Preparation method of carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier

Abstract

The present invention aims to provide a method for preparing a carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier. The method for preparing a carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier, comprising the following steps: step S1, according to a preset ratio, distilled water, hydroxymethyl cellulose, sodium dodecylbenzene sulfonate and a polymer dispersant are mixed to obtain an aqueous phase; step S2, according to a preset ratio, styrene, divinylbenzene, toluene, n-heptane, ethylene dichloride, benzoyl peroxide and carbon nanotubes are mixed to obtain an oil phase; step S3, oil phase and oil phase mixing, suspension polymerization, after processing, carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier can be obtained. The preparation method's overall process flow is simple, without the processes such as raw material processing and prepolymerization, without using strong acid or strong base, with a higher safety factor, lower production cost, and easy operation.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and in particular to a method for preparing a carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier. Background Art

[0002] Currently, hydrogen-water liquid phase catalytic exchange (LPCE) technology is one of the most effective methods for treating tritium-containing wastewater generated by nuclear power generation. The key materials in LPCE technology are hydrophobic catalysts, their catalyst supports, and active components. Examples include hydrophobic catalysts supported by polytetrafluoroethylene (PTFE) and those supported by styrene-divinylbenzene copolymer (SDB). SDB hydrophobic catalyst supports have attracted considerable attention due to their simple synthesis process and large specific surface area. For example, a Chinese invention patent application (CN104262521B) discloses a method for preparing a styrene-divinylbenzene copolymer hydrophobic catalyst support. However, the sphericity, specific surface area, and hydrophobicity of SDB hydrophobic catalyst supports still require improvement, necessitating doping and modification to enhance their properties.

[0003] Carbon nanotubes (MWCNTs) are a type of nanomaterial composed solely of carbon. Their light, closed, hollow tubular structure combines the excellent properties of graphite with excellent thermodynamic and electrical properties. They have great research and application value in physics, chemistry, biology, and mechanical manufacturing.

[0004] Chinese patent (CN101850242B) discloses a method for preparing a styrene-divinylbenzene-carbon nanotube copolymer chromatographic filler. The method specifically involves three steps: seed preparation, carbon nanotube esterification, and styrene-divinylbenzene-carbon nanotube copolymer chromatographic filler formation. Using styrene, divinylbenzene, and esterified multi-walled carbon nanotubes as raw materials, a dispersion polymerization method is used to prepare monodisperse linear polystyrene microsphere seeds. After activating the seeds, styrene-divinylbenzene-carbon nanotube copolymer microspheres are synthesized using a single-step seed swelling method. The porogen is then extracted and removed. The resulting chromatographic filler is then packed into a column using a homogenization method. This simple preparation process results in a uniform particle size, eliminating the need for screening. The filler exhibits enhanced mechanical properties, heat resistance, and stability, making it suitable for ultra-high pressure liquid chromatography and high-temperature liquid chromatography. This method is relatively complex, requiring seed preparation, carbon nanotube treatment, and finally, seed swelling to synthesize the styrene-divinylbenzene-carbon nanotube copolymer microspheres. At the same time, a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid is used in the treatment of carbon nanotubes, which is highly dangerous, and the final product is suitable for chromatographic columns.

[0005] This application intends to use styrene, divinylbenzene and multi-walled carbon nanotubes as raw materials, and prepare carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier by a relatively simple and safe process, and can be used as a hydrophobic catalyst in LPCE technology. Summary of the Invention

[0006] The present invention aims to provide a method for preparing a carbon nanotube hybrid-modified styrene-divinylbenzene copolymer hydrophobic catalyst support. This method has a simple overall process flow, does not require raw material processing or prepolymerization, and does not use strong acids or bases. It offers a high safety factor, low production costs, and ease of operation.

[0007] The technical solution adopted in the present invention is:

[0008] The preparation method of a carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier comprises the following steps:

[0009] Step S1, mixing distilled water, hydroxymethyl cellulose, sodium dodecylbenzene sulfonate and a polymer dispersant according to a preset ratio to obtain an aqueous phase;

[0010] Step S2, mixing styrene, divinylbenzene, toluene, n-heptane, ethylene dichloride, benzoyl peroxide, and carbon nanotubes according to a preset ratio to obtain an oil phase;

[0011] Step S3, the oil phase is mixed with the oil phase, suspended and polymerized, and the carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier is obtained after treatment.

[0012] Furthermore, in step S1, the amount of each raw material of the aqueous phase is as follows, in parts by mass:

[0013] Distilled water, 200-400 parts;

[0014] Hydroxymethyl cellulose, 0.1-0.4 parts;

[0015] Sodium dodecylbenzenesulfonate, 0.1-0.4 parts;

[0016] Polymer dispersant, 2-4 parts;

[0017] And / or, in step S2, the amount of each raw material of the oil phase is calculated by weight:

[0018] Styrene, 2-10 parts;

[0019] Divinylbenzene, 2-10 parts;

[0020] Benzoyl peroxide, 0.1-0.6 parts;

[0021] Toluene, 1-16 parts;

[0022] n-heptane, 12-24 parts;

[0023] 5-12 parts of dichloroethane;

[0024] Carbon nanotubes, 0.01~1 parts.

[0025] Furthermore, in step S1, the polymer dispersant is polyvinyl alcohol-1788, polyvinyl alcohol-1799, polyvinyl alcohol-2099, polyvinyl alcohol-2499 or polyvinyl alcohol-2699.

[0026] Furthermore, in step S2, the mass ratio of styrene, divinylbenzene and carbon nanotubes is 10:10:0.05-0.2.

[0027] Furthermore, in step S1, when preparing the aqueous phase, the mixing temperature is controlled to be 70-80° C. and the mixing time is 1-2 hours.

[0028] Furthermore, in step S3, the mixing temperature of the oil phase and the water phase is 45° C., and then the temperature is raised to 90-95° C. for suspension polymerization, and the reaction time is 7-8 hours.

[0029] Furthermore, in step S3, the temperature is first raised to 70°C before being raised to 90-95°C, kept warm for 1 hour, and then continued to be raised.

[0030] Furthermore, in step S3, the carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier is treated by sequentially filtering, washing and drying.

[0031] Furthermore, in step S3, deionized water, anhydrous ethanol and acetone are used for washing in sequence during filtration; wherein, the amount of deionized water and anhydrous ethanol is 2 to 3 times the mass of the carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst support, and the amount of acetone is 1 to 2 times the mass of the carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst support.

[0032] Furthermore, in step S3, the drying temperature is 60-70° C. and the drying time is 5-6 hours.

[0033] The beneficial effects of the present invention are:

[0034] 1. The present invention uses styrene, divinylbenzene, carbon nanotubes, etc. as raw materials to prepare a carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier through suspension polymerization. The overall process flow is simple, without the steps of raw material treatment and prepolymerization, and without the use of strong acids or strong bases. It has a high safety factor, low production cost, and is easy to operate.

[0035] 2. The carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier prepared in the present invention is a spherical ball with a large specific surface area and pore size, rich coordinating functional groups such as carbonyl groups and residual double bonds, good hydrophobicity (hydrophobic angle can reach 141.37°), high compressive strength (compressive strength can reach 111.5N), large particle size (carrier particle diameter reaches 2~3mm), controllable pore structure, and can provide the characteristics of loading active sites.

[0036] 3. The carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier prepared by the present invention has a high loading stability for the active component, can improve the catalytic performance of the catalyst, has the advantages of reducing the mass transfer resistance of the bed, preventing liquid flooding, and improving the fluid exchange efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0038] Figure 1 This is the infrared spectrum of the MWCNTs / SDB hydrophobic catalyst support in Example 2.

[0039] Figure 2 This is the TG curve of the MWCNTs / SDB hydrophobic catalyst support in Example 2.

[0040] Figure 3 This is the SEM image of the MWCNTs / SDB hydrophobic catalyst support in Example 2.

[0041] Figure 4 This is the XRD pattern of the MWCNTs / SDB hydrophobic catalyst support in Example 2.

[0042] Figure 5 This is the Raman spectrum of the MWCNTs / SDB hydrophobic catalyst support in Example 2. DETAILED DESCRIPTION

[0043] In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential" and the like to indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as limiting the present invention.

[0044] The disclosure below provides many different embodiments or examples to realize different structures of the present invention. In order to simplify the disclosure of the present invention, the parts and settings of specific examples are described below. Of course, they are only examples, and the purpose is not to limit the present invention.

[0045] The embodiments of the invention are described in detail below with reference to the accompanying drawings.

[0046] The preparation method of a carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier comprises the following steps:

[0047] Step S1, mixing distilled water, hydroxymethyl cellulose, sodium dodecylbenzene sulfonate and a polymer dispersant according to a preset ratio to obtain an aqueous phase;

[0048] Step S2, mixing styrene, divinylbenzene, toluene, n-heptane, ethylene dichloride, benzoyl peroxide, and carbon nanotubes according to a preset ratio to obtain an oil phase;

[0049] Step S3, the oil phase is mixed with the oil phase, suspended and polymerized, and the carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier is obtained after treatment.

[0050] Furthermore, in step S1, the amount of each raw material of the aqueous phase is as follows, in parts by mass:

[0051] Distilled water, 200-400 parts;

[0052] Hydroxymethyl cellulose, 0.1-0.4 parts;

[0053] Sodium dodecylbenzenesulfonate, 0.1-0.4 parts;

[0054] Polymer dispersant, 2-4 parts;

[0055] And / or, in step S2, the amount of each raw material of the oil phase is calculated by weight:

[0056] Styrene, 2-10 parts;

[0057] Divinylbenzene, 2-10 parts;

[0058] Benzoyl peroxide, 0.1-0.6 parts;

[0059] Toluene, 1-16 parts;

[0060] n-heptane, 12-24 parts;

[0061] 5-12 parts of dichloroethane;

[0062] Carbon nanotubes, 0.01~1 parts.

[0063] Furthermore, in step S1, the polymer dispersant is polyvinyl alcohol-1788, polyvinyl alcohol-1799, polyvinyl alcohol-2099, polyvinyl alcohol-2499 or polyvinyl alcohol-2699.

[0064] Furthermore, in step S2, the mass ratio of styrene, divinylbenzene and carbon nanotubes is 10:10:0.05-0.2.

[0065] Furthermore, in step S1, when preparing the aqueous phase, the mixing temperature is controlled to be 70-80° C. and the mixing time is 1-2 hours.

[0066] Furthermore, in step S3, the mixing temperature of the oil phase and the water phase is 45° C., and then the temperature is raised to 90-95° C. for suspension polymerization, and the reaction time is 7-8 hours.

[0067] Furthermore, in step S3, the temperature is first raised to 70°C before being raised to 90-95°C, kept warm for 1 hour, and then continued to be raised.

[0068] Furthermore, in step S3, the carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier is treated by sequentially filtering, washing and drying.

[0069] Furthermore, in step S3, deionized water, anhydrous ethanol and acetone are used for washing in sequence during filtration; wherein, the amount of deionized water and anhydrous ethanol is 2 to 3 times the mass of the carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst support, and the amount of acetone is 1 to 2 times the mass of the carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst support.

[0070] Furthermore, in step S3, the drying temperature is 60-70° C. and the drying time is 5-6 hours.

[0071] The present application is further described below through specific implementation methods.

[0072] Examples 1 to 5

[0073] 200g of distilled water, 0.10g of hydroxymethyl cellulose, 0.12g of sodium dodecylbenzene sulfonate, and 4g of polyvinyl alcohol were added to a reactor and reacted at 75°C for 1.5h until the powder was completely dissolved, yielding an aqueous phase. The mixture was then cooled to 45°C. An oil phase consisting of a mixture of 10g of styrene, 10g of divinylbenzene, 15.8g of toluene, 11.6g of n-heptane, 12.4g of ethylene dichloride, 0.2g of benzoyl peroxide, and carbon nanotubes (MWCNTs) was then added to the reactor. The mixture was then heated to 70°C for 1h and then heated to 90-95°C for 7-8h. The mixture was then filtered, dried, and sieved to yield a carbon nanotube hybrid-modified styrene-divinylbenzene copolymer hydrophobic catalyst support (MWCNTs / SDB hydrophobic catalyst support). The MWCNT dosage and hydrophobicity test results for Examples 1-5 are shown in Table 1.

[0074] Comparative Example 1

[0075] The preparation process in Control Example 1 was similar to that in Examples 1 to 5, except that MWCNTs were not added, thereby obtaining a SDB hydrophobic catalyst support.

[0076] Comparative Examples 2-4

[0077] The preparation process of control examples 2 to 4 is similar to that of examples 1 to 5, except that modified MWCNTs are added to obtain m-MWCNTs / SDB hydrophobic catalyst carriers.

[0078] MWCNTs were modified as follows: 1g of carbon nanotubes was weighed and placed in a mixed solution of concentrated sulfuric acid and concentrated nitric acid in a ratio of 3:1, ultrasonically dispersed for 20min, and then the mixed solution was transferred to a flask and refluxed in an oil bath at 110°C for 2-3h. The obtained solution was washed alternately with distilled water and ethanol, filtered 3-4 times, and dried at 80°C for 6-8h to obtain acidified multi-walled carbon nanotubes (OH-MWCNTs); 1g of OH-MWCNTs was uniformly dispersed in a mixed solution of ethanol and water in a ratio of 3:1, and 0.1g of KH570 (KH560, KH550) was ultrasonically dispersed for 30 minutes, and the modified solution was placed in a 250ml three-necked flask and refluxed in an oil bath at 110°C for 4-6 hours. After cooling, it was centrifuged for 10 minutes. The obtained solution was washed with deionized water and ethanol 2-3 times in sequence, filtered, and dried at 80°C for 6 hours to obtain KH570-modified multi-walled carbon nanotubes (m-MWCNTs).

[0079] Table 1 Hydrophobic angle of MWCNTs / SDB hydrophobic catalyst supports in Examples 1 to 5

[0080] serial number MWCNTs / g Hydrophobic angle / ° Example 1 0.05 135.64 Example 2 0.07 141.37 Example 3 0.1 134.62 Example 4 0.15 135.83 Example 5 0.2 132.22 Comparative Example 1 / 117.07 Comparative Example 2 KH570 modified after acidification, 0.1 138.30 Comparative Example 3 KH560 modified after acidification, 0.1 136.45 Comparative Example 4 KH550 modified after acidification, 0.1 137.50

[0081] The results of Examples 1-5 and Comparative Example 1 in Table 1 show that the hydrophobicity of the MWCNTs / SDB hydrophobic catalyst support prepared by adding MWCNTs is significantly improved. Furthermore, the results of Examples 1-5 and Comparative Examples 3-4 show that both MWCNTs and modified MWCNTs can improve the hydrophobicity of the support, with comparable effects. However, the MWCNTs in Examples 1-5 were not subjected to acidification or coupling agent treatment, resulting in a simpler and easier-to-use process overall.

[0082] Taking the MWCNTs / SDB hydrophobic catalyst carrier in Example 2 and the SDB hydrophobic catalyst carrier in Comparative Example 1 as examples, the infrared detection results are shown in the attached figure. Figure 1 As shown in the . Figure 1 The middle blue curve (top curve in the figure) is the infrared spectrum of the SDB hydrophobic catalyst support, and the red curve is the infrared spectrum of the MWCNTs / SDB hydrophobic catalyst support. As can be seen from the figures, the SDB and MWCNTs / SDB hydrophobic catalyst supports have abundant benzene ring structures. The SDB hydrophobic catalyst support modified with MWCNTs also contains double bonds and -CH2-C-H bonds, which facilitate the loading of active components.

[0083] Taking the MWCNTs / SDB hydrophobic catalyst carrier in Example 2 and the SDB hydrophobic catalyst carrier in Comparative Example 1 as examples, the thermal stability results are shown in the attached figure. Figure 2 As shown in the . Figure 2 The blue curve in the middle shows the TG curve for the SDB hydrophobic catalyst support, while the red curve shows the TG curve for the MWCNTs / SDB hydrophobic catalyst support. As can be seen from the figure, the initial thermal decomposition temperature of the SDB hydrophobic catalyst support is 397.69°C, while the initial thermal decomposition temperature of the MWCNTs / SDB hydrophobic catalyst support is 409.89°C. Therefore, the addition of MWCNTs slightly improves the thermal stability of the support.

[0084] Taking the MWCNTs / SDB hydrophobic catalyst carrier in Example 2 as an example, the scanning electron microscopy observation results are shown in the attached figure. Figure 3 As shown in the figure, it can be seen that the MWCNTs / SDB hydrophobic catalyst support has good sphericity at the macro level, while the surface of the MWCNTs / SDB hydrophobic catalyst support presents a porous structure at the micro level, which is conducive to the loading of active components.

[0085] Taking the MWCNTs / SDB hydrophobic catalyst carrier in Example 2 and the SDB hydrophobic catalyst carrier in Comparative Example 1 as examples, the X-ray detection results are shown in the attached figure. Figure 4 As shown in the . Figure 4The red curve (top) is the XRD curve of the SDB hydrophobic catalyst support, and the blue curve (bottom) is the XRD curve of the MWCNTs / SDB hydrophobic catalyst support. As can be seen from the figure, the MWCNTs / SDB hydrophobic catalyst support has similar XRD patterns to the SDB hydrophobic catalyst support. The curve exhibits a broad peak between 2θ = 10° and 30°, representing the amorphous dispersion peak of the polymer matrix. In contrast, the MWCNTs / SDB hydrophobic catalyst support exhibits a distinct diffraction peak at 2θ = 20°, representing the amorphous dispersion peak of the polymer matrix.

[0086] Taking the MWCNTs / SDB hydrophobic catalyst carrier in Example 2 as an example, the Raman detection results are shown in the attached figure. Figure 5 As shown in the figure, the green curve is the Raman spectrum of MWCNTs, and the red curve is the Raman spectrum of MWCNTs / SDB hydrophobic catalyst support. It can be seen from the figure that at 1300 cm -1 to 1600 cm -1 The peak near the MWCNTs is 1580 cm -1 The G peak near 1360 cm -1 The D peak and G peak of the modified sample are both near the characteristic peaks of MWCNTs, which indicates that the modification is successful, that is, the MWCNTs / SDB hydrophobic catalyst support is successfully prepared.

[0087] Taking the MWCNTs / SDB hydrophobic catalyst support in Example 2 and the SDB hydrophobic catalyst support in Comparative Example 1 as examples, the compressive strength results (7 groups were tested and the average value was taken) are shown in Table 2.

[0088] Table 2 Compressive strength of MWCNTs / SDB hydrophobic catalyst support in Example 2

[0089] serial number Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 1 111.5 35.3 65.3 41.4 46.0 2 104.1 26.1 45.9 42.7 42.9 3 117.6 30.6 44.3 33.8 42.3 4 90.4 28.4 44.5 53.3 37.7 5 110.4 30.2 65.5 40.2 55.3 6 108.6 32.0 51.9 35.4 38.1 7 113.9 29.7 47.6 49.5 42.4 8 99.85 37.6 42.5 48.1 48.1 9 98.24 23.4 59.4 45.5 56.5 10 99.83 27.3 56.3 46.9 39.2 mean 105.8 25.9 52.3 43.7 44.6

[0090] The test results in Table 2 show that the compressive strength of the MWCNTs / SDB hydrophobic catalyst support is approximately four times that of the SDB hydrophobic catalyst support. This indicates that MWCNTs significantly enhance the support's compressive strength. Furthermore, MWCNTs are more effective than modified MWCNTs in improving the support's compressive strength.

Claims

1. A method for preparing a carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier, characterized in that: The following steps are involved: Step S1, mixing distilled water, hydroxymethyl cellulose, sodium dodecylbenzene sulfonate and a polymer dispersant according to a preset ratio to obtain an aqueous phase; Step S2, mixing styrene, divinylbenzene, toluene, n-heptane, ethylene dichloride, benzoyl peroxide, and carbon nanotubes according to a preset ratio to obtain an oil phase; wherein the carbon nanotubes are unmodified, and the mass ratio of styrene, divinylbenzene, and carbon nanotubes is 10:10:0.05-0.2; Step S3, the oil phase is mixed with the oil phase, suspended and polymerized, and the carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier is obtained after treatment.

2. The method for preparing a carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier according to claim 1, characterized in that: In step S1, the amount of each raw material in the aqueous phase is as follows, in parts by mass: Distilled water, 200-400 parts; Hydroxymethyl cellulose, 0.1-0.4 parts; Sodium dodecylbenzenesulfonate, 0.1-0.4 parts; Polymer dispersant, 2-4 parts; And / or, in step S2, the amount of each raw material of the oil phase is calculated by weight: Styrene, 2-10 parts; Divinylbenzene, 2-10 parts; Benzoyl peroxide, 0.1-0.6 parts; Toluene, 1-16 parts; n-heptane, 12-24 parts; 5-12 parts of dichloroethane; Carbon nanotubes, 0.01~1 parts.

3. The method for preparing a carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier according to claim 1, characterized in that: In the step S1, the polymer dispersant is polyvinyl alcohol-1788, polyvinyl alcohol-1799, polyvinyl alcohol-2099, polyvinyl alcohol-2499 or polyvinyl alcohol-2699.

4. The method for preparing a carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier according to any one of claims 1 to 3, characterized in that: In step S1, when preparing the aqueous phase, the mixing temperature is controlled to be 70-80° C. and the mixing time is 1-2 hours.

5. The method for preparing the carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier according to any one of claims 1 to 3, characterized in that: In step S3, the mixing temperature of the oil phase and the water phase is 45° C., and then the temperature is raised to 90-95° C. for suspension polymerization, and the reaction time is 7-8 hours.

6. The method for preparing the carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier according to claim 5, characterized in that: In step S3, the temperature is first raised to 70°C before being raised to 90-95°C, kept at this temperature for 1 hour, and then continued to be raised.

7. The method for preparing a carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier according to any one of claims 1 to 3 and 6, characterized in that: In the step S3, the carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier is treated by sequentially filtering, washing and drying.

8. The method for preparing the carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier according to claim 7, characterized in that: In step S3, deionized water, anhydrous ethanol and acetone are used for washing in sequence during filtration; wherein the amount of deionized water and anhydrous ethanol is 2 to 3 times the mass of the carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst support, and the amount of acetone is 1 to 2 times the mass of the carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst support.

9. The method for preparing a carbon nanotube hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier according to claim 7, characterized in that: In step S3, the drying temperature is 60-70° C. and the drying time is 5-6 hours.

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