Preparation method of porous material for removing organic compounds from gas

Abstract

The invention discloses a preparation method of a porous material for removing organic compounds from gas, and belongs to the technical field of organic synthesis.The preparation method comprises the steps that a tetrabenzaldehyde derivative with pyrene as a core is used as a connecting node of the flexible porous material, fluorene and fluorenone derivatives are used as connecting arms, and the three components are mutually connected through an amine-aldehyde condensation reaction; the porous material for removing the organic compounds from the gas, which is prepared by the preparation method disclosed by the invention, has relatively high specific surface area, relatively large porosity, function adjustability, thermal stability and chemical stability, has relatively high adsorption rate on VOCs (Volatile Organic Compounds), and can be used for removing the organic compounds from the gas.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and in particular is a method for preparing a porous material for removing organic compounds from gas. Background Art

[0002] VOCs, or 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. They are widely present in our daily lives, such as paints, cleaners, building materials, etc.

[0003] VOCs are quite harmful to the environment and human health. In terms of the environment, VOCs are important precursors to 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 will cause global warming. For human health, VOCs have different toxicity and irritation. When exceeding a certain concentration, they will irritate people's eyes and respiratory tract, cause skin allergies, sore throat and fatigue. In severe cases, they will cause imbalance in the body's immune level, affect the function of the central nervous system, and damage the digestive system, liver function and hematopoietic system. 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 to improving air quality and protecting human health. At present, the materials that can be used for VOCs adsorption mainly include activated carbon, activated carbon fiber, diatomaceous earth, mesoporous silica, metal organic frameworks (MOFs) and molecular sieves. However, these materials generally have problems such as decreased adsorption capacity for VOCs under high humidity conditions, low adsorption capacity and difficulty in regeneration.

[0004] Patent CN 107128932A discloses a method for preparing 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 a preparation method, wherein a silicon source, an aluminum source and a template are used to prepare a VOCs adsorbent precursor 1; the adsorbent precursor 1 is treated to obtain a VOCs adsorbent precursor 2; finally, the obtained VOCs adsorbent precursor 2 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 capacity; in addition, the adsorbent obtained by extrusion molding has poor mechanical properties and is easily broken under filling or airflow impact; high-temperature desorption may destroy the adsorbent structure and reduce its regeneration performance. Therefore, the development of a material with good adsorption performance for VOCs is of great significance to improving environmental quality and human health and safety. Summary of the invention

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

[0006] In order to achieve the above object, the present invention is implemented through the following technical solutions: A method for preparing a porous material for removing organic compounds from gas comprises the following steps: 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 organic solvent 1 and water, stirring and mixing evenly, heating to 100-150° C., sealing the tube to react for 3-7 days, filtering, and washing the obtained filter cake with organic solvent 2 and water for 3-5 times respectively, and drying to obtain a compound; 2) adding the compound prepared in step 1) to an organic solvent 3, and then adding 3 mol / L hydrochloric acid thereto, heating to 50-100° C. to react for 12-24 hours, filtering by 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 structural formula of the double-terminated amino-dimethylfluorene derivative is: ;The structural formula of the double-terminated amino-dioxolane derivative is: .

[0007] In step 1), the organic solvent 1 is ethanol, acetone or dimethylformamide.

[0008] In step 1), 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.

[0009] The mass ratio of the double-terminated amino-dimethylfluorene derivative, the double-terminated amino-dioxolane derivative, 1,3,6,8-tetrakis(4-formaldehydephenyl)pyrene and the mixed solvent in step 1) is 1:1.1-1.4:1.8-2.2:10-20.

[0010] The organic solvent 2 in step 1) is methanol, ethanol, ether or acetone.

[0011] The organic solvent 3 in step 2) is tetrahydrofuran, ethanol, acetone, dimethylformamide or dimethyl sulfoxide.

[0012] The mass ratio of the compound, the organic solvent 3 and the hydrochloric acid in step 2) is 1:5~10:3~8.

[0013] 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.

[0014] The organic solvent 4 is acetone, acetonitrile, dimethylformamide or dimethyl sulfoxide.

[0015] The inorganic base is potassium carbonate, sodium carbonate, potassium hydroxide or sodium hydroxide.

[0016] 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.

[0017] 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.

[0018] The organic solvent 5 in step (1) is dichloromethane, chloroform, acetonitrile and ethyl acetate.

[0019] 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.

[0020] 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.

[0021] Compared with the prior art, the present invention has the following advantages: The porous material for removing organic compounds from gas of the present invention uses a tetrabenzaldehyde derivative with pyrene as the core as the connecting node of the flexible porous material, uses fluorene and fluorenone derivatives as connecting arms, and connects the three components to each other through an amine-aldehyde condensation reaction to prepare a two-dimensional porous polymer network. The schematic diagram of its structure is shown in FIG. Figure 1 As shown. The introduction of pyrene can make different two-dimensional monolayers stack 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 as the concentration of adsorbed VOCs changes, so that this porous material has the function of displaying 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 multiple VOCs species, including polar and non-polar VOCs molecules.

[0022] The porous material for removing organic compounds from gas of the present invention has a flexible linker that can cause the overall porous material framework to twist and deform at high temperatures, thereby weakening its ability to accommodate and adsorb VOCs molecules, thereby releasing the adsorbed VOCs from the bulk material and completing a cycle regeneration of the porous material; in addition, the framework is composed of a hydrophobic skeleton, thereby also improving the adsorption of VOCs by the porous material in a humid environment.

[0023] The porous material for removing organic compounds from gas prepared by the present invention has a high specific surface area, a large porosity, functional adjustability, thermal stability and chemical stability, has a high adsorption rate for VOCs, and can be used for removing organic compounds from gas. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 A schematic diagram of the structure of a porous material for removing organic compounds from gas according to the present invention; Figure 2 This is a thermogravimetric curve of the porous material for removing organic compounds from gas prepared in Example 3 of the present invention. DETAILED DESCRIPTION

[0025] In order to better understand the technical solution of the present invention, the above content of the present invention is further described in detail below through specific implementation methods in the form of embodiments, but this should not be understood as the scope of the above subject matter of the present invention being limited to the following examples. All technologies realized based on the above content of the present invention belong to the scope of the present invention. Example 1

[0026] Preparation of double-terminated amino-dimethylfluorene derivatives: 0.1 kg of 2,7-dihydroxy-9,9-dimethylfluorene and 0.2 kg of 3-bromopropylamine hydrobromide were added to 0.8 kg of acetone, stirred to dissolve, and then 0.1 kg of sodium carbonate was added. The mixture was heated to 50°C and reacted for 12 hours. After the reaction was completed, the mixture was filtered and the solvent was removed by vacuum distillation of the filtrate. The residue was washed 3 times with water and dried to obtain a double-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).

[0027] Preparation of double-terminated amino-dioxolane derivatives: 0.1 kg of 2,7-dihydroxy-9-fluorenone and 0.03 kg of ethylene glycol were added to 0.5 kg of dichloromethane, stirred and dissolved, and then 0.001 kg of p-toluenesulfonic acid was added, and the mixture was reacted at 25° C. for 8 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the residue was washed with water 3 times and dried to obtain a dioxolane derivative; 0.1 kg of dioxolane derivative and 0.18 kg of 3-bromopropylamine hydrobromide were added to 0.8 kg of acetone, stirred to dissolve, and then 0.09 kg of sodium carbonate was added. The mixture was heated to 50°C and reacted for 12 hours. After the reaction was completed, the mixture was filtered and the solvent was removed by vacuum distillation of the filtrate. The residue was washed 3 times with water and dried to obtain a double-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).

[0028] Preparation of porous materials for the removal of organic compounds from gases: 0.1 kg of a double-terminal amino-dimethylfluorene derivative, 0.11 kg of a double-terminal amino-dioxolane derivative and 0.18 kg of 1,3,6,8-tetrakis(4-formaldehydephenyl)pyrene were added to a mixed solvent of 1 kg of ethanol and water, wherein the volume ratio of ethanol to water was 1:0.1, stirred and mixed evenly, heated to 100°C, sealed and reacted for 7 days, filtered, and the obtained filter cake was washed 3 times with methanol and water respectively, and dried to obtain a compound; 0.1 kg of the compound was added to 0.5 kg of tetrahydrofuran, and then 0.3 kg of 3 mol / L hydrochloric acid was added thereto, and the mixture was heated to 50° C. and reacted for 24 hours. The mixture was filtered and the filter cake was washed three times with water and dried to obtain a porous material for removing organic compounds from gas. Example 2

[0029] Preparation of double-terminated amino-dimethylfluorene derivatives: 0.1 kg of 2,7-dihydroxy-9,9-dimethylfluorene and 0.25 kg of 3-bromopropylamine hydrobromide were added to 0.9 kg of acetonitrile, stirred to dissolve, and then 0.23 kg of potassium carbonate was added. The mixture was heated to 70°C and reacted for 11 hours. After the reaction was completed, the mixture was filtered and the solvent was removed by vacuum distillation of the filtrate. The residue was washed 4 times with water and dried to obtain a double-terminated amino-dimethylfluorene derivative.

[0030] Preparation of double-terminated amino-dioxolane derivatives: 0.1 kg of 2,7-dihydroxy-9-fluorenone and 0.035 kg of ethylene glycol were added to 0.6 kg of chloroform, and after stirring to dissolve, 0.003 kg of p-toluenesulfonic acid was added, and the mixture was reacted at 30° C. for 7 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the residue was washed with water 4 times and dried to obtain a dioxolane derivative; 0.1 kg of dioxolane derivative and 0.22 kg of 3-bromopropylamine hydrobromide were added to 1 kg of acetonitrile, stirred to dissolve, and then 0.14 kg of sodium hydroxide was added. The mixture was heated to 60°C and reacted for 12 hours. After the reaction was completed, the mixture was filtered and the solvent was removed by vacuum distillation of the filtrate. The residue was washed with water 4 times and dried to obtain a double-terminated amino-dioxolane derivative.

[0031] Preparation of porous materials for the removal of organic compounds from gases: 0.1 kg of a double-terminal amino-dimethylfluorene derivative, 0.12 kg of a double-terminal amino-dioxolane derivative and 0.19 kg of 1,3,6,8-tetrakis(4-formaldehydephenyl)pyrene were added to a mixed solvent of 1.2 kg of acetone and water, wherein the volume ratio of acetone to water was 1:0.2, and after stirring and mixing evenly, the mixture was heated to 110° C., sealed and reacted for 6 days, and filtered, and the filter cake was washed 4 times with ethanol and water respectively, and dried to obtain a compound; 0.1 kg of the compound was added to 0.6 kg of ethanol, and then 0.4 kg of 3 mol / L hydrochloric acid was added thereto, and the mixture was heated to 60° C. and reacted for 22 hours. The mixture was filtered and the filter cake was washed 4 times with water and dried to obtain a porous material for removing organic compounds from gas. Example 3

[0032] Preparation of double-terminated amino-dimethylfluorene derivatives: 0.1 kg of 2,7-dihydroxy-9,9-dimethylfluorene and 0.3 kg of 3-bromopropylamine hydrobromide were added to 1.2 kg of dimethyl sulfoxide, stirred to dissolve, and then 0.18 kg of sodium hydroxide was added. The mixture was heated to 90°C and reacted for 10 hours. After the reaction was completed, the mixture was filtered and the solvent was removed by vacuum distillation of the filtrate. The residue was washed with water 5 times and dried to obtain a double-terminal amino-dimethylfluorene derivative.

[0033] Preparation of double-terminated amino-dioxolane derivatives: 0.1 kg of 2,7-dihydroxy-9-fluorenone and 0.04 kg of ethylene glycol were added to 0.7 kg of acetonitrile, and after stirring and dissolving, 0.005 kg of p-toluenesulfonic acid was added, and the mixture was reacted at 35° C. for 7 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the residue was washed with water 5 times and dried to obtain a dioxolane derivative; 0.1 kg of dioxolane derivative and 0.28 kg of 3-bromopropylamine hydrobromide were added to 1.1 kg of dimethyl sulfoxide, stirred to dissolve, and then 0.18 kg of potassium hydroxide was added. The mixture was heated to 80°C and reacted for 10 hours. After the reaction was completed, the mixture was filtered and the solvent was removed by distillation under reduced pressure. The residue was washed with water 5 times and dried to obtain a double-terminal amino dioxolane derivative.

[0034] Preparation of porous materials for the removal of organic compounds from gases: 0.1 kg of a double-terminal amino-dimethylfluorene derivative, 0.12 kg of a double-terminal amino-dioxolane derivative and 0.2 kg of 1,3,6,8-tetrakis(4-formaldehydephenyl)pyrene were added to a mixed solvent of 1.5 kg of dimethylformamide and water, wherein the volume ratio of dimethylformamide to water was 1:0.3, and after stirring and mixing evenly, the mixture was heated to 120° C., sealed and reacted for 5 days, and filtered, and the filter cake was washed 5 times with acetone and water respectively, and dried to obtain a compound; 0.1 kg of the compound was added to 0.7 kg of acetone, and then 0.5 kg of 3 mol / L hydrochloric acid was added thereto, and the mixture was heated to 80° C. and reacted for 18 hours. The mixture was filtered and the filter cake was washed 5 times with water and dried to obtain a porous material for removing organic compounds from gas. Example 4

[0035] Preparation of double-terminated amino-dimethylfluorene derivatives: 0.1 kg of 2,7-dihydroxy-9,9-dimethylfluorene and 0.35 kg of 3-bromopropylamine hydrobromide were added to 1.4 kg of dimethylformamide, stirred to dissolve, and then 0.2 kg of potassium hydroxide was added. The mixture was heated to 100 °C and reacted for 9 hours. After the reaction was completed, the mixture was filtered and the solvent was removed by vacuum distillation of the filtrate. The residue was washed with water 5 times and dried to obtain a double-terminated amino-dimethylfluorene derivative.

[0036] Preparation of double-terminated amino-dioxolane derivatives: 0.1 kg of 2,7-dihydroxy-9-fluorenone and 0.045 kg of ethylene glycol were added to 0.8 kg of ethyl acetate, and after stirring and dissolving, 0.008 kg of p-toluenesulfonic acid was added, and the mixture was reacted at 35° C. for 6.5 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the residue was washed with water 5 times and dried to obtain a dioxolane derivative; 0.1 kg of dioxolane derivative and 0.32 kg of 3-bromopropylamine hydrobromide were added to 1.4 kg of dimethylformamide, stirred to dissolve, and then 0.2 kg of potassium carbonate was added. The mixture was heated to 100 °C and reacted for 9 hours. After the reaction was completed, the mixture was filtered and the solvent was removed by vacuum distillation of the filtrate. The residue was washed with water 5 times and dried to obtain a double-terminal amino dioxolane derivative.

[0037] Preparation of porous materials for the removal of organic compounds from gases: 0.1 kg of a double-terminal amino dimethylfluorene derivative, 0.13 kg of a double-terminal amino dioxolane derivative and 0.21 kg of 1,3,6,8-tetrakis(4-formaldehyde phenyl)pyrene were added to a mixed solvent of 1.8 kg of acetone and water, wherein the volume ratio of acetone to water was 1:0.4, and after stirring and mixing evenly, the mixture was heated to 140° C., sealed and reacted for 4 days, and filtered, and the filter cake was washed 5 times with acetone and water respectively, and dried to obtain a compound; 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, and the mixture was heated to 90° C. and reacted for 15 hours. The mixture was filtered and the filter cake was washed 5 times with water and dried to obtain a porous material for removing organic compounds from gas. Example 5

[0038] Preparation of double-terminated amino-dimethylfluorene derivatives: 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, stirred to dissolve, and then 0.25 kg of potassium carbonate was added. The mixture was heated to 110°C and reacted for 8 hours. After the reaction was completed, the mixture was filtered and the solvent was removed by vacuum distillation of the filtrate. The residue was washed 5 times with water and dried to obtain a double-terminated amino-dimethylfluorene derivative.

[0039] Preparation of double-terminated amino-dioxolane derivatives: 0.1 kg of 2,7-dihydroxy-9-fluorenone and 0.05 kg of ethylene glycol were added to 1 kg of chloroform, stirred and dissolved, and then 0.01 kg of p-toluenesulfonic acid was added, and the mixture was reacted at 40° C. for 6 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the residue was washed with water 5 times and dried to obtain a dioxolane derivative; 0.1 kg of dioxolane derivative and 0.35 kg of 3-bromopropylamine hydrobromide were added to 1.5 kg of acetonitrile, stirred to dissolve, and then 0.22 kg of potassium carbonate was added. The mixture was heated to 110°C and reacted for 8 hours. After the reaction was completed, the mixture was filtered and the solvent was removed by vacuum distillation of the filtrate. The residue was washed with water 5 times and dried to obtain a double-terminal amino dioxolane derivative.

[0040] Preparation of porous materials for the removal of organic compounds from gases: 0.1 kg of a double-terminal amino-dimethylfluorene derivative, 0.14 kg of a double-terminal amino-dioxolane derivative and 0.22 kg of 1,3,6,8-tetrakis(4-formaldehydephenyl)pyrene were added to a mixed solvent of 2 kg of ethanol and water, wherein the volume ratio of ethanol to water was 1:0.5, and after stirring and mixing evenly, the mixture was heated to 150° C., sealed and reacted for 3 days, and filtered, and the filter cake was washed 3 times with acetone and water respectively, and dried to obtain a compound; 0.1 kg of the compound was added to 1 kg of acetone, and then 0.8 kg of 3 mol / L hydrochloric acid was added thereto, and the mixture was heated to 100° C. and reacted for 12 hours. The mixture was filtered and the filter cake was washed three times with water and dried to obtain a porous material for removing organic compounds from gas. Example 6

[0041] Preparation of double-terminated amino-dimethylfluorene derivatives: 0.1 kg of 2,7-dihydroxy-9,9-dimethylfluorene and 0.33 kg of 3-bromopropylamine hydrobromide were added to 1.3 kg of acetone, stirred to dissolve, and then 0.25 kg of sodium hydroxide was added. The mixture was heated to 110°C and reacted for 12 hours. After the reaction was completed, the mixture was filtered and the solvent was removed by vacuum distillation of the filtrate. The residue was washed with water 5 times and dried to obtain a double-terminated amino-dimethylfluorene derivative.

[0042] Preparation of double-terminated amino-dioxolane derivatives: 0.1 kg of 2,7-dihydroxy-9-fluorenone and 0.04 kg of ethylene glycol were added to 0.8 kg of dichloromethane, stirred and dissolved, and then 0.001 kg of p-toluenesulfonic acid was added, and the mixture was reacted at 25°C for 6 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the residue was washed with water 5 times and dried to obtain a dioxolane derivative; 0.1 kg of dioxolane derivative and 0.3 kg of 3-bromopropylamine hydrobromide were added to 1.2 kg of acetone, stirred to dissolve, and then 0.2 kg of sodium hydroxide was added. The mixture was heated to 110°C and reacted for 12 hours. After the reaction was completed, the mixture was filtered and the solvent was removed by vacuum distillation of the filtrate. The residue was washed with water 5 times and dried to obtain a double-terminal amino dioxolane derivative.

[0043] Preparation of porous materials for the removal of organic compounds from gases: 0.1 kg of a double-terminal amino-dimethylfluorene derivative, 0.12 kg of a double-terminal amino-dioxolane derivative and 0.2 kg of 1,3,6,8-tetrakis(4-formaldehydephenyl)pyrene were added to a mixed solvent of 2 kg of dimethylformamide and water, wherein the volume ratio of ethanol to water was 1:0.1, and after stirring and mixing evenly, the mixture was heated to 150° C. and sealed to react for 7 days, and filtered, and the filter cake was washed 4 times with ether and water respectively, and dried to obtain a compound; 0.1 kg of the compound was added to 1 kg of dimethyl sulfoxide, and then 0.5 kg of 3 mol / L hydrochloric acid was added thereto, and the mixture was heated to 50°C for reaction for 24 hours. The mixture was filtered and the filter cake was washed 4 times with water and dried to obtain a porous material for removing organic compounds from gas.

[0044] The porous materials for removing organic compounds from gas prepared in Examples 1 to 6 were tested using a Micromeritics Tristar II 3020 fully automatic specific surface area and porosity analyzer, and the test results are shown in Table 1. It can be seen from the results in Table 1 that the porous material for removing organic compounds from gas prepared in the present invention has a large specific surface area and pore volume.

[0045] Table 1 Performance parameter results of porous materials prepared in Examples 1 to 6

[0046] The porous material for removing organic compounds from gas prepared in Example 3 of the present invention was subjected to thermogravimetric analysis, and its detection spectrum is as follows: Figure 2 As shown. Figure 2 The results show that the porous material prepared by the present invention for removing organic compounds from gas has basically no weight loss before 400°C, indicating that it has good thermal stability and will not cause material leakage when working at high temperature, thus avoiding environmental pollution.

[0047] The porous materials for removing organic compounds from gas prepared in Examples 1 to 6 of the present invention were evaluated for VOCs removal performance. 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 -1After 1 hour of reaction, samples were taken to determine the VOCs content. The comparative example used activated carbon as an adsorbent, and the test results are shown in Table 2. It can be seen from the results in Table 2 that the porous material for removing organic compounds from gas prepared by the present invention has a higher VOCs removal rate than the comparative example, and can be used for the removal of organic compounds in gas.

[0048] Table 2 VOCs removal results of materials prepared in Examples 1 to 6 and comparative examples

[0049] Although the above describes the specific implementation methods of the present invention, it does not limit the scope of protection of the present invention. Based on the technical solution of the present invention, various modifications or variations that can be made by those skilled in the art without creative work are still within the scope of protection 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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