of the MOF-808-S6 is as follows:

[0011] a. Place pyromellitic acid, ZrOCl2·8H2O, DMF and formic acid into a container, sonicate for 10-30 min, and then place at 130-135℃ for 5-7 days. After the reaction is complete, separate the solid and liquid and collect the white precipitate 1.

[0012] b. White precipitate 1 was first soaked in DMF overnight and then the solid and liquid were separated to obtain white precipitate 2. White precipitate 2 was then soaked in ultrapure water overnight and then the solid and liquid were separated to obtain white precipitate 3.

[0013] c. White precipitate 3 was soaked in methanol overnight and then separated into solid and liquid phases to obtain white precipitate 4. White precipitate 4 was dried under vacuum to obtain white crystals of MOF-808-S6.

[0014] Furthermore, in the aforementioned application, the ratio of trimesic acid to ZrOCl2·8H2O reactants is 1:3 according to a molar mass meter.

[0015] Furthermore, in the aforementioned application, the solution containing phenolic substances is an acrylic acid solution, and the phenolic substances are o-methoxyphenol, p-methoxyphenol, hydroquinone, and / or 2,6-di-tert-butyl-p-methylphenol.

[0016] Furthermore, in the aforementioned application, the specific loading steps are as follows: MOF-808-S6 is uniformly dispersed in a polyamic acid solution, a wire mesh is placed in the solution, and the mesh is left to stand for 10-60 minutes. After PAA@MOFs grow on the wire mesh, it is then soaked and cleaned in an ultrapure water beaker. After a light yellow gel adheres to the wire mesh, it is transferred to a tube furnace at 130-160℃ for calcination for 0.5-1 hour to obtain Fe-PAA@MOFs.

[0017] Furthermore, in the aforementioned application, the solid content of the polyamic acid solution is 25%-30%, and the preparation method is as follows: under ice bath conditions, 4,4-diaminodiphenyl ether is first dissolved in DMF, and then pyromellitic dianhydride is added in batches. After the pyromellitic dianhydride is completely dissolved, stirring is continued for 6-8 hours.

[0018] Preferably, the solid content of the polyamic acid solution is 25%.

[0019] Furthermore, in the aforementioned application, the amounts of 4,4-diaminodiphenyl ether and pyromellitic dianhydride added are equal.

[0020] 2. Based on the above-mentioned technical solution for the application of MOFs material loaded on iron wire in adsorbing solutions containing phenolic substances, a method for adsorbing phenolic substances in acrylic monomer solutions is also provided. The MOFs material loaded on iron wire is directly placed into the acrylic solution containing phenolic substances for adsorption, and the adsorption time is 12 hours or more.

[0021] The specific steps for loading are as follows: MOFs are uniformly dispersed in a polyamic acid solution, placed in a wire mesh, and left to stand for 10-60 minutes. After PAA@MOFs grow on the wire mesh, it is then soaked and washed in an ultrapure water beaker. After a light yellow gel adheres to the wire mesh, it is transferred to a tube furnace at 130℃ and calcined for 0.5-1 hour to obtain Fe-PAA@MOFs.

[0022] Furthermore, the solid content of the polyamic acid solution is 25%-30%, and the preparation method is as follows: under ice bath conditions, 4,4-diaminodiphenyl ether is first dissolved in DMF, and then pyromellitic dianhydride is added in batches. After the pyromellitic dianhydride is completely dissolved, stirring is continued for 6-8 hours.

[0023] Preferably, the solid content of the polyamic acid solution is 25%.

[0024] Furthermore, in the method described above, the MOFs are MOF-808-S6.

[0025] Furthermore, in the aforementioned method, the preparation method of MOF-808-S6 is as follows:

[0026] a. Place pyromellitic acid, ZrOCl2·8H2O, DMF and formic acid into a container, sonicate for 10-30 min, and then place at 130-135℃ for 5-7 days. After the reaction is complete, separate the solid and liquid and collect the white precipitate 1.

[0027] b. White precipitate 1 was first soaked in DMF overnight and then the solid and liquid were separated to obtain white precipitate 2. White precipitate 2 was then soaked in ultrapure water overnight and then the solid and liquid were separated to obtain white precipitate 3.

[0028] c. White precipitate 3 was soaked in methanol overnight and then separated into solid and liquid phases to obtain white precipitate 4. White precipitate 4 was dried under vacuum to obtain white crystals of MOF-808-S6.

[0029] Furthermore, in the aforementioned application, the ratio of trimesic acid to ZrOCl2·8H2O reactants is 1:3 according to a molar mass meter.

[0030] Furthermore, in the method described above, the phenolic substance is o-methoxyphenol, p-methoxyphenol, hydroquinone, or / and 2,6-di-tert-butyl-p-methylphenol.

[0031] The beneficial effects of this invention are as follows: The MOF-808-S6 porous metal-organic framework material of this invention is synthesized using a simple solvothermal method, which is simple and easy to operate. By optimizing the synthesis conditions and purification path, MOF-808-S6 crystals with a large specific surface area and good performance were obtained. The obtained MOF-808-S6 crystals not only have high stability, but their regular octahedral shape with uniform particle size provides a large specific surface area and abundant porosity. Furthermore, they exhibit certain adsorption properties for phenolic polymerization inhibitors, unaffected by solution polarity. They can adsorb phenolic substances such as o-methoxyphenol, p-methoxyphenol, hydroquinone, and / or 2,6-di-tert-butyl-p-methylphenol in both polar and non-polar solutions. The adsorption of phenolic polymerization inhibitors by MOF-808-S6 mainly comes from the van der Waals forces and electrostatic forces between phenol and Zr metal sites. Phenol is adsorbed and occupies Zr atomic sites, forming complexes with Zr atoms at a certain angle. Using PAA as a carrier, MOF-808-S6 was loaded onto a wire mesh. Experimental investigations revealed that the PAA solution, upon incorporating water, forms a gel. Utilizing the intermolecular hydrogen bonds within the gel, the MOF material is "locked" in place, allowing the wire mesh to be successfully sintered and loaded with the MOF material. Loading onto the wire mesh enhances the adsorption capacity of the MOF material, further simplifying the subsequent separation and purification process of acrylic acid and the adsorbent. After adsorption, the adsorbent material can be directly removed. It also exhibits highly efficient adsorption capacity for trace amounts of polymerization inhibitors in acrylic acid. Using the Fe-PAA@MOF material provided by this invention to adsorb phenolic substances in acrylic acid monomer solutions reduces the time and operation of subsequent processing in acrylic acid industrial production, significantly lowering production costs. It also simplifies the acrylic acid process, correspondingly increasing production capacity. This invention has advantages such as low equipment requirements, no need for expensive reaction equipment, low reaction conditions, and ease of large-scale production, and is expected to generate significant social and economic benefits. Attached Figure Description

[0032] To make the objectives, technical solutions, and beneficial effects of this invention clearer, the following figures are provided for illustration:

[0033] Figure 1 The adsorption efficiency curves of MOF-808-S6 in methanol solution for o-methoxyphenol at different adsorption times in Example 1 are shown.

[0034] Figure 2 The adsorption efficiency curves of different masses of MOF-808-S6 for o-methoxyphenol in methanol solution in Example 2 are shown.

[0035] Figure 3 The adsorption efficiency curve of MOF-808-S6 in the acrylic acid-n-hexane mixed solution in Example 3 is shown.

[0036] Figure 4 The graph shows the adsorption efficiency of MOF-808-S6 on a portion of the phenolic polymerization inhibitor in an acrylic acid-n-hexane mixture in Example 4.

[0037] Figure 5 The adsorption diagrams of Fe-PAA@MOFs on o-methoxyphenol in n-hexane and acrylic acid-n-hexane mixtures in Example 5 are shown.

[0038] Figure 6 FTIR images of MOF-808-S6, H3BTC, and Fe-PAA@MOFs;

[0039] Figure 7 XRD image of MOF-808-S6;

[0040] Figure 8 XRD images of Fe-PAA@MOFs;

[0041] Figure 9 These are SEM images of the MOF-808-S6 crystal at different magnifications;

[0042] Figure 10 SEM images of Fe-PAA@MOFs;

[0043] Figure 11 The gas chromatogram of o-methoxyphenol in step 16 is shown.

[0044] Figure 12 This is the gas chromatogram of p-methoxyphenol detected in step 17;

[0045] Figure 13 This is the gas chromatogram of hydroquinone detection in step 18;

[0046] Figure 14 This is the gas chromatogram of 2,6-di-tert-butyl in step 19. Detailed Implementation

[0047] The preferred embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention. Experimental methods not specified with specific conditions in the embodiments are generally performed under conventional conditions or as recommended by the manufacturer.

[0048] Example 1:

[0049] 1. Place 2.10 g of trimesic acid, 9.70 g of ZrOCl2·8H2O, 450 ml of DMF, and 450 ml of formic acid into a 2.0 L glass Durand pressure flask, and transfer it to an ultrasonicator for sonication for 10 min. Then place the mixture in an oven at 130-135 °C for 5 days. After the reaction is complete, filter and collect the white precipitate 1. The glass Durand pressure flask can also be a reaction vessel lined with polytetrafluoroethylene.

[0050] 2. White precipitate 1 was first soaked in 100.0 ml of DMF overnight and then filtered to obtain white precipitate 2. White precipitate 2 was then soaked in 100.0 ml of ultrapure water overnight and then filtered to obtain white precipitate 3.

[0051] 3. The white precipitate 3 was then soaked in 100.0 ml of methanol overnight and filtered to obtain white precipitate 4. White precipitate 4 was dried in a vacuum drying oven at 80℃ for 12 h to obtain white crystals of MOF-808-S6.

[0052] 4. At room temperature, weigh 0.05 g MOF-808-S6 and 0.05 g o-methoxyphenol, transfer 19.95 g of methanol solution to a glass bottle, and stir mechanically for 3 hours. Transfer the white turbid liquid to a centrifuge tube and centrifuge (5000 r / min, 5 min), and collect the supernatant. Analyze the adsorption performance using gas chromatography.

[0053] 5. At room temperature, weigh 0.05 g MOF-808-S6 and 0.05 g o-methoxyphenol, transfer 19.95 g of methanol solution to a glass bottle, and stir mechanically for 6 h. Transfer the white turbid liquid to a centrifuge tube and centrifuge (5000 r / min, 5 min), and collect the supernatant. Analyze the adsorption performance using gas chromatography.

[0054] 6. At room temperature, weigh 0.05 g MOF-808-S6 and 0.05 g o-methoxyphenol, transfer 19.95 g of methanol solution to a glass bottle, and stir mechanically for 9 h. Transfer the white turbid liquid to a centrifuge tube and centrifuge (5000 r / min, 5 min), and collect the supernatant. Analyze the adsorption performance using gas chromatography.

[0055] 7. At room temperature, weigh 0.05 g of MOF-808-S6 and 0.05 g of o-methoxyphenol, transfer 19.95 g of methanol solution to a glass bottle, and stir mechanically for 12 h. Transfer the white turbid liquid to a centrifuge tube and centrifuge (5000 r / min, 5 min), and collect the supernatant. Analyze the adsorption performance using gas chromatography.

[0056] Figure 1 The figures show the adsorption efficiency curves of MOF-808-S6 for o-methoxyphenol in methanol solution at different adsorption times in steps 4-7. The adsorption data were directly output from gas chromatography. With increasing adsorption time, the adsorption capacity of MOF-808-S6 for o-methoxyphenol gradually increases and reaches adsorption equilibrium. The adsorption of o-methoxyphenol by MOF-808-S6 mainly originates from the van der Waals forces and electrostatic forces between o-methoxyphenol and Zr atomic sites. O-methoxyphenol is primarily adsorbed at Zr atomic sites and forms complexes with Zr atoms at a certain angle.

[0057] Example 2:

[0058] 8. At room temperature, weigh 0.10 g of MOF-808-S6 and 0.50 g of o-methoxyphenol, transfer them to a glass bottle containing 19.50 g of methanol solution, and stir mechanically for 12 h. Transfer the white turbid liquid to a centrifuge tube and centrifuge (5000 r / min, 5 min), and collect the supernatant. Analyze the adsorption performance using a gas chromatograph.

[0059] 9. At room temperature, weigh 0.20 g of MOF-808-S6 and 0.50 g of o-methoxyphenol, transfer them to a glass bottle containing 19.50 g of methanol solution, and stir mechanically for 12 h. Transfer the white turbid liquid to a centrifuge tube and centrifuge (5000 r / min, 5 min), and collect the supernatant. Analyze the adsorption performance using a gas chromatograph.

[0060] 10. At room temperature, weigh 0.30 g of MOF-808-S6 and 0.50 g of o-methoxyphenol, transfer them to a glass bottle containing 19.50 g of methanol solution, and stir mechanically for 12 h. Transfer the white turbid liquid to a centrifuge tube and centrifuge (5000 r / min, 5 min), and collect the supernatant. Analyze the adsorption performance using gas chromatography.

[0061] 11. At room temperature, weigh 0.40 g of MOF-808-S6 and 0.50 g of o-methoxyphenol, transfer them to a glass bottle containing 19.50 g of methanol solution, and stir mechanically for 12 h. Transfer the white turbid liquid to a centrifuge tube and centrifuge (5000 r / min, 5 min), and collect the supernatant. Analyze the adsorption performance using gas chromatography.

[0062] 12. At room temperature, weigh 0.50 g of MOF-808-S6 and 0.50 g of o-methoxyphenol, transfer them to a glass bottle containing 19.50 g of methanol solution, and stir mechanically for 12 h. Transfer the white turbid liquid to a centrifuge tube and centrifuge (5000 r / min, 5 min), and collect the supernatant. Analyze the adsorption performance using a gas chromatograph.

[0063] Figure 2 The figures show the adsorption efficiency curves of different masses of MOF-808-S6 for o-methoxyphenol in methanol solution during steps 8-12. As the mass of MOF-808-S6 crystals increases, the adsorption capacity of MOF-808-S6 for o-methoxyphenol also increases. The results show that the adsorption of o-methoxyphenol by MOF-808-S6 is dose-dependent, indicating that MOF-808-S6 exhibits a good linear relationship with this polymerization inhibitor.

[0064] Combination Figure 1 and Figure 2 The results show that MOF-808-S6 exhibits good adsorption efficiency for o-methoxyphenol in methanol (polar solvent) solution, indicating that polar solution does not affect the adsorption of phenolic substances by MOF-808-S6. After the addition of MOF-808-S6, the Zr atomic sites are occupied (adsorbed) by free o-methoxyphenol molecules and form complexes with a certain angle.

[0065] Example 3:

[0066] 13. At room temperature, weigh 0.025 g MOF-808-S6 and 0.20 g o-methoxyphenol, transfer 8 ml of acrylic acid and 2 ml of n-hexane solution to a glass bottle, and stir mechanically for 12 h. Transfer the white turbid liquid to a centrifuge tube and centrifuge (5000 r / min, 5 min), and collect the supernatant. Analyze the adsorption performance using gas chromatography.

[0067] 14. At room temperature, weigh 0.05 g MOF-808-S6 and 0.20 g o-methoxyphenol, transfer 8 ml of acrylic acid and 2 ml of n-hexane solution to a glass bottle, and stir mechanically for 12 h. Transfer the white turbid liquid to a centrifuge tube and centrifuge (5000 r / min, 5 min), and collect the supernatant. Analyze the adsorption performance using a gas chromatograph.

[0068] Figure 3This is the adsorption efficiency curve of MOF-808-S6 in an acrylic acid-n-hexane mixture for o-methoxyphenol solution, as shown in steps 13-14. In the mixed solution, the adsorption capacity of MOF-808-S6 for o-methoxyphenol gradually increases with increasing adsorption time. The results show that MOF-808-S6 has a strong adsorption capacity for o-methoxyphenol in a hexane (non-polar)-acrylic acid solution, and does not affect the purity of acrylic acid. This indicates that MOF-808-S6 has the potential to act as a polymerization inhibitor for adsorbing acrylic acid monomer solutions, and is not affected by the non-polar solution.

[0069] Example 4:

[0070] 15. Transfer 72 ml of acrylic acid solution and 18 ml of n-hexane solution into 250 ml beakers respectively, sonicate for 10 min, and let stand for later use.

[0071] 16. At room temperature, weigh 0.5 g of MOF-808-S6 and 0.5 g of o-methoxyphenol into an Erlenmeyer flask, transfer 20 ml of the mixture from step 15, and stir mechanically for 48 h. Transfer the mixture into a centrifuge tube and centrifuge (5000 r / min, 5 min), and collect the supernatant. Analyze the adsorption performance using a gas chromatograph.

[0072] 17. At room temperature, weigh 0.5 g of MOF-808-S6 and 0.5 g of p-methoxyphenol into an Erlenmeyer flask, transfer 20 ml of the mixture from step 15, and stir mechanically for 48 h. Transfer the mixture into a centrifuge tube and centrifuge (5000 r / min, 5 min), and collect the supernatant. Analyze the adsorption performance using a gas chromatograph.

[0073] 18. At room temperature, weigh 0.5 g of MOF-808-S6 and 0.5 g of hydroquinone into an Erlenmeyer flask. Transfer 20 ml of the mixture from step 15 and stir mechanically for 48 h. Transfer the mixture into a centrifuge tube and centrifuge (5000 r / min, 5 min), and collect the supernatant. Analyze the adsorption performance using a gas chromatograph.

[0074] 19. At room temperature, weigh 0.5 g of MOF-808-S6 and 0.5 g of 2,6-di-tert-butyl-p-methylphenol into an Erlenmeyer flask. Transfer 20 ml of the mixture from step 15 and stir mechanically for 48 h. Transfer the mixture into a centrifuge tube and centrifuge (5000 r / min, 5 min), collecting the supernatant. Analyze the adsorption performance using gas chromatography.

[0075] Figure 4 This is the adsorption efficiency diagram of MOF-808-S6 in acrylic acid-n-hexane solution for various polymerization inhibitors, as shown in steps 16-19. The adsorption efficiency was measured at 0h, 12h, and 48h. Figures 11-14The following are the gas chromatograms of steps 16-19 at 12 hours. Figure 4 It is known that MOFs exhibit excellent adsorption performance for MEHQ, BHT, and hydroquinone in a nonpolar solvent (n-hexane) environment.

[0076] The above experiments fully demonstrate that MOF-808-S6 is favorable for adsorbing o-methoxyphenol in polar solvents (methanol) and for adsorbing polymerization inhibitors such as p-methoxyphenol, BHT, and hydroquinone in non-polar solvents (n-hexane).

[0077] Example 5:

[0078] Measure 60 mL of DMF into a beaker. Under ice bath conditions, first dissolve 10 g of ODA (4,4-diaminodiphenyl ether) in DMF, then add 10 g of PMDA (pyromellitic dianhydride) in batches. After all PMDA has dissolved, continue stirring for 6 hours to obtain a PAA (polyamic acid) solution with a solid content of 25%.

[0079] 20. At room temperature, weigh 4g of MOF-808-S6 and add it to a beaker containing 60ml of 25% PAA solution. Stir the mixture mechanically for 4 hours to ensure the MOF-808-S6 powder is uniformly dispersed in the PAA (wt%). MOFs =5%). Transfer the mixture to a petri dish, place a 5×5cm wire mesh (wire diameter 1.1mm) inside, let stand for 10min, and after PAA@MOFs grow on the wire mesh, immerse the wire mesh in a beaker containing 100ml of ultrapure water for 30min, and after a light yellow gel adheres to the wire mesh, transfer it to a tube furnace at 130℃ and calcine for 0.5h to obtain Fe-PAA@MOFs. Weigh 1.0g of o-methoxyphenol, transfer 50.0ml of n-hexane solution to a petri dish and after complete dispersion, add Fe-PAA@MOFs, and adsorb for 12h. Pipette the solution, centrifuge (5000r / min, 5min), collect the supernatant, and output the adsorption performance graph using a gas chromatograph. In actual production applications, Fe-PAA@MOFs can be directly taken out for the next step without separating the adsorbent and acrylic acid.

[0080] 21. At room temperature, weigh 4g of MOF-808-S6 and add it to a beaker containing 60ml of 25wt% PAA solution. Stir the mixture mechanically for 4 hours to ensure the MOF-808-S6 powder is uniformly dispersed in the PAA (wt%). MOFs=5%, MOFS mass / (MOFs mass + PAA mass)). Transfer the mixture to a petri dish, place a 5×5cm wire mesh in it, and let it stand for 10 min. After PAA@MOFs grow on the wire mesh, immerse the wire mesh in a beaker containing 100ml of ultrapure water for 30 min. After a light yellow gel adheres to the wire mesh, transfer it to a tube furnace at 130℃ and calcine for 0.5 h to obtain Fe-PAA@MOFs. Weigh 1.0g of o-methoxyphenol, transfer 40ml of acrylic acid and 10ml of n-hexane solution to a petri dish, and after complete dispersion, add Fe-PAA@MOFs and adsorb for 12 h. Pipette the solution, centrifuge (5000r / min, 5min), and collect the supernatant. Use a gas chromatograph to output the adsorption performance graph.

[0081] Figure 5 This is the adsorption diagram of Fe-PAA@MOFs on o-methoxyphenol in a mixture of n-hexane and acrylic acid-n-hexane, as shown in steps 24-25. (Compared to...) Figure 4 Compared with the control group of o-methoxyphenol (7.35%→7.10%), the adsorption performance of MOFs materials was significantly improved after being attached to wire mesh (3.21%→2.80%, 4%→3.16%).

[0082] The above experiments show that MOF-808-S6, with PAA as a carrier, is attached to the wire mesh, which not only increases the contact area and adsorption sites between MOFs and the polymerization inhibitor, but also exhibits solvent selectivity.

[0083] Figure 6 These are the FTIR spectra of MOF-808-S6 crystals, pyromellitic acid, and Fe-PAA@MOFs. Figure 6 It can be seen that at 3450cm -1 (Black line), 3336cm -1 The peak at (red line) is broad and diffuse, belonging to the asymmetric stretching vibration peak of the OH bond in -COOH; 1892 cm⁻¹ -1 (Black line), 1379cm -1 (Black line) and 1886cm -1 (Red line), 1396cm -1 (Red line) The characteristic peak belongs to both the asymmetric stretching vibration peak and the symmetric stretching peak of -C=O in -COOH; 761cm -1 (Black line), 746cm -1 (Red line) The characteristic peak belongs to the stretching vibration peak of the C-C bond in the benzene ring; 943 cm⁻¹ -1 (Black line) and 931cm -1 (Red line) Characteristic peak indicates meta-trisubstituted benzene ring; 1606 cm⁻¹ -1The characteristic peaks at (red and blue lines) are vibrational peaks caused by the coordination of deprotonated -COOH with the central ion Zr, indicating the successful formation of MOF-808-S6. The specific FTIR spectrum of Fe-PAA@MOFs is obtained by performing infrared spectroscopy on the solid Fe-PAA@MOFs stripped from the wire mesh. Figure 6 It can be proven that Fe-PAA@MOFs have been successfully loaded with MOF-808-S6 on wire mesh.

[0084] Figure 7 It is an XRD image of MOF-808-S6. Figure 8 XRD images of Fe-PAA@MOFs. Figure 9 These are SEM images of the MOF-808-S6 crystal at different magnifications.

[0085] Figure 10 The image shows a SEM image of Fe-PAA@MOFs, and SEM-EDS elemental analysis was performed. The elemental composition is shown in Table 1. Fe element belongs to other classes.

[0086] Table 1

[0087] element Wt% C 25.51 O 40.48 Zr 8.19 other 25.11 Total 100

[0088] The above experiments show that MOF-808-S6, when attached to the wire mesh with PAA as a carrier, exhibits characteristics such as high temperature resistance and strong stability.

[0089] Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that various changes can be made to it in form and detail without departing from the scope defined by the claims of the present invention.

Claims

1. Use of MOFs material supported on iron wire in adsorbing solution containing phenolic substances, characterized in that, The MOF is MOF-808; the MOF-808 is loaded on a wire by polyamic acid; the solution containing the phenolic substance is an acrylic acid solution, and the phenolic substance is o-methoxyphenol, p-methoxyphenol, hydroquinone or / and 2,6-di-tert-butyl-p-methylphenol; the specific loading step is: uniformly dispersing the MOF-808 in the polyamic acid solution, placing it in a wire mesh, and standing for 10 min to 60 min; after the wire mesh grows PAA@MOFs, it is cleaned by soaking in an ultrapure water beaker; after the wire mesh is attached to a light yellow gel, it is transferred to a 130 DEG C to 160 DEG C tube furnace and calcined for 0.5 h to 1 h to obtain Fe-PAA@MOFs.

2. Use according to claim 1, characterized in that, The MOF-808 is MOF-808-S6, and the preparation method of the MOF-808-S6 is: a. Put trimesic acid, ZrOCl2.8H2O, DMF and formic acid into a container, ultrasonic treatment for 10-30 min, and then stand at 130-135 DEG C for 5-7 days; after the reaction is completed, collect the white precipitate 1 by solid-liquid separation; b. The white precipitate 1 is first soaked in DMF overnight and then solid-liquid separated to obtain white precipitate 2, and the white precipitate 2 is then soaked in ultrapure water overnight and then solid-liquid separated to obtain white precipitate 3; c. The white precipitate 3 is soaked in methanol overnight and then solid-liquid separated to obtain white precipitate 4, and the white precipitate 4 is vacuum dried to obtain MOF-808-S6 white crystals.

3. Use according to claim 2, characterized in that, The molar mass ratio of trimesic acid to ZrOCl2.8H2O reactant is 1:

3.

4. Use according to claim 1, characterized in that, The solid content of the polyamic acid solution is 25%-30%, and the preparation method is: first, dissolve 4,4-diamino diphenyl ether in DMF under ice bath conditions, then add pyromellitic dianhydride in batches, and after all the pyromellitic dianhydride is dissolved, continue to stir for 6 h to 8 h.

5. Use according to claim 4, characterized in that, The added mass of 4,4-diamino diphenyl ether and pyromellitic dianhydride is equal.

6. Use according to any one of claims 1 to 5, characterized in that, The use method is specifically to directly place the MOFs material loaded on the wire into the acrylic acid solution containing the phenolic substance for adsorption, and the adsorption time is 12 hours or more.

7. The method of claim 6, wherein, The phenolic substance is o-methoxyphenol, p-methoxyphenol, hydroquinone or / and 2,6-di-tert-butyl-p-methylphenol.

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