A honeycomb activated carbon composite adsorbent material and its preparation method

Abstract

This invention provides a honeycomb activated carbon composite adsorbent material and its preparation method. The honeycomb activated carbon composite adsorbent material includes the following raw materials: powdered activated carbon, modified montmorillonite dispersion, organic binder, and water. The modified montmorillonite dispersion is obtained by in-situ generation of MOFs between and on the surface of acidified montmorillonite layers, followed by intercalation and exfoliation. The exfoliated montmorillonite will generate a new inorganic interface, which has good compatibility with activated carbon. The interface with attached MOFs has a large number of adsorption sites, while not affecting the surface charge density of activated carbon. The honeycomb activated carbon composite adsorbent material containing this modified montmorillonite exhibits large adsorption capacity and good adsorption performance for both polar and non-polar VOCs.

Description

Technical Field

[0001] This invention belongs to the field of activated carbon technology, specifically relating to a honeycomb activated carbon composite adsorption material and its preparation method. Background Technology

[0002] Volatile organic compounds (VOCs) are a class of organic compounds characterized by low boiling points. The World Health Organization defines VOCs as various organic compounds with boiling points between 50 and 260°C at room temperature. VOCs have diverse sources and complex compositions, and most are toxic and carcinogenic, posing a serious threat to the ecological environment and human health. To reduce the harm of VOCs, many strategies and technologies have been developed to control VOC emissions, mainly divided into source control and end-of-pipe treatment. Due to current technological limitations and costs, eliminating VOC emissions at the source has had limited effectiveness; end-of-pipe treatment remains the most important aspect of controlling VOC emissions.

[0003] Adsorption is the most common end-of-pipe treatment technology for VOCs. It uses adsorption materials to physically and chemically interact with VOCs in waste gas, thereby achieving the purpose of enriching and separating VOCs. Due to its low cost-effectiveness, flexible operation and low energy consumption, adsorption is considered one of the most promising VOCs treatment technologies.

[0004] Common adsorbent materials include activated carbon, activated carbon fiber, diatomaceous earth, mesoporous silica, metal-organic frameworks (MOFs), and molecular sieves. Activated carbon is an adsorbent material obtained by placing carbon-rich organic materials, such as coal, wood, fruit shells, coconut shells, walnut shells, apricot shells, and jujube shells, in an activation furnace and applying high temperature and pressure to convert them through pyrolysis. It is characterized by its low price and wide availability. Metal-organic frameworks (MOFs) are a class of crystalline hybrid porous materials formed by the self-assembly of metal ions or metal clusters with organic ligands. They have advantages that traditional porous materials such as activated carbon, zeolites, and molecular sieves cannot match, such as large specific surface area, high porosity, ordered pore structure, and diverse pore size and framework structure. At the same time, MOFs also have highly dispersed metal centers, which can serve as active sites for adsorption or catalysis. The application of MOFs combined with activated carbon in gas adsorption and separation is currently a research hotspot. For example, patent CN113908809A discloses an activated carbon embedded MOF adsorbent material, its preparation method, and its application. The preparation method provided by this patent uses in-situ synthesis technology to synthesize MOFs within the pores of activated carbon. The MOFs are used to adjust the pore size of the activated carbon to match the size of the adsorbate molecules, thereby improving its adsorption capacity. Patent CN112705167A discloses a method for preparing MOF-modified activated carbon bricks and their application in high-volume air filtration. The method involves dispersing the raw materials for preparing MOFs in a suitable solvent. After uniform dispersion, porous block activated carbon bricks are immersed in the dispersion and subjected to a MOF preparation reaction at a certain temperature. After the reaction is completed, the material is dried to obtain MOF-modified porous block activated carbon brick air filter material. The porous block activated carbon is a waterproof activated carbon brick with a honeycomb structure.

[0005] The above technology utilizes MOFs synthetic raw materials to produce composite adsorbent materials through in-situ reactions on the surface of activated carbon. On the one hand, it solves the problems of difficulty in direct blending of activated carbon and metal-organic framework materials, uneven mixing, stress concentration, and decreased mechanical properties. On the other hand, this composite adsorbent material can combine the adsorption advantages of MOFs and activated carbon, possessing strong adsorption capacity, especially exhibiting polarity selectivity for strongly polar organic VOCs such as organic sulfur, with large adsorption capacity and good adsorption performance. However, this type of composite adsorbent material prepared by in-situ reaction also has the following drawbacks: First, MOFs are crystalline, brittle, porous solid materials, and activated carbon itself is also a very brittle substance that is easily broken and pulverized. The in-situ generation of MOFs in activated carbon increases the number of stress concentration points in activated carbon, which is not conducive to improving the toughness of activated carbon. Second, because MOFs enhance the asymmetry and polarity of the charge density delocalization on the surface of activated carbon, the adsorption performance of the adsorbent material for non-polar organic compounds such as methane and butane deteriorates, and it does not have universal applicability to non-polar organic compounds. If the gas to be adsorbed and recovered changes or if there is a large content of non-polar gas in the gas to be adsorbed and recovered, the adsorbent material needs to be replaced in time, which will not only increase the workload, but also cause the emission and leakage of polluting gases in severe cases, and cannot achieve effective adsorption and recovery.

[0006] Therefore, it is of great significance to develop a MOFs / activated carbon composite material that also has excellent adsorption capacity and adsorption ability for non-polar gases. Summary of the Invention

[0007] To address the aforementioned technical problems, this invention provides a honeycomb activated carbon composite adsorbent material and its preparation method. MOFs are generated in situ between and on the surface of acidified montmorillonite layers, followed by intercalation and exfoliation to obtain a modified montmorillonite dispersion. The exfoliated montmorillonite produces a new inorganic interface that exhibits good compatibility with activated carbon. The interface with attached MOFs has numerous adsorption sites without affecting the surface charge density of the activated carbon. The honeycomb activated carbon composite adsorbent material containing this modified montmorillonite demonstrates high adsorption capacity and excellent adsorption performance for both polar and non-polar VOCs.

[0008] To achieve the above objectives, the following specific technical solutions are adopted:

[0009] A honeycomb activated carbon composite adsorbent material comprises the following raw materials: powdered activated carbon, modified montmorillonite dispersion, organic binder, and water.

[0010] The modified montmorillonite dispersion was prepared by a method comprising the following steps:

[0011] S1 acidification: Montmorillonite is added to a sulfuric acid solution, heated and kept at a constant temperature, and the reaction is carried out under stirring. After the reaction is completed, the solution is cooled, filtered, washed, and dried to obtain acidified montmorillonite.

[0012] S2 Preparation of precursor solution: Add metal salt and organic ligand to organic solvent, stir to obtain precursor solution;

[0013] S3 Modification of Montmorillonite: Add acidified montmorillonite to the precursor solution, heat to carry out the reaction, and after the reaction is completed, filter, wash, and dry for later use.

[0014] S4 Intercalation and Exfoliation: The montmorillonite, benzyl quaternary ammonium salt, and organic solvent obtained from the drying in step S3 are added to a ball mill for ball milling. After grinding, water is added to obtain a modified montmorillonite dispersion.

[0015] Furthermore, the honeycomb activated carbon composite adsorbent material comprises the following raw materials in parts by weight: 100 parts powdered activated carbon, 70-80 parts modified montmorillonite dispersion with a solid content of 30-40 wt%, 3-5 parts organic binder, and 30-50 parts water.

[0016] The montmorillonite in step S1 has a cation exchange capacity of 100-150 mmol / 100g and a particle size of 200-300 mesh, and is selected from one or a combination of sodium-based montmorillonite and calcium-based montmorillonite; the sulfuric acid solution concentration is 20-30 wt%, the solid-liquid ratio of montmorillonite to sulfuric acid solution is 1:10-15, the temperature is raised to 80-100℃, the reaction time is 5-8 h, and the drying is carried out in a drying oven at 90-120℃ for 5-12 h;

[0017] The metal salt in step S2 is selected from at least one of zinc salt, nickel salt, cobalt salt, and iron salt; for example, zinc nitrate hexahydrate, cobalt nitrate hexahydrate, nickel chloride hexahydrate, ferric chloride hexahydrate, ferric nitrate hexahydrate, and ferric sulfate hexahydrate; the organic ligand is selected from one or a combination of two or more of terephthalic acid, trimesic acid, 4,4'-biphenyldicarboxylic acid, 2-methylimidazole, succinic acid, and glutaric acid; the organic solvent is selected from one or a combination of two or more of DMF, methanol, and ethylene glycol; the molar ratio of the metal salt to the organic ligand is 1-3:1-3, and the concentration of the organic ligand in the precursor solution is 0.5-0.9 mol / L.

[0018] In step S3, the mass-to-volume ratio of acidified montmorillonite to precursor solution is (10-15) g: 100 mL, the temperature is raised to 120-150 °C, and the reaction time is 12-48 h.

[0019] The benzyl quaternary ammonium salt in step S4 is selected from one or a combination of two or more of benzyl dimethyl hydroxyethyl ammonium chloride, benzyl dimethyl hydroxyethyl ammonium bromide, benzyl butyl dimethyl ammonium chloride, benzyl trimethyl ammonium chloride, and benzyl trimethyl ethyl ammonium chloride. The organic solvent is selected from one or a combination of two or more of ethanol, methanol, and isopropanol. The amount of the benzyl quaternary ammonium salt used is 10-15 wt% of the amount of montmorillonite used in step S3 for drying, and the amount of the organic solvent used is 1-2 times the amount of montmorillonite obtained in step S3 for drying. The bulk-liquid solid content is 30-40 wt%. The grinding balls in the ball mill are selected from one or a combination of two of corundum and agate. The grinding balls include large-diameter grinding balls and small-diameter grinding balls. The diameter of the large-diameter grinding balls is 8-10 mm, and the diameter of the small-diameter grinding balls is 3-6 mm. The weight ratio of the large-diameter grinding balls to the small-diameter grinding balls is 4-5:1. The ball-to-material ratio of the grinding balls to the montmorillonite obtained by drying in step S3 is 12-15:1. The ball milling speed is 300-800 rpm, and the ball milling time is 2-6 h.

[0020] The powdered activated carbon is selected from one or a combination of two or more of coal-based activated carbon, wood-based activated carbon, and fruit shell activated carbon.

[0021] The organic binder is selected from one or a combination of two or more of methylcellulose, carboxymethylcellulose, polyvinyl alcohol, hydroxyethylcellulose, and hydroxypropylcellulose.

[0022] The present invention also provides a method for preparing the above-mentioned honeycomb activated carbon composite adsorbent material, comprising the following steps:

[0023] 1) Mix powdered activated carbon, modified montmorillonite dispersion, organic binder, and water evenly to form a plastic slurry;

[0024] 2) Put the plastic clay obtained in step 1) into a ply mash machine and ply it under vacuum conditions;

[0025] 3) Load the clay material after kneading in step 2) into the barrel of the extruder, vacuum it and let it stand, then use a honeycomb mold to extrude the honeycomb preform.

[0026] 4) Microwave-set and dry the embryo obtained in step 3) to obtain the above-mentioned honeycomb activated carbon composite adsorption material.

[0027] Step 2) The vacuum degree is 0.08-0.1 MPa, and the number of kneading cycles is 1-5.

[0028] Step 3) The vacuum level of the vacuum pump is 0.08-0.1 MPa, and the standing time is 5-15 min;

[0029] Step 4) The microwave setting is performed in a microwave oven with a power of 500-1000W for 5-10 minutes, and the drying is performed at 90-130℃ for 12-24 hours.

[0030] Compared with the prior art, the beneficial effects of the present invention are:

[0031] This invention generates MOFs in situ on acidified montmorillonite, and then obtains a modified montmorillonite dispersion through intercalation and exfoliation. The exfoliated montmorillonite produces a new interface without attached MOFs, which has good compatibility with activated carbon. The interface with attached MOFs has a large number of adsorption sites, and at the same time, it does not affect the surface charge density of activated carbon. The honeycomb activated carbon composite adsorbent material containing this modified montmorillonite exhibits large adsorption capacity and good adsorption performance for both polar and non-polar VOCs, which can reduce the workload of replacing adsorbent materials, prevent the leakage of polluting gases, and protect people's health. Detailed Implementation

[0032] The present invention will be further described below with reference to specific embodiments, but is not limited to the contents of the specification. Unless otherwise specified, all "parts" mentioned in the embodiments of the present invention are parts by weight. All reagents used are commercially available in the art.

[0033] Powdered coal-based activated carbon powder was purchased from Fujian Xinsen Carbon Industry Co., Ltd., with an average particle size of 500 mesh and a specific surface area of ​​1760 m². 2 / g.

[0034] Sodium-based montmorillonite was purchased from Wuxi Shentu Trading Co., Ltd., with a cation exchange capacity of 130 mmol / 100g and an average particle size of 300 mesh.

[0035] Preparation of modified montmorillonite dispersion

[0036] Preparation Example 1

[0037] S1 acidification: Add 100g of montmorillonite to 1500g of 30wt% sulfuric acid solution, heat to 80℃ and keep at a constant temperature, and react for 6h under stirring. After the reaction is completed, cool, filter, wash with water 3 times, and vacuum dry at 60℃ for 4h to obtain acidified montmorillonite.

[0038] S2 Preparation of precursor solution: Add 0.9 mol ferric chloride hexahydrate and 0.9 mol terephthalic acid to 1 L DMF, stir, and prepare the precursor solution;

[0039] S3 Modification of Montmorillonite: Take 15g of acidified montmorillonite and add it to 100mL of the precursor solution obtained in step S2. Heat the solution to 150℃ and react for 24h. After the reaction is completed, filter, wash and dry for later use.

[0040] S4 Intercalation and Exfoliation: Take 10g of montmorillonite obtained from step S3 (drying), 1.5g of benzyltrimethylammonium chloride, and 20g of isopropanol and add them to a ball mill for ball milling for 3 hours at a speed of 450r / min and reverse rotation for 30 minutes. The grinding balls consist of 100g of spherical agate with a diameter of 10mm and 25g of spherical agate with a diameter of 6mm. After grinding, add water and control the amount of water added to prepare a modified montmorillonite dispersion with a solid content of 40wt%.

[0041] Preparation Example 2

[0042] The rest is the same as in Preparation Example 1, except that an equal amount of benzyl dimethyl hydroxyethyl ammonium chloride is used instead of benzyl trimethyl ammonium chloride.

[0043] Preparation Example 3

[0044] The rest is the same as in Preparation Example 1, except that the amount of ferric chloride hexahydrate used is 0.3 mol.

[0045] Preparation Example 4

[0046] The rest is the same as in Preparation Example 1, except that the amount of benzyltrimethylammonium chloride used is 1g.

[0047] Preparation Example 5

[0048] The rest is the same as in Preparation Example 1, except that the amount of benzyltrimethylammonium chloride used is 0.5g.

[0049] Preparation Example 6

[0050] The rest is the same as in Preparation Example 1, except that the amount of benzyltrimethylammonium chloride used is 2g.

[0051] Preparation Example 7

[0052] The rest is the same as in Preparation Example 1, except that equimolar amounts of nickel chloride hexahydrate are used instead of ferric chloride hexahydrate.

[0053] Comparative Preparation Example 1

[0054] The rest is the same as in Preparation Example 1, except for step S4 intercalation and exfoliation: take 10g of montmorillonite obtained from drying in step S3, 1.5g of benzyltrimethylammonium chloride, 20g of isopropanol, and add water to prepare a modified montmorillonite dispersion with a solid content of 40wt%.

[0055] Comparative Preparation Example 2

[0056] The rest is the same as in Preparation Example 1, except that in step S4, benzyltrimethylammonium chloride is replaced with an equal amount of hexadecyltrimethylammonium chloride.

[0057] Preparation of honeycomb activated carbon composite adsorption materials

[0058] Example 1

[0059] 1) Mix 100 parts of powdered coal-based activated carbon, 80 parts of modified montmorillonite dispersion prepared in Preparation Example 1, 5 parts of carboxymethyl cellulose, and 50 parts of water evenly to prepare a plastic slurry.

[0060] 2) Put the plastic clay obtained in step 1) into a ply mill and ply it 3 times under a vacuum of 0.08 MPa;

[0061] 3) Load the clay material after kneading in step 2) into the barrel of the extruder, let it stand for 10 minutes under a vacuum of 0.09 MPa, and then extrude the honeycomb preform using a honeycomb mold.

[0062] 4) The preform obtained in step 3) is microwave-set in an 800W microwave oven for 10 minutes and dried at 100℃ for 20 hours to obtain a honeycomb activated carbon composite adsorbent material with 200 pores, an outer wall thickness of 0.8 mm, an inner wall thickness of 0.5 mm, a diameter of 30 mm, a length of 100 mm, and a weight of 40 g.

[0063] Examples 2-7

[0064] The rest is the same as in Example 1, except that the modified montmorillonite dispersion used corresponds to Preparation Examples 2-7.

[0065] Example 8

[0066] The rest is the same as in Example 1, except that the amount of modified montmorillonite dispersion prepared in Example 1 is 70 parts.

[0067] Comparative Examples 1-2

[0068] The rest is the same as in Example 1, except that the modified montmorillonite dispersion used was prepared in Comparative Preparation Examples 1-2.

[0069] Comparative Example 3

[0070] The rest is the same as in Example 1, except that no modified montmorillonite dispersion is added, the amount of powdered activated carbon is 132g, and the amount of water is 98 parts.

[0071] Comparative Example 4

[0072] Honeycomb activated carbon was prepared by referring to the method of Example 1 of patent CN112705167A and combining it with the preparation method of honeycomb activated carbon of the present invention. The specific steps are as follows:

[0073] 1) Add 0.9 mol ferric chloride hexahydrate and 0.9 mol terephthalic acid to 1 L of DMF, stir, and prepare a precursor solution;

[0074] 2) Add 132g of powdered coal-based activated carbon to 0.213L of the precursor solution obtained in step 1), heat to 150℃ and react for 24h. After the reaction is completed, filter, wash with water 3 times, dry at 80℃ to constant weight, grind through a 500-mesh sieve to obtain dry activated carbon for later use.

[0075] 3) Mix the dried activated carbon obtained in step 2), 5g of carboxymethyl cellulose, and 98g of water evenly to make a plastic mud.

[0076] 4) Put the plastic clay obtained in step 3) into a ply mill and ply it 3 times under a vacuum of 0.08 MPa;

[0077] 5) Load the clay material after kneading in step 4) into the barrel of the extruder, let it stand for 10 minutes under a vacuum of 0.09 MPa, and then extrude the honeycomb preform using a honeycomb mold.

[0078] 6) The preform obtained in step 5) is microwave-set in an 800W microwave oven for 10 minutes and dried at 100℃ for 20 hours to obtain a honeycomb activated carbon composite adsorbent material with 200 pores, an outer wall thickness of 0.8 mm, an inner wall thickness of 0.5 mm, a diameter of 30 mm, a length of 100 mm, and a weight of 40 g.

[0079] The honeycomb activated carbon composite adsorbent materials prepared in the above embodiments and comparative examples were subjected to the following performance tests:

[0080] Compressive strength: Tested in accordance with standard GB / T 5072-2008.

[0081] Butane performance: The test was conducted according to the standard test method for determining the working capacity of activated carbon with butane, as specified in ASTM D5228-2016.

[0082] SO2 equilibrium adsorption capacity: SO2 adsorption performance was tested in a constant-temperature fixed-bed reactor with an inner diameter of 30 mm and a height of 500 mm. The flue gas consisted of N2, O2, SO2, and H2O. The flow rates of N2, O2, SO2, and H2O were controlled by flow meters. H2O was carried by N2 impacting a constant-temperature water bath. After the gases were mixed, they entered the reactor. The pipeline from the mixer to the reactor was insulated to ensure that H2O existed in gaseous form. 2 g of honeycomb activated carbon composite adsorption material (outer diameter 30 mm, length 5 mm) was placed on a fixed frame 250 mm above the bottom of the reactor, with its porous side facing the airflow. The flue gas contained 6% O2, 0.3% SO2, and 8% H2O by volume. N2 was used as the equilibrium gas. The gas flow rate was 400 mL / min, and the reactor temperature was 65 °C. The volume fraction of SO2 in the reactor outlet gas was measured online using a flue gas analyzer (Gasboard-3000). The amount of SO2 adsorbed by the honeycomb activated carbon composite adsorbent material was calculated using the SO2 breakthrough curve. The SO2 adsorption capacity was expressed as the amount of SO2 (mg) adsorbed per gram of honeycomb activated carbon.

[0083] Table 1

[0084] project compressive strength (MPa) Butane working capacity g / 100mL <![CDATA[SO2 equilibrium adsorption capacity mg / g]]> Example 1 3.0 14.1 85.5 Example 2 3.0 13.7 85.4 Example 3 2.6 14.7 87.1 Example 4 2.7 14.3 86.2 Example 5 2.3 15.2 89.3 Example 6 2.8 14.0 85.7 Example 7 2.9 13.9 85.9 Example 8 2.6 11.7 77.7 Comparative Example 1 1.7 13.8 90.0 Comparative Example 2 1.6 15.6 91.8 Comparative Example 3 2.6 12.3 60.6 Comparative Example 4 2.3 7.9 100.8

[0085] As shown in Table 1, the compressive strength test results indicate that modified montmorillonite and activated carbon have good compatibility. The honeycomb activated carbon composite adsorbent containing this modified montmorillonite has high mechanical strength and exhibits excellent adsorption capacity for both polar and non-polar VOCs.

[0086] The test results of compressive strength, butane performance, and SO2 equilibrium adsorption capacity of Example 1 and Comparative Example 2 show that the mechanical properties of the honeycomb activated carbon with benzyltrimethylammonium chloride replacing hexadecyltrimethylammonium chloride are significantly improved. It is speculated that benzyltrimethylammonium chloride is more likely to intercalate and exfoliate montmorillonite with MOFs already grown in situ, exposing more new interfaces with good compatibility with activated carbon. However, at the same time, since the exfoliation changes the internal pore structure of montmorillonite, its specific surface area decreases, which leads to a certain degree of decrease in butane performance and SO2 equilibrium adsorption capacity.

[0087] The above detailed description is a specific description of one of the feasible embodiments of the present invention. This embodiment is not intended to limit the patent scope of the present invention. All equivalent implementations or modifications that do not depart from the present invention should be included within the scope of the technical solution of the present invention.

Claims

1. A honeycomb activated carbon composite adsorbent material, characterized by, The honeycomb activated carbon composite adsorption material comprises the following raw materials by weight: 100 parts of powdered activated carbon, 70-80 parts of modified montmorillonite dispersion liquid with a solid content of 30-40 wt%, 3-5 parts of organic binder, and 30-50 parts of water. The modified montmorillonite dispersion liquid is prepared by a method comprising the following steps: S1 acidification: montmorillonite is added to a sulfuric acid solution, and the reaction is carried out under stirring at a constant temperature after warming up, and the acidified montmorillonite is obtained after cooling, filtering, washing, and drying; S2 preparation of precursor solution: metal salt and organic ligand are added to an organic solvent, and the precursor solution is obtained after stirring; S3 modification of montmorillonite: the acidified montmorillonite is added to the precursor solution, and the reaction is carried out after warming up, and the modified montmorillonite is obtained after filtering, washing, and drying; S4 intercalation and exfoliation: the montmorillonite obtained after drying in step S3, benzyl quaternary ammonium salt, and organic solvent are added to a ball mill for ball milling, and the modified montmorillonite dispersion liquid is obtained after adding water after the grinding is completed; the benzyl quaternary ammonium salt is selected from one or more than two combinations of benzyl dimethyl hydroxyethyl ammonium chloride, benzyl dimethyl hydroxyethyl ammonium bromide, benzyl butyl dimethyl ammonium chloride, benzyl trimethyl ammonium chloride, and benzyl trimethyl ethyl ammonium chloride, and the amount of the benzyl quaternary ammonium salt is 10-15 wt% of the amount of the montmorillonite obtained after drying in step S3.

2. The honeycomb activated carbon composite adsorbent material of claim 1, wherein, In step S1, the concentration of the sulfuric acid solution is 20-30 wt%, the solid-liquid ratio of the montmorillonite to the sulfuric acid solution is 1:10-15, the temperature is raised to 80-100℃, and the reaction time is 5-8 h.

3. The honeycomb activated carbon composite adsorbent material of claim 1, wherein, In step S2, the metal salt is selected from one of zinc nitrate hexahydrate, cobalt nitrate hexahydrate, nickel chloride hexahydrate, iron chloride hexahydrate, iron nitrate hexahydrate, and iron sulfate hexahydrate; the organic ligand is selected from one or more than two combinations of terephthalic acid, trimesic acid, 4,4'-diphenyldicarboxylic acid, 2-methyl imidazole, succinic acid, and glutaric acid; and the molar ratio of the metal salt to the organic ligand is 1-3:1-3, and the concentration of the organic ligand in the precursor solution is 0.5-0.9 mol / L.

4. The honeycomb activated carbon composite adsorbent material of claim 1, wherein, In step S3, the mass-volume ratio of the acidified montmorillonite to the precursor solution is (10-15) g:100 mL, the temperature is raised to 120-150℃, and the reaction time is 12-48 h.

5. The honeycomb activated carbon composite adsorbent material of claim 1, wherein, In step S4, the organic solvent is selected from one or more than two combinations of ethanol, methanol, and isopropyl alcohol, and the amount of the organic solvent is 1-2 times of the montmorillonite obtained after drying in step S3.

6. The honeycomb activated carbon composite adsorbent material of claim 1, wherein, In step S4, the ball-to-material ratio of the grinding ball to the montmorillonite obtained after drying in step S3 is 12-15:1, the ball milling speed is 300-800 rpm, and the ball milling time is 2-6 h.

7. The honeycomb activated carbon composite adsorbent material of claim 1, wherein, The powdered activated carbon is selected from one or more than two combinations of coal-based activated carbon, wood-based activated carbon, and nutshell activated carbon.

8. The honeycomb activated carbon composite adsorbent material of claim 1, wherein, The organic binder is selected from one or more than two combinations of methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, hydroxyethyl cellulose, and hydroxypropyl cellulose.

9. The method of claim 1-8, wherein the method is characterized by, The method comprises the following steps: 1) powdered activated carbon, modified montmorillonite dispersion liquid, organic binder, and water are uniformly mixed to prepare plastic clay; 2) The plastic paste obtained in step 1) is put into a pug mill, and pugged under vacuum; 3) The pugged paste in step 2) is loaded into a barrel of an extruder, vacuumized and kept, and then extruded into a honeycomb body using a honeycomb die; 4) The body obtained in step 3) is microwave-shaped and dried, and the honeycomb activated carbon composite adsorption material is obtained.