CN111440278B - Activated carbon material and preparation method and application thereof - Google Patents

Activated carbon material and preparation method and application thereof Download PDF

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CN111440278B
CN111440278B CN202010398455.9A CN202010398455A CN111440278B CN 111440278 B CN111440278 B CN 111440278B CN 202010398455 A CN202010398455 A CN 202010398455A CN 111440278 B CN111440278 B CN 111440278B
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activated carbon
carbon material
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phosphonium salt
quaternary phosphonium
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CN111440278A (en
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张喆
张涛
廖元飞
郑学森
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Beijing Foton Daimler Automobile Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0687—Reactant purification by the use of membranes or filters
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Abstract

The invention provides a method for preparing an activated carbon material, the activated carbon material prepared by the method and application of the activated carbon material in a filter. The method for preparing the activated carbon material comprises the following steps: (1) adding a quaternary phosphonium salt monomer into deionized water, and uniformly stirring to ensure that the molar concentration of the quaternary phosphonium salt monomer is 0.5-1.0 mol/L so as to obtain a solution A; (2) adding an initiator into the solution A to obtain a solution B; (3) adding granular activated carbon into the solution B and uniformly stirring to obtain a mixture C; (4) introducing nitrogen into the mixture C, bubbling for 10min, sealing, and carrying out redox grafting reaction in a constant-temperature water bath; and (5) washing a product after the oxidation-reduction grafting reaction with acetone, then extracting for 24 hours, and drying to obtain the activated carbon material. The activated carbon material prepared by the method has strong adsorption performance and good antibacterial and antiseptic properties.

Description

Activated carbon material and preparation method and application thereof
Technical Field
The invention belongs to the field of materials, and particularly relates to a method for preparing an activated carbon material, the activated carbon material prepared by the method and application of the activated carbon material in a filter.
Background
With the continuous development of economy in China, automobiles are indispensable transportation means in daily life of people. With the increase of the possession of private automobiles in cities year by year, the air pollution condition on roads is increasingly serious, the space in the automobiles is narrow, the air circulation is poor, the diffusion of pollutants is not facilitated, bacteria are easy to breed, and great harm is brought to the health of automobile owners. How to improve the quality of air in the vehicle becomes a topic of close attention of the majority of vehicle owners, and an air conditioner filter with an antibacterial function is an effective means for solving the problem.
A Proton Exchange Membrane Fuel Cell (PEMFC) is a device that can directly convert chemical energy of fuel (usually hydrogen or methanol) and oxidant (oxygen or air) into electrical energy, and has the advantages of high energy conversion efficiency, no environmental pollution, simple structure, and low influence of load change on power generation efficiency, and is considered to be a type of cell with the greatest development prospect. In recent years, Fuel Cell Vehicles (FCV) and proton exchange membrane fuel cell (pem) technologies have been rapidly promoted along with the rapid development of new energy vehicles. An air filter with high efficiency and gas adsorption and antibacterial functions is required to be used in the fuel cell system, and the device is an important accessory of the fuel cell system and directly influences the service life of the fuel cell.
Therefore, it is desired to develop a material suitable for an air filter and having both adsorption and antibacterial functions.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide an activated carbon material for a vehicle air conditioner filter and a preparation method thereof, wherein the activated carbon material has antibacterial and antifungal properties on the premise of maintaining its adsorptive property, and therefore, the activated carbon material can be used in the application fields of vehicle air conditioner filters, proton exchange membrane fuel cell air filters, and the like, and can effectively improve the quality of air in vehicles and prolong the service life of fuel cells.
According to one aspect of the present invention, there is provided a method of preparing an activated carbon material, the method comprising:
(1) adding a quaternary phosphonium salt monomer into deionized water, and uniformly stirring to ensure that the molar concentration of the quaternary phosphonium salt monomer is 0.5-1.0 mol/L so as to obtain a solution A;
(2) adding an initiator into the solution A to ensure that the molar concentration of the initiator is 0.02-0.05 mol/L so as to obtain a solution B;
(3) adding granular activated carbon into the solution B, and uniformly stirring to ensure that the mass ratio of the granular activated carbon to the solution B is 1: 6-1: 20 so as to obtain a mixture C;
(4) filling nitrogen into the mixture C, bubbling for 10min, sealing, and carrying out redox grafting reaction in a constant-temperature water bath; and
(5) washing the product after the oxidation-reduction grafting reaction with acetone, extracting for 24 hours, and drying to obtain the activated carbon material.
Therefore, the method for preparing the activated carbon material can be used for preparing the activated carbon material with both the adsorption performance and the antibacterial and mildewproof performance, the preparation method is simple and feasible, the cost is low, and quaternary phosphonium salt can be effectively grafted on the surface of the granular activated carbon, so that the activated carbon has good antibacterial and mildewproof performance, and the application range of the activated carbon is expanded. Therefore, the activated carbon product prepared by the method can be used for an air filter in an automobile and an air filter in a fuel cell system, and further can effectively improve the quality of air in the automobile and prolong the service life of the fuel cell.
In addition, the method for preparing the activated carbon material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the quaternary phosphonium salt monomer is methacryloyloxyheptyl-tributylphosphonium chloride.
In some embodiments of the invention, the initiator is cerium ammonium nitrate, cerium ammonium sulfate, or ammonium thiosulfate.
In some embodiments of the invention, the granular activated carbon is a natural plant-based char material.
In some embodiments of the present invention, the natural plant-made charcoal material is at least one selected from bamboo charcoal, coconut shell charcoal, rice hull charcoal and wheat straw charcoal.
In some embodiments of the present invention, the redox grafting reaction is performed at a reaction temperature of 30 ℃ to 60 ℃ for a reaction time of 60min to 120 min.
According to another aspect of the present invention, there is also provided an activated carbon material prepared by the method of the previous embodiment, the activated carbon material comprising, according to an embodiment of the present invention: the particle activated carbon comprises a particle activated carbon matrix and a quaternary phosphonium salt monomer layer, wherein the quaternary phosphonium salt monomer layer is formed on the surface of the particle activated carbon matrix through oxidation-reduction grafting reaction.
According to a further aspect of the invention, the invention further provides the use of the activated carbon material according to the previous embodiment in a filter, which is an air conditioning filter for a vehicle or a filter for a fuel cell.
Drawings
FIG. 1 is a schematic diagram of a grafting reaction in preparing an activated carbon material according to one embodiment of the present invention.
FIG. 2 is a graph showing the EDS element distribution of the activated carbon material prepared in example 3 of the present invention, and the presence of N element, O element and Cl element indicates that the quaternary phosphonium salt monomer has been grafted to the surface of the activated carbon material.
Detailed Description
The following detailed description of the embodiments of the invention, which is intended to be illustrative and not to be construed as limiting the invention.
According to one aspect of the present invention, there is provided a method of preparing an activated carbon material, the method comprising:
(1) adding a quaternary phosphonium salt monomer into deionized water, and uniformly stirring to ensure that the molar concentration of the quaternary phosphonium salt monomer is 0.5-1.0 mol/L so as to obtain a solution A;
(2) adding an initiator into the solution A to ensure that the molar concentration of the initiator is 0.02-0.05 mol/L so as to obtain a solution B;
(3) adding granular activated carbon into the solution B, and uniformly stirring to ensure that the mass ratio of the granular activated carbon to the solution B is 1: 6-1: 20 so as to obtain a mixture C;
(4) filling nitrogen into the mixture C, bubbling for 10min, sealing, and carrying out redox grafting reaction in a constant-temperature water bath; and
(5) washing the product after the oxidation-reduction grafting reaction with acetone, then extracting for 24 hours, and drying at the temperature of below 60 ℃ so as to obtain the activated carbon material.
Therefore, the method for preparing the activated carbon material can be used for preparing the activated carbon material with both the adsorption performance and the antibacterial and mildewproof performance, the preparation method is simple and easy to implement, and quaternary phosphonium salt can be effectively grafted on the surface of the granular activated carbon, so that the activated carbon has good antibacterial and mildewproof performance, and the application range of the activated carbon is expanded. Therefore, the activated carbon product prepared by the method can be used for an air filter in an automobile and an air filter in a fuel cell system, and further can effectively improve the quality of air in the automobile and prolong the service life of the fuel cell.
The method for preparing the activated carbon material according to the above embodiment of the present invention will be described in detail.
(1) Firstly, adding a quaternary phosphonium salt monomer into deionized water, and uniformly stirring to ensure that the molar concentration of the quaternary phosphonium salt monomer is 0.5-1.0 mol/L so as to obtain a solution A. Thereby preparing a quaternary phosphonium salt monomer solution.
According to a specific embodiment of the present invention, the quaternary phosphonium salt monomer is preferably methacryloyloxyheptyl-tributylphosphonium chloride. Because, the inventors found that by grafting activated carbon using methacryloyloxyheptyl-tributylphosphine chloride as a quaternary phosphonium salt monomer, the specific surface area and pore volume of activated carbon were hardly affected, and 95% or more of the original pore volume could be maintained, and thus it could be judged that the adsorption performance of activated carbon was hardly decreased. In addition, methacryloxypentyl heptyl-tributyl phosphonium chloride is used as the quaternary phosphonium salt monomer grafted activated carbon, antibacterial performance evaluation is carried out on the quaternary phosphonium salt monomer grafted activated carbon, evaluation results on escherichia coli and staphylococcus aureus are good, and the antibacterial effect is achieved. The antibacterial and mildewproof grade can reach 0 grade by testing, which shows that the mildewproof effect is good. Therefore, the inventor considers that the methacryloxy heptyl-tributyl phosphonium chloride is the best choice for the granular activated carbon material as the quaternary phosphonium salt monomer, and the two can not only exert respective performances, but also do not influence the performances of the other, thereby further improving the adsorbability and the mildew-proof antibacterial performance of the prepared activated carbon material to the maximum extent.
In addition, the molar concentration of the quaternary phosphonium salt monomer in the solution A prepared is 0.5-1.0 mol/L. Therefore, the concentration of the quaternary phosphonium salt monomer can be ensured to be enough to improve the grafting rate, and further, the sufficient mildew-proof antibacterial performance is obtained, and in addition, the concentration is not easy to be too high, so that the influence of grafting of too much quaternary phosphonium salt monomer on the adsorption performance of the activated carbon is avoided. Specifically, the quaternary phosphonium salt monomer molar concentration in the solution A can be 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1.0 mol/L. And then the active carbon material with good adsorptivity, antibiosis and mildew resistance can be prepared.
(2) Then, an initiator is added to the solution A so that the molar concentration of the initiator is 0.02mol/L to 0.05mol/L, thereby obtaining a solution B.
According to a specific embodiment of the present invention, the initiator is cerium ammonium nitrate, cerium ammonium sulfate or ammonium thiosulfate. The inventors have found that the grafting efficiency and grafting yield of the quaternary phosphonium salt monomer can be significantly improved by employing several of the above initiators. Therefore, in order to effectively graft the quaternary phosphonium salt monomer with antibacterial activity on the granular activated carbon, the inventor optimizes the combination of the initiator of ammonium ceric nitrate, ammonium ceric sulfate or ammonium thiosulfate and methacryloyloxyheptyl-tributylphosphine chloride, and further ensures that the quaternary phosphonium salt monomer can be effectively grafted on the surface of the activated carbon.
In addition, in the solution B containing the quaternary phosphonium salt monomer and the initiator prepared in the above way, the concentrations of the quaternary phosphonium salt monomer and the initiator are respectively 0.5mol/L to 1.0mol/L of the molar concentration of the quaternary phosphonium salt monomer and 0.02mol/L to 0.05mol/L of the molar concentration of the initiator. Therefore, the grafting efficiency and the grafting rate of the quaternary phosphonium salt monomer can be obviously improved by adopting the concentration ratio. The mass percentage concentration of the photoinitiator is obtained by matching according to the molar concentration of the quaternary phosphonium salt monomer, and the photoinitiator has the most suitable initiating effect in the solution B, so that the grafting efficiency can be effectively improved. If the initiator concentration is too high, two problems arise:
1. the grafting reaction speed is too high, the grafting reaction is incomplete, the degradation and chain opening of a high molecular chain can be caused, the grafting efficiency is reduced, and the antibacterial effect is influenced;
2. the cost of the initiator is increased, so that the cost of the grafted activated carbon is increased, and the application of the product is not facilitated.
(3) And then adding granular activated carbon into the solution B containing the quaternary phosphonium salt monomer and the initiator, and uniformly stirring to ensure that the mass ratio of the granular activated carbon to the solution B is 1: 6-1: 20 so as to obtain a mixture C.
According to the specific embodiment of the invention, the mass ratio of the granular activated carbon to the solution B is controlled to be 1: 6-1: 20, so that the moderate ratio of the quaternary phosphonium salt monomer to the granular activated carbon can be ensured, and the prepared activated carbon monomer can maintain the adsorption performance to the maximum extent and simultaneously increase the effective antibacterial and anticorrosive performance. According to a specific example of the present invention, the mass ratio of the granular activated carbon to the solution B may be 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, or 1: 20. Therefore, the quaternary phosphonium salt monomer with enough quantity can be grafted on the surface of the activated carbon, so that the prepared activated carbon monomer has good antibacterial effect and 0-grade mildew-proof grade. In addition, the inventor also finds that in the mixture C, the adding amount of the activated carbon is not easy to be too large or too small, because the adding amount is too small, the yield of the grafted activated carbon is reduced, the production efficiency and the cost are influenced, a multi-graft network is easy to form on single-particle activated carbon, and the phenomenon of the barrier of a penetrating step caused by similar long molecular chains is generated, so that the antibacterial performance is reduced; and too much addition can cause poor dispersibility of the activated carbon particles in the solution and easy agglomeration, and the grafting reaction can not be carried out on the surfaces of most activated carbon particles, so that the antibacterial performance is reduced, and the product performance and the production efficiency of the grafted activated carbon are influenced.
In addition, according to the specific embodiment of the present invention, the adopted granular activated carbon can be a natural plant carbon material. According to a specific example of the present invention, the natural plant charcoal material is preferably at least one of bamboo charcoal, coconut charcoal, rice hull charcoal and wheat straw charcoal. The activated carbon material prepared by the granular activated carbon has more stable volume form, and can easily keep the original adsorption performance, so that the influence of the grafted quaternary phosphonium salt monomer on the adsorption performance is reduced. In addition, the inventor finds that the activated carbon material prepared by adopting the preferred natural plant carbon-making materials is more suitable for an air filter in an automobile and an air filter in a fuel cell system, and further can effectively improve the quality of air in the automobile and prolong the service life of a fuel cell.
(4) Then, nitrogen is filled into the mixture C, the mixture C is sealed after bubbling for 10min, and the redox grafting reaction is carried out in a constant-temperature water bath.
According to the specific embodiment of the invention, the initiator in the mixture C enables the activated carbon surface to form carbon free radicals, and the quaternary phosphonium salt monomer and the carbon free radicals undergo redox grafting reaction to be grafted on the activated carbon.
According to the specific embodiment of the present invention, the inventors have found that when the quaternary phosphonium salt monomer is preferably methacryloyloxyheptyl-tributylphosphine chloride, the formula of which is shown in the specification
Figure BDA0002488549190000061
The grafting reaction with activated carbon is shown in figure 1. When the methacryloxy heptyl-tributyl phosphine chloride is adopted, the inventor finds that the length of a methacryloxy heptyl molecular chain on the tributyl phosphonium salt is moderate from the antibacterial mechanism analysis of a quaternary phosphonium salt antibacterial agent, so that the antibacterial group density can be improved, the antibacterial performance of a grafted activated carbon product can be improved, the gas penetration step caused by a high molecular weight long molecular chain can be prevented from being blocked, and the high molecular chain is prevented from being degraded under the action of high temperature, illumination and oxygen to be separated, so that harmful gases such as acetaldehyde and formaldehyde are formed, and the air quality in a finished automobile is influenced. In addition, the adoption of the tributyl can improve the antibacterial property and reduce the toxicity of the quaternary phosphonium salt antibacterial agent, so that when the methacryloxypropyl-tributyl phosphine chloride is adopted, the filter is more suitable for an air conditioner filter and a fuel cell filter for a vehicle compared with other types of quaternary phosphonium salt antibacterial agents and the like.
According to the specific embodiment of the present invention, the inventor further studied the reaction conditions of grafting the quaternary phosphonium salt monomer on the surface of the activated carbon, and when the reaction temperature of the redox grafting reaction is controlled to be 30 ℃ to 60 ℃, specifically 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃, and the reaction time is 60min to 120min, specifically 60min, 65min, 70min, 75min, 80min, 85min, 90min, 95min, 100min, 105min, 110min, 115min or 120 min. The grafting reaction can be further ensured to be smooth, the optimal grafting effect is achieved, namely the finally obtained activated carbon material basically keeps the original adsorption performance and effectively increases the antibacterial and anticorrosive performance, and the antibacterial effect is good through tests, and the anticorrosive grade reaches 0 level.
(5) And finally, washing the product after the redox grafting reaction by using acetone, extracting for 24 hours, and drying at the temperature of below 60 ℃ so as to obtain the activated carbon material.
According to a specific embodiment of the present invention, the method for preparing the obtained activated carbon material is preferably as follows:
(1) adding methacryloxy heptyl-tributyl phosphine chloride into deionized water, and uniformly stirring to ensure that the molar concentration of the methacryloxy heptyl-tributyl phosphine chloride is 0.5-1.0 mol/L so as to obtain a solution A;
(2) adding ammonium ceric nitrate, ammonium ceric sulfate or ammonium thiosulfate into the solution A, wherein the molar concentration is 0.02-0.05 mol/L, so as to obtain a solution B;
(3) adding granular activated carbon into the solution B, and uniformly stirring to ensure that the mass ratio of the granular activated carbon to the solution B is 1: 6-1: 20 so as to obtain a mixture C;
(4) filling nitrogen into the mixture C, bubbling for 10min, sealing, and performing oxidation-reduction grafting reaction in a constant-temperature water bath at the reaction temperature of 30-60 ℃ for 60-120 min; and
(5) washing the product after the oxidation-reduction grafting reaction with acetone, extracting for 24 hours, and drying at the temperature of below 60 ℃ to obtain the activated carbon material.
Therefore, by adopting the method, a proper amount of methacryloyloxyheptyl-tributylphosphine chloride can be effectively grafted on the surface of the granular activated carbon, so that the finally obtained activated carbon material basically keeps the original adsorption performance and effectively increases the antibacterial and anticorrosive performances, and the antibacterial effect is good through tests, and the anticorrosive grade reaches 0 level.
According to another aspect of the present invention, the present invention further provides an activated carbon material prepared by the method of the previous embodiment, and according to an embodiment of the present invention, the activated carbon material comprises: the particle activated carbon comprises a particle activated carbon matrix and a quaternary phosphonium salt monomer layer, wherein the quaternary phosphonium salt monomer layer is grafted on the surface of the particle activated carbon matrix through oxidation-reduction reaction. The activated carbon material basically keeps the original adsorption performance, simultaneously effectively increases the antibacterial and antiseptic performance, and has good antibacterial effect through tests, and the antiseptic grade reaches 0 grade.
According to a further aspect of the invention, the invention further provides the use of the activated carbon material according to the previous embodiment in a filter, which is an air conditioning filter for a vehicle or a filter for a fuel cell. The activated carbon material has strong adsorption performance and good antibacterial and anticorrosive performance, so that the activated carbon material can be used for an air conditioner filter or a fuel cell filter for a vehicle, and can obviously improve the quality of air in the vehicle and prolong the service life of the fuel cell.
Example 1:
the invention provides a grafted quaternary phosphonium salt activated carbon material for an air-conditioning filter for a vehicle and a preparation method thereof, which are characterized in that the surface of the activated carbon for the air-conditioning filter is modified by oxidation-reduction grafting, and a grafted layer is formed by a grafted quaternary phosphonium salt monomer, and the method comprises the following steps:
(1) adding a quaternary phosphonium salt monomer material (methacryloyloxyheptyl-tributyl phosphonium chloride) into deionized water, and uniformly stirring to ensure that the molar concentration of the quaternary phosphonium salt monomer is 0.5mol/L, which is defined as a solution A;
(2) adding a cerium ammonium nitrate initiator into the solution A to ensure that the molar concentration of the cerium ammonium nitrate initiator is 0.02mol/L, and defining the solution A as a solution B;
(3) adding 10g of activated carbon (rice husk carbon) prepared by using rice husks as raw materials into the solution B, and uniformly stirring to ensure that the mass ratio of the activated carbon to the solution is 1:6, thereby defining the mixture C;
(4) introducing nitrogen into the mixture C, bubbling for 10min, exhausting air, sealing, and carrying out oxidation-reduction grafting reaction in a constant-temperature water bath at the reaction temperature of 60 ℃ for 60 min;
(5) the grafted active carbon is washed by acetone, then extracted for 10 hours and dried.
The activated carbon materials prepared by the steps (1) to (5) are tested, and the results are as follows: the specific surface grade of the rice hull activated carbon material before surface grafting treatment is 1375m 2 G, average pore diameter of 2.28nm and pore volume of 0.568cm 3 (ii) in terms of/g. After the surface grafting treatment, the specific surface grade of the activated carbon material is 1251m 2 G, average pore diameter of 1.88nm and pore volume of 0.545cm 3 (ii) in terms of/g. From the change of the specific surface area, it was judged that the adsorption performance of the activated carbon was hardly lowered. In addition, the rice hull activated carbon material for in-vehicle air purification has good antibacterial and mildewproof effects, and according to GB/T20944.1-2007 evaluation part 1 of antibacterial properties of textiles: the evaluation results of the agar plate diffusion method are good, which shows that the antibacterial effect is achieved; the test is carried out according to the GB/T24346-one 2009 evaluation of the mildew resistance of textiles, the mildew resistance grade is 0, and the good mildew resistance effect is shown.
Example 2:
the invention provides a grafted quaternary phosphonium salt activated carbon material for an air-conditioning filter for a vehicle and a preparation method thereof, which are characterized in that the surface of the activated carbon for the air-conditioning filter is modified by oxidation-reduction grafting, and a grafted layer is formed by a grafted quaternary phosphonium salt monomer, and the method comprises the following steps:
(1) adding a quaternary phosphonium salt monomer material (methacryloyloxyheptyl-tributyl phosphonium chloride) into deionized water, and uniformly stirring to ensure that the molar concentration of the quaternary phosphonium salt monomer is 1.0mol/L, which is defined as a solution A;
(2) adding a cerium ammonium sulfate initiator into the solution A to ensure that the molar concentration of the cerium ammonium sulfate initiator is 0.04mol/L, and defining the solution A as a solution B;
(3) adding 10g of activated carbon (rice husk carbon) prepared by using rice husks as raw materials into the solution B, and uniformly stirring to ensure that the mass ratio of the activated carbon to the solution is 1:10, thereby defining the mixture C;
(4) introducing nitrogen into the mixture C, bubbling for 10min, exhausting air, sealing, and carrying out oxidation-reduction grafting reaction in a constant-temperature water bath at the reaction temperature of 60 ℃ for 90 min;
(5) the grafted active carbon is washed by acetone, then extracted for 10 hours and dried.
The activated carbon materials prepared by the steps (1) to (5) are tested, and the results are as follows: the specific surface grade of the rice hull activated carbon material before surface grafting treatment is 1375m 2 G, average pore diameter of 2.28nm, pore volume of 0.568cm 3 (ii) in terms of/g. After surface grafting treatment, the specific surface grade of the activated carbon material is 1236m 2 G, average pore diameter of 1.85nm and pore volume of 0.516cm 3 (ii) in terms of/g. From the change in the specific surface area, it was judged that the adsorption performance of the activated carbon was hardly lowered. In addition, the rice hull activated carbon material for in-vehicle air purification has good antibacterial and mildewproof effects, and according to GB/T20944.1-2007 evaluation part 1 of antibacterial properties of textiles: the evaluation results of the agar plate diffusion method are good, which shows that the antibacterial effect is achieved; the test is carried out according to the GB/T24346-one 2009 evaluation of the mildew resistance of textiles, the mildew resistance grade is 0, and the good mildew resistance effect is shown.
Example 3:
the invention provides a grafted quaternary phosphonium salt activated carbon material for an air-conditioning filter for a vehicle and a preparation method thereof, which are characterized in that the surface of the activated carbon for the air-conditioning filter is modified by oxidation-reduction grafting, and a grafted layer is formed by a grafted quaternary phosphonium salt monomer, and the method comprises the following steps:
(1) adding a quaternary phosphonium salt monomer material (methacryloyloxyheptyl-tributyl phosphonium chloride) into deionized water, and uniformly stirring to ensure that the molar concentration of the quaternary phosphonium salt monomer is 1.0mol/L, which is defined as a solution A;
(2) adding an ammonium thiosulfate initiator into the solution A to ensure that the molar concentration of the ammonium thiosulfate initiator is 0.05mol/L, and defining the solution A as a solution B;
(3) adding 10g of activated carbon (coconut shell carbon) prepared by taking coconut shells as raw materials into the solution B, and uniformly stirring to ensure that the mass ratio of the activated carbon to the solution is 1:20, thereby defining the mixture C;
(4) introducing nitrogen into the mixture C, bubbling for 10min, exhausting air, sealing, and carrying out oxidation-reduction grafting reaction in a constant-temperature water bath at the reaction temperature of 30 ℃ for 120 min;
(5) the grafted active carbon is washed by acetone, then extracted for 10 hours and dried.
The activated carbon materials prepared by the steps (1) to (5) are tested, and the results are as follows: the specific surface level of the coconut shell activated carbon material before surface grafting treatment is 1280m 2 Per g, average pore diameter of 1.95nm and pore volume of 0.555cm 3 (ii) in terms of/g. After the surface grafting treatment, the specific surface level of the activated carbon material is 1252m 2 G, average pore diameter of 1.78nm and pore volume of 0.540cm 3 (iv) g. From the change in the specific surface area, it was judged that the adsorption performance of the activated carbon was hardly lowered. In addition, the rice hull activated carbon material for in-vehicle air purification has good antibacterial and mildewproof effects, and is prepared according to GB/T20944.1-2007 evaluation part 1 of antibacterial performance of textiles: the evaluation results of the agar plate diffusion method are good, which shows that the antibacterial effect is achieved; the test is carried out according to the GB/T24346-one 2009 evaluation of the mildew-proof performance of the textile, the mildew-proof grade is 0 grade, and the good mildew-proof effect is shown. The EDS element distribution diagram of the prepared activated carbon material is shown in figure 2.
Comparative example 1
A comparative experiment was carried out using another type of quaternary phosphonium salt monomer acryloyloxycetanyl-trimethyl phosphonium chloride, with respect to example 1, comprising the following steps:
(1) adding a quaternary phosphonium salt monomer material (acryloyloxy hexadecyl-trimethyl phosphine chloride) into deionized water, and uniformly stirring to ensure that the molar concentration of the quaternary phosphonium salt monomer is 0.5mol/L, which is defined as a solution A;
(2) adding a cerium ammonium nitrate initiator into the solution A to ensure that the molar concentration of the cerium ammonium nitrate initiator is 0.02mol/L, and defining the solution A as a solution B;
(3) adding 10g of activated carbon (rice husk carbon) prepared by using rice husks as raw materials into the solution B, and uniformly stirring to ensure that the mass ratio of the activated carbon to the solution is 1:6, thereby defining the mixture C;
(4) introducing nitrogen into the mixture C, bubbling for 10min, exhausting air, sealing, and carrying out oxidation-reduction grafting reaction in a constant-temperature water bath at the reaction temperature of 60 ℃ for 60 min;
(5) the grafted active carbon is washed by acetone, then extracted for 10 hours and dried.
The activated carbon material prepared by the steps (1) to (5) is tested, and the results are as follows: the rice hull activated carbon material of the comparative example had a specific surface grade of 1375m before the surface graft treatment 2 G, average pore diameter of 2.28nm and pore volume of 0.568cm 3 (ii) in terms of/g. After surface grafting treatment, the specific surface grade of the activated carbon material is 1235m 2 G, average pore diameter of 1.82nm and pore volume of 0.509cm 3 (ii) in terms of/g. The change of the specific surface area can be used for judging that the adsorption performance of the activated carbon is reduced to a certain degree. The grafted activated carbon material obtained by the process has good antibacterial and mildewproof effects, and is prepared according to GB/T20944.1-2007 evaluation part 1 of antibacterial properties of textiles: when the evaluation results of escherichia coli and staphylococcus aureus are better when the standard of agar plate diffusion method is tested, the antibacterial effect is shown, but the antibacterial effect is reduced compared with that of the example 1; the test is carried out according to the GB/T24346-one 2009 evaluation of the mildew-proof performance of the textile, the mildew-proof grade is grade 1, which shows that the mildew-proof effect is better, but the effect is reduced compared with the embodiment 1. In addition, compared with the grafted activated carbon material obtained in example 1, the grafted activated carbon material obtained by the process has the advantage that the toxicity of the grafted activated carbon material is greatly improved, and the grafted activated carbon material is not beneficial to application.
Comparative example 2
A comparative test was carried out with respect to example 1, using other temperature conditions, comprising the following steps:
(1) adding a quaternary phosphonium salt monomer material (methacryloyloxyheptyl-tributyl phosphonium chloride) into deionized water, and uniformly stirring to ensure that the molar concentration of the quaternary phosphonium salt monomer is 0.5mol/L, which is defined as a solution A;
(2) adding a cerium ammonium nitrate initiator into the solution A to ensure that the molar concentration of the cerium ammonium nitrate initiator is 0.02mol/L, and defining the solution A as a solution B;
(3) adding 10g of activated carbon (rice husk carbon) prepared by using rice husks as raw materials into the solution B, and uniformly stirring to ensure that the mass ratio of the activated carbon to the solution is 1:6, thereby defining the mixture C;
(4) introducing nitrogen into the mixture C, bubbling for 10min, exhausting air, sealing, and carrying out oxidation-reduction grafting reaction in a constant-temperature water bath at the reaction temperature of 90 ℃ for 60 min;
(5) the grafted active carbon is washed by acetone, then extracted for 10 hours and dried.
The activated carbon material prepared by the steps (1) to (5) is tested, and the results are as follows: the rice hull activated carbon material of the comparative example had a specific surface level of 1375m before the surface graft treatment 2 G, average pore diameter of 2.28nm, pore volume of 0.568cm 3 (iv) g. After the surface grafting treatment, the specific surface level of the activated carbon material is 1206m 2 G, average pore diameter of 1.77nm and pore volume of 0.499cm 3 (ii) in terms of/g. The change of the specific surface area can be used for judging that the adsorption performance of the activated carbon is reduced to a certain degree. The grafted activated carbon material obtained by the process has good antibacterial and mildewproof effects, and is prepared according to GB/T20944.1-2007 evaluation part 1 of antibacterial properties of textiles: the evaluation results of Escherichia coli and Staphylococcus aureus are good when tested according to the standard of agar plate diffusion method, which shows that the antibacterial effect is achieved, but the effect is reduced compared with that of example 1; the test is carried out according to the GB/T24346-one 2009 evaluation of the mildew-proof performance of the textile, the mildew-proof grade is grade 1, which shows that the mildew-proof effect is better, but the effect is reduced compared with the embodiment 1.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (7)

1. A method of preparing an activated carbon material, comprising the steps of:
(1) adding a quaternary phosphonium salt monomer into deionized water, and uniformly stirring to ensure that the molar concentration of the quaternary phosphonium salt monomer is 0.5-1.0 mol/L so as to obtain a solution A; the quaternary phosphonium salt monomer is methacryloyloxyheptyl-tributylphosphine chloride;
(2) adding an initiator into the solution A to enable the molar concentration of the initiator to be 0.02-0.05 mol/L so as to obtain a solution B;
(3) adding granular activated carbon into the solution B, and uniformly stirring to ensure that the mass ratio of the granular activated carbon to the solution B is 1: 6-1: 20 so as to obtain a mixture C;
(4) filling nitrogen into the mixture C, bubbling for 10min, sealing, and performing redox grafting reaction in a constant-temperature water bath; and
(5) and washing the product after the oxidation-reduction grafting reaction with acetone, then extracting for 24 hours, and drying to obtain the activated carbon material.
2. The method of claim 1, wherein the initiator is cerium ammonium nitrate, cerium ammonium sulfate, or ammonium thiosulfate.
3. The method of claim 1 or 2, wherein the granular activated carbon is a natural plant-made charcoal material.
4. The method as claimed in claim 3, wherein the natural plant charcoal material is at least one selected from bamboo charcoal, coconut shell charcoal, rice hull charcoal and wheat straw charcoal.
5. The method of claim 4, wherein the redox grafting reaction is carried out at a temperature of 30 ℃ to 60 ℃ for a time of 60min to 120 min.
6. An activated carbon material produced by the method of any one of claims 1-5, comprising: the particle activated carbon comprises a particle activated carbon matrix and a quaternary phosphonium salt monomer layer, wherein the quaternary phosphonium salt monomer layer is formed on the surface of the particle activated carbon matrix through oxidation-reduction grafting reaction.
7. Use of the activated carbon material of claim 6 in a filter, which is an air conditioner filter for a vehicle or a filter for a fuel cell.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103289015A (en) * 2012-02-26 2013-09-11 河南工业大学 Method for preparing quaternary phosphonium salt type cationic starch
CN109251432A (en) * 2018-08-01 2019-01-22 安徽省绩溪县华宇防火滤料有限公司 A kind of quaternary phosphonium insulation board material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103289015A (en) * 2012-02-26 2013-09-11 河南工业大学 Method for preparing quaternary phosphonium salt type cationic starch
CN109251432A (en) * 2018-08-01 2019-01-22 安徽省绩溪县华宇防火滤料有限公司 A kind of quaternary phosphonium insulation board material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Surface Functionalization of Activated Carbon with Phosphonium Ionic Liquid for CO2 Adsorption";Xiaodong He等;《coatings》;20190918(第9期);第590页 *

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