A method for preparing a porous material for removing organic compounds from a gas

Abstract

The present invention discloses a preparation method of a porous material for removing organic compounds from gases, belonging to the technical field of organic synthesis. A tetraphenylaldehyde derivative with pyrene as the core is used as the connecting node of the flexible porous material, and fluorene and fluorene ketone derivatives are used as the connecting arms. The three components are interconnected through an amine-aldehyde condensation reaction to prepare a two-dimensional porous polymer network. The porous material for removing organic compounds from gases prepared by the present invention has a high specific surface area, a large porosity, functional adjustability, thermal stability and chemical stability, and has a high adsorption rate for VOCs, and can be used for removing organic compounds from gases.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis, and specifically relates to a preparation method of a porous material for removing organic compounds from gases. Background Art

[0002] VOCs, namely volatile organic compounds, are a class of organic compounds that are volatile at room temperature. Their main components include benzene series, organic chlorides, Freon series, organic ketones, amines, alcohols, ethers, esters, acids, and petroleum hydrocarbon compounds, etc. They widely exist in our daily life, such as paints, cleaners, building materials, etc.

[0003] VOCs pose a considerable threat to the environment and human health. In terms of the environment, VOCs are important precursors for the formation of fine particulate matter (PM2.5) and ozone. They react under the action of light and heat to form ozone, resulting in poor air quality. At the same time, VOCs are also an important component of atmospheric PM2.5. In addition, most VOCs are greenhouse gases, which can cause global warming. For human health, VOCs have different toxicities and irritations. When exceeding a certain concentration, they will irritate people's eyes and respiratory tracts, cause skin allergies, sore throats, and fatigue. Seriously, they will cause disorders in the body's immune system level, affect the function of the central nervous system, and damage the digestive system, liver function, and hematopoietic system, etc. Some VOCs have been listed as carcinogens, such as vinyl chloride, benzene, polycyclic aromatic hydrocarbons, etc. Therefore, the control and treatment of VOCs are of great significance for improving air quality and protecting human health. Currently, the materials available for VOCs adsorption mainly include activated carbon, activated carbon fiber, diatomite, mesoporous silica, metal-organic frameworks (MOFs), and molecular sieves, etc. However, these materials generally have problems such as a decrease in the adsorption capacity for VOCs under high humidity conditions, low adsorption capacity, and difficult regeneration.

[0004] Patent CN 107128932A discloses a preparation method of hydrophobic silica for VOC adsorption, but there are problems of poor adsorption stability and low adsorption capacity. Patent CN 110339809A discloses an adsorbent for VOCs adsorption and its preparation method. A VOCs adsorbent precursor one is prepared from a silicon source, an aluminum source, and a template agent; the adsorbent precursor one is processed to obtain a VOCs adsorbent precursor two; finally, the obtained VOCs adsorbent precursor two is mixed with alumina to obtain a VOCs adsorbent. The adsorbent prepared by this method has good hydrothermal stability and a large surface area, but there is a problem of poor selective adsorption ability; in addition, the adsorbent obtained by extrusion molding has poor mechanical properties and is easy to break under loading or air flow impact; high-temperature desorption may damage the structure of the adsorbent and reduce its regeneration performance. Therefore, developing a material with good adsorption performance for VOCs is of great significance for improving environmental quality and human health and safety. Summary of the Invention

[0005] To solve the above problems, the object of the present invention is to provide a method for preparing a porous material for removing organic compounds from gases.

[0006] To achieve the above object, the present invention is realized through the following technical solutions:

[0007] A method for preparing a porous material for removing organic compounds from gases, comprising the following steps:

[0008] 1) Add a bis(amino)dimethylfluorene derivative, a bis(amino)dioxolane derivative, and 1,3,6,8-tetrakis(4-formylphenyl)pyrene to a mixed solvent of organic solvent 1 and water. After stirring and mixing evenly, heat to 100 - 150 °C, seal the tube and react for 3 - 7 days, then perform suction filtration. The obtained filter cake is washed 3 - 5 times with organic solvent 2 and water respectively, and dried to obtain a compound;

[0009] 2) Add the compound prepared in step 1) to organic solvent 3, and then add 3 mol / L hydrochloric acid thereto. Heat to 50 - 100 °C and react for 12 - 24 h, then perform suction filtration. The obtained filter cake is washed 3 - 5 times with water and dried to obtain a porous material for removing organic compounds from gases;

[0010] The structural formula of the bis(amino)dimethylfluorene derivative is: ; The structural formula of the bis(amino)dioxolane derivative is: .

[0011] The organic solvent 1 in step 1) is ethanol, acetone, or dimethylformamide.

[0012] In the mixed solvent of organic solvent 1 and water in step 1), the volume ratio of organic solvent 1 to water is 1:0.1 - 0.5.

[0013] In step 1), the mass ratio of the bis(amino)dimethylfluorene derivative, the bis(amino)dioxolane derivative, 1,3,6,8-tetrakis(4-formylphenyl)pyrene, and the mixed solvent is 1:1.1 - 1.4:1.8 - 2.2:10 - 20.

[0014] The organic solvent 2 in step 1) is methanol, ethanol, ether, or acetone.

[0015] The organic solvent 3 in step 2) is tetrahydrofuran, ethanol, acetone, dimethylformamide, or dimethyl sulfoxide.

[0016] In step 2), the mass ratio of the compound, organic solvent 3, and hydrochloric acid is 1:5 - 10:3 - 8.

[0017] The bis(amino)dimethylfluorene derivative is prepared by the following method:

[0018] 2,7-Dihydroxy-9,9-dimethylfluorene and 3-bromopropylamine hydrobromide are added to organic solvent 4. After stirring and dissolving, an inorganic base is added, and the mixture is heated to 50-110 °C for reaction for 8-12 h. After the reaction is completed, suction filtration is carried out, and the obtained filtrate is distilled under reduced pressure to remove the solvent. The obtained residue is washed with water 3-5 times and dried to obtain the bis(amino)dimethylfluorene derivative.

[0019] The organic solvent 4 is acetone, acetonitrile, dimethylformamide or dimethyl sulfoxide.

[0020] The inorganic base is potassium carbonate, sodium carbonate, potassium hydroxide or sodium hydroxide.

[0021] The mass ratio of 2,7-dihydroxy-9,9-dimethylfluorene, 3-bromopropylamine hydrobromide, organic solvent 4 and inorganic base is 1:2-3.8:8-15:1-2.5.

[0022] The preparation method of the bis(amino)dioxolane derivative includes the following steps:

[0023] (1) 2,7-Dihydroxy-9-fluorenone and ethylene glycol are added to organic solvent 5. After stirring and dissolving, p-toluenesulfonic acid is added, and the reaction is carried out at 25-40 °C for 6-8 h. After the reaction is completed, the solvent is removed by distillation under reduced pressure. The obtained residue is washed with water 3-5 times and dried to obtain the dioxolane derivative;

[0024] (2) The dioxolane derivative prepared in step (1) and 3-bromopropylamine hydrobromide are added to organic solvent 4. After stirring and dissolving, an inorganic base is added, and the mixture is heated to 50-110 °C for reaction for 8-12 h. After the reaction is completed, suction filtration is carried out, and the obtained filtrate is distilled under reduced pressure to remove the solvent. The obtained residue is washed with water 3-5 times and dried to obtain the bis(amino)dioxolane derivative.

[0025] The organic solvent 5 in step (1) is dichloromethane, chloroform, acetonitrile and ethyl acetate.

[0026] The mass ratio of 2,7-dihydroxy-9-fluorenone, ethylene glycol, organic solvent 5 and p-toluenesulfonic acid in step (1) is 1:0.3-0.5:5-10:0.01-0.1.

[0027] The mass ratio of the dioxolane derivative, 3-bromopropylamine hydrobromide, organic solvent 4 and inorganic base in step (2) is 1:1.8-3.5:8-15:0.9-2.2.

[0028] The present invention has the following advantages compared with the prior art:

[0029] The porous material for removing organic compounds from gas in the present invention uses a pyrene-based tetraphenylaldehyde derivative as the linking node of the flexible porous material, and fluorene and fluorenone derivatives as the linking arms. The three components are interconnected through an amine-aldehyde condensation reaction to prepare a two-dimensional porous polymer network. The schematic structural diagram is as Figure 1 shown. Among them, the introduction of pyrene can stack different two-dimensional monolayers together through π-π interactions, thereby enhancing the pore depth of the porous material structure and further enhancing its adsorption capacity. In addition, the introduction of pyrene can also change its fluorescence intensity with the change of the concentration of adsorbed VOCs, so that this porous material can display the concentration of VOCs in the environment. The introduction of fluorene and fluorenone respectively adds non-polar and polar functional groups to the pores of the porous material, so that this flexible porous material has the adsorption capacity and compatibility for a variety of VOCs species, including polar and non-polar VOCs molecules.

[0030] The porous material for removing organic compounds from gas in the present invention, wherein the flexible linker can cause the overall porous material framework to twist and deform at high temperature, weakening its ability to accommodate and adsorb VOCs molecules, so that the adsorbed VOCs are released from the bulk material, completing a cycle regeneration of the porous material. In addition, this framework is composed of a hydrophobic skeleton, so it also improves the adsorption of VOCs by this porous material in a humid environment.

[0031] The porous material for removing organic compounds from gas prepared in the present invention has a high specific surface area, a large porosity, adjustable functionality, thermal stability and chemical stability, and has a high adsorption rate for VOCs, and can be used for the removal of organic compounds in gas. Brief Description of the Drawings

[0032] Figure 1 is a schematic structural diagram of the porous material for removing organic compounds from gas in the present invention;

[0033] Figure 2 is a thermogravimetric curve of the porous material for removing organic compounds from gas prepared in Example 3 of the present invention. Detailed Embodiments

[0034] In order to better understand the technical solution of the present invention, the above content of the present invention will be further described in detail through specific embodiments in the form of examples. However, this should not be understood that the scope of the above subject matter of the present invention is limited to the following examples. Any technology implemented based on the above content of the present invention belongs to the scope of the present invention. Example 1

[0035] Preparation of bis(amino)dimethylfluorene derivative:

[0036] Add 0.1 kg of 2,7-dihydroxy-9,9-dimethylfluorene and 0.2 kg of 3-bromopropylamine hydrobromide to 0.8 kg of acetone. After stirring and dissolving, add 0.1 kg of sodium carbonate, heat to 50 °C and react for 12 h. After the reaction is completed, filter by suction. The obtained filtrate is distilled under reduced pressure to remove the solvent. The obtained residue is washed with water 3 times and dried to obtain a bis-terminal amino dimethylfluorene derivative. 1 H NMR(300 MHz, DMSO- d 6 , 293 K): δ 7.88 (d, 2H), 7.18 (s, 2H), 7.03 (d, 2H), 4.07(t, 4H), 2.72 (t, 4H), 1.93 - 2.08 (m, 4H), 1.64 (s, 6H), 1.45 (s, 4H).

[0037] Preparation of bis-terminal amino dioxolane derivative:

[0038] Add 0.1 kg of 2,7-dihydroxy-9-fluorenone and 0.03 kg of ethylene glycol to 0.5 kg of dichloromethane. After stirring and dissolving, add 0.001 kg of p-toluenesulfonic acid and react at 25 °C for 8 h. After the reaction is completed, the solvent is removed by distillation under reduced pressure. The obtained residue is washed with water 3 times and dried to obtain a dioxolane derivative;

[0039] Add 0.1 kg of the dioxolane derivative and 0.18 kg of 3-bromopropylamine hydrobromide to 0.8 kg of acetone. After stirring and dissolving, add 0.09 kg of sodium carbonate, heat to 50 °C and react for 12 h. After the reaction is completed, filter by suction. The obtained filtrate is distilled under reduced pressure to remove the solvent. The obtained residue is washed with water 3 times and dried to obtain a bis-terminal amino dioxolane derivative. 1 H NMR (300 MHz,DMSO- d 6 , 293 K): δ 7.91 (d, 2H), 7.20 (s, 2H), 7.02 (d, 2H), 4.06 (t, 4H),3.85 (t, 4H), 2.69 (t, 4H), 1.95 - 2.05 (m, 4H), 1.50 (s, 4H).

[0040] Preparation of a porous material for removing organic compounds from gases:

[0041] Add 0.1 kg of bis(amino)dimethylfluorene derivative, 0.11 kg of bis(amino)dioxolane derivative, and 0.18 kg of 1,3,6,8-tetrakis(4-formylphenyl)pyrene to 1 kg of a mixed solvent of ethanol and water, where the volume ratio of ethanol to water is 1:0.1. After stirring and mixing evenly, heat to 100 °C and react in a sealed tube for 7 days. Then, perform suction filtration. Wash the obtained filter cake 3 times each with methanol and water, and dry it to obtain a compound.

[0042] Add 0.1 kg of the compound to 0.5 kg of tetrahydrofuran, and then add 0.3 kg of 3 mol / L hydrochloric acid thereto. Heat to 50 °C and react for 24 h. Perform suction filtration. Wash the obtained filter cake 3 times with water and dry it to obtain a porous material for removing organic compounds from gas. Example 2

[0043] Preparation of bis(amino)dimethylfluorene derivative:

[0044] Add 0.1 kg of 2,7-dihydroxy-9,9-dimethylfluorene and 0.25 kg of 3-bromopropylamine hydrobromide to 0.9 kg of acetonitrile. After stirring and dissolving, add 0.23 kg of potassium carbonate and heat to 70 °C to react for 11 h. After the reaction is completed, perform suction filtration. Distill off the solvent from the obtained filtrate under reduced pressure. Wash the obtained residue 4 times with water and dry it to obtain bis(amino)dimethylfluorene derivative.

[0045] Preparation of bis(amino)dioxolane derivative:

[0046] Add 0.1 kg of 2,7-dihydroxy-9-fluorenone and 0.035 kg of ethylene glycol to 0.6 kg of chloroform. After stirring and dissolving, add 0.003 kg of p-toluenesulfonic acid and react at 30 °C for 7 h. After the reaction is completed, distill off the solvent under reduced pressure. Wash the obtained residue 4 times with water and dry it to obtain a dioxolane derivative.

[0047] Add 0.1 kg of the dioxolane derivative and 0.22 kg of 3-bromopropylamine hydrobromide to 1 kg of acetonitrile. After stirring and dissolving, add 0.14 kg of sodium hydroxide and heat to 60 °C to react for 12 h. After the reaction is completed, perform suction filtration. Distill off the solvent from the obtained filtrate under reduced pressure. Wash the obtained residue 4 times with water and dry it to obtain bis(amino)dioxolane derivative.

[0048] Preparation of the porous material for removing organic compounds from gas:

[0049] Add 0.1 kg of bis(amino)dimethylfluorene derivative, 0.12 kg of bis(amino)dioxolane derivative, and 0.19 kg of 1,3,6,8-tetrakis(4-formylphenyl)pyrene into 1.2 kg of a mixed solvent of acetone and water, where the volume ratio of acetone to water is 1:0.2. After stirring and mixing evenly, heat to 110 °C, seal the tube and react for 6 days. Then, perform suction filtration. Wash the obtained filter cake 4 times with ethanol and water respectively, and dry it to obtain a compound.

[0050] Add 0.1 kg of the compound into 0.6 kg of ethanol, then add 0.4 kg of 3 mol / L hydrochloric acid thereto, heat to 60 °C and react for 22 h. Perform suction filtration. Wash the obtained filter cake 4 times with water and dry it to obtain a porous material for removing organic compounds from gas. Example 3

[0051] Preparation of bis(amino)dimethylfluorene derivative:

[0052] Add 0.1 kg of 2,7-dihydroxy-9,9-dimethylfluorene and 0.3 kg of 3-bromopropylamine hydrobromide into 1.2 kg of dimethyl sulfoxide. After stirring and dissolving, add 0.18 kg of sodium hydroxide, heat to 90 °C and react for 10 h. After the reaction is completed, perform suction filtration. Distill off the solvent from the obtained filtrate under reduced pressure. Wash the obtained residue 5 times with water and dry it to obtain bis(amino)dimethylfluorene derivative.

[0053] Preparation of bis(amino)dioxolane derivative:

[0054] Add 0.1 kg of 2,7-dihydroxy-9-fluorenone and 0.04 kg of ethylene glycol into 0.7 kg of acetonitrile. After stirring and dissolving, add 0.005 kg of p-toluenesulfonic acid and react at 35 °C for 7 h. After the reaction is completed, distill off the solvent under reduced pressure. Wash the obtained residue 5 times with water and dry it to obtain a dioxolane derivative.

[0055] Add 0.1 kg of the dioxolane derivative and 0.28 kg of 3-bromopropylamine hydrobromide into 1.1 kg of dimethyl sulfoxide. After stirring and dissolving, add 0.18 kg of potassium hydroxide, heat to 80 °C and react for 10 h. After the reaction is completed, perform suction filtration. Distill off the solvent from the obtained filtrate under reduced pressure. Wash the obtained residue 5 times with water and dry it to obtain bis(amino)dioxolane derivative.

[0056] Preparation of the porous material for removing organic compounds from gas:

[0057] Add 0.1 kg of bis(amino)dimethylfluorene derivative, 0.12 kg of bis(amino)dioxolane derivative, and 0.2 kg of 1,3,6,8-tetrakis(4-formylphenyl)pyrene into a mixed solvent of 1.5 kg of dimethylformamide and water, where the volume ratio of dimethylformamide to water is 1:0.3. After stirring and mixing evenly, heat to 120 °C, seal the reaction tube for 5 days, perform suction filtration, and wash the obtained filter cake 5 times with acetone and water respectively, then dry it to obtain the compound;

[0058] Add 0.1 kg of the compound into 0.7 kg of acetone, then add 0.5 kg of 3 mol / L hydrochloric acid thereto, heat to 80 °C and react for 18 h, perform suction filtration, wash the obtained filter cake 5 times with water, and dry it to obtain the porous material for removing organic compounds from gas. Example 4

[0059] Preparation of bis(amino)dimethylfluorene derivative:

[0060] Add 0.1 kg of 2,7-dihydroxy-9,9-dimethylfluorene and 0.35 kg of 3-bromopropylamine hydrobromide into 1.4 kg of dimethylformamide, stir to dissolve, then add 0.2 kg of potassium hydroxide, heat to 100 °C and react for 9 h. After the reaction is completed, perform suction filtration, distill off the solvent under reduced pressure for the obtained filtrate, wash the obtained residue 5 times with water, and dry it to obtain the bis(amino)dimethylfluorene derivative.

[0061] Preparation of bis(amino)dioxolane derivative:

[0062] Add 0.1 kg of 2,7-dihydroxy-9-fluorenone and 0.045 kg of ethylene glycol into 0.8 kg of ethyl acetate, stir to dissolve, then add 0.008 kg of p-toluenesulfonic acid, and react at 35 °C for 6.5 h. After the reaction is completed, distill off the solvent under reduced pressure, wash the obtained residue 5 times with water, and dry it to obtain the dioxolane derivative;

[0063] Add 0.1 kg of the dioxolane derivative and 0.32 kg of 3-bromopropylamine hydrobromide into 1.4 kg of dimethylformamide, stir to dissolve, then add 0.2 kg of potassium carbonate, heat to 100 °C and react for 9 h. After the reaction is completed, perform suction filtration, distill off the solvent under reduced pressure for the obtained filtrate, wash the obtained residue 5 times with water, and dry it to obtain the bis(amino)dioxolane derivative.

[0064] Preparation of the porous material for removing organic compounds from gas:

[0065] 0.1 kg of the bis(amino)-dimethylfluorene derivative, 0.13 kg of the bis(amino)-dioxolane derivative, and 0.21 kg of 1,3,6,8-tetrakis(4-formylphenyl)pyrene were added to a mixed solvent of 1.8 kg of acetone and water, where the volume ratio of acetone to water was 1:0.4. After stirring and mixing evenly, it was heated to 140 °C and reacted in a sealed tube for 4 days. Then, it was filtered by suction. The obtained filter cake was washed 5 times with acetone and water respectively, and then dried to obtain the compound;

[0066] 0.1 kg of the compound was added to 0.8 kg of tetrahydrofuran, and then 0.7 kg of 3 mol / L hydrochloric acid was added thereto. It was heated to 90 °C and reacted for 15 h. Then, it was filtered by suction. The obtained filter cake was washed 5 times with water and then dried to obtain the porous material for removing organic compounds from gases. Example 5

[0067] Preparation of the bis(amino)-dimethylfluorene derivative:

[0068] 0.1 kg of 2,7-dihydroxy-9,9-dimethylfluorene and 0.38 kg of 3-bromopropylamine hydrobromide were added to 1.5 kg of acetonitrile. After stirring and dissolving, 0.25 kg of potassium carbonate was added, and it was heated to 110 °C and reacted for 8 h. After the reaction was completed, it was filtered by suction. The obtained filtrate was distilled under reduced pressure to remove the solvent. The obtained residue was washed 5 times with water and then dried to obtain the bis(amino)-dimethylfluorene derivative.

[0069] Preparation of the bis(amino)-dioxolane derivative:

[0070] 0.1 kg of 2,7-dihydroxy-9-fluorenone and 0.05 kg of ethylene glycol were added to 1 kg of chloroform. After stirring and dissolving, 0.01 kg of p-toluenesulfonic acid was added, and it was reacted at 40 °C for 6 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure. The obtained residue was washed 5 times with water and then dried to obtain the dioxolane derivative;

[0071] 0.1 kg of the dioxolane derivative and 0.35 kg of 3-bromopropylamine hydrobromide were added to 1.5 kg of acetonitrile. After stirring and dissolving, 0.22 kg of potassium carbonate was added, and it was heated to 110 °C and reacted for 8 h. After the reaction was completed, it was filtered by suction. The obtained filtrate was distilled under reduced pressure to remove the solvent. The obtained residue was washed 5 times with water and then dried to obtain the bis(amino)-dioxolane derivative.

[0072] Preparation of the porous material for removing organic compounds from gases:

[0073] Add 0.1 kg of bis(amino)dimethylfluorene derivative, 0.14 kg of bis(amino)dioxolane derivative, and 0.22 kg of 1,3,6,8-tetrakis(4-formylphenyl)pyrene to 2 kg of a mixed solvent of ethanol and water, where the volume ratio of ethanol to water is 1:0.5. After stirring and mixing evenly, heat to 150 °C, seal the tube and react for 3 days. Then, perform suction filtration. Wash the obtained filter cake 3 times with acetone and water respectively, and dry it to obtain a compound.

[0074] Add 0.1 kg of the compound to 1 kg of acetone, then add 0.8 kg of 3 mol / L hydrochloric acid thereto, heat to 100 °C and react for 12 h. Perform suction filtration. Wash the obtained filter cake 3 times with water and dry it to obtain a porous material for removing organic compounds from gas. Example 6

[0075] Preparation of bis(amino)dimethylfluorene derivative:

[0076] Add 0.1 kg of 2,7-dihydroxy-9,9-dimethylfluorene and 0.33 kg of 3-bromopropylamine hydrobromide to 1.3 kg of acetone. After stirring and dissolving, add 0.25 kg of sodium hydroxide, heat to 110 °C and react for 12 h. After the reaction is completed, perform suction filtration. Distill off the solvent under reduced pressure from the obtained filtrate. Wash the obtained residue 5 times with water and dry it to obtain bis(amino)dimethylfluorene derivative.

[0077] Preparation of bis(amino)dioxolane derivative:

[0078] Add 0.1 kg of 2,7-dihydroxy-9-fluorenone and 0.04 kg of ethylene glycol to 0.8 kg of dichloromethane. After stirring and dissolving, add 0.001 kg of p-toluenesulfonic acid and react at 25 °C for 6 h. After the reaction is completed, distill off the solvent under reduced pressure. Wash the obtained residue 5 times with water and dry it to obtain a dioxolane derivative.

[0079] Add 0.1 kg of the dioxolane derivative and 0.3 kg of 3-bromopropylamine hydrobromide to 1.2 kg of acetone. After stirring and dissolving, add 0.2 kg of sodium hydroxide, heat to 110 °C and react for 12 h. After the reaction is completed, perform suction filtration. Distill off the solvent under reduced pressure from the obtained filtrate. Wash the obtained residue 5 times with water and dry it to obtain bis(amino)dioxolane derivative.

[0080] Preparation of the porous material for removing organic compounds from gas:

[0081] Add 0.1 kg of bis(amino)dimethylfluorene derivative, 0.12 kg of bis(amino)dioxolane derivative, and 0.2 kg of 1,3,6,8-tetrakis(4-formylphenyl)pyrene into a mixed solvent of 2 kg of dimethylformamide and water, where the volume ratio of ethanol to water is 1:0.1. After stirring and mixing evenly, heat to 150 °C and react in a sealed tube for 7 days. Then, perform suction filtration. Wash the obtained filter cake 4 times with ether and water respectively, and dry it to obtain a compound;

[0082] Add 0.1 kg of the compound into 1 kg of dimethyl sulfoxide, and then add 0.5 kg of 3 mol / L hydrochloric acid thereto. Heat to 50 °C and react for 24 h. Perform suction filtration. Wash the obtained filter cake 4 times with water and dry it to obtain a porous material for removing organic compounds from gas.

[0083] Test the porous materials for removing organic compounds from gas prepared in Examples 1 to 6 respectively using a Micromeritics Tristar II 3020 automatic specific surface area and porosity analyzer. The test results are shown in Table 1. It can be seen from the results in Table 1 that the porous materials for removing organic compounds from gas prepared in the present invention have a relatively large specific surface area and pore volume.

[0084] Table 1 Results of performance parameters of the porous materials prepared in Examples 1 to 6

[0085]

[0086] Perform thermogravimetric analysis on the porous material for removing organic compounds from gas prepared in Example 3 of the present invention. Its test spectrum is as Figure 2 shown. It can be seen from the Figure 2 results that the porous material for removing organic compounds from gas prepared in the present invention basically has no weight loss before 400 °C, indicating that it has good thermal stability. When working at high temperature, it will not cause leakage of the material and avoid environmental pollution.

[0087] Evaluate the performance of removing VOCs from the porous materials for removing organic compounds from gas prepared in Examples 1 to 6 of the present invention respectively. The specific evaluation method is as follows: The raw gas is a mixture of VOCs with a concentration of 100 ppm and high-purity air. The reaction temperature is 30 °C, and the gas volume space velocity is 400 min -1 . After reacting for 1 h, take a sample to measure the content of VOCs. The activated carbon is used as an adsorbent in the comparative example. The test results are shown in Table 2. It can be seen from the results in Table 2 that the porous materials for removing organic compounds from gas prepared in the present invention have a higher VOCs removal rate compared with the comparative example and can be used for removing organic compounds from gas.

[0088] Table 2 VOC removal results of the materials prepared in Examples 1 - 6 and the comparative example materials

[0089]

[0090] Although the specific embodiments of the present invention are described above, it is not a limitation on the protection scope of the present invention. Based on the technical solutions of the present invention, various modifications or deformations that can be made by those skilled in the art without creative efforts are still within the protection scope of the present invention.

Claims

1. A method for preparing a porous material for removing organic compounds from gas, characterized in that: The following steps are involved: 1) Adding a double-terminal amino dimethylfluorene derivative, a double-terminal amino dioxolane derivative and 1,3,6,8-tetrakis(4-formaldehyde phenyl)pyrene to a mixed solvent of an organic solvent 1 and water, stirring and mixing evenly, heating to 100-150° C., sealing the tube for reaction for 3-7 days, filtering, washing the obtained filter cake with an organic solvent 2 and water for 3-5 times respectively, and drying to obtain a compound; the organic solvent 1 is ethanol, acetone or dimethylformamide; the organic solvent 2 is methanol, ethanol, ether or acetone; The mass ratio of the double-terminal amino dimethylfluorene derivative, the double-terminal amino dioxolane derivative, 1,3,6,8-tetrakis(4-formaldehyde phenyl)pyrene and the mixed solvent is 1:1.1-1.4:1.8-2.2:10-20; 2) adding the compound prepared in step 1) to an organic solvent 3, then adding 3 mol / L hydrochloric acid thereto, heating to 50-100° C. to react for 12-24 hours, filtering with suction, washing the obtained filter cake with water for 3-5 times, and drying to obtain a porous material for removing organic compounds from gas; the organic solvent 3 is tetrahydrofuran, ethanol, acetone, dimethylformamide or dimethyl sulfoxide; The mass ratio of the compound, the organic solvent 3 and the hydrochloric acid is 1:5~10:3~8; The structural formula of the double-terminated amino-dimethylfluorene derivative is: ;The structural formula of the double-terminated amino-dioxolane derivative is: .

2. The method for preparing a porous material for removing organic compounds from gas according to claim 1, characterized in that: The volume ratio of the organic solvent 1 to water in the mixed solvent of the organic solvent 1 and water is 1:0.1-0.

5.

3. The method for preparing a porous material for removing organic compounds from gas according to claim 1, characterized in that: The double-terminated amino-dimethylfluorene derivative is prepared according to the following method: Add 2,7-dihydroxy-9,9-dimethylfluorene and 3-bromopropylamine hydrobromide to organic solvent 4, stir to dissolve, then add inorganic base, heat to 50-110°C to react for 8-12 hours. After the reaction is completed, filter, distill the filtrate under reduced pressure to remove the solvent, wash the residue with water 3-5 times, and dry to obtain a double-terminal amino-dimethylfluorene derivative.

4. The method for preparing a porous material for removing organic compounds from gas according to claim 3, characterized in that: The organic solvent 4 is acetone, acetonitrile, dimethylformamide or dimethyl sulfoxide.

5. The method for preparing a porous material for removing organic compounds from gas according to claim 3, characterized in that: The inorganic base is potassium carbonate, sodium carbonate, potassium hydroxide or sodium hydroxide.

6. The method for preparing a porous material for removing organic compounds from gas according to claim 3, characterized in that: The mass ratio of the 2,7-dihydroxy-9,9-dimethylfluorene, 3-bromopropylamine hydrobromide, the organic solvent 4 and the inorganic base is 1:2-3.8:8-15:1-2.

5.

7. The method for preparing a porous material for removing organic compounds from gas according to claim 1, characterized in that: The preparation method of the double-terminal amino-dioxolane derivative comprises the following steps: (1) Add 2,7-dihydroxy-9-fluorenone and ethylene glycol to an organic solvent 5, stir to dissolve, then add p-toluenesulfonic acid, and react at 25-40° C. for 6-8 hours. After the reaction is completed, remove the solvent by distillation under reduced pressure, wash the residue with water for 3-5 times, and dry to obtain a dioxolane derivative; (2) The dioxolane derivative and 3-bromopropylamine hydrobromide prepared in step (1) are added to an organic solvent 4, stirred to dissolve, and then an inorganic base is added, and the mixture is heated to 50-110° C. to react for 8-12 hours. After the reaction is completed, the mixture is filtered, and the solvent is removed by vacuum distillation of the obtained filtrate. The obtained residue is washed with water for 3-5 times and dried to obtain a double-terminal amino dioxolane derivative.

8. The method for preparing a porous material for removing organic compounds from gas according to claim 7, characterized in that: The organic solvent 5 in step (1) is dichloromethane, chloroform, acetonitrile and ethyl acetate; the mass ratio of the 2,7-dihydroxy-9-fluorenone, ethylene glycol, organic solvent 5 and p-toluenesulfonic acid is 1:0.3~0.5:5~10:0.01~0.

1.

9. The method for preparing a porous material for removing organic compounds from gas according to claim 7, characterized in that: The mass ratio of the dioxolane derivative, 3-bromopropylamine hydrobromide, organic solvent 4 and inorganic base in step (2) is 1:1.8~3.5:8~15:0.9~2.2.

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