Polymer material for adsorbing VOCs organic waste gas

Abstract

The application discloses a kind of polymer materials for adsorbing VOCs organic waste gas, belong to polymer material processing technical field, for solving the technical problems that polymer material in prior art further improves the adsorption performance and cyclic adsorption performance of VOCs organic waste gas;The application includes the following raw materials by weight parts: 30-40 parts of epoxy modified porous bio-based carbon, 50-55 parts of solvent A, 50-55 parts of solvent B, 70-80 parts of polyolefin modified by amination, 3-5 parts of template agent and 30-40 parts of phenyl modified silicone resin.In the application, first, porous bio-based carbon is prepared by carbonization and activation of sludge and wheat straw, then polyolefin modified by amination is prepared by free radical polymerization, and finally, the polymer material is prepared by ring-opening reaction and hard-templating method, which not only improves the adsorption performance of the polymer material, but also effectively improves its cyclic adsorption performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer material processing, and particularly relates to a high polymer material for adsorbing VOCs organic waste gas. BACKGROUND

[0002] As an important air pollutant, VOCs exist widely in industrial emissions, automobile exhaust and daily life, which not only poses a serious threat to the environmental air quality, but also participates in atmospheric photochemical reactions, leading to ozone layer destruction and photochemical smog formation.

[0003] In recent years, with the increasingly stringent environmental regulations and the enhancement of public environmental awareness, the treatment of VOCs has become a research hotspot worldwide. As a typical organic waste gas, toluene is mainly derived from chemical, paint, printing and other industries. The emission not only pollutes the environment, but also poses a threat to human health. In view of the volatility and toxicity of toluene, its effective treatment has become an important issue in the field of environmental protection.

[0004] At present, the treatment methods of toluene organic waste gas mainly include adsorption, condensation, combustion and biological methods. Among them, the adsorption method is widely used due to its high efficiency, economy and easy operation. By selecting high-performance adsorption materials such as activated carbon and molecular sieve, toluene molecules can be effectively captured to achieve waste gas purification treatment, providing strong protection for environmental protection and human health.

[0005] Although activated carbon has good adsorption capacity when applied to toluene waste gas adsorption, it is usually brittle, fragile and not wear-resistant in long-term use. It may produce debris during adsorption or after use, reducing its adsorption performance for toluene waste gas. In particular, in a high-concentration waste gas environment, a large amount of activated carbon may be required to achieve good removal effect. The combination of organic macromolecules and activated carbon for co-adsorption of toluene waste gas is difficult to achieve good adsorption effect due to poor interfacial compatibility. In addition, the preparation of activated carbon requires a large amount of energy consumption and waste gas emission. Activated carbon has a developed pore structure, which provides adsorption sites for toluene molecules, and can effectively adsorb toluene waste gas. However, water molecules can also be adsorbed during the adsorption process, which will compete with toluene molecules for adsorption sites, thereby reducing the adsorption efficiency of activated carbon for toluene. Conventional high polymer materials have poor heat resistance, which is difficult to adapt to the process of activated carbon thermal desorption, reducing the cyclic adsorption performance. SUMMARY

[0006] The present application aims to provide a high polymer material for adsorbing VOCs organic waste gas, which solves the technical problem that the adsorption efficiency and cyclic adsorption performance of the high polymer material for VOCs organic waste gas need to be further improved in the prior art.

[0007] The purpose of the application can be realized by the following technical scheme: a high polymer material for adsorbing VOCs organic waste gas, comprising the following raw materials by weight parts: 30-40 parts of epoxy modified porous bio-based carbon, 50-55 parts of solvent A, 50-55 parts of solvent B, 70-80 parts of ammonia modified polyolefin, 3-5 parts of template agent and 30-40 parts of phenyl modified silicone resin;

[0008] The high polymer material is prepared by the following steps:

[0009] A1, ammonia modified polyolefin, epoxy modified porous bio-based carbon and solvent A are placed in a reaction kettle under nitrogen protection, heated to 60-70 DEG C, and kept for 1-2 h, and then treated to obtain a composite polyolefin;

[0010] The preparation reaction principle of the composite polyolefin is:

[0011] During the reaction, under the weak alkaline action of ammonia, the amino group of ammonia modified polyolefin and the epoxy group on the surface of epoxy modified porous bio-based carbon undergo ring opening reaction to form chemical bond, and the composite polyolefin is obtained.

[0012] A2, the composite polyolefin, template agent and phenyl modified silicone resin are added into a twin screw extruder, melt extruded, and pelletized to obtain a high polymer material precursor;

[0013] A3, the high polymer material precursor and solvent B are placed in a reaction kettle, heated to 45-55 DEG C, stirred for 1-2 h, and then treated to obtain a high polymer material.

[0014] The preparation reaction principle of the high polymer material is:

[0015] During the reaction, low concentration acetic acid solution reacts with calcium carbonate particles in the high polymer material precursor to generate calcium acetate, carbon dioxide and water by stirring, in the post-treatment step, calcium acetate is dissolved and removed by deionized water, and the water produced in the reaction is evaporated under the action of the drying oven to obtain a high polymer material with pore structure.

[0016] Further, in step A1, the solvent A is composed of N,N-dimethylformamide and ammonia water in a volume ratio of 50:10, the concentration of the ammonia water is 5-10wt%, and the post-treatment step includes: after the reaction is completed, suction filtration, the filter cake is washed with deionized water and ethanol for 1-2 times, the filter cake is transferred to a drying oven with a temperature of 60-70 DEG C, and dried to constant weight to obtain the composite polyolefin; in step A2, the template agent is calcium carbonate particles, the temperature of the eight temperature zones of the twin screw extruder from the feeding end to the discharging end is 200 DEG C, 210 DEG C, 210 DEG C, 215 DEG C, 215 DEG C, 215 DEG C, 215 DEG C, 220 DEG C, respectively, and the main shaft rotation speed of the twin screw extruder is 15 r / min;

[0017] Further, in step A3, the solvent B consists of a 10wt% acetic acid solution, and the post-treatment step includes: after the reaction is completed, the reaction is cooled to room temperature, suction filtration, the filter cake is washed with deionized water for 1-2 times, and then transferred to a drying oven with a temperature of 60-70℃, and dried to room temperature to obtain the polymer material.

[0018] Further, the preparation method of the ammonia-modified polyolefin is as follows: 4-pentene-1-amine, trimethylolpropane triacrylate, divinylbenzene, sodium dodecylbenzenesulfonate and toluene are placed in a reaction kettle, stirred for 10-15 min, benzoyl peroxide is added, heated to 45-55℃, deionized water is added, high-speed stirring for 0.5-1h, N,N-dimethyl-p-toluidine is added, and incubated for 1-3 min, and then ammonia-modified polyolefin is obtained by post-treatment.

[0019] The preparation reaction principle of the ammonia-modified polyolefin is as follows:

[0020] During the reaction, the olefin double bonds of 4-pentene-1-amine, trimethylolpropane triacrylate and divinylbenzene undergo free radical polymerization under the initiation of benzoyl peroxide, N,N-dimethyl-p-toluidine is added as a reducing agent to form a redox system with benzoyl peroxide, promoting the generation of free radicals of benzoyl peroxide, and ammonia-modified polyolefin is obtained.

[0021] Further, the amount of 4-pentene-1-amine, trimethylolpropane triacrylate, divinylbenzene, sodium dodecylbenzenesulfonate, toluene, benzoyl peroxide, deionized water and N,N-dimethyl-p-toluidine is 2-4g:0.5-1g:2-2.5g:0.10-0.15g:5-10mL:0.2-0.5g:25-30mL:0.5-0.7mL, and the post-treatment step includes: after the reaction is completed, the reaction system is heated to 120-130℃, and distilled under reduced pressure until no liquid is produced, to obtain ammonia-modified polyolefin.

[0022] Further, the epoxy-modified porous bio-based carbon is prepared by the following steps:

[0023] B1, the bio-based substrate is placed in a drying oven with a temperature of 100-110℃, dried for 1-2h, crushed, and sieved through a 100-mesh screen to obtain a porous bio-based carbon precursor;

[0024] B2, the porous bio-based carbon precursor is placed in a tube furnace under the protection of nitrogen atmosphere, heated to 550-600℃, incubated for 1-2h, heated to 750-800℃, and water vapor is introduced, incubated for 1-2h to obtain a porous bio-based carbon;

[0025] The preparation reaction principle of the porous activated carbon is as follows:

[0026] During the reaction, humus and minerals in the sludge form a microporous framework in pyrolysis, and wheat straw cellulose carbonizes to form a mesoporous structure, and high temperature promotes the deoxidation and condensation of wheat cellulose to form a highly aromatic graphite crystalline structure. The addition of water vapor activation can reduce the dirt on the surface of the epoxy modified porous biobased carbon, and the pyrolysis reaction reduces the internal oxygen-containing functional groups to obtain porous biobased carbon.

[0027] B3, the porous biobased carbon, ethanol and deionized water are placed in a reaction kettle, heated to 40-50℃, KH-560 is added, and the reaction is kept for 0.5-1h, and the epoxy modified porous biobased carbon is obtained after treatment.

[0028] The preparation reaction principle of the epoxy modified porous biobased carbon is:

[0029] During the reaction, the silicon-oxygen bond in KH-560 is hydrolyzed into silanol under the action of deionized water, and the silanol further condenses with the hydroxyl groups on the surface of the porous biocarbon to obtain silane coupling agent modified epoxy modified porous biobased carbon.

[0030] Further, in step B1, the biobased substrate is composed of sludge and wheat straw in a weight ratio of 6:4; in step B2, the heating rate is 10℃ / min; in step B3, the amount of porous biobased carbon, ethanol, deionized water and KH-560 is 6-10g:80-100mL:5-10mL:1-1.5g, and the post-treatment step includes: after the reaction is completed, the reaction liquid is cooled to room temperature, filtered, and the filter cake is washed with deionized water and ethanol for 1-2 times, and then transferred to a drying oven with a temperature of 60-80℃, and dried to constant weight to obtain the epoxy modified porous biobased carbon.

[0031] Further, the preparation method of the phenyl modified silicone resin is: ethanol, deionized water and tetramethylammonium hydroxide are placed in a reaction kettle, heated to 30-40℃, stirred for 10-15min, then tetraethyl orthosilicate, hexamethyldisiloxane and methyl diphenyl ethoxy silane are added, and the reaction is kept for 1.5-2h, then the temperature is raised to 60-70℃, and the reaction is kept for 5-6h, and the phenyl modified silicone resin is obtained after treatment.

[0032] The preparation reaction formula of the phenyl modified silicone resin is:

[0033]

[0034] In the formula:

[0035] The preparation reaction principle of the phenyl modified silicone resin is:

[0036] During the reaction, the tetramethylammonium hydroxide improves the alkaline environment, promotes the hydrolysis of the silicon-oxygen bond of tetraethyl orthosilicate, hexamethyldisiloxane and methyl diphenyl ethoxysilane to form silanol, and the silanol further undergoes condensation reaction to form a three-dimensional network structure, thereby obtaining the phenyl modified silicone resin capped and modified by methyl and phenyl.

[0037] Further, the amount ratio of the ethanol, deionized water, tetramethylammonium hydroxide, tetraethyl orthosilicate, hexamethyldisiloxane and methyl diphenyl ethoxysilane is 20-40 mL:10-15 mL:0.10-0.15 g:3-4 g:0.5-1 g:1-1.5 g, and the post-treatment step comprises: after the reaction is completed, the reaction system is heated to 100-110 DEG C, and distilled under reduced pressure until no liquid is produced, thereby obtaining the phenyl modified silicone resin.

[0038] The present application has the following advantages:

[0039] 1、The polymer material for adsorbing VOCs organic waste gas prepared by the present application first utilizes sludge and wheat straw to prepare porous bio-based carbon through carbonization and activation, then modifies the porous bio-based carbon with silane coupling agent to obtain epoxy modified porous bio-based carbon with epoxy groups on the surface, then prepares polyolefin with amino modification by using acrylate substances as raw materials through free radical polymerization, and finally forms chemical bonding between the epoxy modified porous bio-based carbon and the polyolefin with amino modification through ring-opening reaction to obtain composite polyolefin, which is melt extruded and cut into particles with a template agent and phenyl modified silicone resin, and then the calcium carbonate particles are removed through acetic acid solution and deionized water, thereby preparing the polymer material; the polyolefin with amino modification prepared by the present application uses 4-pentene-1-amine, trimethylolpropane triacrylate and divinylbenzene as polymer monomers, forms polyolefin with amino modification under the initiation of benzoyl peroxide, adds N,N-dimethyl-p-toluidine as a reducing agent to form an oxidation-reduction system with benzoyl peroxide, promotes the generation of free radicals of benzoyl peroxide, and obtains polyolefin with amino modification, which has high chemical stability and can reduce the swelling phenomenon caused by the adsorption of toluene gas by the polymer material, thereby further improving the cyclic adsorption performance of the polymer material.

[0040] 2、The present application is to prepare a porous epoxy-modified bio-based carbon by high-temperature carbonization and steam activation, using sludge and wheat straw as raw materials. Humic substances and minerals in the sludge form microporous frameworks in pyrolysis, while the carbonization of wheat straw cellulose generates mesoporous structures. High temperature promotes the deoxidation and condensation of wheat cellulose, forming highly aromatic graphite crystalline structures. The pi electron cloud of the graphite crystalline structures interacts with the toluene benzene ring through pi-pi conjugation, significantly improving the adsorption capacity of toluene gas. The micropores directly capture toluene gas molecules through van der Waals forces, enhancing the physical adsorption efficiency. The mesopores act as mass transfer channels, reducing the diffusion resistance of toluene and improving the dynamic adsorption rate. Steam reacts with the carbon skeleton to etch the closed pores and expand the pore volume, increasing the specific surface area. After activation, the micropore rate increases, further strengthening the van der Waals interaction between toluene molecules and the pore wall, improving the adsorption capacity and adsorption rate of the polymer material for toluene. Steam activation can also reduce the dirt on the surface of the porous epoxy-modified bio-based carbon, while the pyrolysis reaction reduces the internal oxygen-containing functional groups, reducing the hydrophilicity and forming a hydrophobic surface. This avoids the competitive adsorption of water molecules and toluene, allowing the polymer material to maintain high adsorption capacity in a humid environment. The use of biological materials to prepare bioactive carbon can also improve the environmental performance of the polymer material.

[0041] 3、The present application also combines the porous epoxy-modified bio-based carbon with the ammonia-modified polyolefin through ring-opening reaction to obtain a composite polyolefin, reducing the interfacial tension between the porous epoxy-modified bio-based carbon and the ammonia-modified polyolefin, improving the dispersibility of the porous epoxy-modified bio-based carbon in the polymer material, and further improving the adsorption performance of the polymer material for toluene gas. The composite polyolefin is then prepared into a polymer material with a hierarchical porous structure by using a template agent and phenyl-modified silicone resin, improving the specific surface area and adsorption performance of the polymer material. The phenyl-modified silicone resin is formed by the hydrolysis of the silicon-oxygen bond of tetraethyl orthosilicate, hexamethyldisiloxane, and methyl diphenyl ethoxy silane to form silanol. The silanol then undergoes condensation reaction to form a three-dimensional network structure, resulting in methyl and phenyl end-capped modified phenyl-modified silicone resin. The silicon-oxygen chain structure is stable, with good thermal stability and chemical inertness. The methyl groups and phenyl groups are hydrophobic, improving the stability and hydrophobicity of the polymer material, which is beneficial to maintaining the structural stability of the polymer material during thermal desorption and improving its cyclic adsorption performance. DETAILED DESCRIPTION

[0042] The technical solutions of the present application will be described below in conjunction with the embodiments, obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of protection of the present application.

[0043] The calcium carbonate particles used in the application are purchased from Shijiazhuang Weijia Mining Products Co., Ltd., and the model numbers are 10-120 mesh, 200 mesh and 325 mesh.

[0044] Example 1

[0045] The embodiment provides a preparation method of a polymer material for adsorbing VOCs organic waste gas, and comprises the following steps:

[0046] S1, preparing an aminated modified polyolefin

[0047] Take 200 g of 4-penten-1-amine, 50 g of trimethylolpropane triacrylate, 200 g of divinylbenzene, 10 g of sodium dodecylbenzenesulfonate and 500 mL of toluene, and place them in a reaction kettle, stir for 10 min, add 20 g of benzoyl peroxide, heat to 45 DEG C, add 2500 mL of deionized water, stir at a speed of 8000 r / min for 0.5 h, add 50 mL of N, N-dimethyl-p-toluidine, and heat for 1 min, after the reaction is completed, heat the reaction system to 120 DEG C, and distill under reduced pressure until no liquid is collected, to obtain the aminated modified polyolefin.

[0048] S2, preparing an epoxy modified porous bio-based carbon

[0049] The bio-based substrate is placed in a drying oven with a temperature of 100 DEG C, dried for 1 h, crushed, and sieved through a 100 mesh sieve to obtain a porous bio-based carbon precursor;

[0050] The porous bio-based carbon precursor is placed in a tube furnace under the protection of a nitrogen atmosphere, heated to 550 DEG C at a rate of 10 DEG C / min, heat treated for 1-2 h, heated to 750 DEG C at a rate of 10 DEG C / min, and water vapor is introduced, heat treated for 1 h, to obtain the porous bio-based carbon;

[0051] Take 600 g of the porous bio-based carbon, 8000 mL of ethanol and 500 mL of deionized water, and place them in a reaction kettle, heat to 40 DEG C, add 100 g of KH-560, heat for 0.5 h, after the reaction is completed, wait for the reaction liquid to cool to room temperature, filter, wash the filter cake with deionized water and ethanol once, transfer to a drying oven with a temperature of 60 DEG C, and dry to constant weight to obtain the epoxy modified porous bio-based carbon.

[0052] S3. preparing a phenyl modified silicon resin

[0053] Take: ethanol 2000 mL, deionized water 1000 mL and tetramethylammonium hydroxide 10 g into the reaction kettle, heated to 30 DEG C, stirring for 10 min, add tetraethyl orthosilicate 300 g, hexamethyldisiloxane 50 g and methyl diphenyl ethoxy silane 100 g, incubation reaction 1.5 h, heated to 60 DEG C, incubation reaction 5 h, after the reaction is completed, the reaction system is heated to 100 DEG C, distillation under reduced pressure until no liquid is produced, to obtain phenyl modified silicon resin.

[0054] S4, preparation of high molecular material

[0055] Mix N,N-dimethylformamide and 5wt% ammonia water uniformly according to the volume ratio of 50:10 to obtain solvent A;

[0056] Take by mass parts: 30 parts of epoxy modified porous bio-based carbon, 50 parts of solvent A, 50 parts of 10wt% acetic acid solution, 70 parts of ammonia modified polyolefin, 3 parts of calcium carbonate particles and 30 parts of phenyl modified silicon resin, standby;

[0057] Put the ammonia modified polyolefin and solvent A into the reaction kettle under nitrogen protection, add the epoxy modified porous bio-based carbon, heat to 60 DEG C, incubation reaction 1h, after the reaction is completed, filter, the filter cake is washed with deionized water and ethanol for 1 time, the filter cake is transferred to the drying oven with the temperature of 60 DEG C, dried to constant weight, to obtain the composite polyolefin;

[0058] The composite polyolefin, calcium carbonate particles and phenyl modified silicon resin are added into the double screw extruder, and the temperature of the eight temperature zones of the double screw extruder from the feeding end to the discharging end is 200 DEG C, 210 DEG C, 210 DEG C, 215 DEG C, 215 DEG C, 215 DEG C, 215 DEG C and 220 DEG C respectively, the main shaft rotation speed of the double screw extruder is 15r / min, melt extrusion, granulation, to obtain the high molecular material precursor;

[0059] Put the high molecular material precursor and 10wt% acetic acid solution into the reaction kettle, heat to 45 DEG C, stir for 1h, after the reaction is completed, wait for the reaction to room temperature, filter, the filter cake is washed with deionized water for 1 time, transferred to the drying oven with the temperature of 60 DEG C, dried to room temperature, to obtain the high molecular material.

[0060] Example 2

[0061] The embodiment provides a preparation method of a high molecular material for adsorbing VOCs organic waste gas, comprising the following steps:

[0062] S1, preparation of ammonia modified polyolefin

[0063] Take: 4-pentene-1-amine 300 g, trimethylolpropane triacrylate 70 g, divinylbenzene 220 g, sodium dodecylbenzenesulfonate 12 g and toluene 700 mL in the reaction kettle, stirring 13 min, add benzoyl peroxide 35 g, heating to 50℃, add deionized water 2700 mL, stirring at a rate of 8000 r / min for 0.5 h, add N,N-dimethyl-p-toluidine 60 mL, incubate for 2 min, after the reaction is completed, the reaction system is heated to 125℃, and distilled under reduced pressure until no liquid is collected. Ammoniated modified polyolefin is obtained.

[0064] S2, preparation of epoxy modified porous bio-based carbon

[0065] The bio-based substrate is placed in a drying oven at a temperature of 105℃, dried for 1.5 h, crushed, and passed through a 100 mesh sieve to obtain a porous bio-based carbon precursor;

[0066] The porous bio-based carbon precursor is placed in a tube furnace under the protection of nitrogen atmosphere, heated to 570℃ at a rate of 10℃ / min, incubated for 1.5 h, heated to 770℃ at a rate of 10℃ / min, and water vapor is introduced, incubated for 1.5 h, to obtain a porous bio-based carbon;

[0067] Take: porous bio-based carbon 800 g, ethanol 9000 mL and deionized water 700 mL in the reaction kettle, heating to 45℃, add KH-560 120 g, incubate for 1 h, after the reaction is completed, the reaction liquid is cooled to room temperature, filtered, the filter cake is washed with deionized water and ethanol for 2 times, transferred to a drying oven at a temperature of 70℃, dried to constant weight, to obtain an epoxy modified porous bio-based carbon.

[0068] S3. Preparation of phenyl modified silicon resin

[0069] Take: ethanol 3000 mL, deionized water 1250 mL and tetramethylammonium hydroxide 12 g in the reaction kettle, heating to 35℃, stirring for 12 min, add tetraethyl orthosilicate 3504 g, hexamethyldisiloxane 70 g and methyl diphenyl ethoxy silane 125 g, incubate for 2 h, heating to 65℃, incubate for 5.5 h, after the reaction is completed, the reaction system is heated to 105℃, and distilled under reduced pressure until no liquid is collected. Phenyl modified silicon resin is obtained.

[0070] S4, preparation of high molecular material

[0071] Mix N,N-dimethylformamide and 5wt% ammonia water uniformly according to the volume ratio of 50:10 to obtain solvent A;

[0072] 35 parts of the epoxy-modified porous bio-based carbon, 52 parts of the solvent A, 52 parts of the 10wt% acetic acid solution, 75 parts of the ammonia-modified polyolefin, 4 parts of the calcium carbonate particles, and 35 parts of the phenyl-modified silicone resin are weighed according to the mass fraction, and are prepared for use;

[0073] The ammonia-modified polyolefin and the solvent A are placed in a reaction kettle under nitrogen protection, the epoxy-modified porous bio-based carbon is added, the temperature is increased to 65℃, and the reaction is kept for 1.5h. After the reaction is completed, the filter cake is washed with deionized water and ethanol for 2 times, and the filter cake is transferred to a drying oven with a temperature of 65℃, and is dried to a constant weight to obtain a composite polyolefin.

[0074] The composite polyolefin, the calcium carbonate particles, and the phenyl-modified silicone resin are added to a double-screw extruder, the temperature of each of the 8 temperature zones of the double-screw extruder from the feeding end to the discharging end is 200℃, 210℃, 210℃, 215℃, 215℃, 215℃, 215℃, and 220℃, respectively, the main shaft rotation speed of the double-screw extruder is 15r / min, and the composite polyolefin is melt-extruded to obtain a high polymer material precursor.

[0075] The high polymer material precursor and the 10wt% acetic acid solution are placed in a reaction kettle, the temperature is increased to 50℃, and the reaction is stirred for 1.5h. After the reaction is completed, the reaction is cooled to room temperature, the filter cake is washed with deionized water for 2 times, and the filter cake is transferred to a drying oven with a temperature of 65℃, and is dried to room temperature to obtain a high polymer material.

[0076] Example 3

[0077] The present embodiment provides a preparation method of a high polymer material for adsorbing VOCs organic waste gas, which comprises the following steps:

[0078] S1, preparation of ammonia-modified polyolefin

[0079] The 4-penten-1-amine 400g, the trimethylolpropane triacrylate 100g, the divinylbenzene 250g, the sodium dodecylbenzenesulfonate 15g, and the toluene 1000mL are placed in a reaction kettle, stirred for 15min, the benzoyl peroxide 50g is added, the temperature is increased to 55℃, the deionized water 3000mL is added, the stirring speed is 8000r / min, and the reaction is stirred for 1h. The N,N-dimethyl-p-toluidine 70mL is added, the reaction is kept for 3min, the reaction system is heated to 130℃, and the liquid is distilled under reduced pressure until no liquid is collected to obtain the ammonia-modified polyolefin.

[0080] S2, preparation of epoxy-modified porous bio-based carbon

[0081] The 10mm zirconium oxide and the 6mm zirconium oxide are mixed uniformly according to the mass ratio of 1:1 to obtain a ball milling medium, which is prepared for use;

[0082] The bio-based substrate was placed in an oven at a temperature of 110°C, dried for 2h, crushed, and sieved through a 100-mesh screen to obtain a porous bio-based carbon precursor;

[0083] The porous bio-based carbon precursor was placed in a tube furnace under a nitrogen atmosphere, heated to 600°C at a rate of 10°C / min, and held for 2h. Then, the temperature was increased to 800°C at a rate of 10°C / min, and water vapor was introduced. The reaction was held for 2h to obtain a porous bio-based carbon.

[0084] The following were weighed into a reaction kettle: 1000g of porous bio-based carbon, 10000mL of ethanol, and 1000mL of deionized water. The temperature was raised to 50°C, and 150g of KH-560 was added. The reaction was held for 1h. After the reaction was completed, the reaction liquid was allowed to cool to room temperature, filtered, and the filter cake was washed twice with deionized water and ethanol. The filter cake was transferred to an oven at a temperature of 80°C, and dried to a constant weight to obtain an epoxy-modified porous bio-based carbon.

[0085] S3. Preparation of phenyl-modified silicon resin

[0086] The following were weighed into a reaction kettle: 4000mL of ethanol, 1500mL of deionized water, and 15g of tetramethylammonium hydroxide. The temperature was raised to 40°C, and stirring was performed for 15min. Then, 400g of tetraethyl orthosilicate, 100g of hexamethyldisiloxane, and 150g of methyldiphenyl ethoxysilane were added. The reaction was held for 2h, and the temperature was raised to 70°C. The reaction was held for 6h. After the reaction was completed, the reaction system was raised to 110°C, and distilled under reduced pressure until no liquid was collected. A phenyl-modified silicon resin was obtained.

[0087] S4. Preparation of high molecular material

[0088] N,N-dimethylformamide and 5wt% ammonia water were mixed uniformly at a volume ratio of 50:10 to obtain solvent A;

[0089] The following were weighed in parts by mass: 40 parts of epoxy-modified porous bio-based carbon, 55 parts of solvent A, 55 parts of 10wt% acetic acid solution, 80 parts of ammonia-modified polyolefin, 5 parts of calcium carbonate particles, and 40 parts of phenyl-modified silicon resin, and were reserved for use;

[0090] The ammonia-modified polyolefin and solvent A were placed in a reaction kettle under nitrogen protection, and the epoxy-modified porous bio-based carbon was added. The temperature was raised to 70°C, and the reaction was held for 2h. After the reaction was completed, suction filtration was performed, the filter cake was washed twice with deionized water and ethanol, and the filter cake was transferred to an oven at a temperature of 70°C, and dried to a constant weight to obtain a composite polyolefin.

[0091] The composite polyolefin, calcium carbonate particles and phenyl-modified silicone resin are added into a twin-screw extruder, the temperature of the eight temperature zones of the twin-screw extruder from the feeding end to the discharging end is 200℃, 210℃, 210℃, 215℃, 215℃, 215℃, 215℃, 220℃ respectively, the main shaft rotation speed of the twin-screw extruder is 15r / min, melt extrusion, granulation, to obtain a polymer material precursor;

[0092] The polymer material precursor and 10wt% acetic acid solution are placed in a reaction kettle, heated to 55℃, stirred for 2h, after the reaction is completed, the reaction is cooled to room temperature, suction filtration, the filter cake is washed with deionized water for 2 times, transferred to a drying oven with a temperature of 70℃, dried to room temperature, to obtain a polymer material.

[0093] Comparative Example 1

[0094] The difference between this comparative example and Example 2 is that in step S1, the step of preparing the aminated modified polyolefin is cancelled, and in step S4, the epoxy modified porous bio-based carbon is used instead of the composite polyolefin in an equal amount.

[0095] Comparative Example 2

[0096] The difference between this comparative example and Example 2 is that in step S2, the step of passing water vapor during the preparation of the porous bio-based carbon is cancelled, and in step S2, the porous bio-based carbon precursor is used instead of the porous bio-based carbon in an equal amount when preparing the epoxy modified porous bio-based carbon.

[0097] Comparative Example 3

[0098] The difference between this comparative example and Example 2 is that step S3 is cancelled, and the step of adding phenyl-modified silicone resin in step S4 is cancelled.

[0099] Comparative Example 4

[0100] The difference between this comparative example and Example 2 is that in step S4, the step of adding the template agent is cancelled.

[0101] Performance test:

[0102] The specific surface area of the polymer materials prepared in Examples 1-3 and Comparative Examples 1-4 is tested according to GB / T 19587-2017 “Gas adsorption BET method for determining the specific surface area of solid substances”;

[0103] The toluene adsorption rate of the polymer materials prepared in Examples 1-3 and Comparative Examples 1-4 under humidity conditions of 0RT% and 50RT% is tested according to GB / T 35815-2018 “Wood activated carbon test method for determination of toluene adsorption rate”;

[0104] The high molecular material prepared in Examples 1-3 and Comparative Examples 1-4 was loaded into a fixed bed adsorption column, and under the conditions of a temperature of 40℃ and a humidity of 15RH%, toluene gas with a concentration of 2400mg / m 3 was introduced into the gas inlet. The toluene adsorption rate of the gas outlet was determined according to the toluene adsorption rate determination method of GB / T 35815-2018 "Wood Activated Carbon Test Method Determination of Toluene Adsorption Rate", and when the toluene gas concentration of the gas outlet reached 5% of the toluene gas concentration of the gas inlet, it was recorded as the toluene breakthrough time.

[0105] The specific adsorption volume of the high molecular material prepared in Examples 1-3 and Comparative Examples 1-4 was tested according to GB / T 21650.2-2008 "Mercury Intrusion Method and Gas Adsorption Method for Determining Pore Size Distribution and Porosity of Solid Materials Part 2: Gas Adsorption Method for Analysis of Mesopores and Macropores", and the adsorbed high molecular material was placed in a drying oven at a temperature of 150℃ for thermal desorption for 1h. The high molecular material after thermal desorption was subjected to cyclic adsorption, and the specific adsorption volume after 5 cycles of adsorption was tested. The specific data are shown in Table 1.

[0106] Table 1. Performance test data table of the sample

[0107]

[0108] Data analysis:

[0109] Comparative analysis of the data in Table 1 shows that the specific surface area of the high molecular material prepared by the present application for adsorbing VOCs organic waste gas reaches 135.14m 2 ·g, the toluene adsorption rates under 0RH% and 50RH% conditions are 220.89mg·g -1 and 210.46mg·g -1 , the toluene adsorption breakthrough time is 55min, the first toluene gas specific adsorption volume is 2.51cm·g -1 , and the toluene gas specific adsorption volume after 5 cycles is 2.16cm·g -1 .

[0110] By analyzing and comparing the data of Comparative Example 1 and Example 2, it is found that the specific adsorption volume of toluene gas of Comparative Example 1 after 5 cycles is significantly reduced, indicating that the ammonia-modified polyolefin prepared in the present application, using 4-pentene-1-amine, trimethylolpropane triacrylate, and divinylbenzene as polymerization monomers, under the initiation of benzoyl peroxide, adding N,N-dimethyl-p-toluidine as a reducing agent to form a redox system with benzoyl peroxide to promote the generation of free radicals of benzoyl peroxide, obtaining ammonia-modified polyolefin, the polyolefin molecular chain has high chemical stability, which can reduce the swelling phenomenon caused by the adsorption of toluene gas by the high polymer material, and further improves the cyclic adsorption performance of the high polymer material.

[0111] By analyzing and comparing the data of Comparative Example 2 and Example 2, it is found that the specific surface area, toluene adsorption rate under 0 RH% and 50 RH% conditions, toluene adsorption breakthrough time, and first toluene gas specific adsorption volume of Comparative Example 2 are significantly reduced, indicating that the epoxy-modified porous bio-based carbon is prepared by high-temperature carbonization and steam activation using sludge and wheat straw as raw materials. Humic substances and minerals in the sludge form microporous skeletons during pyrolysis, while the cellulose in the wheat straw forms mesoporous structures after carbonization, and the high temperature promotes the deoxidation and condensation of the wheat cellulose, forming highly aromatic graphite crystalline structures. The π-electron cloud of the graphite crystalline structure interacts with the benzene ring of toluene through π-π conjugation, significantly improving the adsorption affinity of toluene gas. The micropores directly capture toluene gas molecules through van der Waals forces, enhancing the physical adsorption efficiency. The mesopores act as mass transfer channels, reducing the diffusion resistance of toluene, and improving the dynamic adsorption rate. Water vapor reacts with the carbon skeleton to etch and close the pores and expand the pore volume, increasing the specific surface area. After activation, the micropore rate increases, further strengthening the van der Waals interaction between toluene molecules and the pore wall, increasing the adsorption capacity and adsorption rate of the high polymer material for toluene. Steam activation can also reduce the dirt on the surface of the epoxy-modified porous bio-based carbon, while the pyrolysis reaction reduces the oxygen-containing functional groups on the surface, reducing the hydrophilicity and forming a hydrophobic surface. This avoids the competitive adsorption of water molecules and toluene, allowing the high polymer material to maintain high adsorption capacity in a humid environment.

[0112] By analyzing and comparing the data of Comparative Example 3 and Example 2, it is found that the toluene adsorption rate, toluene adsorption breakthrough time, first toluene gas specific adsorption volume and toluene gas specific adsorption volume after 5 cycles under 0RH% and 50RH% conditions of Comparative Example 3 are significantly reduced, which shows that the composite polyolefin obtained by combining the ring-opening reaction of the epoxy-modified porous bio-based carbon with the aminated modified polyolefin in the application reduces the interfacial tension between the epoxy-modified porous bio-based carbon and the aminated modified polyolefin, improves the dispersibility of the epoxy-modified porous bio-based carbon in the polymer material, and further improves the adsorption performance of the polymer material to toluene gas. Then, the composite polyolefin and the phenyl-modified silicone resin are prepared into a polymer material with a hierarchical porous structure by using a template agent. The phenyl-modified silicone resin is formed by hydrolysis of the siloxane bond of tetraethyl orthosilicate, hexamethyldisiloxane and methyl diphenyl ethoxy silane to form silanol, and the silanol further undergoes condensation reaction to form a three-dimensional network structure, thereby obtaining the phenyl-modified silicone resin capped and modified by methyl and phenyl groups. The siloxane chain structure is stable, has good thermal stability and chemical inertness, and the methyl groups and phenyl groups have hydrophobicity, which improves the stability and hydrophobicity of the polymer material, and is beneficial to maintaining the structural stability of the polymer material in the thermal desorption process and improving its cyclic adsorption performance.

[0113] By analyzing and comparing the data of Comparative Example 4 and Example 2, it is found that the specific surface area, toluene adsorption rate, toluene adsorption breakthrough time and first toluene gas specific adsorption volume under 0RH% and 50RH% conditions of Comparative Example 4 are significantly reduced, which shows that the composite polyolefin and the phenyl-modified silicone resin are prepared into a polymer material with a hierarchical porous structure by using a template agent in the application, which improves the specific surface area and adsorption performance of the polymer material.

[0114] The preferred embodiments of the application disclosed above are only used to help explain the application. The preferred embodiments do not describe all the details and limit the application to the specific embodiments. Obviously, many modifications and changes can be made according to the content of the present application. The embodiments are selected and described in detail in order to better explain the principles and practical applications of the application, so that those skilled in the art can well understand and utilize the application. The application is limited by the claims and their entire scope and equivalents.

Claims

1. A polymeric material for adsorbing VOCs organic waste gas, characterized in that, It includes the following raw materials by weight: 30-40 parts epoxy-modified porous bio-based carbon, 50-55 parts solvent A, 50-55 parts solvent B, 70-80 parts ammoniated modified polyolefin, 3-5 parts template agent and 30-40 parts phenyl-modified silicone resin. The polymer material is prepared by the following steps: A1. Place the ammonified polyolefin, epoxy-modified porous bio-based carbon and solvent A in a nitrogen-protected reactor, heat to 60-70℃, keep the temperature for 1-2 hours, and then process to obtain the composite polyolefin. A2. The composite polyolefin, template agent and phenyl modified silicone resin are added to a twin-screw extruder, melt extruded and pelletized to obtain a polymer precursor. A3. Place the polymer precursor and solvent B in a reaction vessel, heat to 45-55℃, stir for 1-2 hours, and then perform post-treatment to obtain the polymer material. The preparation method of the amination-modified polyolefin is as follows: 4-penten-1-amine, trimethylolpropane triacrylate, divinylbenzene, sodium dodecylbenzenesulfonate and toluene are placed in a reaction vessel and stirred for 10-15 min. Benzoyl peroxide is added, the temperature is raised to 45-55℃, deionized water is added, and the mixture is stirred at high speed for 0.5-1 h. The reaction is kept at this temperature for 1-3 min, and the amination-modified polyolefin is obtained after post-treatment. The epoxy-modified porous bio-based carbon was prepared by the following steps: B1. Place the bio-based material in a drying oven at 100-110℃ and dry for 1-2 hours. Then, pulverize it and pass it through a 100-mesh sieve to obtain a porous bio-based carbon precursor. B2. Place the porous bio-based char precursor in a tube furnace under nitrogen atmosphere protection, heat to 550-600℃, hold for 1-2 hours, heat to 750-800℃, introduce steam, hold for 1-2 hours to obtain porous bio-based char. B3. Place porous bio-based carbon, ethanol and deionized water in a reaction vessel, heat to 40-50℃, add KH-560, keep the reaction at this temperature for 0.5-1h, and then perform post-treatment to obtain epoxy-modified porous bio-based carbon. In step B1, the biological substrate is composed of sludge and wheat straw.

2. The polymeric material for adsorbing VOCs organic waste gas according to claim 1, characterized in that, In step A1, solvent A is composed of N,N-dimethylformamide and ammonia in a volume ratio of 50:10, and the concentration of ammonia is 5-10 wt%; in step A2, the template agent is calcium carbonate granules; in step A3, solvent B is composed of a 10 wt% acetic acid solution.

3. The polymeric material for adsorbing VOCs organic waste gas according to claim 1, characterized in that, The ratio of the amounts of 4-penten-1-amine, trimethylolpropane triacrylate, divinylbenzene, sodium dodecylbenzenesulfonate, toluene, benzoyl peroxide, deionized water, and N,N-dimethyl-p-toluidine is 2-4 g: 0.5-1 g: 2-2.5 g: 0.10-0.15 g: 5-10 mL: 0.2-0.5 g: 25-30 mL: 0.5-0.7 mL.

4. The polymeric material for adsorbing VOCs organic waste gas according to claim 1, characterized in that, In step B2, the heating rate is 10℃ / min; in step B3, the ratio of the porous bio-based carbon, ethanol, deionized water and KH-560 is 6-10g:80-100mL:5-10mL:1-1.5g.

5. The polymeric material for adsorbing VOCs organic waste gas according to claim 1, characterized in that, The preparation method of the phenyl-modified silicone resin is as follows: Ethanol, deionized water and tetramethylammonium hydroxide are placed in a reaction vessel, heated to 30-40℃, stirred for 10-15 min, tetraethyl orthosilicate, hexamethyldisiloxane and methyldiphenylethoxysilane are added, the reaction is kept at the temperature for 1.5-2 h, the temperature is raised to 60-70℃, and the reaction is kept at the temperature for 5-6 h to obtain the phenyl-modified silicone resin.

6. The polymeric material for adsorbing VOCs organic waste gas according to claim 5, characterized in that, The ratio of the amounts of ethanol, deionized water, tetramethylammonium hydroxide, tetraethyl orthosilicate, hexamethyldisiloxane, and methyldiphenylethoxysilane is 20-40 mL: 10-15 mL: 0.10-0.15 g: 3-4 g: 0.5-1 g: 1-1.5 g.

Images