CN117658135A - An activated carbon material for vehicles and its preparation method and application - Google Patents

Abstract

The invention provides an activated carbon material for a vehicle, and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing and reacting a polyhydroxy phenol compound, a multi-aldehyde compound, a first catalyst, a high molecular surfactant, metal salt and a second catalyst to obtain a reaction product; and sequentially carrying out solid-liquid separation, molding, freezing and pyrolysis on the obtained reaction product to obtain the activated carbon material. The preparation method provided by the invention has low cost, and the defect that the basic properties of the traditional active carbon raw materials are uncontrollable is avoided; the preparation process is directly molded and then activated, so that the problem of hole blocking effect caused by adding the binder in the traditional active carbon molding process is solved; the pore size distribution of the activated carbon material is accurately controlled, and the adsorption and desorption effects of the activated carbon material are improved; and a heat storage medium is introduced, so that the adsorption and desorption thermal effect is reasonably utilized, and the adsorption capacity of the activated carbon material is improved.

Description

An activated carbon material for vehicles and its preparation method and application

Technical field

The invention belongs to the technical field of environmental functional materials and relates to an activated carbon material, and in particular to an activated carbon material for vehicles and its preparation method and application.

Background technique

The car carbon canister is an important environmental protection device used to absorb and store gasoline vapor. When the car is turned off and the ambient temperature rises, the gasoline in the fuel tank will evaporate to form steam. If these steams are directly discharged into the atmosphere, they will cause pollution to the atmospheric environment. Therefore, the activated carbon in the car carbon canister is used to adsorb gasoline vapor to prevent gasoline vapor from polluting the atmosphere. When the car is started again, air is used to purge the activated carbon in the carbon canister, releasing the adsorbed gasoline vapor so that the engine can burn more efficiently.

Public patents such as CN102698724A, CN107570112A, and CN113753891A provide methods for preparing activated carbon in vehicle carbon canisters. In the preparation methods of activated carbon provided by the prior art, woody raw materials such as wood chips and wood powder are usually used as raw materials, and zinc chloride and phosphoric acid are added. Wait for the activator to activate and expand the pores, add a strengthening binder, and prepare activated carbon products through a certain molding process to improve the adsorption capacity and wear resistance of the activated carbon.

A large number of studies have shown that when activated carbon absorbs gasoline vapor, not all pores can play a role. Only mesopores with a pore diameter in the range of 2-6nm can effectively participate in the adsorption and desorption of gasoline vapor. Therefore, designing the pore structure in a targeted manner to obtain mesoporous activated carbon with a narrow pore size distribution is an important optimization direction for the activated carbon preparation process; in addition, during the adsorption process of gasoline, adsorption heat will be released. In traditional carbon canisters, a single filling of activated carbon material makes the adsorption heat unable to be effectively transferred, and the temperature of the activated carbon will rise, thereby reducing the adsorption capacity of the material. Therefore, solving the impact of adsorption heat on the adsorption process is also an important direction to improve the performance of activated carbon materials.

In addition, although the binder added during the traditional activated carbon molding process can give the molded columnar carbon a certain mechanical strength, it also greatly changes the pore structure of the carbon powder, thus affecting the adsorption and desorption performance of the activated carbon. Therefore, it is of great significance to the activated carbon industry to develop new molding processes to retain the pore structure of activated carbon to the maximum extent.

Contents of the invention

In view of the shortcomings of the existing technology, the purpose of the present invention is to provide an activated carbon material for vehicles and its preparation method and application, accurately control the pore size distribution of the activated carbon material, introduce a metal salt as a heat storage medium, and directly shape it during the preparation process. After reactivation, a mesoporous columnar activated carbon material with narrow pore size distribution and integrated heat storage is obtained.

To achieve this goal, the present invention adopts the following technical solutions:

In a first aspect, the present invention provides a preparation method of activated carbon material, which preparation method includes the following steps:

(1) Mix and react a polyhydroxyphenolic compound, a polyhydric aldehyde compound, a first catalyst, a polymer surfactant, a metal salt and a second catalyst to obtain a reaction product;

(2) The reaction product obtained in step (1) is sequentially subjected to solid-liquid separation, shaping, freezing and pyrolysis to obtain the activated carbon material.

The preparation method provided by the invention uses chemical raw materials to replace traditional activated carbon raw materials such as biomass and charcoal, which is low in cost and avoids the shortcomings of uncontrollable basic properties of traditional activated carbon raw materials. It accurately controls the pore size distribution of the activated carbon and introduces metal salts as heat storage media. , improve the adsorption capacity and adsorption and desorption efficiency of activated carbon materials. At the same time, the preparation process of the activated carbon precursor is directly shaped, then carbonized and activated, which solves the problem of pore blocking caused by the addition of binders during the traditional columnar activated carbon molding process, and the consequent reduction in adsorption and desorption performance. The earth retains the pore structure of activated carbon.

Preferably, the polyhydroxyphenolic compound in step (1) includes any one or a combination of at least two of resorcinol, catechol, hydroquinone, phloroglucinol or pyrogallol, Typical but non-limiting combinations include resorcin with catechol, hydroquinone with phloroglucinol, resorcin with pyrogallol, phloroglucinol with pyrogallol. A combination of pyrogallol, a combination of catechol, hydroquinone and pyrogallol, or, a combination of resorcinol, catechol, hydroquinone, phloroglucinol and pyrogallol. combination.

Preferably, the polybasic aldehyde compound in step (1) includes glyoxal, malondialdehyde, succinic aldehyde, glutaraldehyde, terephthalaldehyde, o-phthalaldehyde, isophthalaldehyde or trimesaldehyde. Any one or a combination of at least two, typical but non-limiting combinations include a combination of glyoxal and malondialdehyde, a combination of succinic aldehyde and glutaraldehyde, a combination of isophthalaldehyde and trimesaldehyde, The combination of glyoxal and terephthalaldehyde, the combination of malondialdehyde and o-phthalaldehyde, the combination of butyraldehyde and isophthalaldehyde, the combination of glutaraldehyde and trimesaldehyde, glyoxal, butylene A combination of aldehydes and terephthalaldehyde, or a combination of malondialdehyde, glutaraldehyde and trimesaldehyde.

Preferably, the molar ratio of the polyhydroxyphenolic compound and the polyhydric aldehyde compound in step (1) is 1:(0.5-5), for example, it can be 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5, but not limited to the listed values, other unlisted values within the value range are also applicable.

Preferably, the first catalyst in step (1) includes any one or a combination of at least two of NH ₄ OH, triethylamine, sodium bicarbonate or sodium carbonate. Typical but non-limiting combinations include NH ₄ OH and Combinations of triethylamine, combinations of triethylamine and sodium bicarbonate, combinations of sodium bicarbonate and sodium carbonate, combinations of NH ₄ OH, triethylamine and sodium bicarbonate, combinations of triethylamine, sodium bicarbonate and sodium carbonate A combination, or a combination of NH ₄ OH, triethylamine, sodium bicarbonate and sodium carbonate.

Preferably, the molar ratio of the first catalyst to the polyhydroxyphenolic compound in step (1) is 1:(100-500), for example, it can be 1:100, 1:150, 1:200, 1:250, 1 :300, 1:350, 1:400, 1:450 or 1:500, but not limited to the listed values, other unlisted values within the value range are also applicable.

Preferably, the polymer surfactant in step (1) includes any one or a combination of at least two of F127, P123 or P407. Typical but non-limiting combinations include the combination of F127 and P123, and the combination of P123 and P407. , the combination of F127 and P407, or the combination of F127, P123 and P407.

Preferably, the molar ratio of the polymer surfactant and the polyhydroxyphenolic compound in step (1) is 1:(100-300), for example, it can be 1:100, 1:150, 1:200, 1:250 Or 1:300, but not limited to the listed values, other unlisted values within the value range are also applicable.

Preferably, the metal salt in step (1) includes any one or a combination of at least two of FeCl ₃ , ZnCl ₂ , NiCl ₂ , MgCl ₂ or CuCl ₂ . Typical but non-limiting combinations include FeCl ₃ and ZnCl ₂ A combination of ZnCl _{and NiCl} , a combination of _NiCl and MgCl, a combination of MgCl and _CuCl , a combination of _{FeCl , ZnCl} and _NiCl , a combination of _NiCl , _MgCl and _{CuCl ,} or , a combination of FeCl ₃ , ZnCl ₂ , NiCl ₂ , MgCl ₂ and CuCl ₂ .

Preferably, the molar ratio of the metal salt and the polyhydroxyphenolic compound in step (1) is 1:(5-20), for example, it can be 1:5, 1:6, 1:8, 1:10, 1: 12, 1:14, 1:15, 1:16, 1:18 or 1:20, but not limited to the listed values, other unlisted values within the value range are also applicable.

Preferably, the second catalyst in step (1) includes any one or a combination of at least two of hydrochloric acid, sulfuric acid, formic acid or acetic acid. Typical but non-limiting combinations include a combination of hydrochloric acid and sulfuric acid, a combination of sulfuric acid and formic acid. , the combination of formic acid and acetic acid, the combination of hydrochloric acid, sulfuric acid and formic acid, the combination of sulfuric acid, formic acid and acetic acid, or the combination of hydrochloric acid, sulfuric acid, formic acid and acetic acid.

Preferably, the molar ratio of the second catalyst and the polyhydroxyphenolic compound in step (1) is 1:(5-20), for example, it can be 1:5, 1:6, 1:8, 1:10, 1 :12, 1:14, 1:15, 1:16, 1:18 or 1:20, but not limited to the listed values, other unlisted values within the value range are also applicable.

Preferably, the mixing in step (1) is performed in a solvent medium. For example, the solvent includes deionized water and/or ethanol.

Preferably, the reaction temperature in step (1) is 60-120°C, for example, it can be 60°C, 70°C, 80°C, 90°C, 100°C, 110°C or 120°C, but is not limited to the listed values. The same applies to other values within the numerical range that are not listed.

Preferably, the reaction time in step (1) is 12-36h, for example, it can be 12h, 14h, 15h, 16h, 18h, 20h, 22h, 24h, 25h, 26h, 28h, 30h, 32h, 34h, 35h or 36h, but not limited to the listed values, other unlisted values within the value range are also applicable.

Preferably, the freezing temperature in step (2) is -22°C to -196°C, for example, it can be -22°C, -30°C, -40°C, -50°C, -60°C, -70°C, -80°C ℃, -90℃, -100℃, -110℃, -120℃, -130℃, -140℃, -150℃, -160℃, -170℃, -180℃, -190℃ or -196℃, However, it is not limited to the listed values, and other unlisted values within the numerical range are also applicable.

Preferably, the freezing time in step (2) is 2-48h, for example, it can be 2h, 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h or 48h, but is not limited to the listed values. The same applies to other values within the numerical range that are not listed.

Preferably, the pyrolysis atmosphere in step (2) includes N ₂ and/or CO ₂ .

Preferably, the temperature rise rate of the pyrolysis in step (2) is 1-5°C/min, for example, it can be 1°C/min, 2°C/min, 3°C/min, 4°C/min or 5°C/min, However, it is not limited to the listed values, and other unlisted values within the numerical range are also applicable.

Preferably, the pyrolysis temperature in step (2) is 800-1600°C, for example, it can be 800°C, 900°C, 1000°C, 1100°C, 1200°C, 1300°C, 1400°C, 1500°C or 1600°C, but Not limited to the numerical values listed, other unlisted values within the numerical range are also applicable.

Preferably, the pyrolysis time in step (2) is 1-2h, for example, it can be 1h, 1.2h, 1.4h, 1.5h, 1.6h, 1.8h or 2h, but is not limited to the listed values and ranges Other values not listed within are also applicable.

In a second aspect, the present invention provides an activated carbon material, which is prepared by the preparation method described in the first aspect.

The activated carbon material provided by the invention is a cylindrical carbon with a diameter of 2-3mm and a length of 3-5mm. The carbon has a narrow pore size distribution, the pore size range is 1-10nm, and the mesopores with a pore size of 2-6nm account for the total pore volume. 50-80% of the pore volume, achieving precise control of the pore size distribution of activated carbon, improving the adsorption and desorption effect of activated carbon materials, and avoiding desorption difficulties caused by too many micropores; at the same time, metal salts are creatively introduced as storage Thermal medium effectively stores the adsorption heat during the adsorption process to avoid the temperature rise of activated carbon and improve the adsorption capacity of the material. During the desorption process, the heat is released again, which is beneficial to desorption and also reduces the input of external heat and can be used rationally. The thermal effect of adsorption and desorption is beneficial to energy saving. In addition, direct molding and then carbonization activation during the preparation process of activated carbon precursor solves the problem of pore blocking caused by adding binders during the traditional columnar activated carbon molding process and the consequent reduction in adsorption and desorption performance, greatly retaining the The pore structure of activated carbon improves the adsorption and desorption performance of columnar carbon.

In a third aspect, the present invention provides an application of the activated carbon material as described in the second aspect, which is used for adsorbing gasoline vapor in a vehicle carbon canister.

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

The preparation method provided by the invention uses chemical raw materials to replace traditional activated carbon raw materials such as biomass and charcoal, which is low-cost and avoids the shortcomings of uncontrollable basic properties of traditional activated carbon raw materials; according to the gasoline adsorption characteristics, the pore size distribution of the activated carbon material is accurately controlled, so that a large number of The pore size is distributed between 2-6nm, which improves the adsorption and desorption effect of activated carbon materials; the heat storage medium is introduced to rationally utilize the adsorption and desorption thermal effects to improve the adsorption capacity of activated carbon materials; the activated carbon precursor is directly formed and recarbonized during the preparation process, solving the traditional problem of The formation process of columnar activated carbon requires the addition of binders to cause pore blocking and the consequent reduction in adsorption and desorption performance. This greatly retains the pore structure of activated carbon and improves the adsorption and desorption performance of columnar carbon.

Detailed ways

The technical solution of the present invention will be further described below through specific implementations.

Example 1

This embodiment provides a method for preparing activated carbon material. The preparation method includes the following steps:

(1) Disperse resorcinol and glyoxal in deionized water at a molar ratio of 1:3, then add sodium bicarbonate as a catalyst. The molar ratio of sodium bicarbonate to resorcinol is 1:200, and stir until completely dissolved;

(2) Add surfactant F127 to the above completely dissolved solution. The molar ratio of F127 to resorcinol is 1:200. Add the metal salt FeCl ₃ . The molar ratio of FeCl ₃ to resorcinol is 1:20. , after evenly dispersed, add dilute hydrochloric acid, then transfer to the oven, keep at 80°C for 24h for reaction;

(3) After the reaction, fully wash and filter the reaction product, retain the filter residue, and use extrusion equipment to extrude the product into a cylinder with a diameter of 3 mm and a length of 5 mm, freeze it at -22°C for 48 hours, and then transfer to the freezer. Dry thoroughly in drying box;

(4) Pyrolyze the above-mentioned dried sample in a tube furnace, the pyrolysis atmosphere is N ₂ , and the temperature is raised to 800°C at a heating rate of 1°C/min. The pyrolysis time is 1h. After the pyrolysis is completed, the above-mentioned sample is obtained. Activated carbon material.

Example 2

This embodiment provides a method for preparing activated carbon material. The preparation method includes the following steps:

(1) Disperse catechol, phloroglucinol and trimesaldehyde in deionized water at a molar ratio of 1:1:5, then add sodium bicarbonate as a catalyst, sodium bicarbonate and two polyhydroxyphenols The molar ratio of the total amount of compounds is 1:500, stir until completely dissolved;

(2) Add surfactant F127 to the above completely dissolved mixture. The molar ratio of F127 to the total amount of the two polyhydroxyphenolic compounds is 1:200. Add ZnCl ₂ , ZnCl ₂ and the two polyhydroxyphenolic compounds. The molar ratio of the total amount is 1:20. After even dispersion, add dilute hydrochloric acid to the mixed system, then transfer it to the oven and keep it at 80°C for 24 hours;

(3) At the end of the reaction, fully wash and filter the reaction product, retain the filter residue, and use extrusion equipment to extrude the product into a cylinder with a diameter of 3 mm and a length of 5 mm, freeze it at -22°C for 24 hours, and then transfer to the freezer Dry thoroughly in drying box;

(4) Pyrolyze the above-mentioned dried sample in a tube furnace in a N ₂ pyrolysis atmosphere. The temperature is raised to 800°C at a rate of 1°C/min. The pyrolysis time is 1 hour. After the pyrolysis is completed, the activated carbon material is obtained. .

Example 3

This embodiment provides a method for preparing activated carbon material. The preparation method includes the following steps:

(1) Disperse catechol, resorcin, phloroglucinol, glyoxal and glutaraldehyde in deionized water according to the molar ratio of 1:1:1:6:6, and then add NH ₄ OH as Catalyst, the molar ratio of NH ₄ OH to the total amount of three polyhydroxyphenolic compounds is 1:300, stir until completely dissolved;

(2) Add surfactant F127 to the above completely dissolved mixture. The molar ratio of F127 to the total amount of three polyhydroxyphenolic compounds is 1:200. Add NiCl ₂ , NiCl ₂ and three polyhydroxyphenolic compounds. The molar ratio of the total amount is 1:5. After even dispersion, add dilute hydrochloric acid to the mixed system, then transfer it to the oven and keep it at 80°C for 24 hours;

(3) At the end of the reaction, fully wash and filter the reaction product, retain the filter residue, and use extrusion equipment to extrude the product into a cylinder with a diameter of 3 mm and a length of 5 mm, freeze it at -22°C for 24 hours, and then transfer to freeze drying. Dry thoroughly in the box;

(4) The above dried sample is further pyrolyzed in a tube furnace. The pyrolysis atmosphere is N ₂ . The temperature is raised to 800°C at a rate of 1°C/min. The pyrolysis time is 1 hour. After the pyrolysis is completed, the activated carbon is obtained. Material.

Example 4

This embodiment provides a method for preparing activated carbon material. The preparation method includes the following steps:

(1) Disperse resorcinol and glyoxal in deionized water at a molar ratio of 1:3, then add sodium bicarbonate as a catalyst. The molar ratio of sodium bicarbonate to resorcinol is 1:200, and stir until complete dissolve; dissolve

(2) Add surfactant P123 to the above completely dissolved mixture. The molar ratio of P123 to resorcinol is 1:250. Add MgCl ₂ . The molar ratio of MgCl ₂ to resorcinol is 1:5. After uniform dispersion, add dilute hydrochloric acid to the mixed system, then transfer it to the oven and keep it at 100°C for 18 hours;

(3) At the end of the reaction, fully wash and filter the reaction product, retain the filter residue, and use extrusion equipment to extrude the product into a cylinder with a diameter of 3 mm and a length of 5 mm, freeze it at -22°C for 48 hours, and then transfer to freeze drying. Dry thoroughly in the box;

(4) The above dried sample is further pyrolyzed in a tube furnace. The pyrolysis atmosphere is N ₂ . The temperature is raised to 800°C at a rate of 1°C/min. The pyrolysis time is 1 hour. After the pyrolysis is completed, the activated carbon is obtained. Material.

Example 5

This embodiment provides a method for preparing activated carbon material. The preparation method includes the following steps:

(1) Disperse resorcinol and glyoxal in deionized water at a molar ratio of 1:0.5, then add sodium bicarbonate as a catalyst, the molar ratio of sodium bicarbonate to resorcinol is 1:100, and stir until completely dissolved;

(2) Add surfactant F127 to the above completely dissolved solution. The molar ratio of F127 to resorcinol is 1:100. Add the metal salt FeCl ₃ . The molar ratio of FeCl ₃ to resorcinol is 1:10. , after evenly dispersed, add dilute hydrochloric acid, then transfer to the oven, keep at 60°C for 36h for reaction;

(3) After the reaction, fully wash and filter the reaction product, retain the filter residue, and use extrusion equipment to extrude the product into a cylinder with a diameter of 3 mm and a length of 5 mm, freeze it at -22°C for 48 hours, and then transfer to the freezer. Dry thoroughly in drying box;

(4) Pyrolyze the above-mentioned dried sample in a tube furnace, the pyrolysis atmosphere is N ₂ , and the temperature is raised to 800°C at a heating rate of 1°C/min. The pyrolysis time is 1h. After the pyrolysis is completed, the above-mentioned sample is obtained. Activated carbon material.

Example 6

This embodiment provides a method for preparing activated carbon material. The preparation method includes the following steps:

(1) Disperse resorcinol and glyoxal in deionized water at a molar ratio of 1:5, then add sodium bicarbonate as a catalyst. The molar ratio of sodium bicarbonate to resorcinol is 1:500, and stir until completely dissolved;

(2) Add surfactant F127 to the above completely dissolved solution. The molar ratio of F127 to resorcinol is 1:300. Add the metal salt FeCl ₃ . The molar ratio of FeCl ₃ to resorcinol is 1:10. , after evenly dispersed, add dilute hydrochloric acid, then transfer to the oven, keep at 120°C for 12 hours for reaction;

(3) After the reaction, fully wash and filter the reaction product, retain the filter residue, and use extrusion equipment to extrude the product into a cylinder with a diameter of 3 mm and a length of about 5 mm, freeze it at -22°C for 48 hours, and then transfer it to Fully dry in freeze-drying box;

(4) Pyrolyze the above dried sample in a tube furnace, the pyrolysis atmosphere is N ₂ , and the temperature is raised to 1600°C at a heating rate of 1°C/min. The pyrolysis time is 1h. After the pyrolysis is completed, the above-mentioned sample is obtained. Activated carbon material.

Example 7

This embodiment provides a method for preparing activated carbon materials. Compared with Example 1, the metal salt used in step (2) is replaced by CuCl ₂ in equal amounts, and the rest is the same as Example 1.

Example 8

This embodiment provides a method for preparing activated carbon materials. Compared with Example 1, the freezing temperature in step (3) is controlled to -196°C and the freezing time is 2 hours. The rest are the same as Example 1.

Example 9

This embodiment provides a method for preparing activated carbon materials. Compared with Example 1, the pyrolysis atmosphere in step (4) is controlled to be CO ₂ , and the rest are the same as Example 1.

Example 10

This embodiment provides a method for preparing activated carbon materials. Compared with Example 1, the pyrolysis temperature in step (4) is controlled to be 1000°C, and the rest is the same as Example 1.

Example 11

This embodiment provides a method for preparing activated carbon materials. Compared with Example 1, the pyrolysis temperature in step (4) is controlled to 700°C, and the rest is the same as Example 1.

Example 12

This embodiment provides a method for preparing activated carbon materials. Compared with Example 1, the pyrolysis temperature in step (4) is controlled to 1700°C, and the rest is the same as Example 1.

Example 13

This embodiment provides a method for preparing activated carbon materials. Compared with Example 1, the pyrolysis time of step (4) is controlled to 2 hours, and the rest is the same as Example 1.

Example 14

This embodiment provides a method for preparing activated carbon materials. Compared with Example 1, the temperature rise rate of pyrolysis in step (4) is controlled to be 5°C/min, and the rest is the same as Example 1.

Example 15

This embodiment provides a method for preparing activated carbon materials. Compared with Example 1, the temperature rise rate of pyrolysis in step (4) is controlled to be 10°C/min, and the rest is the same as Example 1.

Comparative example 1

This comparative example provides a method for preparing activated carbon materials. Compared with Example 1, no metal salt is added in step (2), and the rest is the same as Example 1.

Comparative example 2

This comparative example provides a preparation method of activated carbon material. Compared with Example 1, the freezing in step (3) is not performed, and the rest is the same as Example 1.

Performance characterization

The pore size data of the activated carbon materials prepared in the examples and comparative examples are measured. The test method is as follows:

The SSA-7300 pore size and specific surface analyzer of Beijing Biotech Electronics Co., Ltd. was used to obtain the pore structure of activated carbon materials. By testing the N ₂ adsorption-desorption isotherm of the activated carbon material, the pore size distribution and pore volume of the material were obtained, and the BET method was used to calculate the specific surface area of the material. The results are listed in Table 1.

Table 1

It can be seen from Table 1 that the activated carbon material provided by the present invention has a good specific surface area, the pore volume of mesopores with a pore diameter of 2-6 nm can account for 50-80% of the total pore volume, and the pore diameter and pore volume distribution are reasonable. For gasoline The characteristics of the molecule have good adsorption effect on gasoline, and the adsorption and desorption experiments on butane reflect that the activated carbon material has high adsorption capacity, strong adsorption capacity, and good desorption effect, which is beneficial to the recycling application of activated carbon; at the same time, using this With the preferred preparation parameters provided by the invention, activated carbon materials can achieve better performance. Compared with Example 1, in Comparative Example 1, no metal salt is added, the adhesion data of butane is significantly reduced, and the desorption ability of the material is reduced. It can be seen that the introduction of metal salt as a heat storage medium can rationally utilize the adsorption capacity of the material. The thermal effect of desorption has significantly improved the desorption effect of activated carbon materials; in Comparative Example 2, no freeze drying was used, but direct thermal oven drying was used. The pore structure of the material changed and various performance data declined. Freezing was used. Drying can increase the microscopic porosity of the material, thereby improving the specific surface area and adsorption properties of the material.

In summary, the preparation method provided by the present invention uses chemical raw materials to replace traditional activated carbon raw materials such as biomass and charcoal, which is low-cost and avoids the shortcomings of uncontrollable basic properties of traditional activated carbon raw materials; according to the gasoline adsorption characteristics, the activated carbon material can be accurately controlled. The pore size distribution allows a large number of pores to be distributed between 2-6nm, improving the adsorption and desorption effect of activated carbon materials; introducing heat storage media to rationally utilize the adsorption and desorption thermal effects to improve the adsorption capacity of activated carbon materials; directly forming and recarbonizing the activated carbon precursor during the preparation process Activation solves the problem of pore blocking caused by adding binders during the traditional columnar activated carbon molding process, as well as the consequent reduction in adsorption and desorption performance. It greatly retains the pore structure of activated carbon and improves the adsorption and desorption of columnar carbon. Comes with performance.

The above-mentioned specific embodiments further describe the purpose, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above-mentioned are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims (10)

1. The preparation method of the activated carbon material is characterized by comprising the following steps:

(1) Mixing and reacting a polyhydroxy phenol compound, a multi-aldehyde compound, a first catalyst, a high molecular surfactant, metal salt and a second catalyst to obtain a reaction product;

(2) And (3) sequentially carrying out solid-liquid separation, molding, freezing and pyrolysis on the reaction product obtained in the step (1) to obtain the activated carbon material.

2. The method of claim 1, wherein the polyhydric phenol compound of step (1) comprises any one or a combination of at least two of resorcinol, catechol, hydroquinone, phloroglucinol, or pyrogallol;

preferably, the polyaldehyde compound in step (1) comprises any one or a combination of at least two of glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, terephthalaldehyde, phthalaldehyde, isophthalaldehyde or trimellitaldehyde;

preferably, the molar ratio of the polyhydroxy phenolic compound to the polyaldehyde compound in the step (1) is 1 (0.5-5).

3. The method of claim 1 or 2, wherein the first catalyst of step (1) comprises NH ₄ OH, triethylamine, sodium bicarbonate or sodium carbonateMeaning one or a combination of at least two;

preferably, the molar ratio of the first catalyst to the polyhydroxy phenolic compound in step (1) is 1 (100-500).

4. A method of preparation according to any one of claims 1 to 3 wherein the polymeric surfactant of step (1) comprises any one or a combination of at least two of F127, P123 or P407;

preferably, the molar ratio of the macromolecular surfactant to the polyhydroxy phenolic compound in the step (1) is 1 (100-300).

5. The process of any one of claims 1 to 4, wherein the metal salt of step (1) comprises FeCl ₃ 、ZnCl ₂ 、NiCl ₂ 、MgCl ₂ Or CuCl ₂ Any one or a combination of at least two of the following;

preferably, the molar ratio of the metal salt to the polyhydroxy phenolic compound in the step (1) is 1 (5-20);

preferably, the second catalyst of step (1) comprises any one or a combination of at least two of hydrochloric acid, sulfuric acid, formic acid or acetic acid;

preferably, the molar ratio of the second catalyst to the polyhydroxy phenolic compound in step (1) is 1 (5-20).

6. The process according to any one of claims 1 to 5, wherein the temperature of the reaction in step (1) is 60 to 120 ℃;

preferably, the reaction time of step (1) is 12-36 hours.

7. The method of any one of claims 1-6, wherein the freezing temperature in step (2) is from-22 ℃ to-196 ℃;

preferably, the freezing time of step (2) is 2-48 hours.

8. The preparation method according to any one of claims 1 to 7, whereinWherein the atmosphere for pyrolysis of step (2) comprises N ₂ And/or CO ₂ ；

Preferably, the heating rate of the pyrolysis in the step (2) is 1-5 ℃/min;

preferably, the temperature of the pyrolysis of step (2) is 800-1600 ℃;

preferably, the pyrolysis of step (2) takes 1-2 hours.

9. An activated carbon material, characterized in that the activated carbon material is prepared by the preparation method of any one of claims 1-8;

the active carbon material is cylindrical carbon with the diameter of 2-3mm and 3-5 mm.

10. Use of the activated carbon material of claim 9 for the vapor adsorption of gasoline in a vehicle carbon canister.