Composite materials, methods of making and using the same

Abstract

The application relates to the technical field of composite material preparation, and discloses a composite material and a preparation method and application thereof.The composite material contains activated carbon loaded with a polymerization inhibitor and activated carbon loaded with a phase change material, wherein the activated carbon loaded with the polymerization inhibitor contains mesoporous activated carbon activated by first metal ions and a polymerization inhibitor, and the activated carbon loaded with the phase change material contains mesoporous activated carbon activated by second metal ions and a phase change material.The composite material has the functions of polymerization inhibition and heat storage, and has a high adsorption capacity for olefins (especially styrene) which are prone to polymerization in an adsorption process.

Description

Technical Field

[0001] This invention relates to the field of composite material preparation technology, specifically to a composite material, its preparation method, and its application. Background Technology

[0002] Styrene is an important organic chemical raw material and also a typical volatile organic compound (VOC) gas, which has adverse effects on the ecological environment and human health. In recent years, the national emission standards for styrene and other toxic and harmful gases have become increasingly stringent. Therefore, the safe and effective treatment of styrene waste gas is imperative. Commonly used VOCs treatment methods mainly fall into two categories: one is the recovery method, which mainly includes adsorption, absorption, condensation, and membrane separation; the other is the destruction method, which mainly includes incineration, photocatalytic oxidation, ozone catalytic oxidation, plasma catalysis, and biodegradation.

[0003] Adsorbents, as the core of adsorption technology, are commonly used in the field of VOCs treatment. Activated carbon, as a common adsorbent material, has the characteristics of high porosity, large specific surface area, and high adsorption activity, and can be used for the recovery and treatment of styrene gas. However, during the adsorption and aggregation of styrene on the surface of activated carbon, a polymerization reaction is prone to occur, releasing heat and causing a severe temperature rise in the activated carbon adsorption bed, even leading to an explosion. The main reason is that after styrene is adsorbed, the heat released by the polymerization reaction cannot be quickly conducted away, causing the activated carbon to continuously heat up. This temperature rise further intensifies the styrene polymerization reaction, ultimately leading to spontaneous combustion of the bed. Therefore, how to avoid the spontaneous polymerization of styrene during adsorption and control the continuous temperature rise during adsorption is the key to solving the problem. Summary of the Invention

[0004] The purpose of this invention is to overcome the problem in existing technologies where styrene polymerizes on the surface of activated carbon during adsorption, leading to a severe temperature rise in the activated carbon and potentially causing spontaneous combustion or even explosion. This invention provides a composite material, its preparation method, and its application. The composite material according to this invention effectively avoids the drastic temperature rise during styrene adsorption on the composite material surface, thereby improving the adsorption performance of the composite material for styrene.

[0005] To achieve the above objectives, the present invention provides a composite material comprising activated carbon supported on a polymerization inhibitor and activated carbon supported on a phase change material, wherein the activated carbon supported on the polymerization inhibitor comprises mesoporous activated carbon activated by a first metal ion and a polymerization inhibitor, and the activated carbon supported on the phase change material comprises mesoporous activated carbon activated by a second metal ion and a phase change material.

[0006] Preferably, the mass ratio of activated carbon supporting the phase change material to activated carbon supporting the polymerization inhibitor is 1:(1-10), more preferably 1:(2-9).

[0007] Preferably, in the activated carbon supported with the polymerization inhibitor, the mass ratio of the polymerization inhibitor to the mesoporous activated carbon activated by the first metal ions is (0.5-20):100, more preferably (1-15):100.

[0008] Preferably, in the activated carbon loaded with phase change material, the mass ratio of the phase change material to the mesoporous activated carbon activated by the second metal ion is 1:(0.1-2.5), more preferably 1:(0.25-0.7).

[0009] Preferably, the mesoporous activated carbon activated by the first metal ion is the same as the mesoporous activated carbon activated by the second metal ion.

[0010] Preferably, the metal ions in the first metal ion-activated mesoporous activated carbon and the second metal ion-activated mesoporous activated carbon are Zn. 2+ Cu 2+ and Mg 2+ At least one of them.

[0011] Preferably, the specific surface area of ​​the first metal ion-activated mesoporous activated carbon and the second metal ion-activated mesoporous activated carbon is 1300 m². 2 The content is above / g, the average pore size is 2.5-3.5nm, and the mesoporous volume is above 70%.

[0012] Preferably, the polymerization inhibitor is at least one selected from hydroquinone, 2,6-di-tert-butyl-p-methylphenol, 4,4'-dihydroxybiphenyl, bisphenol A, p-tert-butylcatechol, 2-sec-butyl-4,6-dinitrophenol, 2,4-dinitro-p-cresol, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-carboxy-2,2,6,6-tetramethylpiperidine nitroxide radical, tris(4-oxo-2,2,6,6-tetramethylpiperidine nitroxide radical) phosphine, 1,1-diphenyl-2-picrylhydrazine radical, tetrachlorobenzoquinone, 1,4-naphthoquinone, phenothiazine, p-toluidine, diphenylamine, benzidine, p-phenylenediamine, N-nitrosodiphenylamine, 1,1-diphenyl-2-trinitrophenylhydrazine, and tris(N-nitroso-N-phenylhydroxylamine) aluminum salt.

[0013] Preferably, the phase change material is at least one selected from paraffin, lauric acid, n-tetradecanoic acid, palmitic acid, n-hexadecane, n-octadecane, n-eicosane, n-docosahexadecane, n-tetracosane, dodecyl alcohol, and polyethylene glycol.

[0014] A second aspect of the present invention provides a method for preparing a composite material, the method comprising the following steps:

[0015] (1) Preparation of mesoporous activated carbon activated by metal ions;

[0016] (2) The mesoporous activated carbon with metal ion activation obtained in step (1) is immersed in a solution containing a polymerization inhibitor, then the solvent is removed, and then dried to obtain activated carbon loaded with polymerization inhibitor.

[0017] (3) The mesoporous activated carbon with metal ions activated in step (1) is mixed with a solution containing phase change material, then the solvent is removed, and then dried to obtain activated carbon loaded with phase change material.

[0018] (4) Mix the activated carbon of the polymer inhibitor with the activated carbon of the phase change material.

[0019] Preferably, the process for preparing metal ion-activated mesoporous activated carbon includes: immersing biomass raw material in a metal salt solution, followed by dehydration and drying, subjecting the obtained material to a first high-temperature activation treatment under an inert atmosphere, followed by a second high-temperature activation treatment under a carbon dioxide atmosphere, then cooling under an inert atmosphere, and sequentially washing the cooled activated carbon with water, acid washing, water washing, and drying.

[0020] Preferably, the mass ratio of the biomass raw material to the metal salt in the metal salt solution is 1:(1-3).

[0021] Preferably, the temperatures of the first high-temperature activation treatment and the second high-temperature activation treatment are each 800-850°C.

[0022] Preferably, the metal salt is at least one of ZnCl2, CuCl2 and MgCl2.

[0023] Preferably, the biomass raw material is coconut shell.

[0024] Preferably, in step (2), the mass ratio of the polymerization inhibitor to the metal ion-modified mesoporous activated carbon is (0.5-20):100, more preferably (2-9):100.

[0025] Preferably, the concentration of the polymerization inhibitor in the solution containing the polymerization inhibitor is 0.05-0.3 g / 10 mL.

[0026] Preferably, the polymerization inhibitor is at least one selected from hydroquinone, 2,6-di-tert-butyl-p-methylphenol, 4,4'-dihydroxybiphenyl, bisphenol A, p-tert-butylcatechol, 2-sec-butyl-4,6-dinitrophenol, 2,4-dinitro-p-cresol, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-carboxy-2,2,6,6-tetramethylpiperidine nitroxide radical, tris(4-oxo-2,2,6,6-tetramethylpiperidine nitroxide radical) phosphine, 1,1-diphenyl-2-picrylhydrazine radical, tetrachlorobenzoquinone, 1,4-naphthoquinone, phenothiazine, p-toluidine, diphenylamine, benzidine, p-phenylenediamine, N-nitrosodiphenylamine, 1,1-diphenyl-2-trinitrophenylhydrazine, and tris(N-nitroso-N-phenylhydroxylamine) aluminum salt.

[0027] Preferably, in step (3), the mass ratio of the phase change material to the metal ion activated mesoporous activated carbon is 1:(0.1-2.5), more preferably 1:(0.25-0.7).

[0028] Preferably, the concentration of the phase change material in the solution containing the phase change material is 0.2-5 g / mL, and more preferably 0.5-3 g / mL.

[0029] Preferably, the phase change material is at least one selected from paraffin, lauric acid, n-tetradecanoic acid, palmitic acid, n-hexadecane, n-octadecane, n-eicosane, n-docosahexadecane, n-tetracosane, dodecyl alcohol, and polyethylene glycol.

[0030] Preferably, in step (4), the mass ratio of activated carbon supporting the phase change material to activated carbon supporting the polymerization inhibitor is 1:(1-10), more preferably 1:(4-8).

[0031] A third aspect of the present invention provides the application of the aforementioned composite material in the olefin adsorption process.

[0032] Preferably, the olefin is styrene.

[0033] According to the composite material of the present invention, activated carbon supported on a polymerization inhibitor is combined with activated carbon supported on a phase change material. The polymerization inhibitor inhibits the polymerization reaction of styrene, while the phase change material absorbs or releases a large amount of heat during the phase change process. This effectively transfers the large amount of heat generated during gas adsorption by the composite material, preventing a significant temperature increase, thus enabling the composite material to have a high adsorption capacity for styrene gas. Specifically, the composite material of the present invention can achieve a styrene adsorption capacity of up to 0.88 g / g at room temperature. Attached Figure Description

[0034] Figure 1 The nitrogen adsorption isotherm of the composite material prepared in Example 1;

[0035] Figure 2 The image shows the pore size distribution of the composite material prepared in Example 1. Detailed Implementation

[0036] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0037] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0038] The composite material of the present invention contains activated carbon supported on a polymerization inhibitor and activated carbon supported on a phase change material. The activated carbon supported on the polymerization inhibitor contains mesoporous activated carbon activated by a first metal ion and a polymerization inhibitor, and the activated carbon supported on the phase change material contains mesoporous activated carbon activated by a second metal ion and a phase change material.

[0039] According to the composite material of the present invention, the mass ratio of activated carbon of the supported phase change material to activated carbon of the supported polymerization inhibitor can be 1:(1-10), preferably 1:(2-9), more preferably 1:(4-8), and even more preferably 1:(5-7). When the activated carbon of the supported phase change material and the activated carbon of the supported polymerization inhibitor are compounded in the above-mentioned proportion range, the composite material has superior adsorption performance for olefins (especially styrene).

[0040] According to the activated carbon supported on the polymerization inhibitor of the present invention, the mass ratio of the polymerization inhibitor to the mesoporous activated carbon activated by the first metal ion can be (0.5-20):100, preferably (1-15):100, more preferably (2-9):100, and even more preferably (3-8):100. When the polymerization inhibitor is loaded on the mesoporous activated carbon activated by the first metal ion in the above-mentioned ratio range, the composite material has superior adsorption performance for olefins (especially styrene).

[0041] According to the activated carbon supported on phase change material of the present invention, the mass ratio of the phase change material to the mesoporous activated carbon activated by the second metal ion can be 1:(0.1-2.5), preferably 1:(0.25-0.7), and more preferably 1:(0.3-0.6). When the phase change material is loaded on the mesoporous activated carbon activated by the second metal ion within the above-mentioned ratio range, the composite material has superior adsorption performance for olefins (especially styrene).

[0042] In the composite material described in this invention, the mesoporous activated carbon activated by the first metal ion and the mesoporous activated carbon activated by the second metal ion may be the same or different, preferably the same.

[0043] In the composite material described in this invention, the metal ions in the first metal ion-activated mesoporous activated carbon and the second metal ion-activated mesoporous activated carbon can be Zn. 2+ Cu 2+ and Mg 2+ At least one of the following. In the most preferred embodiment, the metal ion is Zn. 2+ .

[0044] In the composite material described in this invention, the specific surface area of ​​the first metal ion-activated mesoporous activated carbon and the second metal ion-activated mesoporous activated carbon is 1300 m². 2 The composite material has an average pore size of 2.5-3.5 nm and a mesoporous pore volume of 70% or more. When the performance parameters of the first metal ion-activated mesoporous activated carbon and the second metal ion-activated mesoporous activated carbon are within the above range, the composite material has superior adsorption performance for olefins (especially styrene).

[0045] In the activated carbon supported with the polymerization inhibitor, the polymerization inhibitor may be at least one of hydroquinone, 2,6-di-tert-butyl-p-methylphenol, 4,4'-dihydroxybiphenyl, bisphenol A, p-tert-butylcatechol, 2-sec-butyl-4,6-dinitrophenol, 2,4-dinitro-p-cresol, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-carboxy-2,2,6,6-tetramethylpiperidine nitroxide radical, tris(4-oxo-2,2,6,6-tetramethylpiperidine nitroxide radical) phosphine, 1,1-diphenyl-2-picrylhydrazine radical, tetrachlorobenzoquinone, 1,4-naphthoquinone, phenothiazine, p-toluidine, diphenylamine, benzidine, p-phenylenediamine, N-nitrosodiphenylamine, 1,1-diphenyl-2-trinitrophenylhydrazine, and tris(N-nitroso-N-phenylhydroxylamine) aluminum salt. In the most preferred embodiment, the polymerization inhibitor is p-tert-butylcatechol.

[0046] In the activated carbon loaded with the phase change material, the phase change material can be a low-melting-point solid hydrocarbon. In a preferred embodiment, the phase change material is at least one selected from paraffin wax, lauric acid, n-tetradecanoic acid, palmitic acid, n-hexadecane, n-octadecane, n-eicosane, n-docosahexadecane, n-tetracosane, dodecyl alcohol, and polyethylene glycol. In the most preferred embodiment, the phase change material is paraffin wax. According to this most preferred embodiment, the phase change material can be well encapsulated in the pores of the activated carbon, and after the phase change material melts, leakage of the liquid phase change material can be better prevented, thereby giving the composite material superior adsorption performance for olefins (especially styrene).

[0047] The method for preparing the composite material of the present invention includes the following steps:

[0048] (1) Preparation of mesoporous activated carbon activated by metal ions;

[0049] (2) The mesoporous activated carbon with metal ion activation obtained in step (1) is immersed in a solution containing a polymerization inhibitor, then the solvent is removed, and then dried to obtain activated carbon loaded with polymerization inhibitor.

[0050] (3) The mesoporous activated carbon with metal ions activated in step (1) is mixed with a solution containing phase change material, then the solvent is removed, and then dried to obtain activated carbon loaded with phase change material.

[0051] (4) Mix the activated carbon of the polymer inhibitor with the activated carbon of the phase change material.

[0052] In step (1), the process of preparing metal ion activated mesoporous activated carbon may include: immersing biomass raw material in a metal salt solution, then dehydrating and drying it, subjecting the obtained material to a first high-temperature activation treatment under an inert atmosphere, then subjecting it to a second high-temperature activation treatment under a carbon dioxide atmosphere, then cooling it under an inert atmosphere, and then sequentially washing the cooled activated carbon with water, acid washing, water washing and drying.

[0053] In step (1), the mass ratio of the biomass raw material to the metal salt in the metal salt solution can be 1:(1-3), specifically, for example, 1:1, 1:1.5, 1:2, 1:2.5 or 1:3.

[0054] In step (1), the temperatures of the first high-temperature activation treatment and the second high-temperature activation treatment can each be 800-850℃.

[0055] In step (1), the first high-temperature activation temperature can be 800-850℃, preferably 805-845℃, and more preferably 810-840℃. When the first high-temperature activation temperature is within the above-mentioned preferred range, the prepared composite material has better olefin (styrene) adsorption performance.

[0056] More preferably, in the first high-temperature activation treatment in step (1), the heating rate to the target temperature is 2-12℃ / min, the gas flow rate is 0.2-1.5L / min, and the activation time is 1-5h. More preferably, in the first high-temperature activation treatment in step (1), the heating rate to the target temperature is 3-8℃ / min, the gas flow rate is 0.4-1L / min, and the activation time is 2-3h. Even more preferably, in the first high-temperature activation treatment in step (1), the heating rate to the target temperature is 4-6℃ / min, the gas flow rate is 0.6-0.9L / min, and the activation time is 2-2.5h.

[0057] In step (1), the second high-temperature activation temperature can be 800-850℃, preferably 805-845℃, and more preferably 810-840℃. When the second high-temperature activation temperature is within the above-mentioned preferred range, the prepared composite material has better olefin (styrene) adsorption performance.

[0058] More preferably, in the second high-temperature activation process of step (1), the heating rate to the target temperature is 2-12℃ / min, the gas flow rate is 0.2-1.5L / min, and the activation time is 1-5h. More preferably, in the first high-temperature activation process of step (1), the heating rate to the target temperature is 3-8℃ / min, the gas flow rate is 0.4-1L / min, and the activation time is 2-3h. Even more preferably, in the first high-temperature activation process of step (1), the heating rate to the target temperature is 4-6℃ / min, the gas flow rate is 0.6-0.9L / min, and the activation time is 2-2.5h.

[0059] In the method described in this invention, the temperature of the first high-temperature activation treatment and the temperature of the second high-temperature activation treatment may be the same or different. Preferably, the temperature of the first high-temperature activation treatment and the temperature of the second high-temperature activation treatment are the same.

[0060] In the method described in this invention, the first high-temperature activation process and the second high-temperature activation process in step (1) can be carried out in various conventional reaction apparatuses. In some embodiments, the dehydrated and dried material is placed in a crucible, placed in a tube furnace, and then heated to the target activation temperature for activation treatment.

[0061] In the method described in this invention, the inert atmosphere may be provided by nitrogen and / or an inert gas (such as argon). Preferably, the inert atmosphere is provided by nitrogen.

[0062] In step (1), the metal salt is at least one selected from ZnCl2, CuCl2, and MgCl2. In the most preferred embodiment, the metal salt is ZnCl2. According to this most preferred embodiment, the prepared composite material exhibits significantly enhanced olefin (especially styrene) adsorption performance.

[0063] In step (1), the biomass raw material can be any biomass raw material conventionally used in the art for preparing activated carbon, preferably coconut shell.

[0064] More preferably, when coconut shell is used as a biomass raw material, the method for preparing mesoporous activated carbon of the present invention further includes: grinding, milling and sieving the coconut shell raw material in sequence, collecting coconut shell particles with a particle size of 1-3 mm, and drying the coconut shell particles.

[0065] In step (1), the soaking time can be 1-48h, preferably 12-36h, and more preferably 20-30h.

[0066] In step (1), the concentration of the metal salt solution can be 1-8 mol / L, preferably 2-5 mol / L, specifically, for example, 2 mol / L, 2.5 mol / L, 3 mol / L, 3.5 mol / L, 4 mol / L, 4.5 mol / L or 5 mol / L.

[0067] In step (1), the dehydration and drying conditions may include: a temperature of 100-120°C, and a drying time that continues until the weight of the material no longer changes within 24 hours.

[0068] In step (1), the washing conditions may include: the washing liquid is deionized water, and the washing is performed until the pH of the filtrate is 6-8, preferably 6.5-7.5. The washing process can be carried out in a conventional container.

[0069] In step (1), the pickling conditions may include: the pickling liquid may be hydrochloric acid and / or sulfuric acid, preferably hydrochloric acid. The mass fraction of the acid is 4-6%, preferably 4.5-5%. The pickling process can be carried out in a water bath environment at 45-55°C. The number of washes may be once or multiple times, preferably twice. The pickling process can be carried out in a conventional container.

[0070] In step (2), the mass ratio of the polymerization inhibitor to the metal ion-modified mesoporous activated carbon can be (0.5-20):100, preferably (2-9):100, and more preferably (3-8):100.

[0071] In step (2), the concentration of the polymerization inhibitor in the solution containing the polymerization inhibitor can be 0.05-0.3 g / 10 mL, preferably 0.1-0.25 g / 10 mL, and more preferably 0.15-0.2 g / 10 mL.

[0072] In step (2), the polymerization inhibitor may be at least one of hydroquinone, 2,6-di-tert-butyl-p-methylphenol, 4,4'-dihydroxybiphenyl, bisphenol A, p-tert-butylcatechol, 2-sec-butyl-4,6-dinitrophenol, 2,4-dinitro-p-cresol, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-carboxy-2,2,6,6-tetramethylpiperidine nitroxide radical, tris(4-oxo-2,2,6,6-tetramethylpiperidine nitroxide radical) phosphine, 1,1-diphenyl-2-picrylhydrazine radical, tetrachlorobenzoquinone, 1,4-naphthoquinone, phenothiazine, p-toluidine, diphenylamine, benzidine, p-phenylenediamine, N-nitrosodiphenylamine, 1,1-diphenyl-2-trinitrophenylhydrazine, and tris(N-nitroso-N-phenylhydroxylamine) aluminum salt. In the most preferred embodiment, the polymerization inhibitor is p-tert-butylcatechol.

[0073] In step (2), the preparation process of the solution containing the polymerization inhibitor includes: dissolving the polymerization inhibitor in an ethanol solution and stirring it evenly at room temperature. This process can be carried out in various conventional containers. The volume ratio of water to anhydrous ethanol in the ethanol solution can be 1:(1-8), preferably 1:(2-6), and more preferably 1:(3-4).

[0074] In step (2), the impregnation process can be carried out at room temperature for 8-24 hours.

[0075] In step (2), the solvent removal process can be carried out in a rotary evaporator at a temperature of 25-95°C.

[0076] In step (2), the drying process can be carried out in a vacuum oven at a temperature of 50-90°C, preferably 60-80°C, for a time of 4-48 hours, preferably 8-24 hours.

[0077] In step (3), the mass ratio of the phase change material to the metal ion activated mesoporous activated carbon can be 1:(0.1-2.5), preferably 1:(0.25-0.7), and more preferably 1:(0.3-0.6).

[0078] In step (3), the concentration of the phase change material in the solution containing the phase change material can be 0.2-5 g / mL, preferably 0.5-3 g / mL, specifically, for example, 0.5 g / mL, 0.1 g / mL, 0.15 g / mL, 0.2 g / mL, 0.25 g / mL or 0.3 g / mL.

[0079] In step (3), the phase change material can be at least one selected from paraffin, lauric acid, n-tetradecanoic acid, palmitic acid, n-hexadecane, n-octadecane, n-eicosane, n-docosahexadecane, n-tetracosane, dodecyl alcohol, and polyethylene glycol. In the most preferred embodiment, the phase change material is paraffin.

[0080] In step (3), the preparation process of the solution containing the polymerization inhibitor may include: adding the phase change material to anhydrous ethanol and stirring it evenly at room temperature. This process can be carried out in various conventional containers.

[0081] In step (3), the solvent removal process can be carried out in a rotary evaporator at a temperature of 25-80°C.

[0082] In step (3), the drying process can be carried out in a vacuum oven at a temperature of 65-90°C, preferably 70-80°C.

[0083] The present invention also provides a composite material prepared by the above method. This composite material has both polymerization inhibition and heat storage functions. Compared with traditional adsorption materials, it has good thermal conductivity and can reduce the self-polymerization reaction of organic gases during adsorption. It has a higher adsorption capacity for olefins (especially styrene) and can be used for efficient adsorption and treatment of olefin VOCs.

[0084] This invention also provides the application of the composite material in the olefin adsorption process. The olefin is preferably styrene. In practical applications, under room temperature and atmospheric pressure conditions, the styrene adsorption capacity of the activated carbon composite material can reach up to 0.88 g / g.

[0085] The following examples further illustrate the composite material, its preparation method, and its application according to the present invention. These examples are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures; however, the scope of protection of the present invention is not limited to the following examples.

[0086] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available.

[0087] In the following examples and comparative examples, the relevant parameters of the test samples were tested according to the following methods:

[0088] Specific surface area and pore size analysis: The specific surface area and pore size of the samples were analyzed using a Bestech BSD-PM2 specific surface area and micropore analyzer. Before testing, the samples were placed in a vacuum and pretreated at 150℃ for 6 hours, followed by N2 adsorption isotherm testing at 77K. The BET and Langmuir specific surface areas of the materials were calculated using the BET and Langmuir equations, respectively, and the average mesopore size was calculated using DFT.

[0089] Styrene adsorption test: The styrene adsorption breakthrough curve was determined using a BSD-MAB breakthrough curve analyzer. The column inner diameter was 0.6 cm, and the sample loading height was approximately 8 cm. Before testing, the sample was activated by nitrogen purging at 150 °C for 3 hours. Nitrogen was used as the carrier gas at a total flow rate of 400 sccm, and the test temperature was 25 °C. The concentration and composition of the gas exiting the adsorption column were detected using an online mass spectrometer.

[0090] Example 1

[0091] (1) After grinding, sifting and screening the coconut shell raw material, collect the coconut shell particles (particle size is 1-3mm), place 10g of coconut shell particles in a vacuum oven for drying, set the temperature to 100℃, and the duration is 12h.

[0092] (2) The dried coconut shell particles were soaked in 100 mL of 2.2 mol / L ZnCl2 solution (30 g of ZnCl2) for 24 h, and then placed in a vacuum oven for dehydration and drying. The temperature was set at 110 °C and continued for 24 h until the weight of the material no longer changed.

[0093] (3) Place the soaked and dried coconut shell particles in a crucible, place it in a tube furnace, introduce nitrogen gas at a flow rate of 0.8 L / min, heat it to 835 °C at a heating rate of 5 °C / min, and continue the activation treatment for 2 h; then switch the nitrogen gas to carbon dioxide gas at a flow rate of 0.8 L / min, and activate it at 835 °C for 2 h; then switch the carbon dioxide gas back to nitrogen gas until the tube furnace cools down to room temperature, and obtain activated carbon dioxide activated carbon.

[0094] (4) The activated carbon activated by carbon dioxide was washed five times with deionized water, and the pH of the filtrate after washing was measured to be 6.8 using a pH meter. Then it was washed twice with a 5% hydrochloric acid solution in a water bath at 50°C, and then washed eight times with deionized water. The pH of the filtrate after washing was measured to be 6.5 using a pH meter. The washed activated carbon was placed in a vacuum oven for drying at 100°C for 12 hours to obtain zinc ion activated mesoporous activated carbon A1.

[0095] (5) Prepare an ethanol solution by mixing deionized water and anhydrous ethanol at a volume ratio of 1:3. Dissolve 0.19 g of p-tert-butylcatechol in 10 mL of the ethanol solution and stir evenly at room temperature to obtain a polymerization inhibitor solution.

[0096] (6) Weigh 5g of mesoporous activated carbon A1 and add it to the polymerization inhibitor solution. Stir well at room temperature and soak for 24h. Place the resulting activated carbon suspension in a rotary evaporator to remove the solvent. Set the temperature to 75℃ and continue until it is apparently dry. Place the remaining solid in a vacuum oven to dry at 60℃ for 24h to obtain activated carbon B1 loaded with polymerization inhibitor.

[0097] (7) Dissolve 5g of paraffin in 4mL of anhydrous ethanol and stir until homogeneous at room temperature to obtain a phase change material solution. Add 2.5g of mesoporous activated carbon A1 to the phase change material solution and stir until homogeneous at room temperature. Remove the ethanol solvent from the mixed suspension using a rotary evaporator at 68°C. Then place the remaining solid in a vacuum drying oven at 70°C for 12 hours to obtain activated carbon C1 loaded with phase change material.

[0098] (8) The activated carbon C1 supported by the phase change material and the activated carbon B1 supported by the polymerization inhibitor are physically mixed in a mass ratio of 1:6 to obtain the composite material D1 of the present invention.

[0099] The samples obtained above were tested and calculated using a physical adsorption instrument. The test results are as follows:

[0100] Mesoporous activated carbon A1: carbon yield 32.6%, specific surface area 1321 m² 2 / g, with an average pore size of 3.4nm and a mesoporous volume of 70.2%.

[0101] Activated carbon B1 with supported polymerization inhibitor: specific surface area of ​​1250 m² 2 The average pore size is 3.1 nm, and the adsorption capacity for styrene is 0.65 g / g under room temperature and normal pressure conditions.

[0102] Composite material D1: Specific surface area is 1030 m² 2 / g, under room temperature and normal pressure conditions, the adsorption capacity for styrene is 0.88g / g.

[0103] Example 2

[0104] (1) After grinding, sifting and screening the coconut shell particles, collect the coconut shell particles (particle size is 1-3mm), place 10g of coconut shell particles in a vacuum oven for drying, set the temperature to 110℃, and the duration is 14h.

[0105] (2) The dried coconut shell particles were soaked in 39 mL of 5 mol / L ZnCl2 solution (ZnCl2 mass is 27 g) for 30 h, and then placed in a vacuum oven for dehydration and drying. The temperature was set to 110 °C and continued for 24 h until the weight of the material no longer changed.

[0106] (3) Place the soaked and dried coconut shell particles in a crucible, place it in a tube furnace, introduce nitrogen gas at a flow rate of 0.6 L / min, heat it to 840 °C at a heating rate of 6 °C / min, and continue the activation treatment for 2.2 h; then switch the nitrogen gas to carbon dioxide gas at a flow rate of 0.6 L / min, and activate it at 830 °C for 2.2 h; then switch the carbon dioxide gas back to nitrogen gas until the tube furnace cools down to room temperature, and obtain activated carbon dioxide activated carbon.

[0107] (4) The activated carbon activated by carbon dioxide was washed 6 times with deionized water, and the pH of the filtrate after washing was measured to be 6.7 using a pH meter. Then it was washed twice with a 4.5% hydrochloric acid solution in a water bath at 55°C, and then washed 9 times with deionized water. The pH of the filtrate after washing was measured to be 6.6 using a pH meter. The washed activated carbon was placed in a vacuum oven for drying at 105°C for 14 hours to obtain zinc ion activated mesoporous activated carbon A2.

[0108] (5) Prepare an ethanol solution by mixing deionized water and anhydrous ethanol at a volume ratio of 1:3.5. Dissolve 0.15 g of p-tert-butylcatechol in 10 mL of the ethanol solution and stir evenly at room temperature to obtain a polymerization inhibitor solution.

[0109] (6) Weigh 5g of mesoporous activated carbon A2 and add it to the polymerization inhibitor solution. Stir well at room temperature and soak for 22h. Place the resulting activated carbon suspension in a rotary evaporator to remove the solvent. Set the temperature to 73℃ and let it dry until it appears dry. Place the remaining solid in a vacuum oven to dry at 70℃ for 15h to obtain activated carbon B2 loaded with polymerization inhibitor.

[0110] (7) Dissolve 2g of paraffin in 4mL of anhydrous ethanol and stir until homogeneous at room temperature to obtain a phase change material solution. Add 0.12g of mesoporous activated carbon A2 to the phase change material solution and stir until homogeneous at room temperature. Remove the ethanol solvent from the mixed suspension using a rotary evaporator at a temperature of 69°C. Then, place the remaining solid in a vacuum drying oven at a temperature of 72°C for 13 hours to obtain activated carbon C2 loaded with phase change material.

[0111] (8) The activated carbon C2 loaded with the phase change material and the activated carbon B2 loaded with the polymerization inhibitor are physically mixed in a mass ratio of 1:7 to obtain the composite material D2 of the present invention.

[0112] The samples obtained above were tested and calculated using a physical adsorption instrument. The test results are as follows:

[0113] Mesoporous activated carbon A2: carbon yield 31.8%, specific surface area 1320 m² 2 / g, with an average pore size of 3.4nm and a mesoporous volume of 69.7%.

[0114] Activated carbon B2 with supported polymerization inhibitor: specific surface area of ​​1261 m² 2 The average pore size is 3.2 nm, and the adsorption capacity for styrene is 0.65 g / g under room temperature and normal pressure conditions.

[0115] Composite material D2: Specific surface area is 1045 m² 2 / g, under room temperature and normal pressure conditions, the adsorption capacity for styrene is 0.82g / g.

[0116] Example 3

[0117] (1) After grinding, sifting and screening the coconut shell particles, collect the coconut shell particles (particle size is 1-3mm), place 20g of coconut shell particles in a vacuum oven for drying, set the temperature to 105℃, and the duration is 15h.

[0118] (2) The dried coconut shell particles were soaked in 73 mL of 2 mol / L ZnCl2 solution (ZnCl2 mass is 20 g) for 20 h, and then placed in a vacuum oven for dehydration and drying. The temperature was set at 105 °C and continued for 24 h until the weight of the material no longer changed.

[0119] (3) Place the soaked and dried coconut shell particles in a crucible, place it in a tube furnace, introduce nitrogen gas at a flow rate of 0.9 L / min, heat it to 810 °C at a heating rate of 6 °C / min, and continue the activation treatment for 2.5 h; then switch the nitrogen gas to carbon dioxide gas at a flow rate of 0.8 L / min, and activate it at 810 °C for 2.5 h; then switch the carbon dioxide gas back to nitrogen gas until the tube furnace cools down to room temperature, and obtain activated carbon dioxide activated carbon.

[0120] (4) The activated carbon activated by carbon dioxide was washed 6 times with deionized water, and the pH of the filtrate after washing was measured to be 6.9 using a pH meter. Then it was washed twice with a 4.8% hydrochloric acid solution in a water bath at 55°C, and then washed 8 times with deionized water. The pH of the filtrate after washing was measured to be 6.7 using a pH meter. The washed activated carbon was placed in a vacuum oven for drying at 115°C for 12 hours to obtain zinc ion activated mesoporous activated carbon A3.

[0121] (5) Prepare an ethanol solution by mixing deionized water and anhydrous ethanol at a volume ratio of 1:4. Dissolve 0.4 g of p-tert-butylcatechol in 20 mL of the ethanol solution and stir evenly at room temperature to obtain a polymerization inhibitor solution.

[0122] (6) Weigh 5g of mesoporous activated carbon A3 and add it to the polymerization inhibitor solution. Stir evenly at room temperature and then impregnate for 21h. Place the resulting activated carbon suspension in a rotary evaporator to remove the solvent. Set the temperature to 75℃ and continue until it is apparently dry. Place the remaining solid in a vacuum oven to dry at 80℃ for 8h to obtain activated carbon B3 loaded with polymerization inhibitor.

[0123] (7) Dissolve 12g of paraffin in 4mL of anhydrous ethanol and stir until homogeneous at room temperature to obtain a phase change material solution. Add 3.6g of mesoporous activated carbon A3 to the phase change material solution and stir until homogeneous at room temperature. Remove the ethanol solvent from the mixed suspension using a rotary evaporator at 65°C. Then, place the remaining solid in a vacuum drying oven at 80°C for 10 hours to obtain activated carbon C3 loaded with phase change material.

[0124] (8) The activated carbon C3 loaded with the phase change material and the activated carbon B3 loaded with the polymerization inhibitor are physically mixed at a mass ratio of 1:5 to obtain the composite material D3 of the present invention.

[0125] The samples obtained above were tested and calculated using a physical adsorption instrument. The test results are as follows:

[0126] Mesoporous activated carbon A3: carbon yield 30.1%, specific surface area 1312 m² 2 / g, with an average pore size of 3.2nm and a mesoporous volume of 69.7%.

[0127] Activated carbon B3 with supported polymerization inhibitor: specific surface area of ​​1238 m² 2 The average pore size is 3.2 nm, and the adsorption capacity for styrene is 0.63 g / g under room temperature and normal pressure conditions.

[0128] Composite material D3: Specific surface area is 10¹² m²2 / g, under room temperature and normal pressure conditions, the adsorption capacity for styrene is 0.86g / g.

[0129] Example 4

[0130] The composite material was prepared according to the method of Example 1, except that in step (5), the mass ratio of p-tert-butylcatechol to activated carbon was adjusted to 1:100, and finally mesoporous activated carbon A4, activated carbon B4 supported with polymerization inhibitor and composite material D4 were obtained.

[0131] The samples obtained above were tested and calculated using a physical adsorption instrument. The test results are as follows:

[0132] Mesoporous activated carbon A4: carbon yield 32.6%, specific surface area 1321 m² 2 / g, with an average pore size of 3.4nm and a mesoporous volume of 70.2%.

[0133] Activated carbon B4 with supported polymerization inhibitor: specific surface area of ​​1307 m² 2 The average pore size is 3.3 nm, and the adsorption capacity for styrene is 0.56 g / g under room temperature and normal pressure conditions.

[0134] Composite material D4: Specific surface area is 1120 m² 2 / g, under room temperature and normal pressure conditions, the adsorption capacity for styrene is 0.78g / g.

[0135] Example 5

[0136] The composite material was prepared according to the method of Example 1, except that in step (5), the mass ratio of p-tert-butylcatechol to activated carbon was adjusted to 10:100, and finally mesoporous activated carbon A5, activated carbon B5 supported with polymerization inhibitor and composite material D5 were obtained.

[0137] The samples obtained above were tested and calculated using a physical adsorption instrument. The test results are as follows:

[0138] Mesoporous activated carbon A5: carbon yield 32.6%, specific surface area 1321 m² 2 / g, with an average pore size of 3.4nm and a mesoporous volume of 70.2%.

[0139] Activated carbon B5 with supported polymerization inhibitor: specific surface area of ​​1186 m² 2 The average pore size is 2.8 nm, and the adsorption capacity for styrene is 0.60 g / g under room temperature and normal pressure conditions.

[0140] Composite material D5: Specific surface area is 956 m² 2 / g, under room temperature and normal pressure conditions, the adsorption capacity for styrene is 0.80g / g.

[0141] Example 6

[0142] The composite material was prepared according to the method of Example 1, except that in step (7), the mass ratio of paraffin to activated carbon was adjusted to 1:0.2, and finally mesoporous activated carbon A6, activated carbon B6 supported with polymerization inhibitor and composite material D6 were obtained.

[0143] The samples obtained above were tested and calculated using a physical adsorption instrument. The test results are as follows:

[0144] Mesoporous activated carbon A6: carbon yield 32.6%, specific surface area 1321 m² 2 / g, with an average pore size of 3.4nm and a mesoporous volume of 70.2%.

[0145] Activated carbon B6 with supported polymerization inhibitor: specific surface area of ​​1250 m² 2 The average pore size is 3.1 nm, and the adsorption capacity for styrene is 0.65 g / g under room temperature and normal pressure conditions.

[0146] Composite material D6: Specific surface area is 1021 m² 2 / g, under room temperature and normal pressure conditions, the adsorption capacity for styrene is 0.74g / g.

[0147] Example 7

[0148] The composite material was prepared according to the method of Example 1, except that in step (7), the mass ratio of paraffin to activated carbon was adjusted to 1:0.7, and finally mesoporous activated carbon A7, activated carbon B7 supported with polymerization inhibitor and composite material D7 were obtained.

[0149] The samples obtained above were tested and calculated using a physical adsorption instrument. The test results are as follows:

[0150] Mesoporous activated carbon A7: carbon yield 32.6%, specific surface area 1321 m² 2 / g, with an average pore size of 3.4nm and a mesoporous volume of 70.2%.

[0151] Activated carbon B7 with supported polymerization inhibitor: specific surface area of ​​1250 m² 2 The average pore size is 3.1 nm, and the adsorption capacity for styrene is 0.65 g / g under room temperature and normal pressure conditions.

[0152] Composite material D7: Specific surface area is 1025 m² 2 / g, under room temperature and normal pressure conditions, the adsorption capacity for styrene is 0.77g / g.

[0153] Example 8

[0154] The composite material was prepared according to the method of Example 1, except that in step (8), the mass ratio of activated carbon loaded with phase change material to activated carbon loaded with polymerization inhibitor was adjusted to 1:4, and finally mesoporous activated carbon A8, activated carbon loaded with polymerization inhibitor and composite material D8 were obtained.

[0155] The samples obtained above were tested and calculated using a physical adsorption instrument. The test results are as follows:

[0156] Mesoporous activated carbon A8: carbon yield 32.6%, specific surface area 1321 m² 2 / g, with an average pore size of 3.4nm and a mesoporous volume of 70.2%.

[0157] Activated carbon B8 with supported polymerization inhibitor: specific surface area of ​​1250 m² 2 The average pore size is 3.1 nm, and the adsorption capacity for styrene is 0.65 g / g under room temperature and normal pressure conditions.

[0158] Composite material D8: Specific surface area is 980 m² 2 / g, under room temperature and normal pressure conditions, the adsorption capacity for styrene is 0.71g / g.

[0159] Example 9

[0160] The composite material was prepared according to the method of Example 1, except that in step (8), the mass ratio of activated carbon loaded with phase change material to activated carbon loaded with polymerization inhibitor was adjusted to 1:8, and finally mesoporous activated carbon A9, activated carbon loaded with polymerization inhibitor B9 and composite material D9 were obtained.

[0161] The samples obtained above were tested and calculated using a physical adsorption instrument. The test results are as follows:

[0162] Mesoporous activated carbon A9: carbon yield 32.6%, specific surface area 1321 m² 2 / g, with an average pore size of 3.4nm and a mesoporous volume of 70.2%.

[0163] Activated carbon B9 with supported polymerization inhibitor: specific surface area of ​​1250 m² 2 The average pore size is 3.1 nm, and the adsorption capacity for styrene is 0.65 g / g under room temperature and normal pressure conditions.

[0164] Composite material D9: Specific surface area is 1092 m² 2 / g, under room temperature and normal pressure conditions, the adsorption capacity for styrene is 0.73g / g.

[0165] Comparative Example 1

[0166] Activated carbon B1 with a supported polymerization inhibitor was prepared according to the method in Example 1.

[0167] 5g of paraffin was dissolved in 4mL of anhydrous ethanol and stirred until homogeneous at room temperature to obtain a phase change material solution. 2.5g of activated carbon B1 loaded with polymerization inhibitor was added to the phase change material solution and stirred until homogeneous at room temperature. The ethanol solvent was removed from the mixed suspension using a rotary evaporator at 68°C. The remaining solid was then dried in a vacuum drying oven at 70°C for 12 hours to obtain composite material X1.

[0168] Based on tests and calculations using a physical adsorption instrument, the test results for the composite material X1 are as follows: specific surface area is 1001 m². 2 / g, under room temperature and normal pressure conditions, the adsorption capacity for styrene is 0.61g / g.

[0169] Comparative Example 2

[0170] Activated carbon B1 with a polymerization inhibitor prepared according to the method of Example 1 was used as the comparative test sample X2.

[0171] Based on tests and calculations using a physical adsorption instrument, the test results for the comparative test sample X2 are as follows: specific surface area is 1250 m². 2 / g, under room temperature and normal pressure conditions, the adsorption capacity for styrene is 0.55g / g.

[0172] Comparative Example 3

[0173] The activated carbon C1 loaded with phase change material prepared according to the method of Example 1 was used as the comparative test sample X3.

[0174] Based on tests and calculations using a physical adsorption instrument, the test results for the comparative test sample X3 are as follows: specific surface area is 1068 m². 2 / g, under room temperature and normal pressure conditions, the adsorption capacity for styrene is 0.50g / g.

[0175] The corresponding operating conditions and performance parameters of the composite material samples according to the above embodiments and comparative examples are shown in Table 1 below.

[0176] Table 1

[0177]

[0178] As can be seen from the results in Table 1, the composite material prepared by the method described in this invention has a high styrene adsorption capacity.

[0179] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A composite material, characterized in that, The composite material contains activated carbon supported on a polymerization inhibitor and activated carbon supported on a phase change material. The activated carbon supported on the polymerization inhibitor contains mesoporous activated carbon activated by a first metal ion and a polymerization inhibitor, and the activated carbon supported on the phase change material contains mesoporous activated carbon activated by a second metal ion and a phase change material.

2. The composite material according to claim 1, characterized in that, The mass ratio of activated carbon supporting the phase change material to activated carbon supporting the polymerization inhibitor is 1:(1-10), preferably 1:(2-9).

3. The composite material according to claim 1 or 2, characterized in that, In the activated carbon supported with the polymerization inhibitor, the mass ratio of the polymerization inhibitor to the mesoporous activated carbon activated by the first metal ions is (0.5-20):100, preferably (1-15):

100.

4. The composite material according to claim 1 or 2, characterized in that, In the activated carbon loaded with phase change material, the mass ratio of the phase change material to the mesoporous activated carbon activated by the second metal ion is 1:(0.1-2.5), preferably 1:(0.25-0.7).

5. The composite material according to any one of claims 1-4, characterized in that, The mesoporous activated carbon activated by the first metal ion is the same as the mesoporous activated carbon activated by the second metal ion. Preferably, the metal ions in the first metal ion-activated mesoporous activated carbon and the second metal ion-activated mesoporous activated carbon are Zn. 2+ Cu 2+ and Mg 2+ At least one of them; Preferably, the specific surface area of ​​the first metal ion-activated mesoporous activated carbon and the second metal ion-activated mesoporous activated carbon is 1300 m². 2 The content is above / g, the average pore size is 2.5-3.5nm, and the mesoporous volume is above 70%.

6. The composite material according to any one of claims 1-4, characterized in that, The polymerization inhibitor is at least one selected from hydroquinone, 2,6-di-tert-butyl-p-methylphenol, 4,4'-dihydroxybiphenyl, bisphenol A, p-tert-butylcatechol, 2-sec-butyl-4,6-dinitrophenol, 2,4-dinitro-p-cresol, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-carboxy-2,2,6,6-tetramethylpiperidine nitroxide radical, tris(4-oxo-2,2,6,6-tetramethylpiperidine nitroxide radical) phosphine, 1,1-diphenyl-2-picrylhydrazine radical, tetrachlorobenzoquinone, 1,4-naphthoquinone, phenothiazine, p-toluidine, diphenylamine, benzidine, p-phenylenediamine, N-nitrosodiphenylamine, 1,1-diphenyl-2-trinitrophenylhydrazine, and tris(N-nitroso-N-phenylhydroxylamine) aluminum salt.

7. The composite material according to any one of claims 1-4, characterized in that, The phase change material is at least one of paraffin, lauric acid, tetradecanoic acid, palmitic acid, hexadecane, octadecane, eicosane, dodecane, dodecyl alcohol, and polyethylene glycol.

8. A method for preparing a composite material, characterized in that, The method includes the following steps: (1) Preparation of mesoporous activated carbon activated by metal ions; (2) The mesoporous activated carbon with metal ion activation obtained in step (1) is immersed in a solution containing a polymerization inhibitor, then the solvent is removed, and then dried to obtain activated carbon loaded with polymerization inhibitor. (3) The mesoporous activated carbon with metal ions activated in step (1) is mixed with a solution containing phase change material, then the solvent is removed, and then dried to obtain activated carbon loaded with phase change material. (4) Mix the activated carbon of the polymer inhibitor with the activated carbon of the phase change material.

9. The method according to claim 8, characterized in that, In step (1), the process of preparing metal ion activated mesoporous activated carbon includes: immersing biomass raw materials in a metal salt solution, then dehydrating and drying them, subjecting the obtained material to a first high-temperature activation treatment under an inert atmosphere, then subjecting it to a second high-temperature activation treatment under a carbon dioxide atmosphere, then cooling it under an inert atmosphere, and then sequentially washing the cooled activated carbon with water, acid washing, water washing, and drying.

10. The method according to claim 9, characterized in that, The mass ratio of the biomass raw material to the metal salt in the metal salt solution is 1:(1-3); Preferably, the temperatures of the first high-temperature activation treatment and the second high-temperature activation treatment are each 800-850°C; Preferably, the metal salt is at least one selected from ZnCl2, CuCl2, and MgCl2; Preferably, the biomass raw material is coconut shell.

11. The method according to claim 8, characterized in that, In step (2), the mass ratio of the polymerization inhibitor to the metal ion-modified mesoporous activated carbon is (0.5-20):100, preferably (2-9):100; Preferably, the concentration of the polymerization inhibitor in the solution containing the polymerization inhibitor is 0.05-0.3 g / 10 mL; Preferably, the polymerization inhibitor is at least one selected from hydroquinone, 2,6-di-tert-butyl-p-methylphenol, 4,4'-dihydroxybiphenyl, bisphenol A, p-tert-butylcatechol, 2-sec-butyl-4,6-dinitrophenol, 2,4-dinitro-p-cresol, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-carboxy-2,2,6,6-tetramethylpiperidine nitroxide radical, tris(4-oxo-2,2,6,6-tetramethylpiperidine nitroxide radical) phosphine, 1,1-diphenyl-2-picrylhydrazine radical, tetrachlorobenzoquinone, 1,4-naphthoquinone, phenothiazine, p-toluidine, diphenylamine, benzidine, p-phenylenediamine, N-nitrosodiphenylamine, 1,1-diphenyl-2-trinitrophenylhydrazine, and tris(N-nitroso-N-phenylhydroxylamine) aluminum salt.

12. The method according to claim 8, characterized in that, In step (3), the mass ratio of the phase change material to the metal ion activated mesoporous activated carbon is 1:(0.1-2.5), preferably 1:(0.25-0.7); Preferably, the concentration of the phase change material in the solution containing the phase change material is 0.2-5 g / mL, more preferably 0.5-3 g / mL; Preferably, the phase change material is at least one selected from paraffin, lauric acid, n-tetradecanoic acid, palmitic acid, n-hexadecane, n-octadecane, n-eicosane, n-docosahexadecane, n-tetracosane, dodecyl alcohol, and polyethylene glycol.

13. The method according to any one of claims 8-11, characterized in that, In step (4), the mass ratio of activated carbon supporting the phase change material to activated carbon supporting the polymerization inhibitor is 1:(1-10), preferably 1:(4-8).

14. A composite material prepared by the method according to any one of claims 8-13.

15. The application of the composite material according to any one of claims 1-7 and 14 in the olefin adsorption process; Preferably, the olefin is styrene.

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