An adsorbent material, its preparation method and application

Abstract

The present invention discloses an adsorbent material, a preparation method thereof and an application thereof. Among the synthesis raw materials of the adsorbent material, there are monomers of diallyl phthalate and styrene with a volume ratio of 1:0.05 to 20, and the two are the total volume of the monomers, denoted as the total monomers; there is tert-butylhydroquinone, and the content is 20-10000 ppm, preferably 200-5000 ppm, based on the total monomers contained. The adsorbent material can adsorb polycyclic aromatic hydrocarbons in wastewater and has excellent adsorption selectivity.

Description

Technical Field

[0001] The present invention relates to an adsorbent material, a preparation method thereof and an application, and particularly to a highly selective adsorbent material, a preparation method thereof and an application. Technical Background

[0002] Benzene series compounds refer to the general term including benzene, toluene, xylene, ethylbenzene, isopropylbenzene, styrene and other compounds. Benzene has been proven to be a carcinogen, and the remaining benzene series compounds have varying degrees of toxic effects on the human body. Wastewater and waste gas generated in the processes of petroleum refining, petrochemical industry, coking, etc. are the main industrial pollution sources of benzene series compounds. In addition, the waste water discharged from industries such as paint, medicine, organic chemical industry, pesticide, etc. also contains a large amount of benzene series compounds, because benzene series compounds are also important solvents and production raw materials. Benzene series compounds can enter the human body through the respiratory tract, digestive tract and skin, and have a great correlation with various diseases. Toluene and xylene have great toxic effects on the central nervous system and blood circulation system; other benzene series compounds such as ethylbenzene also pose great hazards to the human body.

[0003] Compounds in which two or more benzene rings are connected in a fused ring form are called polycyclic aromatic hydrocarbons (PAHs), which are a class of pollutants with carcinogenicity and the ability to induce mutations in organisms. Typical PAHs samples contain a variety of PAHs with complex structures, including many isomeric structures, alkylated and non-alkylated forms of PAHs. Among them, 16 polycyclic aromatic hydrocarbons are designated as priority pollutants by the US Environmental Protection Agency, including: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylene.

[0004] PAHs are widely distributed in the natural environment, including air, water bodies and soil, etc. Due to their stable nature and high bioaccumulation rate, they have potential carcinogenic, mutagenic and endocrine disrupting effects on the human body, posing a major threat to human health and the ecological environment, and being widely concerned all over the world.

[0005] 2-3 ring PAHs have significant acute toxicity, and PAHs with more than three rings are carcinogenic. Three polycyclic aromatic hydrocarbons, benzo(b)fluoranthene, benzo(k)fluoranthene and benzo(g,h,i)perylene, have no lowest safety value. As long as these polycyclic aromatic hydrocarbons exist, even at extremely low doses, they will have toxic side effects on organisms.

[0006] For the treatment of PAHs, the current methods mainly include microbial degradation, photocatalytic degradation, adsorption, etc.

[0007] When studying Pseudomonas sp. TN301, Narancic et al. (Narancic T, Kenny ST, Djokic L, et al. Medium-chain-length polyhydroxyalkanoate production by newly isolated Pseudomonas sp. TN301 from a wide range of polyaromatic and monoaromatic hydrocarbons[J]. Journal of Applied Microbiology, 2012, 113, 508-520) found that during the degradation of naphthalene by Pseudomonsa PAO1, the catechol degradation pathway existed, but the gentisic acid pathway was not found. This was because salicylic acid, catechol, etc. were produced during the process, but no gentisic acid was present. The naphthalene degradation genes are highly conserved. The types of degradation genes in the strain determine the naphthalene degradation pathway, and the difference in the naphthalene degradation ability may be due to the different degradation genes in the strain. Microbial degradation technology can effectively remove PAHs to a certain extent, but the main problems faced are slow degradation speed and incomplete degradation. Especially for PAHs with more rings, due to their structural complexity and low water solubility, microorganisms cannot effectively treat them.

[0008] CN201910678761.5 discloses a method for treating polycyclic aromatic hydrocarbons in water using layered lanthanum niobate titanate as a catalyst. The layered lanthanum niobate titanate catalyst is prepared by the following method: dispersing precursors such as lanthanum salt, niobium hydroxide, and titanate ester evenly, and then calcining. Under ultraviolet light irradiation, this catalyst can degrade polycyclic aromatic hydrocarbons such as naphthalene, acenaphthene, acenaphthylene, and fluorene in water. This method has simple process, high efficiency, and low energy consumption, providing reliable technical support for promoting the treatment of pollutants and environmental remediation. It includes the following steps: (1) dispersing lanthanum salt, niobium hydroxide, and titanate ester in 100 ml of absolute ethanol, stirring at 1200 r / min, then heating to 60 °C, and slowly dropping 120 ml of deionized water, continuing to stir and react for 4 hours to fully hydrolyze the titanate ester, and drying at 105 °C for 10 h; obtaining the precursor catalyst; (2) pressing the catalyst precursor into a cylindrical shape, putting it into a ceramic tube furnace, calcining at 1050 °C for 180 min in an air atmosphere, cooling, grinding and pulverizing to obtain the catalyst; (3) adding 0.01 g - 0.05 g of the above catalyst to 150 ml of wastewater, with the pollutant being polycyclic aromatic hydrocarbons at a concentration of 100 mg / L - 800 mg / L, and then stirring and reacting for 120 - 180 min in a 200 mL photocatalytic reactor with an ultraviolet portable lamp as the light source, and the treatment effect is good.

[0009] CN201710348711.1 discloses a solid-phase photocatalytic oxidation method for polycyclic aromatic hydrocarbons, comprising the following steps: 1. Mix polycyclic aromatic hydrocarbons and a catalyst evenly to obtain a solid-phase mixture of the two; 2. React the solid-phase mixture of polycyclic aromatic hydrocarbons and the catalyst under ultraviolet light; the ultraviolet wavelength is 220 - 395 nm; the reaction time is 2 - 10 hours. This method is simple and has low energy consumption.

[0010] CN201910348985.X provides a preparation method of a photocatalyst, which can degrade high-concentration polycyclic aromatic hydrocarbons in wastewater. The method is as follows: Mix nano-TiO 2 , starch, and ethanol, and then add a coupling agent to prepare a starch-nano-TiO 2 composite; after drying and grinding, the photocatalyst for degrading high-concentration polycyclic aromatic hydrocarbon wastewater of the present invention is obtained. The characteristics of the present invention are low raw material cost, simple preparation process, and good degradation performance for high-concentration polycyclic aromatic hydrocarbons in wastewater. It includes the following steps: Mix the raw material nano-TiO 2 , starch, and absolute ethanol evenly by stirring. Calculated based on the total mass of the mixture, the mass percentage contents of nano-TiO 2 , ethanol, and starch are 1% - 10%, 10% - 30%, and 60% - 89%; add a metal salt coupling agent to the above mixture, and its mass percentage content is 0.5% - 5%; add 1 mol / L hydrochloric acid to the above mixture in step and react for 2 - 6 hours; filter, dry, and grind the reaction mixture into powder to obtain the photocatalyst.

[0011] CN201910017853.9 discloses a photocatalyst and its preparation method. In the existing photocatalytic degradation of polycyclic aromatic hydrocarbons, there are problems of low visible light utilization rate and inconvenient recovery of nano-particle photocatalysts. In the present invention, a photocatalyst with visible light catalytic activity is loaded on glass microspheres. The glass microspheres are of a hollow structure. This material can float in wastewater, has photocatalytic activity under visible light, and is easy to recover. Under visible light irradiation, this material degraded 71% of fluorene in water within 24 hours. This invention does not require the design of a catalytic device and can be directly used in wastewater, having the advantages of good treatment effect and easy recovery.

[0012] The adsorption method has the advantages of high removal efficiency, easy operation, easy recovery, etc., and has become the main method for the treatment of PAHs in the environment.

[0013] Wang Fang et al. (Wang Fang, Duan Lin. Study on the π-complexation adsorption of naphthalene by silver ion-exchanged resin [J]. Environmental Chemistry, 2013, 32, 2115-2120) explored the adsorption of naphthalene and 1,3-dichlorobenzene by silver ion resin Amberlyst15-Ag. After loading silver ions, the adsorption capacity of Amberlyst15 for naphthalene increased significantly, while it had little effect on 1,3-dichlorobenzene. In this system, naphthalene can act as a π-electron donor and form a cation-π bond with it, while 1,3-dichlorobenzene cannot act as a π-electron donor and cannot undergo complexation. Therefore, the adsorption of naphthalene by Amberlyst15-Ag was significantly improved compared with that before loading, and with the increase of Ag + content, the adsorption capacity also increased accordingly.

[0014] Yang et al. (Yang X, Li J, Wen T, et al. Adsorption of naphthalene and its derivatives on magnetic graphene composites and the mechanism investigation [J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2013, 422, 118-125.) studied the adsorption behavior of magnetic graphene oxide for naphthalene, 1-naphthol and 1-naphthylamine. The adsorption of naphthalene and its derivatives by graphene oxide is mainly achieved through electron donor-acceptor interactions. Due to the defects on the surface of the composite, the π-electron deficiency is caused, making it a π-electron acceptor, which can form π-π interactions with molecules rich in π-electrons such as naphthalene. Therefore, graphene oxide has a strong adsorption capacity for naphthalene and its derivatives. In addition, the lone pair electrons on oxygen and nitrogen in the molecules of graphene oxide and 1-naphthol and 1-naphthylamine will also form n-π interactions, while naphthalene is a non-polar molecule and cannot form this interaction with graphene oxide, which makes the adsorption capacity of graphene oxide for 1-naphthol and 1-naphthylamine stronger than that for naphthalene.

[0015] Costa et al. (Costa, Wilson W B, Wang H, et al. Comparison of BEA, USY and ZSM-5 for the quantitative extraction of polycyclic aromatic hydrocarbons from water samples [J]. Microporous and Mesoporous Materials, 2012, 149, 186 - 192) compared the adsorption of 15 PAHs by protonated molecular sieves HBEA, HUSY, and HZSM-5. The results showed that HBEA had the highest removal efficiency for PAHs, reaching 85.2% ± 1.7%. In addition to being related to the physical properties of the molecular sieve such as pore volume, pore size, and hydrophobicity, the removal efficiency was also related to the acidic sites on the material surface. HZSM-5 had the strongest hydrophobicity, and HUSY had the most acid centers. However, HBEA had uniformly distributed Lewis acid centers on its surface, so it had the highest removal rate for PAHs. In addition, most of the acidic sites of HZSM-5 molecular sieve were distributed on the inner surface of the pore channels, and only 6% were distributed on the outer surface. Therefore, HZSM-5 had the weakest adsorption ability for PAHs. The results showed that for HBEA with medium hydrophobicity, the interaction between the acidic sites on its surface and the π electrons of PAHs was the main reason for its good adsorption ability.

[0016] Agricultural and forestry waste, such as coconut shells, rice straw, sugarcane, bagasse, rice bran, pine needles, and bamboo chips, mainly consists of cellulose or lignin and contains a large number of active functional groups such as carbonyl, hydroxyl, and carboxyl on the surface. Due to surface hydrophilicity, the adsorption of PAHs is usually not ideal under normal circumstances. However, after heat treatment or chemical treatment, the adsorption effect will be significantly improved. The adsorption effects of activated carbons obtained from the carbonization of agricultural and forestry waste at different carbonization temperatures on naphthalene, phenanthrene, acenaphthene, etc. in aqueous solution increased with the increase of carbonization temperature. The removal rates of activated carbon obtained at 700 °C for naphthalene, phenanthrene, and acenaphthene could reach 99.89%, 100%, and 95.64%, respectively.

[0017] Xi et al. (Xi Z, Chen B. Removal of polycyclic aromatic hydrocarbons from aqueous solution by raw and modified plant residue materials as biosorbents[J]. Journal of Environmental Sciences, 2014, 26, 737-748) compared the adsorption performance of bamboo chips and pine needles before and after acid treatment for PAHs. The polysaccharides on the surface of plant residues were decomposed by acid, the surface polarity decreased, and the covered fat part and aromatic nucleus were exposed, resulting in a greatly improved adsorption capacity for PAHs. These methods all use agricultural waste as raw materials and have good adsorption performance for PAHs after a simple treatment process. This process utilizes agricultural waste resources and provides a basis for the preparation of efficient biomass materials.

[0018] However, photocatalytic degradation may produce more toxic intermediate products, and its cost also limits the application to a certain extent. In the process of treating complex wastewater systems, the existing adsorption materials are extremely vulnerable to competitive adsorption by other pollutants, resulting in poor selectivity for polycyclic aromatic hydrocarbons. Therefore, they cannot be directly used for the treatment of complex wastewater systems. Summary of the Invention

[0019] Aiming at the deficiencies of the prior art, the present invention provides an adsorption material, a preparation method thereof and an application. The adsorption material can adsorb polycyclic aromatic hydrocarbons in wastewater and has excellent adsorption selectivity.

[0020] An adsorption material, in the synthesis raw materials of the adsorption material, there are monomers of diallyl phthalate and styrene with a volume ratio of 1:0.05-20. The two are the total volume of the monomers, denoted as the total monomers; there is tert-butylhydroquinone, with a content of 20-10000 ppm, preferably 200-5000 ppm, based on the total monomers contained.

[0021] In the above adsorption material, the synthesis raw materials of the adsorption material may further contain one or several of diallyl terephthalate, ethylene glycol dimethacrylate, naphthyl methacrylate, and methyl methacrylate, and the dosage is 1-10% of the total monomer volume, preferably 2-5%.

[0022] A synthesis method of an adsorption material, a polymerization system containing diallyl phthalate, styrene, and tert-butylhydroquinone, undergoes a polymerization reaction under the action of an initiator, and the final adsorption material is obtained after the reaction.

[0023] In the above method, the initiator is benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, preferably one or a mixture of two of azobisisobutyronitrile and azobisisoheptonitrile, and further preferably azobisisoheptonitrile; the addition amount is 0.5% - 5% of the total monomers.

[0024] In the above synthesis method, diallyl phthalate, styrene, and tert-butylhydroquinone are added to a solvent to form a polymerization system. The solvent is a mixture of n-hexane and xylene, denoted as the total solvent. The volume ratio of n-hexane to xylene is 1:0.05 - 20, preferably 1:0.1 - 10.

[0025] In the above synthesis method, the ratio of the total monomers to the total solvent is 1:0.5 - 20, preferably 1:1 - 18.6.

[0026] In the above synthesis method, an initiator is added to the polymerization system, and it is charged into a reaction device and continuously stirred (preferably a multi-functional high-pressure reaction kettle). The air in the reaction device is repeatedly replaced with an inert gas (preferably nitrogen). Each time the pressure is increased to 1 - 2 MPa, and the pressure increase - deflation is repeated 4 - 6 times to ensure that all the oxygen is replaced. Then, an inert gas is charged to 0.1 - 2 MPa, and polymerization is carried out under heating conditions. During the heating process, continuous stirring is maintained. After the reaction is completed, the sample is taken out, and the solvent is removed by heating and rotary evaporation to obtain the final product.

[0027] In the above synthesis method, the heating reaction temperature is 40 - 170 °C, preferably 50 - 140 °C, and further preferably 55 - 120 °C.

[0028] In the above synthesis method, the reaction polymerization time is 0.5 - 72 h, preferably 0.5 - 56 h, and further preferably 2 - 48 h.

[0029] In the above synthesis method, the rotary evaporation temperature is 40 - 110 °C, preferably 40 - 90 °C, and further preferably 50 - 80 °C.

[0030] In the above synthesis method, solvent thermal polymerization is carried out under heating conditions; the organic solvent is volatilized to obtain a mesoporous polymer.

[0031] An adsorbent material prepared by the above method, the most probable pore diameter of the adsorbent material varies in the range of 15 - 30 nm, the specific surface area is 600 - 1800 m 2 / g, and the contact angle with water is 120 - 171 degrees, preferably 131 - 163 degrees, and further preferably 141 - 154 degrees.

[0032] The application of the above adsorbent material in treating wastewater, the wastewater contains polycyclic aromatic hydrocarbons, and the mass content of polycyclic aromatic hydrocarbons in the wastewater is 20 - 1000 ppb, preferably 30 - 200 ppb.

[0033] In the above application, the adsorption method is as follows: the wastewater is filtered to remove suspended particulate matter, an adsorbent is added, and the mixture is stirred in a sealed stirring reactor; then the wastewater is discharged from the outlet at the bottom of the reactor, leaving the adsorbent. After the adsorbent is saturated with adsorption, it can be regenerated by heating and reused. After the adsorbent is heated, it is regenerated under the condition of introducing air, and the generated waste gas is treated by catalytic combustion.

[0034] Compared with the prior art, the present invention has the following advantages:

[0035] (1) By adjusting the preparation conditions of the present invention, such as the monomer type ratio, the solvent and additive ratio, temperature, pressure, etc., an adsorption resin with lipophilic characteristics and capable of effectively adsorbing non-polar organic pollutants is prepared;

[0036] (2) The adsorption material of the present invention can selectively adsorb polycyclic aromatic hydrocarbons in a complex wastewater system and has the characteristic of good adsorption selectivity. Specific embodiments

[0037] The following examples and comparative examples are used to further illustrate the function and effect of the method of the present invention, but the following examples do not limit the method of the present invention, and the dosage is in terms of volume.

[0038] Example 1

[0039] 6L of diallyl phthalate and 4L of styrene are mixed and denoted as the total monomers; tert-butylcatechol is added, and based on the total monomers, the concentration is 1860 ppm.

[0040] The synthesis raw materials further contain diallyl terephthalate, and the dosage is 2.1% of the total monomers.

[0041] The solvent is a mixture of 60L of n-hexane and 36L of xylene, denoted as the total solvent.

[0042] The polymerization monomers are dispersed in the solvent, azobisisobutyronitrile as the initiator is added, and the addition amount is 4.2% of the total monomers. The reactants are loaded into a high-pressure reaction kettle, tightened, and stirred. In order to discharge the oxygen in the reaction kettle, it is replaced multiple times by the method of introducing high-pressure nitrogen. Each time the pressure is increased to 1.1 MPa, the pressure is increased - released 5 times; finally, the high-pressure reaction kettle is additionally pressurized to a pressure of 3 bar. Then, the reaction kettle is heated up, and the final temperature is maintained at 89 °C; the reaction polymerization is carried out for 35 h. After the reaction is completed, the pressure is released, the kettle is opened, the product is taken out, and the solvent is removed by rotary evaporation at 67 °C using a rotary evaporator, and the solvent is condensed and recovered.

[0043] The final product is a mesoporous polymer; the most probable pore diameter of the polymer is 18 nm, the specific surface area is 1105 m 2 / g, and the contact angle with water is 146 degrees.

[0044] Example 2

[0045] Mix 7 L of diallyl phthalate and 3 L of styrene, denoted as the total monomers; add tert-butylcatechol with a concentration of 2940 ppm.

[0046] The synthesis raw materials further contain ethylene glycol dimethacrylate, and the dosage is 3.1% of the total monomers.

[0047] The solvent is a mixture of 18 L of n-hexane and 72 L of xylene, denoted as the total solvent.

[0048] Disperse the polymerization monomers into the solvent, add the initiator azobisisoheptonitrile, and the addition amount is 3.8% of the total monomers. Load the reactants into a high-pressure reactor, tighten it, and stir. In order to discharge the oxygen in the reactor, use the method of high-pressure nitrogen inlet to replace it multiple times. Each time, the pressure is increased to 1.1 MPa, and the pressure increase - deflation is carried out 5 times; finally, the high-pressure reactor is additionally pressurized to a pressure of 5 bar. Then, heat up the reactor and maintain the final temperature at 90 °C; carry out the reaction polymerization for 34 h. After the reaction is completed, release the pressure, open the reactor, take out the product, and use a rotary evaporator to rotate and evaporate to remove the solvent at 66 °C, and the solvent is condensed and recovered.

[0049] The final product is a mesoporous polymer; the most probable pore diameter of the polymer is 17.5 nm, the specific surface area is 908 m 2 / g, and the contact angle with water is 151 degrees.

[0050] Example 3

[0051] Mix 8 L of diallyl phthalate and 2 L of styrene, denoted as the total monomers; add tert-butylcatechol with a concentration of 1660 ppm.

[0052] The solvent is a mixture of 19.2 L of n-hexane and 40.8 L of xylene, denoted as the total solvent.

[0053] Disperse the polymerization monomers into the solvent, add the initiator azobisisoheptonitrile, and the addition amount is 3.4% of the total monomers. Load the reactants into a high-pressure reactor, tighten it, and stir. In order to discharge the oxygen in the reactor, use the method of high-pressure nitrogen inlet to replace it multiple times. Each time, the pressure is increased to 1.1 MPa, and the pressure increase - deflation is carried out 5 times; finally, the high-pressure reactor is additionally pressurized to a pressure of 3 bar. Then, heat up the reactor and maintain the final temperature at 90 °C; carry out the reaction polymerization for 39 h. After the reaction is completed, release the pressure, open the reactor, take out the product, and use a rotary evaporator to rotate and evaporate to remove the solvent at 64 °C, and the solvent is condensed and recovered.

[0054] The final product is a mesoporous polymer; the most probable pore diameter of the polymer is 28.9 nm, the specific surface area is 1140 m 2 / g, with a contact angle of 144 degrees with water.

[0055] Example 4

[0056] Mix 8.5 L of diallyl phthalate and 1.5 L of styrene, denoted as the total monomer; add tert-butylcatechol with a concentration of 1950 ppm.

[0057] The synthesis raw materials further contain naphthyl methacrylate with an addition amount of 3.2% of the total monomer.

[0058] The solvent is a mixture of 38.4 L of n-hexane and 41.6 L of xylene, denoted as the total solvent.

[0059] Disperse the polymerization monomer into the solvent, add the initiator azobisisoheptonitrile with an addition amount of 2.6% of the total monomer, load the reactants into a high-pressure reaction kettle, tighten it, stir, and in order to discharge the oxygen in the reaction kettle, use the method of introducing high-pressure nitrogen to displace it multiple times, with each pressurization of 1.1 MPa and pressurization-degassing 5 times; finally, increase the pressure of the high-pressure reaction kettle additionally, and the pressure is 9 bar.

[0060] Then, heat up the reaction kettle, and finally maintain the temperature at 90 °C; react and polymerize for 40 h. After the reaction is completed, relieve the pressure, open the kettle, take out the product, use a rotary evaporator to rotate and evaporate to remove the solvent at 55 °C, and condense and recover the solvent.

[0061] The final product is a mesoporous polymer; the most probable pore diameter of the polymer is 28 nm, and the specific surface area is 1105 m 2 / g, with a contact angle of 138 degrees with water.

[0062] Example 5

[0063] Mix 7.7 L of diallyl phthalate and 2.3 L of styrene, denoted as the total monomer; add tert-butylcatechol with a concentration of 2700 ppm.

[0064] The synthesis raw materials further contain methyl methacrylate with an addition amount of 4.2% of the total monomer.

[0065] The solvent is a mixture of 48.6 L of n-hexane and 41.4 L of xylene, denoted as the total solvent.

[0066] Disperse the polymerization monomer into the solvent, add the initiator azobisisoheptonitrile, and the addition amount is 2.2% of the total monomer. Load the reactants into the high-pressure reactor, tighten it, and stir. In order to discharge the oxygen in the reactor, use the method of introducing high-pressure nitrogen to replace it multiple times. Each time, pressurize to 1.1 MPa and perform the pressurization-degassing process 5 times; finally, increase the pressure of the high-pressure reactor additionally, and the pressure is 12 bar. Then, heat up the reactor and maintain the final temperature at 89 °C; carry out the reaction polymerization for 24 h. After the reaction is completed, release the pressure, open the reactor, take out the product, and use a rotary evaporator to rotate and evaporate the solvent at 60 °C, and condense and recover the solvent.

[0067] The final product is a mesoporous polymer; the most probable pore diameter of the polymer is 22 nm, and the specific surface area is 1225 m 2 / g, and the contact angle with water is 141 degrees.

[0068] Example 6

[0069] Mix 6.6 L of diallyl phthalate and 3.4 L of styrene, and record it as the total monomer; add tert-butylhydroquinone, and the concentration is 1350 ppm.

[0070] The synthesis raw materials further contain ethylene glycol dimethacrylate, and the dosage is 2.8% of the total monomer.

[0071] The solvent is a mixture of 24 L of n-hexane and 51 L of xylene, and is recorded as the total solvent.

[0072] Disperse the polymerization monomer into the solvent, add the initiator azobisisoheptonitrile, and the addition amount is 2% of the total monomer. Load the reactants into the high-pressure reactor, tighten it, and stir. In order to discharge the oxygen in the reactor, use the method of introducing high-pressure nitrogen to replace it multiple times. Each time, pressurize to 1.1 MPa and perform the pressurization-degassing process 5 times; finally, increase the pressure of the high-pressure reactor additionally, and the pressure is 8 bar. Then, heat up the reactor and maintain the final temperature at 88 °C; carry out the reaction polymerization for 35 h. After the reaction is completed, release the pressure, open the reactor, take out the product, and use a rotary evaporator to rotate and evaporate the solvent at 65 °C, and condense and recover the solvent.

[0073] The final product is a mesoporous polymer; the most probable pore diameter of the polymer is 29 nm, and the specific surface area is 865 m 2 / g, and the contact angle with water is 149 degrees.

[0074] Example 7

[0075] Mix 6.5 L of diallyl phthalate and 3.5 L of styrene, and record it as the total monomer; add tert-butylhydroquinone, and the concentration is 1200 ppm.

[0076] The synthesis raw materials further contain diallyl terephthalate, and the dosage is 3.4% of the total monomer.

[0077] The solvent is a mixture of 36 L of n-hexane and 41 L of xylene, denoted as the total solvent.

[0078] The polymerization monomer was dispersed in the solvent, and azobisisobutyronitrile as the initiator was added in an amount of 2% of the total monomer. The reactants were loaded into a high-pressure reactor, tightened, and stirred. To remove the oxygen in the reactor, it was replaced multiple times by introducing nitrogen under high pressure. Each time the pressure was increased to 1.1 MPa, and the pressurization-degasification was carried out 5 times. Finally, the high-pressure reactor was additionally pressurized to a pressure of 7 bar. Then, the reactor was heated up, and the final temperature was maintained at 80 °C. The reaction polymerization was carried out for 46 h. After the reaction was completed, the pressure was released, the reactor was opened, the product was taken out, and the solvent was removed by rotary evaporation at 57 °C. The solvent was condensed and recovered.

[0079] The final product is a mesoporous polymer; the most probable pore diameter of the polymer is 23 nm, the specific surface area is 1410 m 2 / g, and the contact angle with water is 138 degrees.

[0080] Example 8

[0081] 8.4 L of diallyl phthalate and 1.6 L of styrene were mixed, denoted as the total monomer; tert-butylcatechol was added at a concentration of 4200 ppm.

[0082] The solvent is a mixture of 14 L of n-hexane and 55 L of xylene, denoted as the total solvent.

[0083] The polymerization monomer was dispersed in the solvent, and azobisisobutyronitrile as the initiator was added in an amount of 4.1% of the total monomer. The reactants were loaded into a high-pressure reactor, tightened, and stirred. To remove the oxygen in the reactor, it was replaced multiple times by introducing nitrogen under high pressure. Each time the pressure was increased to 1.1 MPa, and the pressurization-degasification was carried out 5 times. Finally, the high-pressure reactor was additionally pressurized to a pressure of 8 bar. Then, the reactor was heated up, and the final temperature was maintained at 105 °C. The reaction polymerization was carried out for 33 h. After the reaction was completed, the pressure was released, the reactor was opened, the product was taken out, and the solvent was removed by rotary evaporation at 66 °C. The solvent was condensed and recovered.

[0084] The final product is a mesoporous polymer; the most probable pore diameter of the polymer is 23 nm, the specific surface area is 1258 m 2 / g, and the contact angle with water is 151 degrees.

[0085] Example 9

[0086] 7.3 L of diallyl phthalate and 2.7 L of styrene were mixed, denoted as the total monomer; tert-butylcatechol was added at a concentration of 3840 ppm.

[0087] The synthesis raw materials may further contain ethylene glycol dimethacrylate, and the dosage is 3.9% of the total monomers.

[0088] The solvent is a mixture of 56 L of n-hexane and 25 L of xylene, denoted as the total solvent.

[0089] Disperse the polymerization monomers into the solvent, add the initiator azobisisobutyronitrile, and the addition amount is 2% of the total monomers. Load the reactants into a high-pressure reaction kettle, tighten it, and stir. In order to discharge the oxygen in the reaction kettle, use the method of introducing high-pressure nitrogen to replace it multiple times. Each time, the pressure is increased to 1.1 MPa, and the pressure increase - deflation is carried out 5 times; finally, the high-pressure reaction kettle is additionally pressurized to a pressure of 9 bar. Then, heat up the reaction kettle and maintain the final temperature at 102 °C; react and polymerize for 34 h. After the reaction is completed, relieve the pressure, open the kettle, take out the product, and use a rotary evaporator to rotate and evaporate the solvent at 55 °C. The solvent is condensed and recovered.

[0090] The final product is a mesoporous polymer; the most probable pore diameter of the polymer is 25 nm, and the specific surface area is 804 m 2 / g, and the contact angle with water is 143 degrees.

[0091] Example 10

[0092] Mix 5.8 L of diallyl phthalate and 4.2 L of styrene, denoted as the total monomers; add tert-butylcatechol, and the concentration is 2100 ppm.

[0093] The synthesis raw materials may further contain methyl methacrylate, and the dosage is 4.3% of the total monomers.

[0094] The solvent is a mixture of 31.5 L of n-hexane and 58.5 L of xylene, denoted as the total solvent.

[0095] Disperse the polymerization monomers into the solvent, add the initiator azobisisobutyronitrile, and the addition amount is 2.5% of the total monomers, and stir continuously. Load it into a high-pressure reaction kettle and stir continuously. In order to discharge the oxygen in the reaction kettle, use the method of introducing high-pressure nitrogen to replace it multiple times. Each time, the pressure is increased to 1.1 MPa, and the pressure increase - deflation is carried out 5 times; finally, the high-pressure reaction kettle is additionally pressurized to a pressure of 6 bar. Then, heat up the reaction kettle and maintain the final temperature at 100 °C; react and polymerize for 48 h. After the reaction is completed, relieve the pressure, open the kettle, take out the product, and use a rotary evaporator to rotate and evaporate the solvent at 60 °C. The solvent is condensed and recovered.

[0096] The final product is a mesoporous polymer; the most probable pore diameter of the polymer is 21 nm, and the specific surface area is 800 m 2 / g, and the contact angle with water is 149 degrees.

[0097] Example 11

[0098] Mix 5.5 L of diallyl phthalate and 4.5 L of styrene, and denote it as the total monomer; add tert-butylcatechol with a concentration of 2300 ppm.

[0099] The synthesis raw materials may further contain naphthyl methacrylate, and the dosage is 4.6% of the total monomer.

[0100] The solvent is a mixture of 14 L of n-hexane and 55 L of xylene, and is denoted as the total solvent.

[0101] Disperse the polymerization monomer into the solvent, add the initiator azobisisoheptonitrile, and the addition amount is 2% of the total monomer. Load the reactants into a high-pressure reaction kettle, tighten it, and stir. In order to discharge the oxygen in the reaction kettle, use the method of high-pressure nitrogen inlet to replace it multiple times. Each time the pressure is increased to 1.1 MPa, the pressure increase - deflation is carried out 5 times; finally, the high-pressure reaction kettle is additionally pressurized to a pressure of 5 bar. Then, heat up the reaction kettle and maintain the final temperature at 95 °C; carry out the reaction polymerization for 37 h. After the reaction is completed, release the pressure, open the kettle, take out the product, and use a rotary evaporator to rotate and evaporate to remove the solvent at 51 °C, and the solvent is condensed and recovered.

[0102] The final product is a mesoporous polymer; the most probable pore diameter of the polymer is 24 nm, the specific surface area is 1200 m 2 / g, and the contact angle with water is 142 degrees.

[0103] Example 12

[0104] Mix 4.8 L of diallyl phthalate and 5.2 L of styrene, and denote it as the total monomer; add tert-butylcatechol with a concentration of 1600 ppm.

[0105] The synthesis raw materials may further contain ethylene glycol dimethacrylate, and the dosage is 2.6% of the total monomer.

[0106] The solvent is a mixture of 40.5 L of n-hexane and 49.5 L of xylene, and is denoted as the total solvent.

[0107] Disperse the polymerization monomer into the solvent, add the initiator azobisisoheptonitrile, and the addition amount is 2% of the total monomer. Load the reactants into a high-pressure reaction kettle, tighten it, and stir. In order to discharge the oxygen in the reaction kettle, use the method of high-pressure nitrogen inlet to replace it multiple times. Each time the pressure is increased to 1.1 MPa, the pressure increase - deflation is carried out 5 times; finally, the high-pressure reaction kettle is additionally pressurized to a pressure of 6 bar. Then, heat up the reaction kettle and maintain the final temperature at 96 °C; carry out the reaction polymerization for 33 h. After the reaction is completed, release the pressure, open the kettle, take out the product, and use a rotary evaporator to rotate and evaporate to remove the solvent at 66 °C, and the solvent is condensed and recovered.

[0108] The final product is a mesoporous polymer; the most probable pore diameter of the polymer is 22 nm, the specific surface area is 977 m 2 / g, and the contact angle with water is 143 degrees.

[0109] Example 13

[0110] Mix 4.4 L of diallyl phthalate and 5.6 L of styrene, and denote it as the total monomer; add tert-butylcatechol with a concentration of 1800 ppm.

[0111] The synthesis raw materials may further contain methyl methacrylate, and the dosage is 3.5% of the total monomer.

[0112] The solvent is a mixture of 22.2 L of n-hexane and 51.8 L of xylene, denoted as the total solvent.

[0113] Disperse the polymerization monomer into the solvent, add the initiator azobisisoheptonitrile, and the addition amount is 3.2% of the total monomer. Load the reactants into a high-pressure reactor, tighten it, and stir. In order to discharge the oxygen in the reactor, use the method of introducing high-pressure nitrogen to replace it multiple times. Each time the pressure is increased to 1.1 MPa, and the pressurization-degasification is carried out 5 times; finally, the high-pressure reactor is additionally pressurized to a pressure of 9 bar. Then, heat up the reactor, and finally maintain the temperature at 105 °C; carry out the reaction polymerization for 36 h. After the reaction is completed, relieve the pressure, open the reactor, take out the product, and use a rotary evaporator to rotate and evaporate the solvent at 66 °C, and the solvent is condensed and recovered.

[0114] The final product is a mesoporous polymer; the most probable pore diameter of the polymer is 21 nm, the specific surface area is 985 m 2 / g, and the contact angle with water is 149 degrees.

[0115] Example 14

[0116] Mix 2.6 L of diallyl phthalate and 7.4 L of styrene, and denote it as the total monomer; add tert-butylcatechol with a concentration of 1860 ppm.

[0117] The synthesis raw materials may further contain naphthyl methacrylate, and the dosage is 4.3% of the total monomer.

[0118] The solvent is a mixture of 14 L of n-hexane and 44 L of xylene.

[0119] Disperse the polymerization monomer into the solvent, add the initiator azobisisoheptonitrile, and the addition amount is 4.3% of the total monomer. Load the reactants into the high-pressure reactor, tighten it, and stir. In order to expel the oxygen in the reactor, use the method of introducing high-pressure nitrogen to replace it multiple times. Each time, pressurize to 1.1 MPa, and perform the pressurization-degasification process 5 times. Finally, increase the pressure of the high-pressure reactor additionally to 6 bar. Then, heat up the reactor and maintain the final temperature at 104 °C; carry out the reaction polymerization for 43 h. After the reaction is completed, relieve the pressure, open the reactor, take out the product, and use a rotary evaporator to rotate and evaporate the solvent at 62 °C to remove the solvent, and condense and recover the solvent.

[0120] The final product is a mesoporous polymer; the most probable pore diameter of the polymer is 16 nm, and the specific surface area is 1090 m 2 / g, and the contact angle with water is 150 degrees.

[0121] Comparative Example 1

[0122] In Example 10, do not add p-tert-butylcatechol, and the other conditions are the same.

[0123] The final product is a mesoporous polymer; the most probable pore diameter of the polymer is 6 nm, and the specific surface area is 550 m 2 / g, and the contact angle with water is 118 degrees.

[0124] Usage method

[0125] This material is suitable for selectively adsorbing non-polar polycyclic aromatic hydrocarbons, etc. in complex water systems. Taking a certain wastewater as an example, the usage method of this material is described below.

[0126] In the above application, the adsorption method: Take 1000 ml of wastewater, filter to remove suspended particulate matter, add 5 g of the adsorbent prepared in Example 10, and stir in a sealed stirring reactor for 2 h; then discharge the wastewater from the outlet at the bottom of the reactor, leaving the adsorbent. Then heat and regenerate the adsorbent, and the adsorbent can still be reused.

[0127] A total of 3 kinds of wastewater containing polycyclic aromatic hydrocarbons were tested. As shown in the following table, in wastewater sample 1, the total concentration of polycyclic aromatic hydrocarbons was 82 ppb, and the concentration after adsorption treatment was 6.3 ppb, with a removal rate of 92.3%; at the same time, the removal rate of COD was only 30%. The removal rate of polycyclic aromatic hydrocarbons is much higher than that of COD, and the selectivity is extremely high. After treatment, the concentration of polycyclic aromatic hydrocarbons in the wastewater is lower than the discharge limit of 20 ppb and can meet the discharge standard.

[0128] Using the same treatment method, when the adsorbent is replaced with the sample in Comparative Example 1, the treated wastewater does not meet the discharge standard, and the selectivity also deteriorates. The specific results are shown in Table 1.

[0129] Table 1

[0130]

Claims

1. An adsorbent material, characterized in that: in the synthesis raw materials of the adsorbent material, there are monomers of diallyl phthalate and styrene with a volume ratio of 1: 0.05 to 20, and the two are the total volume of the monomers, denoted as the total monomers; there is tert-butylhydroquinone, and the content is 20 - 10000 ppm based on the total monomers contained.

2. The adsorbent material according to claim 1, characterized in that: the content of the tert-butylhydroquinone is 200 - 5000 ppm based on the total monomers contained.

3. The adsorbent material according to claim 1, characterized in that: in the synthesis raw materials of the adsorbent material, there is also one or more of diallyl terephthalate, ethylene glycol dimethacrylate, naphthyl methacrylate, and methyl methacrylate, and the dosage is 1 - 10% of the total monomer volume.

4. The adsorbent material according to claim 1, characterized in that: in the synthesis raw materials of the adsorbent material, there is also one or more of diallyl terephthalate, ethylene glycol dimethacrylate, naphthyl methacrylate, and methyl methacrylate, and the dosage is 2 - 5% of the total monomer volume.

5. A synthesis method of the adsorbent material according to claim 1, characterized in that: a polymerization system containing diallyl phthalate, styrene, and tert-butylhydroquinone undergoes a polymerization reaction under the action of an initiator, and the final adsorbent material is obtained after the reaction.

6. The method according to claim 5, characterized in that: the initiator is one or more of benzoyl peroxide, azobisisobutyronitrile, and azobisisoheptonitrile; the addition amount of the initiator is 0.5% - 5% of the total monomer volume.

7. The method according to claim 6, characterized in that: diallyl phthalate, styrene, and tert-butylhydroquinone are added to a solvent to form a polymerization system. The solvent is a mixture of n-hexane and xylene, denoted as the total solvent, and the volume ratio of n-hexane to xylene is 1: 0.05 to 20.

8. The method according to claim 7, characterized in that: the volume ratio of n-hexane to xylene is: 1: 0.1 to 10.

9. The method according to claim 7, characterized in that: the volume ratio of the total monomers to the total solvent is 1: 0.5 to 20.

10. The method according to claim 9, characterized in that: the volume ratio of the total monomers to the total solvent is 1: 1 to 18.

6.

11. The method according to claim 5, characterized in that: an initiator is added to the polymerization system, and it is loaded into a reaction device and continuously stirred. The air in the reaction device is repeatedly replaced with an inert gas, with a pressure of 1 - 2 MPa each time, and the pressure charging - deflation is repeated 4 - 6 times. Then, an inert gas is filled to 0.1 - 2 MPa, and polymerization is carried out under heating conditions. After the reaction is completed, the sample is taken out, and the solvent is evaporated to obtain the final product.

12. The method according to claim 11, characterized in that: the reaction device is a multi-functional high-pressure reaction kettle; the inert gas is nitrogen.

13. The method according to claim 11, characterized in that: the heating reaction temperature is 40 - 170 °C.

14. The method according to claim 13, characterized in that: the heating reaction temperature is 50~140°C.

15. The method according to claim 13, characterized in that: the heating reaction temperature is 55~120°C.

16. The method according to claim 11, characterized in that: the reaction polymerization time is 0.5~72 h.

17. The method according to claim 16, characterized in that: the reaction polymerization time is 0.5~56 h.

18. The method according to claim 16, characterized in that: the reaction polymerization time is 2~48 h.

19. The method according to claim 11, characterized in that: the solvent is removed by rotary evaporation, and the rotary evaporation temperature is 40~110°C.

20. The method according to claim 19, characterized in that: the rotary evaporation temperature is 40~90°C.

21. The method according to claim 19, characterized in that: the rotary evaporation temperature is 50~80°C.

22. An adsorbent material prepared by the method according to any one of claims 5-21, characterized in that: The most probable pore diameter of the adsorption material varies in the range of 15 - 30 nm, the specific surface area is 600 - 1800 m 2 / g, and the contact angle with water is 120 - 171 degrees.

23. The adsorbent material according to claim 22, characterized in that: the contact angle between the adsorbent material and water is 131~163 degrees.

24. The adsorbent material according to claim 22, characterized in that: the contact angle between the adsorbent material and water is 141~154 degrees.

25. Use of the adsorbent material according to claim 22 in treating wastewater.

26. The use according to claim 25, characterized in that: the wastewater contains polycyclic aromatic hydrocarbons, and the mass content of polycyclic aromatic hydrocarbons in the wastewater is 20-1000 ppb.

27. The use according to claim 26, characterized in that: the mass content of polycyclic aromatic hydrocarbons in the wastewater is 30-200 ppb.

28. The use according to claim 25, characterized in that: after the adsorbent material is saturated by adsorption, it is heated for regeneration and reused.

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