Metal-organic framework-activated carbon composite material and preparation method and application thereof

Abstract

The application provides a metal organic framework-activated carbon composite material and a preparation method and application thereof, the metal organic framework is located in the pore of the activated carbon; the pore size of the metal organic framework is 1.5-5 nm; and the metal organic framework-activated carbon composite material is a mesoporous structure. By introducing the metal organic framework adsorbent with a specific pore size range into the activated carbon and by structure regulation of the two, on one hand, the effect of macropore in the activated carbon is reduced through the 'occupation' effect, and on the other hand, the adsorption amount and desorption efficiency of butane are improved by using the unique pore structure of the metal organic framework adsorbent.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of waste gas treatment, and particularly relates to a metal organic framework-activated carbon composite material and a preparation method and application thereof. BACKGROUND

[0002] Due to its high specific surface area and rich pore structure, activated carbon is often used as a gas adsorbent and storage carrier. For example, in a motor vehicle, a carbon tank filled with granular activated carbon can adsorb the oil gas evaporated in the fuel tank to prevent it from escaping into the atmosphere and causing air pollution; at the same time, the oil gas can be returned to the fuel tank through air backflushing, thereby improving the utilization efficiency of fuel.

[0003] Generally speaking, different applications have different requirements for activated carbon. For example, when the pore size of activated carbon is in the mesopore range, the corresponding butane vapor adsorption and desorption performance is good. At present, the activated carbon used for butane adsorption is mainly modified activated carbon. After the raw material is subjected to carbonization, activation, crushing and granulation and other procedures, an adsorbent suitable for butane adsorption is formed. In this process, the purpose of the activation stage is to introduce more mesopores into the carbon material to increase the mesopore rate, thereby improving the butane adsorption and desorption capacity of the product.

[0004] CN107140636B discloses a wooden granular activated carbon for automobile carbon tank and a preparation method thereof. The main raw material components are wooden activated carbon powder, organic sodium-based bentonite and water in a weight ratio of 1:0.2-0.25:0.8-1.0. After the three raw materials are stirred uniformly, granulation is performed, and after drying, physical activation is performed to obtain the wooden activated carbon powder. The wooden activated carbon powder is obtained by mixing aged wood chips and hot-process food-grade phosphoric acid with a concentration of 85% according to a weight ratio of wood chips:hot-process food-grade phosphoric acid=1:1.2-1.5, stirring, static impregnation, high-temperature carbonization and activation, recovery, rinsing, drying and powdering. However, the pore size range of the adsorbent material is not disclosed.

[0005] During the activation and modification process of activated carbon, small pores inevitably collapse into large pores, resulting in unsatisfactory mesopore rate. Therefore, to solve the above problems, it is an urgent technical problem for those skilled in the art to develop an activated carbon composite material with high mesopore rate and excellent adsorption performance. SUMMARY

[0006] The purpose of the present application is to provide a metal organic framework-activated carbon composite material and a preparation method and application thereof. The metal organic framework with a specific pore size and the activated carbon with a specific mesh number are combined, and the structure of the two is regulated, so that the composite material effectively improves the butane gas adsorption capacity and recycling performance.

[0007] To achieve the purpose of the present application, the following technical solutions are adopted:

[0008] In a first aspect, the present application provides a metal organic framework-activated carbon composite material, wherein the metal organic framework is located in the pores of the activated carbon.

[0009] The pore size of the metal organic framework (MOFs) is 1.5-5 nm.

[0010] The metal organic framework-activated carbon composite material is a mesoporous structure.

[0011] The pore size of the metal organic framework is 1.5-5 nm, for example, it can be 1.7 nm, 1.9 nm, 2 nm, 2.5 nm, 3 nm, 3.5 nm, 4 nm, or 4.5 nm, etc., but not limited to the listed values, and other values not listed within the value range are also applicable.

[0012] In the present application, the metal organic framework-activated carbon composite material comprises activated carbon and metal organic framework material grown on the activated carbon by an in-situ method.

[0013] The mesoporous rate of the metal organic framework-activated carbon composite material is ≥75%, for example, it can be 76%, 77%, 78%, 79%, 80%, or 82%, etc., but not limited to the listed values, and other values not listed within the value range are also applicable.

[0014] By introducing a metal organic framework adsorbent with a specific pore size range into activated carbon, and through the structure regulation of both, on the one hand, the effect of large pores in activated carbon is reduced through the "occupying" effect, and on the other hand, the unique pore structure of the metal organic framework adsorbent improves the adsorption capacity and desorption efficiency of fuel vapor.

[0015] As a preferred technical solution of the present application, the particle size of the activated carbon is 30-80 mesh, for example, it can be 30-40 mesh, 30-50 mesh, 40-50 mesh, 40-60 mesh, 50-60 mesh, 50-70 mesh, or 70-80 mesh, etc., but not limited to the listed values, and other values not listed within the value range are also applicable.

[0016] Preferably, the mass ratio of the activated carbon and the metal organic framework is 1:(0.01-0.1), for example, it can be 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.07, 1:0.08, or 1:0.09, etc., but not limited to the listed values, and other values not listed within the value range are also applicable.

[0017] Preferably, the metal organic framework comprises any one of Mn2Cl2(BTDD)(H2O)2, Ni2Cl2(BTDD)(H2O)2, Co2Cl2(BTDD)(H2O)2, ST-4, BUT-23 or BUT-33 or a combination of at least two of them, wherein typical but non-limiting combinations are: a combination of Mn2Cl2(BTDD)(H2O)2and Ni2Cl2(BTDD)(H2O)2, a combination of Co2Cl2(BTDD)(H2O)2and ST-4 or a combination of BUT-23 and BUT-33, etc.

[0018] The pores of the metal organic framework described in the present application are suitable for storing gasoline molecules, which are easily desorbed from the pores when the external pressure is reduced. At the same time, the particle size of this type of material can be adjusted, which has the effect of preferentially occupying the macropores of activated carbon, reducing the macropores by "occupying" the macropores, thereby increasing the mesopore ratio of the composite material as a whole, and achieving the purpose of improving the gasoline vapor adsorption capacity.

[0019] In a second aspect, the present application provides a preparation method of the metal organic framework-activated carbon composite material of the first aspect, the preparation method comprising the following steps:

[0020] (1) mixing a metal salt solution, an organic ligand and a first solvent to obtain a metal organic framework precursor solution;

[0021] (2) impregnating activated carbon in the metal organic framework precursor solution of step (1) and performing a reaction to obtain the metal organic framework-activated carbon composite material.

[0022] As a preferred technical solution of the present application, the mixing method of step (1) is: dissolving the organic ligand in the first solvent, and then adding the metal salt solution to it.

[0023] Preferably, the organic ligand of step (1) comprises H2-BTDD (bis(1H-1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin) or H3TPTA (2,4,6-tris(4-(1h-pyrazol-4-yl)phenyl)-1,3,5-triazine)).

[0024] Preferably, the first solvent of step (1) comprises N,N-dimethylformamide (DMF).

[0025] Preferably, the solid-liquid ratio of the organic ligand and the first solvent in step (1) is 1:(0.8-1.2) g / L, for example, it can be 1:0.85 g / L, 1:0.9 g / L, 1:0.95 g / L, 1:1 g / L, 1:1.05 g / L, 1:1.1 g / L or 1:1.15 g / L, etc., but not limited to the listed values, other values not listed in the value range are also applicable.

[0026] As a preferred technical solution of the present application, the metal salt solution in step (1) comprises a metal salt and a second solvent.

[0027] Preferably, the metal salt comprises any one or a combination of at least two of manganese salt, nickel salt or cobalt salt.

[0028] Preferably, the second solvent comprises any one or a combination of at least two of methanol, hydrochloric acid, ethanol or water.

[0029] Preferably, the molar ratio of the metal salt and the organic ligand is 1:(0.2-1), for example, it can be 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8 or 1:0.9, etc., but not limited to the listed values, other values not listed in the value range are also applicable.

[0030] The present application controls the molar ratio of the metal salt and the organic ligand in the range of 1:(0.2-1), so that the pore size of the metal organic framework prepared is 1.5-5 nm.

[0031] As a preferred technical solution of the present application, the particle size of the activated carbon in step (2) is 30-80 mesh, for example, it can be 30-40 mesh, 30-50 mesh, 40-50 mesh, 40-60 mesh, 50-60 mesh, 50-70 mesh or 70-80 mesh, etc., but not limited to the listed values, other values not listed in the value range are also applicable.

[0032] Preferably, the activated carbon in step (2) is subjected to drying treatment before use.

[0033] In the present application, the immersion method in step (2) includes the following cases:

[0034] (a) full immersion: the activated carbon is immersed in all the metal organic framework precursor solution in step (1); or

[0035] (b) equal volume immersion: the activated carbon is immersed in part of the metal organic framework precursor solution in step (1).

[0036] The equal volume impregnation of the application, that is, the volume of the liquid that can be adsorbed by the activated carbon is calculated in advance, and then the activated carbon is impregnated in the volume of precursor solution, so as to improve the utilization rate of the precursor solution.

[0037] When the equal volume impregnation is used in the application, a steam environment needs to be created during the reaction process in step (2), that is, a small amount of the first solvent is added to the bottom of the reaction container, so that the reaction container can be in a solvent atmosphere.

[0038] The impregnation in step (2) can be carried out in ultrasonic, so as to promote the precursor solution to enter the pore channel of the activated carbon.

[0039] As a preferred technical solution of the application, the mass ratio of the organic ligand in step (1) to the activated carbon in step (2) is (0.008-0.012):1, which can be 0.0085:1, 0.009:1, 0.0095:1, 0.01:1, 0.0105:1, 0.011:1 or 0.0115:1, etc., but not limited to the listed values, and other values not listed in the value range are also applicable.

[0040] The application adjusts the mass ratio range of the organic ligand and the activated carbon,

[0041] As a preferred technical solution of the application, the temperature of the reaction in step (2) is 80-150℃, which can be 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃ or 145℃, etc., but not limited to the listed values, and other values not listed in the value range are also applicable.

[0042] Preferably, the reaction time in step (2) is 6-48h, which can be 10h, 12h, 15h, 18h, 20h, 22h, 25h, 28h, 30h, 35h, 40h or 45h, etc., but not limited to the listed values, and other values not listed in the value range are also applicable.

[0043] Preferably, after the reaction in step (2), it further includes washing and drying.

[0044] As a preferred technical solution of the application, the preparation method includes the following steps:

[0045] (1) Dissolve the organic ligand in the first solvent, then add the metal salt solution to obtain the metal organic framework precursor solution;

[0046] The organic ligand includes H2-BTDD or H3TPTA; the solid-liquid ratio of the organic ligand and the first solvent is 1:(0.8-1.2) g / L;

[0047] The metal salt solution comprises a metal salt and a second solvent; the metal salt comprises any one or a combination of at least two of a manganese salt, a nickel salt or a cobalt salt; the molar ratio of the metal salt to the organic ligand is 1:(0.2-1);

[0048] (2) The activated carbon with a particle size of 30-80 mesh is immersed in the metal organic framework precursor solution in step (1), and a reaction is carried out at a temperature of 80-150℃ for 6-48h, and after washing and drying, the metal organic framework-activated carbon composite material is obtained;

[0049] The mass ratio of the organic ligand to the activated carbon in step (2) is (0.008-0.012):1.

[0050] In a third aspect, the present application provides an application of the metal organic framework-activated carbon composite material in the first aspect, and the metal organic framework-activated carbon composite material is used for adsorbing automobile fuel vapor.

[0051] After the composite material is ground, mixed with a porous filler and a binder, and granulated, an adsorbent for an automobile carbon tank is obtained.

[0052] The porous filler comprises any one or a combination of at least two of sepiolite, kaolin or diatomite; the binder comprises an organic binder and / or an inorganic binder, the organic binder comprises hydroxypropyl cellulose and / or methyl cellulose, and the inorganic binder comprises silica sol.

[0053] The numerical range in the present application not only includes the point values listed above, but also includes any point values between the above numerical ranges that are not listed, and the specific point values included in the range are not listed in the present application due to the length and the consideration of simplicity.

[0054] Compared with the prior art, the present application has the following beneficial effects:

[0055] (1) The metal organic framework-activated carbon composite material provided by the present application introduces a metal organic framework adsorbent with a specific pore size range into activated carbon, which on the one hand reduces the effect of macropores in activated carbon through the "occupation" effect, and on the other hand improves the adsorption capacity and desorption efficiency of fuel vapor by utilizing the unique pore structure of the metal organic framework adsorbent;

[0056] (2) The preparation method provided by the present application uses a one-step method to obtain the composite material, which is simple, mild in reaction conditions, short in process flow and easy to industrialize. DETAILED DESCRIPTION

[0057] The technical solutions of the present application are further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations on the present application.

[0058] The reagents used in the following examples and comparative examples are all commercially available products; among them, 40-60 mesh activated carbon is tested, 1g of 40-60 mesh activated carbon can adsorb 0.5g of DMF; 30-50 mesh activated carbon is tested, 1g of 30-50 mesh activated carbon can adsorb 0.7g of DMF.

[0059] Example 1

[0060] The present embodiment provides a preparation method of a metal organic framework-activated carbon composite material, which comprises the following steps:

[0061] (1) 100mg of H2-BTDD is added to 100mL of DMF, heated to 100℃ for dissolution, and then 100mL of a mixed solution containing 196mg of nickel chloride hexahydrate and 64mL of hydrochloric acid (37%) is added to obtain a metal organic framework precursor solution;

[0062] (2) Commercially available coconut shell activated carbon is sieved, 10g of activated carbon with a particle size of 40-60 mesh is immersed in 5-6mL of the metal organic framework precursor solution of step (1), the mixture is placed in a 100mL reaction kettle, a small bottle containing 2-3mL of DMF is placed in the reaction kettle, and then the reaction is carried out at a temperature of 100℃ for 48h, after washing with methanol for several times and drying, a Ni2Cl2(BTDD)(H2O)2-activated carbon composite material is obtained.

[0063] The Ni2Cl2(BTDD)(H2O)2-activated carbon composite material prepared in this embodiment has a pore size of 1.5-5nm, accounting for 80%.

[0064] Example 2

[0065] The present embodiment provides a preparation method of a metal organic framework-activated carbon composite material, which comprises the following steps:

[0066] Example 3

[0067] The embodiment provides a preparation method of a metal organic framework-activated carbon composite material, and the preparation method comprises the following steps:

[0068] (1) 100 mg of H2-BTDD is added into 100 mL of DMF, heated to 100 DEG C for dissolution, and then a mixed solution containing 196 mg of cobalt chloride hexahydrate, 100 mL of methanol and 64 mL of hydrochloric acid (37%) is added into the H2-BTDD solution to obtain a metal organic framework precursor solution;

[0069] (2) Commercially available coconut shell activated carbon is sieved, 10 g of activated carbon with a particle size of 40-60 mesh is selected, and then the activated carbon is immersed in 5-6 mL of the metal organic framework precursor solution in step (1); the mixture is placed in a 100 mL reaction kettle, a small bottle containing 2-3 mL of DMF is placed in the reaction kettle, and then the mixture is reacted at 100 DEG C for 48 h; after being washed several times with methanol and dried, a Co2Cl2(BTDD)(H2O)2-activated carbon composite material is obtained.

[0070] Example 4

[0071] The embodiment provides a preparation method of a metal organic framework-activated carbon composite material, and the preparation method comprises the following steps:

[0072] (1) 100 mg of H2-BTDD is added into 100 mL of DMF, heated to 100 DEG C for dissolution, and then a mixed solution containing 196 mg of cobalt chloride hexahydrate, 100 mL of methanol and 64 mL of hydrochloric acid (37%) is added into the H2-BTDD solution to obtain a metal organic framework precursor solution;

[0073] (2) Commercially available coconut shell activated carbon is sieved, 10 g of activated carbon with a particle size of 40-60 mesh is selected, and then the activated carbon is immersed in 5-6 mL of the metal organic framework precursor solution in step (1); the mixture is placed in a 100 mL reaction kettle, a small bottle containing 2-3 mL of DMF is placed in the reaction kettle, and then the mixture is reacted at 100 DEG C for 48 h; after being washed several times with methanol and dried, a Co2Cl2(BTDD)(H2O)2-activated carbon composite material is obtained.

[0074] Example 5

[0075] The embodiment provides a preparation method of a metal organic framework-activated carbon composite material, and the preparation method comprises the following steps:

[0076] Example 6

[0077] The embodiment provides a preparation method of a metal organic framework-activated carbon composite material, wherein except that the amount of H2-BTDD in step (1) is 40 mg, other conditions are the same as those in example 1.

[0078] Example 7

[0079] The embodiment provides a preparation method of a metal organic framework-activated carbon composite material, wherein except that the amount of H2-BTDD in step (1) is 252 mg, other conditions are the same as those in example 1.

[0080] Example 8

[0081] The embodiment provides a preparation method of a metal organic framework-activated carbon composite material, wherein except that the amount of H2-BTDD in step (1) is 252 mg, other conditions are the same as those in example 1.

[0082] Example 9

[0083] The embodiment provides a preparation method of a metal organic framework-activated carbon composite material, wherein except that the amount of H2-BTDD in step (1) is 252 mg, other conditions are the same as those in example 1.

[0084] Example 10

[0085] The embodiment provides a preparation method of a metal organic framework-activated carbon composite material, wherein except that the amount of H2-BTDD in step (1) is 252 mg, other conditions are the same as those in example 1.

[0086] Comparative Example 1

[0087] The comparative example provides a preparation method of a metal organic framework-activated carbon composite material, wherein except that the amount of H2-BTDD in step (1) is 252 mg, other conditions are the same as those in example 1.

[0088] Comparative Example 2

[0089] The comparative example provides a preparation method of a metal organic framework-activated carbon composite material, wherein except that the amount of H2-BTDD in step (1) is 252 mg, other conditions are the same as those in example 1.

[0090] The CuBTC-activated carbon composite material prepared in the comparative example has a pore size of 1.5-5 nm, and the proportion is 51%.

[0091] Comparative Example 3

[0092] The comparative example provides an activated carbon, which is a commercially available coconut shell activated carbon with a particle size of 40-60 mesh.

[0093] The materials prepared in the above examples and comparative examples were subjected to pore size characterization, and the mesopore rate results of the materials are shown in Table 1.

[0094] The materials prepared in the above examples and comparative examples were used for adsorbing automobile fuel vapor, which included: grinding the materials prepared in the above examples and comparative examples, adding sepiolite, hydroxypropyl cellulose and silica sol to make a blank, and after vacuum rolling and granulation, cylindrical particles with a diameter of 2 mm and a length of 5 mm were obtained; then the butane adsorption capacity and desorption efficiency were tested, and the results are shown in Table 1.

[0095] The specific test method was determined according to the national standard GB / T20449-2006, Japanese standard TEST-1201 and American standard ASTM-D5228, and the series of standards were all based on butane adsorption capacity and desorption capacity to evaluate the performance of the adsorbent.

[0096] Table 1

[0097]

[0098] From Table 1, it can be seen that:

[0099] (1) The metal organic framework-activated carbon composite material provided by the present application has a mesopore rate of the whole composite material of ≥75%, which is applied to the adsorption of automobile fuel vapor, effectively improves the adsorption capacity and desorption efficiency of fuel vapor, and has a butane adsorption capacity of ≥13.50 g / 100 mL and a desorption efficiency of ≥70%;

[0100] (2) It can be known from the comparison of Example 1 and Examples 6-7 that when the amount of organic ligand is too small, the metal ions are in excess and the combination sites with the organic ligand are less, the pore size of the prepared MOFs material is more in the micropore range, and thus the mesopore rate of the composite material is low; when the amount of organic ligand is too much, the excessive ligand will adhere to the pore channel of the activated carbon, and thus the mesopore rate of the composite material is low;

[0101] (4) It can be known from the comparison of Example 1 and Examples 9-10 that when the temperature of the reaction in step (2) is too low, the temperature does not reach the generation temperature range of MOFs, and thus the activated carbon pore channel is not filled with MOFs material, and the desired effect cannot be achieved; when the temperature of the reaction in step (2) is too high, the high temperature will cause the crystallization rate and growth rate to be too fast, the pore size of the prepared MOFs material is in the micropore range, and thus the mesopore rate of the composite material is low;

[0102] (5)Compared with Comparative Examples 1-2 and Example 1, it can be seen that when the organic ligand is trimesic acid, the pore size of the MOFs material prepared is too large, and thus the mesopore ratio of the composite material is reduced.

[0103] The applicant declares that the detailed structural features of the present application are illustrated by the above examples, but the present application is not limited to the above detailed structural features, i.e. it does not mean that the present application must rely on the above detailed structural features to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of the components selected by the present application, addition of auxiliary components, selection of specific modes, etc. fall within the protection scope and disclosure scope of the present application.

[0104] The preferred embodiments of the present application are described in detail above, but the present application is not limited to the specific details in the above embodiments, and within the technical concept scope of the present application, various simple modifications can be made to the technical solutions of the present application, and these simple modifications all belong to the protection scope of the present application.

[0105] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any appropriate manner without contradiction, and in order to avoid unnecessary repetition, the present application will not further describe various possible combination manners.

[0106] In addition, various different embodiments of the present application can also be combined in any manner, as long as it does not deviate from the idea of the present application, and it should also be considered as disclosed by the present application.

Claims

1. A metal organic framework-activated carbon composite material, characterized by, The metal organic framework material is located in the pore of the activated carbon; The pore size of the metal organic framework is 1.5-5nm; The metal organic framework-activated carbon composite material is mesoporous structure; The mass ratio of the activated carbon and the metal organic framework is 1:(0.01-0.1); The metal organic framework comprises any one or a combination of at least two of Mn2Cl2(BTDD)(H2O)2, Ni2Cl2(BTDD)(H2O)2, Co2Cl2(BTDD)(H2O)2; The metal organic framework-activated carbon composite material is prepared by the following method, which comprises the following steps: (1) mixing a metal salt solution, an organic ligand and a first solvent to obtain a metal organic framework precursor solution; the molar ratio of the metal salt and the organic ligand in step (1) is 1:(0.2-1); (2) immersing activated carbon in the metal organic framework precursor solution of step (1) to react to obtain the metal organic framework-activated carbon composite material; the reaction temperature of step (2) is 80-150℃.

2. The metal organic framework-activated carbon composite material of claim 1, wherein, The particle size of the activated carbon is 30-80 mesh.

3. A method for producing the metal-organic framework-activated carbon composite material according to claim 1 or 2, characterized by, The preparation method comprises the following steps: (1) mixing a metal salt solution, an organic ligand and a first solvent to obtain a metal organic framework precursor solution; the molar ratio of the metal salt and the organic ligand in step (1) is 1:(0.2-1); (2) immersing activated carbon in the metal organic framework precursor solution of step (1) to react to obtain the metal organic framework-activated carbon composite material; the reaction temperature of step (2) is 80-150℃.

4. The production method according to claim 3, characterized by, The mixing method of step (1) is: dissolving the organic ligand in the first solvent, and then adding the metal salt solution thereto.

5. The preparation method according to claim 3, characterized in that, The organic ligand of step (1) comprises H2-BTDD.

6. The preparation method according to claim 3, characterized in that, The first solvent of step (1) comprises N,N-dimethylformamide.

7. The preparation method according to claim 3, characterized in that, The solid-liquid ratio of the organic ligand and the first solvent of step (1) is 1:(0.8-1.2) g / L.

8. The preparation method according to claim 3, characterized in that, The metal salt solution of step (1) comprises a metal salt and a second solvent.

9. The production method according to claim 8, characterized by, The metal salt comprises any one or a combination of at least two of a manganese salt, a nickel salt or a cobalt salt.

10. The preparation method according to claim 8, characterized in that, The second solvent comprises any one or a combination of at least two of methanol, ethanol or water.

11. The preparation method according to claim 3, characterized in that, The particle size of the activated carbon of step (2) is 30-80 mesh.

12. The method of claim 3, wherein, The activated carbon of step (2) is dried before use.

13. The preparation method according to claim 3, characterized in that, The mass ratio of the organic ligand of step (1) and the activated carbon of step (2) is (0.008-0.012):

1.

14. The method of claim 3, wherein, The reaction time of step (2) is 6-48h.

15. The preparation method according to claim 3, characterized in that, After the reaction of step (2), it further comprises washing and drying.

16. The preparation method according to claim 3, characterized in that, The preparation method comprises the following steps: (1) dissolving an organic ligand in a first solvent, and then adding a metal salt solution thereto to obtain a metal organic framework precursor solution; The organic ligand comprises H2-BTDD; the solid-liquid ratio of the organic ligand and the first solvent is 1:(0.8-1.2) g / L; The metal salt solution comprises a metal salt and a second solvent; the metal salt comprises any one or a combination of at least two of a manganese salt, a nickel salt or a cobalt salt; the molar ratio of the metal salt to the organic ligand is 1:(0.2-1); (2) the activated carbon with a particle size of 30-80 meshes is immersed in the metal organic framework precursor solution in step (1), and a reaction is carried out at a temperature of 80-150 DEG C for 6-48 h; after washing and drying, the metal organic framework-activated carbon composite material is obtained; The mass ratio of the organic ligand to the activated carbon in step (2) is (0.008-0.012):

1.

17. Use of the metal organic framework-activated carbon composite material according to claim 1 or 2, characterized in that, The metal organic framework-activated carbon composite material is used for adsorbing butane steam.

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