CN114192187A - Coal series kaolinite-based catalyst, preparation method thereof and application thereof in toluene catalytic degradation - Google Patents

Coal series kaolinite-based catalyst, preparation method thereof and application thereof in toluene catalytic degradation Download PDF

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CN114192187A
CN114192187A CN202111477181.3A CN202111477181A CN114192187A CN 114192187 A CN114192187 A CN 114192187A CN 202111477181 A CN202111477181 A CN 202111477181A CN 114192187 A CN114192187 A CN 114192187A
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coal
kaolinite
intercalation reaction
intercalation
based catalyst
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张印民
张永锋
郝志飞
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Inner Mongolia University of Technology
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Inner Mongolia University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0222—Sulfur-containing compounds comprising sulfonyl groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium

Abstract

The invention provides a coal series kaolinite-based catalyst, a preparation method and application thereof, belonging to the technical field of catalytic materials. The method ensures that acid can activate the short-OH functional group of the coal-series kaolinite lamellar structure in the reaction process by adding acid in the first intercalation reaction, destroys the double charge layers on the surface of the kaolinite structure, promotes the entry of intercalation molecules and improves the intercalation speed, and compared with the prior art, the intercalation time is reduced by 80 percent; the surface structure modification is carried out on the coal series kaolinite by utilizing an acidification intercalation process, so that the acidification intercalation coal series kaolinite can cooperate with manganese oxide to improve the catalytic degradation efficiency of toluene; the coal series kaolin is taken as a carrier material to realizeThe high performance of the catalytic system and the high-value utilization of the coal-series associated minerals are realized. The results of the examples show that when the coal-series kaolinite-based catalyst provided by the invention is used for catalyzing and degrading toluene, T is50≤152℃，T90≤243℃。

Description

Coal series kaolinite-based catalyst, preparation method thereof and application thereof in toluene catalytic degradation
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a coal series kaolinite-based catalyst, a preparation method thereof and application thereof in toluene catalytic degradation.
Background
Toluene is a colorless clear liquid, is used in large quantities as a solvent and a high octane gasoline additive, is also an important raw material for organic chemical industry, and is often used for dealkylation to produce benzene or disproportionation to produce xylene. A series of intermediates derived from toluene are widely used in the production of fine chemicals such as dyes, medicines, pesticides, explosives, auxiliaries and perfumes, and also in the synthetic material industry. Therefore, toluene is an important chemical raw material in production and life.
However, toluene has a benzene-like odor, is harmful to human health, is irritant to skin and mucous membranes, and has an anesthetic effect on the central nervous system. The inhalation of toluene gas with higher concentration in a short time can cause obvious stimulation symptoms of eyes and upper respiratory tract, congestion of conjunctiva and pharynx, dizziness, headache, nausea, vomit, chest distress, myasthenia of limbs, teetering gait and vague consciousness, serious patients can have restlessness, convulsion and coma, neurasthenia syndrome and liver swelling can occur after long-term contact, and simultaneously, the skin is dry, chapped and dermatitis can be caused. And toluene is a serious hazard to the environment and can cause pollution to the air, water environment and water source.
In the prior art, the catalyst adopted in the process of catalyzing and degrading toluene is generally a supported noble metal catalyst and MnO2/Co3O4NiO supported by carbon nanotube2And alumina-supported (CuCo/H) and other catalytic systems, although the catalysts have good catalytic degradation effect on toluene, the catalytic temperature is high, so that the temperature of more than 200 ℃ is generally required for degrading more than 50% of toluene, and the temperature of more than 90% of toluene is even required to reach more than 300 ℃. Meanwhile, the noble metal catalyst has the defects of resource scarcity, high cost, easy poisoning and the like. Although the catalytic performance of the catalyst can be improved through the traditional coal-series kaolin intercalation reaction, the intercalation reaction time is too long, the efficiency is extremely low, the catalyst is not suitable for industrial production, and the application of the coal-series kaolin-based catalyst is severely restricted.
Therefore, it is an urgent technical problem to be solved in the art to provide a coal-series kaolinite-based catalyst which is simple to prepare, short in time and low in catalytic degradation temperature.
Disclosure of Invention
The invention aims to provide a coal-series kaolinite-based catalyst, a preparation method thereof and application thereof in toluene catalytic degradation.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a coal series kaolinite-based catalyst, which comprises the following steps:
(1) mixing coal series kaolinite, dimethyl sulfoxide solution and acid, and then carrying out a first intercalation reaction to obtain a Kaol-DMSO compound;
(2) mixing the Kaol-DMSO compound obtained in the step (1) with a cationic reagent and liquid alcohol, and then carrying out a second intercalation reaction to obtain a Kaol-Me compound;
(3) mixing the Kaol-Me compound obtained in the step (2) with polyhydric alcohol and a manganese source solution, and then carrying out a third intercalation reaction to obtain a coal series kaolinite-based catalyst; the manganese source solution comprises MnSO4·H2O、(NH4)2S2O3And water.
Preferably, the acid in step (1) is an organic acid or an inorganic acid.
Preferably, the temperature of the first intercalation reaction in the step (1) is 50-100 ℃, and the time of the first intercalation reaction is 1-1.5 h.
Preferably, the cationic agent in step (2) is aluminum chloride, ferric chloride, magnesium chloride or calcium chloride.
Preferably, the liquid alcohol in step (2) is methanol or propanol.
Preferably, the temperature of the second intercalation reaction in the step (2) is 20-30 ℃, and the time of the second intercalation reaction is 6-18 h.
Preferably, MnSO is contained in the manganese source solution in the step (3)4·H2Of OAmount of substance, (NH)4)2S2O3The volume ratio of the amount of the substance(s) to water is (0.1-0.3) mol: (0.2-0.4) mol: 1L of the compound.
Preferably, the temperature of the third intercalation reaction in the step (3) is 50-85 ℃, and the time of the third intercalation reaction is 24-48 h.
The invention provides a coal-series kaolinite-based catalyst prepared by the preparation method in the technical scheme, which comprises a carrier and an active component loaded on the surface of the carrier; the carrier is intercalated coal series kaolinite, and the active component is manganese oxide.
The invention provides an application of the coal-series kaolinite-based catalyst in the technical scheme in the catalytic degradation of toluene.
The invention provides a preparation method of a coal series kaolinite-based catalyst, which comprises the following steps: (1) mixing coal series kaolinite, dimethyl sulfoxide solution and acid, and then carrying out a first intercalation reaction to obtain a Kaol-DMSO compound; (2) mixing the Kaol-DMSO compound obtained in the step (1) with a cationic reagent and liquid alcohol, and then carrying out a second intercalation reaction to obtain a Kaol-Me compound; (3) mixing the Kaol-Me compound obtained in the step (2) with polyhydric alcohol and a manganese source solution, and then carrying out a third intercalation reaction to obtain a coal series kaolinite-based catalyst; the manganese source solution comprises MnSO4·H2O、 (NH4)2S2O3And water. The invention can ensure that acid can activate the short-OH functional group of the coal-series kaolinite lamellar structure in the reaction process by adding acid in the first intercalation reaction, destroy the double charge layers on the surface of the kaolinite structure, promote the entry of intercalation molecules and improve the intercalation speed, and compared with the prior art, the intercalation time is reduced by 80 percent; the surface structure modification is carried out on the coal series kaolinite by utilizing an acidification intercalation process, so that the acidification intercalation coal series kaolinite can cooperate with manganese oxide to improve the catalytic degradation efficiency of toluene; the coal-series kaolin is used as a carrier material, so that the high performance of a catalytic system and the high-valued utilization of coal-series associated minerals are realized. The results of the examples show that when the coal-series kaolinite-based catalyst provided by the invention is used for catalyzing and degrading toluene, T is50≤152℃，T90≤243℃。
Drawings
FIG. 1 is an SEM image of a coal-series kaolinite-based catalyst prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a coal-series kaolinite-based catalyst prepared in example 2 of the present invention;
FIG. 3 is an SEM image of a coal-series kaolinite-based catalyst prepared in example 3 according to the invention;
FIG. 4 is an SEM image of a coalite-based catalyst prepared in example 4 of the present invention;
FIG. 5 is a TEM image of a coal-series kaolinite-based catalyst prepared in example 1 of the present invention;
FIG. 6 is a TEM image of a coal-series kaolinite-based catalyst prepared in example 2 of the present invention;
FIG. 7 is a TEM image of a coal-series kaolinite-based catalyst prepared in example 3 of the present invention;
FIG. 8 is a TEM image of a coalite-based catalyst prepared in example 4 of the present invention;
FIG. 9 is a partial enlarged TEM image of a coal-series kaolinite-based catalyst prepared in example 3 of the present invention;
FIG. 10 is a partial enlarged TEM image of a coalite-based catalyst prepared in example 4 of the present invention;
FIG. 11 is a graph showing the variation of the degradation rate of toluene with the catalytic temperature in examples 1 to 6.
Detailed Description
The invention provides a preparation method of a coal series kaolinite-based catalyst, which comprises the following steps:
(1) mixing coal series kaolinite, dimethyl sulfoxide solution and acid, and then carrying out a first intercalation reaction to obtain a Kaol-DMSO compound;
(2) mixing the Kaol-DMSO compound obtained in the step (1) with a cationic reagent and liquid alcohol, and then carrying out a second intercalation reaction to obtain a Kaol-Me compound;
(3) mixing the Kaol-Me compound obtained in the step (2) with polyhydric alcohol and a manganese source solution, and then carrying out a third intercalation reaction to obtain a coal series kaolinite-based catalyst; the manganeseThe source solution comprises MnSO4·H2O、(NH4)2S2O3And water.
The invention mixes coal series kaolinite, dimethyl sulfoxide solution and acid and then carries out the first intercalation reaction to obtain the Kaol-DMSO compound.
In the present invention, the coal-series kaolinite is preferably subjected to a crushing treatment before use. The specific operation of the crushing is not particularly limited, and the coal series kaolinite can meet the requirements.
In the present invention, the mixing of the kaolinite coal, the dimethyl sulfoxide solution and the acid is preferably performed by mixing the kaolinite coal and the dimethyl sulfoxide solution to form a suspension, and then adding the acid to the suspension. In the present invention, the mixing of the coal-series kaolinite, the dimethyl sulfoxide solution and the acid is preferably performed under stirring conditions. The stirring mode is not particularly limited, and all the components can be uniformly mixed.
In the invention, the content of water in the dimethyl sulfoxide solution is preferably 10-20 wt.%. The invention improves the catalytic effect of the coal-series kaolinite by inserting dimethyl sulfoxide into the coal-series kaolinite layer.
In the invention, the content of the coal-series kaolinite in the suspension is preferably 15-30 wt.%, and more preferably 20 wt.%. The invention controls the solid content of the coal series kaolinite within the range, and can ensure that the coal series kaolinite is uniformly dispersed.
In the present invention, the acid is an organic acid or an inorganic acid. In the present invention, the organic acid is preferably formic acid or acetic acid; the volume ratio of the organic acid to the suspension is preferably 1: (10-30), more preferably 1: 10. in the present invention, the inorganic acid is preferably sulfuric acid, hydrochloric acid, nitric acid or heteropoly acid. In the present invention, when the inorganic acid is preferably sulfuric acid, hydrochloric acid, or nitric acid, the mass concentration of the sulfuric acid, hydrochloric acid, or nitric acid is independently preferably 10%, and the volume ratio of the sulfuric acid, hydrochloric acid, or nitric acid to the suspension is independently preferably 1: (10-30), more preferably 1: (12-25). In the present invention, when the inorganic acid is preferably a heteropoly acid, the heteropoly acid is preferably phosphotungstic acid, silicotungstic acid, silicomolybdic acid or phosphomolybdic acid; the mass of the heteropoly acid is preferably 0.5-3% of that of the coal-series kaolinite. The invention adopts the acid of the kind mentioned above, and can further improve the intercalation efficiency.
In the invention, the temperature of the first intercalation reaction is preferably 50-100 ℃, and more preferably 60-90 ℃; the time of the first intercalation reaction is preferably 1-1.5 h. The invention limits the parameters of the first intercalation reaction in the above range, and can ensure the full reaction.
After the first intercalation reaction is finished, the invention preferably carries out suction filtration, washing and drying on the product of the first intercalation reaction in sequence to obtain the Kaol-DMSO compound. The present invention is not particularly limited to the specific operations of suction filtration, washing and drying, and may be carried out by a process known to those skilled in the art.
After the Kaol-DMSO compound is obtained, the Kaol-DMSO compound is mixed with a cationic reagent and liquid alcohol to carry out a second intercalation reaction, and the Kaol-Me compound is obtained.
In the present invention, the mixing of the Kaol-DMSO complex with the cationic agent and the liquid alcohol is preferably performed by mixing the Kaol-DMSO complex with the liquid alcohol to form a dispersion, and then adding the cationic agent. In the present invention, the mixing of the Kaol-DMSO complex with the cationic agent and the liquid alcohol is preferably performed under stirring. The stirring mode is not particularly limited, and all the components can be uniformly mixed.
In the present invention, the liquid alcohol is preferably methanol or propanol. The invention adopts methanol or propanol to prepare dispersion liquid, and can insert liquid alcohol into the Kaol-DMSO compound to obtain the Kaol-Me compound.
In the invention, the content of the Kaol-DMSO complex in the dispersion is preferably 5 to 25 wt.%, and more preferably 10 to 20 wt.%. The invention controls the content of the Kaol-DMSO compound within the range, which is beneficial to the reaction.
In the present invention, the cationic agent is preferably aluminum chloride, ferric chloride, magnesium chloride or calcium chloride; the mass of the cationic reagent is preferably 0.5-2.5% of that of the Kaol-DMSO composite. The invention can improve the intercalation efficiency by adding the cationic reagent.
In the invention, the temperature of the second intercalation reaction is preferably 20-30 ℃; the time of the second intercalation reaction is preferably 6-18 h. The invention controls the parameters of the second intercalation reaction in the above range, so that the reaction can be fully carried out.
After the second intercalation reaction is finished, the invention preferably carries out suction filtration, washing and drying on the product of the second intercalation reaction in sequence to obtain the Kaol-Me compound. The present invention is not particularly limited to the specific operations of suction filtration, washing and drying, and may be carried out by a process known to those skilled in the art.
After the Kaol-Me compound is obtained, the Kaol-Me compound, polyhydric alcohol and manganese source solution are mixed and then subjected to a third intercalation reaction to obtain the coal series kaolinite-based catalyst.
In the present invention, the manganese source solution includes MnSO4·H2O、(NH4)2S2O3And water. In the present invention, MnSO is contained in the manganese source solution4·H2Amount of substance of O, (NH)4)2S2O3The volume ratio of the amount of the substance(s) and water is preferably (0.1 to 0.3) mol: (0.2-0.4) mol: 1L, more preferably 0.2 mol: 0.3 mol: 1L of the compound. By adopting the solution, manganese oxide can be generated in the reaction process and loaded on the surface of the intercalated coal series kaolinite.
In the present invention, the ratio of the mass of the Kaol-Me complex to the volume of the solution is preferably 1 g: (10-50) mL, more preferably 1 g: (20-40) mL. The invention limits the dosage of the Kaol-Me compound and the solution in the range, and can ensure that the surface of the intercalated coal series kaolinite is loaded with sufficient manganese oxide.
In the invention, the polyhydric alcohol is preferably ethylene glycol, propylene glycol, glycerol, polyvinyl alcohol or triethanolamine, and the mass ratio of the volume of the polyhydric alcohol to the Kaol-Me compound is preferably (0.4-1) mL: 1g of the total weight of the composition. The present invention can increase the efficiency of the loading by limiting the mass of the polyol to the above range.
In the invention, the temperature of the third intercalation reaction is preferably 50-85 ℃, and more preferably 60-80 ℃; the time of the third intercalation reaction is preferably 24-48 h, and more preferably 30-36 h. The invention controls the parameters of the third intercalation reaction in the above range, so that the reaction can be fully carried out.
After the third intercalation reaction is finished, the invention preferably carries out suction filtration, washing, drying and crushing treatment on the product of the third intercalation reaction in sequence to obtain the coal series kaolinite-based catalyst. The specific operations of the suction filtration, washing, drying and crushing treatment are not particularly limited, and the particle size of the coal series kaolinite-based catalyst can meet the requirement by adopting the process well known by the technical personnel in the field.
The preparation method is simple, the time of the first intercalation reaction is shortened by introducing the acidification treatment process, the cost is saved, and the preparation method is suitable for industrial large-scale production.
The invention provides a coal-series kaolinite-based catalyst prepared by the preparation method in the technical scheme, which comprises a carrier and an active component, wherein the carrier is intercalated coal-series kaolinite, and the active component is manganese oxide. In the present invention, the carrier is preferably coal-series kaolinite intercalated with dimethyl sulfoxide and alcohol.
In the invention, the mass percent of the carrier in the catalyst is preferably 65-90%. In the present invention, the carrier component and the active component are preferably linked by a chemical bond, preferably an M-O bond, M being derived from the active component and O being derived from the carrier; the M is preferably MnX+Said X is preferably 2, 3 or 4.
In the coal-series kaolinite-based catalyst provided by the invention, dimethyl sulfoxide and alcohol are intercalated in the coal-series kaolinite, so that the surface structure of the coal-series kaolinite can be modified, meanwhile, a double charge layer on the surface of the coal-series kaolinite is damaged after acidification treatment, and manganese oxide is uniformly loaded on the surface of the coal-series kaolinite, so that the coal-series kaolinite-based catalyst can play a synergistic effect with the acidified coal-series kaolinite, and the low-temperature catalytic degradation efficiency of the catalyst on toluene is improved.
In the present invention, the shape of the coal-series kaolinite-based catalyst is preferably a particle, a powder, or a honeycomb; the specific surface area of the coal-series kaolinite-based catalyst is preferably 10-60 m2(ii)/g; the average particle size of the coal-series kaolinite-based catalyst is preferably 1-10 μm.
The invention provides an application of the coal-series kaolinite-based catalyst in the technical scheme in the catalytic degradation of toluene.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a coal series kaolinite-based catalyst comprises the following steps:
(1) crushing coal series kaolinite, mixing the crushed coal series kaolinite with dimethyl sulfoxide solution to form suspension, adding acid into the suspension, mixing, performing a first intercalation reaction, performing suction filtration after the reaction is finished, washing for 3 times by using absolute ethyl alcohol, and finally drying at the temperature of 60 ℃ to obtain a Kaol-DMSO compound;
the amount of water in the dimethylsulfoxide solution was 10 wt.%; the content of coal-series kaolinite in the suspension is 20 wt.%; the acid is sulfuric acid with the mass concentration of 10%, and the volume ratio of the sulfuric acid to the suspension is 1: 25; the temperature of the first intercalation reaction is 75 ℃, and the time of the first intercalation reaction is 1 h;
(2) mixing the Kaol-DMSO compound obtained in the step (1) with methanol to form a dispersion solution, then adding a cationic reagent, mixing, performing a second intercalation reaction, performing suction filtration after the reaction is finished, washing for 3 times by using a saturated methanol solution, and finally drying at the temperature of 60 ℃ to obtain a Kaol-Me compound;
the content of Kaol-DMSO complex in the dispersion was 5 wt.%; the cationic reagent is aluminum chloride, and the mass of the cationic reagent is 1% of that of the Kaol-DMSO composite; the temperature of the second intercalation reaction is 25 ℃; the time of the second intercalation reaction is 12 hours;
(3) mixing the Kaol-Me compound obtained in the step (2) with polyhydric alcohol and a solution, then carrying out a third intercalation reaction, after the reaction is finished, carrying out suction filtration, washing with distilled water and absolute ethyl alcohol to be neutral, and finally drying at the temperature of 70 ℃ for 12 hours to obtain the coal-series kaolinite-based catalyst;
the solution comprises MnSO4·H2O、(NH4)2S2O3And water, the MnSO4·H2The volume ratio of the amount of substance of O to water was 0.2 mol: 1L; said (NH)4)2S2O3The ratio of the amount of substance(s) and the volume of water is 0.3 mol: 1L; the mass of the Kaol-Me compound to volume of the solution is 1 g: 20 mL; the polyhydric alcohol is ethylene glycol, and the mass ratio of the volume of the polyhydric alcohol to the Kaol-Me compound is 2 mL: 5g of the total weight of the mixture; the temperature of the third intercalation reaction is 70 ℃, and the time of the third intercalation reaction is 24 hours.
Example 2
A preparation method of a coal series kaolinite-based catalyst comprises the following steps:
(1) crushing coal series kaolinite, mixing the crushed coal series kaolinite with dimethyl sulfoxide solution to form suspension, adding acid into the suspension, mixing, performing a first intercalation reaction, performing suction filtration after the reaction is finished, washing for 3 times by using absolute ethyl alcohol, and finally drying at the temperature of 60 ℃ to obtain a Kaol-DMSO compound;
the amount of water in the dimethylsulfoxide solution was 10 wt.%; the content of coal-series kaolinite in the suspension is 20 wt.%; the acid is acetic acid, and the volume ratio of the acetic acid to the suspension is 1: 10; the temperature of the first intercalation reaction is 75 ℃, and the time of the first intercalation reaction is 1 h;
(2) mixing the Kaol-DMSO compound obtained in the step (1) with methanol to form a dispersion solution, then adding a cationic reagent, mixing, performing a second intercalation reaction, performing suction filtration after the reaction is finished, washing for 3 times by using a saturated methanol solution, and finally drying at the temperature of 60 ℃ to obtain a Kaol-Me compound;
the content of Kaol-DMSO complex in the dispersion was 5 wt.%; the cationic reagent is ferric chloride, and the mass of the cationic reagent is 1% of that of the Kaol-DMSO composite; the temperature of the second intercalation reaction is 30 ℃; the time of the second intercalation reaction is 10 hours;
(3) mixing the Kaol-Me compound obtained in the step (2) with polyhydric alcohol and a solution, then carrying out a third intercalation reaction, after the reaction is finished, carrying out suction filtration, washing with distilled water and absolute ethyl alcohol to be neutral, and finally drying at the temperature of 70 ℃ for 12 hours to obtain the coal-series kaolinite-based catalyst;
the solution comprises MnSO4·H2O、(NH4)2S2O3And water, the MnSO4·H2The volume ratio of the amount of substance of O to water was 0.2 mol: 1L; said (NH)4)2S2O3The ratio of the amount of substance(s) and the volume of water is 0.3 mol: 1L; the mass of the Kaol-Me compound to volume of the solution is 1 g: 20 mL; the polyol is polyvinyl alcohol, and the mass ratio of the volume of the polyol to the Kaol-Me compound is 1 mL: 1g of a compound; the temperature of the third intercalation reaction is 70 ℃, and the time of the third intercalation reaction is 24 hours.
Example 3
A preparation method of a coal series kaolinite-based catalyst comprises the following steps:
(1) crushing coal series kaolinite, mixing the crushed coal series kaolinite with dimethyl sulfoxide solution to form suspension, adding acid into the suspension, mixing, performing a first intercalation reaction, performing suction filtration after the reaction is finished, washing for 3 times by using absolute ethyl alcohol, and finally drying at the temperature of 60 ℃ to obtain a Kaol-DMSO compound;
the amount of water in the dimethylsulfoxide solution was 10 wt.%; the content of coal-series kaolinite in the suspension is 20 wt.%; the acid is silicotungstic acid, and the mass of the silicotungstic acid is 0.5 percent of that of the coal-series kaolinite; the temperature of the first intercalation reaction is 90 ℃, and the time of the first intercalation reaction is 1 h;
(2) mixing the Kaol-DMSO compound obtained in the step (1) with methanol to form a dispersion solution, then adding a cationic reagent, mixing, performing a second intercalation reaction, performing suction filtration after the reaction is finished, washing for 3 times by using a saturated methanol solution, and finally drying at the temperature of 60 ℃ to obtain a Kaol-Me compound;
the content of Kaol-DMSO complex in the dispersion was 5 wt.%; the cationic reagent is aluminum chloride, and the mass of the cationic reagent is 1% of that of the Kaol-DMSO composite; the temperature of the second intercalation reaction is 30 ℃; the time of the second intercalation reaction is 18 h;
(3) mixing the Kaol-Me compound obtained in the step (2) with polyhydric alcohol and a solution, then carrying out a third intercalation reaction, after the reaction is finished, carrying out suction filtration, washing with distilled water and absolute ethyl alcohol to be neutral, and finally drying at the temperature of 70 ℃ for 12 hours to obtain the coal-series kaolinite-based catalyst;
the solution comprises MnSO4·H2O、(NH4)2S2O3And water, the MnSO4·H2The volume ratio of the amount of substance of O to water was 0.2 mol: 1L; said (NH)4)2S2O3The ratio of the amount of substance(s) and the volume of water is 0.3 mol: 1L; the mass of the Kaol-Me compound to volume of the solution is 1 g: 20 mL; the polyol is polyvinyl alcohol, and the mass ratio of the volume of the polyol to the Kaol-Me compound is 1 mL: 1g of a compound; the temperature of the third intercalation reaction is 70 ℃, and the time of the third intercalation reaction is 24 hours.
Example 4
A preparation method of a coal series kaolinite-based catalyst comprises the following steps:
(1) crushing coal series kaolinite, mixing the crushed coal series kaolinite with dimethyl sulfoxide solution to form suspension, adding acid into the suspension, mixing, performing a first intercalation reaction, performing suction filtration after the reaction is finished, washing for 3 times by using absolute ethyl alcohol, and finally drying at the temperature of 60 ℃ to obtain a Kaol-DMSO compound;
the amount of water in the dimethylsulfoxide solution was 10 wt.%; the content of coal-series kaolinite in the suspension is 20 wt.%; the acid is nitric acid with the mass concentration of 10%, and the volume ratio of the nitric acid to the suspension is 1: 12.5; the temperature of the first intercalation reaction is 100 ℃, and the time of the first intercalation reaction is 1 h;
(2) mixing the Kaol-DMSO compound obtained in the step (1) with propanol to form a dispersion, then adding a cationic reagent, mixing, performing a second intercalation reaction, performing suction filtration after the reaction is finished, washing for 3 times by using a saturated methanol solution, and finally drying at the temperature of 60 ℃ to obtain a Kaol-Me compound;
the content of Kaol-DMSO complex in the dispersion was 5 wt.%; the cationic reagent is calcium chloride, and the mass of the cationic reagent is 2% of that of the Kaol-DMSO composite; the temperature of the second intercalation reaction is 30 ℃; the time of the second intercalation reaction is 18 h;
(3) mixing the Kaol-Me compound obtained in the step (2) with polyhydric alcohol and a solution, then carrying out a third intercalation reaction, after the reaction is finished, carrying out suction filtration, washing with distilled water and absolute ethyl alcohol to be neutral, and finally drying at the temperature of 70 ℃ for 12 hours to obtain the coal-series kaolinite-based catalyst;
the solution comprises MnSO4·H2O、(NH4)2S2O3And water, the MnSO4·H2The volume ratio of the amount of substance of O to water was 0.2 mol: 1L; said (NH)4)2S2O3The ratio of the amount of substance(s) and the volume of water is 0.3 mol: 1L; the mass of the Kaol-Me compound to volume of the solution is 1 g: 20 mL; the polyhydric alcohol is ethylene glycol, and the mass ratio of the volume of the polyhydric alcohol to the Kaol-Me compound is 1 mL: 1g of a compound; the temperature of the third intercalation reaction is 70 ℃, and the time of the third intercalation reaction is 24 hours.
Comparative example 1
The coal-based kaolin used in example 1.
Comparative example 2
Manganese dioxide
Comparative example 3
MnO2/Co3O4
Comparative example 4
NiO supported by carbon nanotube2
Comparative example 5
Halloysite load (CuCo/H)
Application examples 1 to 6
The coal-series kaolinite-based catalyst prepared in example 1 and the catalysts provided in comparative examples 1-5 are used for catalyzing and degrading toluene, and the method specifically comprises the following steps:
100mg of the catalyst was placed in a quartz tube (inner diameter of 7mm, length of 650mm), the quartz tube was heated, the temperature inside the quartz tube was measured by a temperature control instrument until the temperature inside the quartz tube was stabilized, toluene was introduced from one side of the quartz tube and flowed out from the other side, the toluene concentration was adjusted by controlling the gas flow rate by a mass flow controller, and the toluene concentration before and after the oxidation reaction was detected by a gas chromatograph (GC, GC-2014C) equipped with a Flame Ionization Detector (FID). Total gas flow (20 vol% O)2，N2As a balance) was 100 mL. min-1Space velocity of 12000h-1；
The formula for calculating the degradation rate of toluene is shown as formula I:
toluene degradation rate (%) (toluene)Into-tolueneGo out) TolueneIntoX 100% of formula I
In the formula I, tolueneIntoThe concentration of toluene when it entered the quartz tube, tolueneGo outThe concentration of toluene as it flowed out of the quartz tube.
The results of the catalytic degradation temperature of the catalysts in application examples 1-6 for toluene are shown in table 1:
table 1 catalytic degradation temperature of catalyst for toluene in application examples 1-6
Figure BDA0003393890390000111
In Table 1, T50 is the catalytic temperature for 50% degradation of toluene and T90 is the catalytic temperature for 90% degradation of toluene. As can be seen from table 1, compared with the existing coal-series kaolinite-based catalyst, the coal-series kaolinite-based catalyst prepared by the invention requires the lowest catalytic temperature for degrading 50% of toluene, the highest catalytic temperature is only 152 ℃, which is far lower than 220 ℃ in the prior art, and the catalytic temperature for degrading 90% of toluene is also equivalent to the existing lowest temperature. Therefore, the coal-series kaolinite-based catalyst prepared by the invention has lower catalytic temperature.
SEM images of the coal-series kaolinite-based catalysts prepared in examples 1 to 4 are shown in FIGS. 1 to 4. As can be seen from FIGS. 1 to 4, the coal-series kaolinite-based catalyst prepared by the method has a large number of pores, and organic substances are intercalated in the pores of the load.
TEM images of the coal-series kaolinite-based catalysts prepared in examples 1 to 4 are shown in FIGS. 5 to 8. As can be seen from FIGS. 1 to 4, in the coal-series kaolinite-based catalyst prepared by the method, the active component is closely connected with the carrier component.
A partial enlarged view of the TEM image of the coal-series kaolinite-based catalyst prepared in example 3 is shown in fig. 9. A partial enlarged view of the TEM image of the coal-series kaolinite-based catalyst prepared in example 4 is shown in fig. 10. As can be seen from fig. 9 and 10, in the coal-series kaolinite-based catalyst, the active component and the support component are connected by a chemical bond.
The change trend of the degradation rate of toluene with the catalytic temperature in application examples 1-6 is shown in fig. 11, wherein the abscissa in fig. 11 is the catalytic temperature and the ordinate is the degradation rate of toluene. As can be seen from fig. 11, the coal-series kaolinite-based catalyst prepared by the invention has better catalytic efficiency for toluene at lower catalytic temperature.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a coal-series kaolinite-based catalyst comprises the following steps:
(1) mixing coal series kaolinite, dimethyl sulfoxide solution and acid, and then carrying out a first intercalation reaction to obtain a Kaol-DMSO compound;
(2) mixing the Kaol-DMSO compound obtained in the step (1) with a cationic reagent and liquid alcohol, and then carrying out a second intercalation reaction to obtain a Kaol-Me compound;
(3) mixing the Kaol-Me compound obtained in the step (2) with polyhydric alcohol and a manganese source solution, and then carrying out a third intercalation reaction to obtain a coal series kaolinite-based catalyst; the manganese source solution comprises MnSO4·H2O、(NH4)2S2O3And water.
2. The method according to claim 1, wherein the acid in the step (1) is an organic acid or an inorganic acid.
3. The preparation method according to claim 1, wherein the temperature of the first intercalation reaction in the step (1) is 50-100 ℃, and the time of the first intercalation reaction is 1-1.5 h.
4. The method according to claim 1, wherein the cationic agent in the step (2) is aluminum chloride, ferric chloride, magnesium chloride or calcium chloride.
5. The method according to claim 1, wherein the liquid alcohol in step (2) is methanol or propanol.
6. The preparation method according to claim 1, wherein the temperature of the second intercalation reaction in the step (2) is 20-30 ℃, and the time of the second intercalation reaction is 6-18 h.
7. The method according to claim 1, wherein the manganese source solution of step (3) is MnSO4·H2Amount of substance of O, (NH)4)2S2O3Article ofThe volume ratio of the mass to the water is (0.1-0.3) mol: (0.2-0.4) mol: 1L of the compound.
8. The preparation method according to claim 1, wherein the temperature of the third intercalation reaction in the step (3) is 50-85 ℃, and the time of the third intercalation reaction is 24-48 h.
9. The coal-series kaolinite-based catalyst prepared by the preparation method of any one of claims 1 to 8 comprises a carrier and an active component loaded on the surface of the carrier; the carrier is intercalated coal series kaolinite, and the active component is manganese oxide.
10. Use of the coal-derived kaolinite-based catalyst according to claim 9 for the catalytic degradation of toluene.
CN202111477181.3A 2021-12-06 2021-12-06 Coal series kaolinite-based catalyst, preparation method thereof and application thereof in toluene catalytic degradation Pending CN114192187A (en)

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