CN114797844A - Monolithic catalyst for catalytic combustion of volatile organic waste gas and preparation method and application thereof - Google Patents

Monolithic catalyst for catalytic combustion of volatile organic waste gas and preparation method and application thereof Download PDF

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CN114797844A
CN114797844A CN202210331381.6A CN202210331381A CN114797844A CN 114797844 A CN114797844 A CN 114797844A CN 202210331381 A CN202210331381 A CN 202210331381A CN 114797844 A CN114797844 A CN 114797844A
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cordierite
volatile organic
catalytic combustion
monolithic catalyst
sio
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CN114797844B (en
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吴东方
鲍磊
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Southeast University
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
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    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
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    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2209/00—Specific waste
    • F23G2209/14—Gaseous waste or fumes

Abstract

The invention discloses a monolithic catalyst for catalytic combustion of volatile organic waste gas, and a preparation method and application thereof, wherein the catalyst comprises 70-85 wt% of cordierite and SiO 2 10-25 wt% of CM 1-10 wt%, wherein CM is Pd/Al 2 O 3 、Pt/γ‑Al 2 O 3 、Au/CeO 2 、CuMnO 2 、Ni/CeO 2 Or LaMnO 3 . The catalyst is prepared by wrapping CM with glucose and then using porous SiO 2 Wrapping and uniformly attaching the cordierite on the surface of a cordierite carrier, and roasting to obtain the cordierite ceramic. SiO in the catalyst 2 A gap is reserved between the layer and the CM, so that reactants can be effectively enriched, and the conversion rate of the reactants under the high airspeed condition is improved; the core-shell structure of the catalyst can effectively inhibit the sintering of the active component, and has excellent stability; the method has the advantages of simple process, low cost and easy recovery of the catalyst, and has potential application in the field of catalytic purification of volatile organic compounds.

Description

Monolithic catalyst for catalytic combustion of volatile organic waste gas and preparation method and application thereof
Technical Field
The invention relates to a monolithic catalyst for catalytic combustion of volatile organic waste gas, a preparation method and application thereof, belonging to the fields of catalyst technology and industrial catalysis.
Background
The volatile organic exhaust gas generally refers to a volatile organic compound which has a melting point lower than room temperature and a boiling point between 50 ℃ and 260 ℃ in a standard state. In the past decades, with the rapid development of industrialization and economy, the annual emission of volatile organic waste gases has increased dramatically. Among them, industrial processes, especially petrochemical, chemical, coating and printing industries, account for 43% of the man-made sources of volatile organic waste gases in China in the same year. The volatile organic waste gas has the characteristics of easiness in diffusion, toxicity and volatilization and the like, is released into the environment, is easy to cause air pollution, and seriously threatens the ecological environment and human health. The catalytic combustion is considered to be a method for eliminating volatile organic waste gas with high efficiency and wide application due to the advantages of high energy efficiency, low operation cost, secondary pollution and the like. The ceramic-based monolithic catalyst is widely applied to the research of waste gas treatment because of low bed pressure drop and high mass transfer efficiency and easy separation. Among them, the monolithic catalyst with platinum group metals as active components belongs to the mature catalyst and the catalyst with the most extensive industrial application, but the increasing consumption of platinum group metals and the high cost and easy toxicity limit the industrial application.
In recent years, transition metal oxides have good application prospects due to good stability and high catalytic activity, and are widely used in the field of exhaust gas treatment. The honeycomb ceramic monolithic catalyst reported in the prior art is generally prepared by coating a layer of porous carrier oxide and then impregnating with soluble salts of active metals. The method can cause active components to agglomerate on the surface of the coating in the preparation process and is exposed in the air for a long time, so that the service life of the catalyst is reduced; in addition, the catalyst is difficult to be used for the catalytic combustion of the volatile organic waste gas under the condition of high space velocity.
CN104549253A discloses a catalytic combustion catalyst and a preparation method thereof, wherein cordierite is sequentially impregnated with a load silicon-aluminum coating, a composite coating and an active component by a traditional preparation method to prepare an integral catalyst, and the catalyst is characterized by good anti-poisoning property and activity; CN112657525A discloses a monolithic cordierite carrier hydrodechlorination catalyst, a preparation method and application thereof, wherein a nitrogen-doped carbon-coated cordierite carrier is sequentially immersed into a first metal solution and a second metal solution to generate a core-shell structure with the first metal coated by the second metal, and the catalyst is characterized by high activity and stability. However, the above two patents do not consider the problem of enrichment of the volatile organic exhaust gas. Therefore, it is very important to develop a new catalyst with high activity and stability, which can enrich the volatile organic exhaust gas.
Disclosure of Invention
The purpose of the invention is as follows: the first purpose of the invention is to provide a monolithic catalyst for catalyzing and burning volatile organic waste gas, which has high activity and strong stability and can enrich the volatile organic waste gas; the second purpose of the invention is to provide a preparation method of the integral catalyst for catalyzing and burning the volatile organic waste gas; the third purpose of the invention is to provide the application of the monolithic catalyst for catalytic combustion of volatile organic exhaust gas in catalytic combustion reaction of volatile organic exhaust gas of alkanes, alkenes, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons and derivatives thereof.
The technical scheme is as follows: the invention relates to a monolithic catalyst for catalytic combustion of volatile organic waste gas, which is CM @ blank @ SiO 2 The cordierite monolithic catalyst comprises the following components in percentage by mass: 70-85 wt% of cordierite and SiO 2 10-25 wt% of CM and 1-10 wt% of CM; wherein CM is Pd/Al 2 O 3 、 Pt/γ-Al 2 O 3 、Au/CeO 2 、CuMnO 2 、Ni/CeO 2 、LaMnO 3 Any one of (1), the SiO 2 With a gap between them.
Wherein the cordierite is a honeycomb ceramic-like cordierite, and the SiO is 2 Is porous SiO 2 。
The invention relates to CM @ blank @ SiO 2 The preparation method of the cordierite monolithic catalyst comprises the steps of wrapping CM with glucose, wrapping the CM with porous silica, uniformly attaching the wrapped CM to the surface of a cordierite carrier, and roasting to obtain the cordierite monolithic catalyst.
Wherein, the CM@blank@SiO 2 The preparation method of the cordierite monolithic catalyst comprises the following steps:
(1) carrying out acid pretreatment on cordierite, washing, drying and roasting to obtain pretreated cordierite;
(2) grinding CM into CM particles, adding the CM particles into a glucose solution, stirring, aging, centrifuging, washing and drying to obtain CM @ C;
(3) mixing CM @ C, tetrabutyl orthosilicate, absolute ethyl alcohol and ammonia water, grinding into slurry, immersing pretreated cordierite into the slurry, taking out, and drying to obtain CM @ C @ SiO 2 Cordierite;
(4) prepared from CM @ C @ SiO 2 Roasting cordierite to obtain CM @ blank @ SiO 2 A cordierite monolithic catalyst.
In the step (1), the acid pretreatment is to soak cordierite in a 50% acetic acid solution for 30-90 min.
In the step (1), the drying temperature is 80-160 ℃, and the drying time is 2-4 hours.
In the step (1), the roasting temperature is 300-500 ℃, and the roasting time is 2-4 hours.
In the step (2), the diameter of the CM particles is 1-10 μm, the mass ratio of the CM particles to the glucose solution is 1: 40-1: 70, and the concentration of the glucose solution is 1-10 mol/L.
In the step (2), the stirring temperature is 20-60 ℃, the stirring speed is 350-600 rpm, and the stirring time is 1-4 hours.
In the step (2), the aging time is 12-24 h, the centrifugal rotating speed is 4000-8000 rpm, and the centrifugal time is 1-2 min.
In the step (2), the drying temperature is 60-120 ℃, and the drying time is 3-6 hours.
In the step (3), the mass ratio of CM @ C to tetrabutyl orthosilicate to the mass ratio of ammonia water to absolute ethyl alcohol is (3-10): (6-15): (5-15): (65-80).
In the step (3), the mass ratio of cordierite to slurry is 1: 15-1: 30, the drying temperature is 80-150 ℃, and the drying time is 2-6 hours.
In the step (4), the roasting temperature is 300-600 ℃, and the roasting time is 3-5 hours.
The invention also comprises the application of the monolithic catalyst for the catalytic combustion of the volatile organic waste gas in the catalytic combustion reaction of the volatile organic waste gas of alkane, olefin, alcohol, ether, halogenated hydrocarbon, aromatic hydrocarbon and derivatives thereof.
The catalytic combustion reaction mechanism of the high-efficiency volatile organic waste gas catalytic combustion monolithic catalyst is as follows: as shown in fig. 1, a gap exists between the porous silica in the catalyst and the active component CM, so that the reactants can be enriched, and the conversion rate of the reactants under the high space velocity condition is improved; at the same time, porous SiO 2 Provides a high specific surface area and can be used as a coat to prevent the agglomeration of the active component CM and improve the sintering resistance. Has good research value and application prospect in the field of purifying volatile organic compounds such as alkane, olefin, alcohol, ether, halogenated hydrocarbon, aromatic hydrocarbon and derivatives thereof under the condition of high space velocity.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the invention provides CM @ blank @ SiO 2 The cordierite monolithic catalyst is prepared by using porous SiO 2 The carbon coating layer coats the active component and is loaded on the surface of cordierite, and after high-temperature roasting, a gap exists between the silicon dioxide and the active component, which is beneficial to the enrichment of reactants and increases the conversion rate of the reactants under the condition of high airspeed; and prevents the aggregation deactivation of the metal active component during the reaction.
(2) The invention provides CM @ blank @ SiO 2 The cordierite monolithic catalyst has high specific surface area and stable configuration, and the dispersion degree of active components is high, so that the light-off temperature can be reduced, more oxygen vacancies and lattice defects are formed, and the problem of low catalytic activity of the traditional transition metal catalyst is solved.
(3) The invention provides CM @ blank @ SiO 2 The preparation method of the cordierite monolithic catalyst has simple process, and the raw materials are cheap and easy to obtain, thereby being beneficial to large-scale production.
Drawings
FIG. 1 shows a VOC (volatile organic compound) catalytic combustion monolithic catalyst CM @ blank @ SiO of the present invention 2 A mechanism diagram of catalytic combustion reaction of cordierite.
Detailed Description
The technical solution is further explained with reference to the drawings.
Example 1
1. Preparing a monolithic catalyst for catalytic combustion of volatile organic waste gas:
1) soaking commercially available honeycomb ceramic-shaped cordierite in a 50% acetic acid solution for 1h, taking out, washing with deionized water to be neutral, drying at 80 ℃ for 4h, roasting at 500 ℃ for 2h, and weighing 0.6832g to obtain pretreated cordierite for later use;
2) 0.5g of Pd/Al 2 O 3 Ball milling with a ball mill, collecting the sample to obtain Pd/Al 2 O 3 Powder is reserved;
3) dissolving 15g of glucose in 20mL of deionized water, and stirring for 0.5h to form a glucose solution; then Pd/Al 2 O 3 Adding the powder into glucose solution, stirring at 25 deg.C for 2 hr, and aging for 12 hr; then centrifuging the solution at the rotating speed of 4000rpm for 2min, washing the solution three times by using deionized water, putting the washed centrifugal product into a drying box, and drying the product for 3h at the temperature of 120 ℃ to obtain Pd/Al 2 O 3 @C；
4) 0.5g of Pd/Al 2 O 3 Mixing and ball-milling @ C, 1.5ml of tetrabutyl orthosilicate, 12.5ml of absolute ethyl alcohol and 2ml of ammonia water into slurry; the pretreated cordierite was then immersed in the slurry for 2min, removed and the excess suspension in the channels removed under a weak air stream, dried at 80 ℃ for 6h and the coating was repeated 3 times to achieve the desired loading to yield Pd/Al 2 O 3 @C@SiO 2 Cordierite;
5) Pd/Al 2 O 3 @C@SiO 2 The cordierite is roasted for 5 hours at the temperature of 300 ℃ and naturally cooled to obtain the monolithic catalyst Pd/Al for catalytic combustion of volatile organic waste gas 2 O 3 @blank@SiO 2 Cordierite.
2. The volatile organic waste gas catalytic combustion monolithic catalyst Pd/Al prepared in the embodiment 2 O 3 @blank@SiO 2 The cordierite is used for the catalytic combustion of volatile organic waste gas:
respectively carrying out catalytic combustion activity evaluation on o-xylene in a normal-pressure quartz tube reactor (the inner diameter is 10mm), wherein the reaction atmosphere is a mixed gas of o-xylene and air, the concentration of the o-xylene is 1000ppm, and the volume space velocity (GHSV) is about 30000h -1 . The prepared volatile organic waste gas catalytic combustion monolithic catalyst Pd/Al 2 O 3 @blank@SiO 2 The cordierite sample is activated for 1h at 450 ℃ in an air atmosphere and then starts catalytic combustion reaction when naturally cooled to 100 ℃. Detecting the generated product on line by adopting a gas chromatograph, and measuring the ignition temperature T 50 (temperature at which conversion rate reached 50%) was 162 ℃ and complete conversion temperature T 90 The temperature at which the conversion reached 90% was 212 ℃.
Example 2
1. Preparing a monolithic catalyst for catalytic combustion of volatile organic waste gas:
1) soaking commercially available honeycomb ceramic-shaped cordierite in a 50% acetic acid solution for 1h, taking out, washing with deionized water to be neutral, drying at 160 ℃ for 2h, roasting at 300 ℃ for 4h, and weighing 0.6764g to obtain pretreated cordierite for later use;
2) 1g of Pt/gamma-Al 2 O 3 Ball milling is carried out by a ball mill, samples are collected, and Pt/gamma-Al is obtained 2 O 3 Powder is reserved;
3) dissolving 25g of glucose in 20ml of deionized water, and stirring for 0.5h to form a glucose solution; then Pt/gamma-Al is obtained 2 O 3 Adding the powder into glucose solution, stirring at 25 deg.C for 1 hr, and aging for 24 hr; then centrifuging the obtained product at 6000 rpm for 1.5min, washing the product with deionized water for three times, putting the washed centrifugal product into a drying oven, and drying the product at 80 ℃ for 5h to obtain Pt/gamma-Al 2 O 3 @C；
4) 1g of Pt/gamma-Al 2 O 3 @ C and 2.5ml tetrabutyl orthosilicate, 20ml anhydrous ethyl acetateMixing alcohol and 3ml ammonia water, and grinding into slurry; the pretreated cordierite was then immersed in the slurry for 2min, removed and the excess suspension in the channels removed under a weak air stream, dried at 120 ℃ for 4h and the coating was repeated 3 times to achieve the desired loading to obtain Pt/γ -Al 2 O 3 @C@SiO 2 Cordierite;
5) mixing Pt/gamma-Al 2 O 3 @C@SiO 2 The cordierite is roasted for 4 hours at the temperature of 400 ℃ and naturally cooled to obtain the Pt/gamma-Al monolithic catalyst for catalytic combustion of volatile organic waste gas 2 O 3 @blank@SiO 2 Cordierite.
2. The volatile organic waste gas catalytic combustion monolithic catalyst Pt/gamma-Al prepared in the embodiment 2 O 3 @blank@SiO 2 The cordierite is used for the catalytic combustion of volatile organic waste gas:
respectively carrying out toluene catalytic combustion activity evaluation in a normal pressure quartz tube reactor (with an inner diameter of 10mm), wherein the reaction atmosphere is a mixed gas of toluene and air, the toluene concentration is 1000ppm, and the volume space velocity (GHSV) is about 30000h -1 . The prepared volatile organic waste gas is catalyzed and combusted to form a monolithic catalyst Pt/gamma-Al 2 O 3 @blank@SiO 2 The cordierite sample is activated for 1h at 450 ℃ in an air atmosphere and then starts catalytic combustion reaction when naturally cooled to 100 ℃. Detecting the generated product on line by adopting a gas chromatograph, and measuring the ignition temperature T 50 (temperature at which conversion rate reached 50%) was 143 ℃ and complete conversion temperature T 90 The temperature at which the conversion reached 90% was 208 ℃.
Example 3
1. Preparing a monolithic catalyst for catalytic combustion of volatile organic waste gas:
1) soaking commercially available honeycomb ceramic-shaped cordierite in a 50% acetic acid solution for 1h, taking out, washing with deionized water to be neutral, drying at 80 ℃ for 4h, roasting at 500 ℃ for 2h, and weighing 0.6542g to obtain pretreated cordierite for later use;
2) 1g of Au/CeO 2 Ball milling with a ball mill, collecting the sample to obtain Au/CeO 2 Powder is reserved;
3) 15g of glucose was dissolved in 30mlStirring in ionized water for 0.5h to form a glucose solution; then adding Au/CeO 2 Adding the powder into glucose solution, stirring at 20 deg.C for 1 hr, and aging for 18 hr; then centrifuging the solution for 1min at the rotating speed of 8000rpm, washing the solution for three times by using deionized water, putting the washed centrifugal product into a drying box, and drying the product for 4h at the temperature of 100 ℃ to obtain Au/CeO 2 @C；
4) 1g of Au/CeO 2 Mixing and ball-milling @ C, 4ml of tetrabutyl orthosilicate, 20ml of absolute ethyl alcohol and 4.5ml of ammonia water into slurry; the pretreated cordierite was then immersed in the slurry for 2min, removed and the excess suspension in the channels removed under a weak air stream, dried at 100 ℃ for 5h and the coating was repeated 3 times to achieve the desired loading to yield Au/CeO 2 @C@SiO 2 Cordierite;
5) mixing Au/CeO 2 @C@SiO 2 The cordierite is roasted for 3 hours at 500 ℃ and naturally cooled to obtain the monolithic catalyst Au/CeO for catalytic combustion of volatile organic waste gas 2 @blank@SiO 2 Cordierite.
2. The volatile organic waste gas catalytic combustion monolithic catalyst Au/CeO prepared in the embodiment 2 @blank@SiO 2 The cordierite is used for the catalytic combustion of volatile organic waste gas:
respectively carrying out n-butanol catalytic combustion activity evaluation in a normal pressure quartz tube reactor (with an inner diameter of 10mm), wherein the reaction atmosphere is a mixed gas of n-butanol and air, the n-butanol concentration is 1000ppm, and the volume space velocity (GHSV) is about 30000h -1 . The prepared monolithic catalyst sample is activated for 1h at 450 ℃ in an air atmosphere and then starts catalytic combustion reaction when being naturally cooled to 100 ℃. Detecting the generated product on line by adopting a gas chromatograph, and measuring the ignition temperature T 50 (temperature at which conversion rate reached 50%) was 151 ℃ and complete conversion temperature T 90 The temperature at which the conversion reached 90% was 196 ℃.
Example 4
1. Preparing a monolithic catalyst for catalytic combustion of volatile organic waste gas:
1) soaking commercially available honeycomb ceramic-shaped cordierite in a 50% acetic acid solution for 1h, taking out, washing with deionized water to be neutral, drying at 80 ℃ for 4h, roasting at 500 ℃ for 2h, and weighing 0.6341g to obtain pretreated cordierite for later use;
2) mixing 1g of CuMnO 2 Ball milling is carried out by a ball mill, and a sample is collected to obtain CuMnO 2 Powder is reserved;
3) dissolving 15g of glucose in 25ml of deionized water, and stirring for 0.5h to form a glucose solution; then adding CuMnO 2 Adding the powder into glucose solution, stirring at 20 deg.C for 1 hr, and aging for 12 hr; then centrifuging the solution for 1min at the rotating speed of 8000rpm, washing the solution for three times by using deionized water, putting the washed centrifugal product into a drying box, and drying the product for 3h at the temperature of 120 ℃ to obtain CuMnO 2 @C；
4) 0.5g of CuMnO 2 Mixing and ball-milling @ C, 2ml of tetrabutyl orthosilicate, 10ml of absolute ethyl alcohol and 2ml of ammonia water into slurry; the pretreated cordierite was then immersed in the slurry for 2min, removed and excess suspension removed from the channels under a weak air stream, dried at 80 ℃ for 6h, and the coating procedure repeated 3 times to achieve the desired loading to give CuMnO 2 @C@SiO 2 Cordierite;
5) mixing CuMnO 2 @C@SiO 2 The cordierite is roasted for 5 hours at the temperature of 300 ℃ and naturally cooled to obtain the monolithic catalyst CuMnO for catalytic combustion of volatile organic waste gas 2 @blank@SiO 2 Cordierite.
2. The volatile organic waste gas catalytic combustion monolithic catalyst CuMnO prepared in the example is used 2 @blank@SiO 2 The cordierite is used for the catalytic combustion of volatile organic waste gas:
respectively carrying out styrene catalytic combustion activity evaluation in a normal-pressure quartz tube reactor (with an inner diameter of 10mm), wherein the reaction atmosphere is a mixed gas of styrene and air, the styrene concentration is 1000ppm, and the volume space velocity (GHSV) is about 30000h -1 . The prepared monolithic catalyst sample is activated for 1h at 450 ℃ in an air atmosphere and then starts catalytic combustion reaction when being naturally cooled to 100 ℃. Detecting the generated product on line by adopting a gas chromatograph, and measuring the ignition temperature T 50 (temperature at which conversion reached 50%) was 163 ℃ and complete conversion temperature T 90 The temperature at which the conversion reached 90% was 218 ℃.
Example 5
1. Preparing a monolithic catalyst for catalytic combustion of volatile organic waste gas:
1) soaking commercially available honeycomb ceramic-shaped cordierite in a 50% acetic acid solution for 1h, taking out, washing with deionized water to be neutral, drying at 120 ℃ for 3h, roasting at 500 ℃ for 2h, and weighing 0.6428g to obtain pretreated cordierite for later use;
2) 1g of Ni/CeO 2 Ball milling with a ball mill, collecting samples to obtain Ni/CeO 2 Powder is reserved;
3) dissolving 25g of glucose in 20ml of deionized water, and stirring for 0.5h to form a glucose solution; then Ni/CeO will be obtained 2 Adding the powder into glucose solution, stirring at 25 deg.C for 1 hr, and aging for 24 hr; then centrifuging the mixture for 1.5min at the rotating speed of 6000 rpm, washing the mixture for three times by using deionized water, putting the washed centrifugal product into a drying box, and drying the centrifugal product for 5h at the temperature of 80 ℃ to obtain Ni/CeO 2 @C；
4) 1g of Ni/CeO 2 Mixing @ C with 3ml of tetrabutyl orthosilicate, 18ml of absolute ethyl alcohol and 3ml of ammonia water, and ball-milling to obtain slurry; the pretreated cordierite was then immersed in the slurry for 2min, removed and the excess suspension in the channels removed under a weak air stream, dried at 120 ℃ for 4h and the coating was repeated 3 times to achieve the desired loading to give Ni/CeO 2 @C@SiO 2 Cordierite;
5) mixing Ni/CeO 2 @C@SiO 2 Roasting cordierite at 400 ℃ for 4h, and naturally cooling to obtain the Ni/CeO monolithic catalyst for catalytic combustion of volatile organic waste gas 2 @blank@SiO 2 Cordierite.
2. The volatile organic waste gas catalytic combustion monolithic catalyst Ni/CeO prepared in the embodiment 2 @blank@SiO 2 The cordierite is used for the catalytic combustion of volatile organic waste gas:
respectively carrying out toluene catalytic combustion activity evaluation in a normal pressure quartz tube reactor (with an inner diameter of 10mm), wherein the reaction atmosphere is a mixed gas of toluene and air, the toluene concentration is 1000ppm, and the volume space velocity (GHSV) is about 30000h -1 . The prepared volatile organic waste gas is catalyzed by catalytic combustion and integrally catalyzed by Ni/CeO 2 @blank@SiO 2 The cordierite sample is activated for 1h at 450 ℃ in an air atmosphere and then starts catalytic combustion reaction when naturally cooled to 100 ℃. Detecting the generated product on line by adopting a gas chromatograph, and measuring the ignition temperature T 50 (temperature at which conversion reached 50%) was 154 ℃ and complete conversion temperature T 90 The temperature at which the conversion reached 90% was 227 ℃.
Example 6
1. Preparing a monolithic catalyst for catalytic combustion of volatile organic waste gas:
1) soaking commercially available honeycomb ceramic-shaped cordierite in a 50% acetic acid solution for 1h, taking out, washing with deionized water to be neutral, drying at 160 ℃ for 2h, roasting at 500 ℃ for 2h, and weighing 0.6943g to obtain pretreated cordierite for later use;
2) 1g of LaMnO 3 Ball milling with a ball mill, collecting samples to obtain LaMnO 3 Powder is reserved;
3) dissolving 15g of glucose in 15ml of deionized water, and stirring for 0.5h to form a glucose solution; then LaMnO is obtained 3 Adding the powder into glucose solution, stirring at 25 deg.C for 1 hr, and aging for 20 hr; then centrifuging the mixture for 2min at the rotating speed of 4000rpm, washing the mixture for three times by using deionized water, putting the washed centrifugal product into a drying box, and drying the centrifugal product for 5h at the temperature of 80 ℃ to obtain LaMnO 3 @C；
4) 1g of LaMnO 3 Mixing @ C with 2.5ml of tetrabutyl orthosilicate, 12ml of absolute ethyl alcohol and 2.5ml of ammonia water, and ball-milling to obtain slurry; the pretreated cordierite was then immersed in the slurry for 2min, removed and the excess suspension in the channels removed under a weak air stream, dried at 100 ℃ for 5h and the coating was repeated 3 times to achieve the desired loading to obtain LaMnO 3 @C@SiO 2 Cordierite;
5) mixing LaMnO 3 @C@SiO 2 The cordierite is roasted for 3 hours at 500 ℃ and naturally cooled to obtain the monolithic catalyst LaMnO for catalytic combustion of volatile organic waste gas 3 @blank@SiO 2 Cordierite.
2. The volatile organic waste gas catalytic combustion monolithic catalyst LaMnO prepared in the embodiment 3 @blank@SiO 2 Application of cordierite in volatile organic waste gasCatalytic combustion:
respectively carrying out catalytic combustion activity evaluation on o-xylene in a normal-pressure quartz tube reactor (the inner diameter is 10mm), wherein the reaction atmosphere is a mixed gas of o-xylene and air, the concentration of the o-xylene is 1000ppm, and the volume space velocity (GHSV) is about 30000h -1 . The prepared volatile organic waste gas is catalytically combusted to integrally catalyze LaMnO 3 @blank@SiO 2 The cordierite sample is activated for 1h at 450 ℃ in an air atmosphere and then starts catalytic combustion reaction when naturally cooled to 100 ℃. Detecting the generated product on line by adopting a gas chromatograph, and measuring the ignition temperature T 50 (temperature at which conversion rate reached 50%) was 178 ℃ and complete conversion temperature T 90 The temperature at which the conversion reached 90% was 236 ℃.
Comparative example 1
The difference from example 6 is that the synthesis procedure of the monolithic catalyst is different.
1. Preparing a monolithic catalyst for catalytic combustion of volatile organic waste gas:
1) soaking commercially available honeycomb ceramic-shaped cordierite in a 50% acetic acid solution for 1h, taking out, washing with deionized water to be neutral, drying at 160 ℃ for 2h, roasting at 500 ℃ for 2h, and weighing 0.6943g to obtain pretreated cordierite for later use;
2) adding 5ml of tetrabutyl orthosilicate and 20ml of absolute ethyl alcohol into a three-necked bottle, regulating the pH to 3 by hydrochloric acid in a water bath at the temperature of 80 ℃, and violently stirring for 2 hours to form silica sol;
3) 1g of LaMnO 3 Ball milling with ball mill, adding into silica sol prepared in 2), mixing to form coating solution, soaking pretreated cordierite into the coating solution for 2min, taking out, removing excessive suspension in the channel under weak air flow, drying at 100 deg.C for 5 hr, and calcining at 500 deg.C for 3 hr to obtain LaMnO 3 /SiO 2 Cordierite.
2. The volatile organic waste gas catalytic combustion monolithic catalyst LaMnO prepared in the embodiment 3 /SiO 2 The cordierite is used for the catalytic combustion of volatile organic waste gas:
respectively carrying out the catalytic combustion activity evaluation of o-xylene in a normal pressure quartz tube reactor (the inner diameter is 10mm),the reaction atmosphere is a mixed gas of o-xylene and air, the concentration of the o-xylene is 1000ppm, and the volume space velocity (GHSV) is about 30000h -1 . The prepared volatile organic waste gas is catalytically combusted to integrally catalyze LaMnO 3 /SiO 2 The cordierite sample is activated for 1h at 450 ℃ in an air atmosphere and then starts catalytic combustion reaction when naturally cooled to 100 ℃. Detecting the generated product on line by adopting a gas chromatograph, and measuring the ignition temperature T 50 (temperature at which conversion rate reached 50%) was 213 ℃ and complete conversion temperature T 90 The temperature at which the conversion reached 90% was 285 ℃.
From the experimental results of example 6 and comparative example 1, it can be seen that LaMnO according to the present invention is provided 3 @blank@SiO 2 The reaction activity of the cordierite monolithic catalyst under high space velocity o-xylene is superior to that of LaMnO prepared by the conventional method 3 /SiO 2 The cordierite monolithic catalyst has better industrial application prospect.

Claims (10)

1. The integral catalyst for catalytic combustion of the volatile organic exhaust gas is characterized by comprising the following components in percentage by mass: 70-85 wt% of cordierite and SiO 2 10-25 wt% of CM and 1-10 wt% of CM; wherein CM is Pd/Al 2 O 3 、Pt/γ-Al 2 O 3 、Au/CeO 2 、CuMnO 2 、Ni/CeO 2 、LaMnO 3 Any one of (1), the SiO 2 With a gap between it and the CM.
2. The method for preparing a monolithic catalyst for catalytic combustion of volatile organic exhaust gas according to claim 1, wherein the method comprises coating CM with glucose, coating it with porous silica, uniformly adhering it to the surface of cordierite carrier, and calcining.
3. The method for preparing the monolithic catalyst for catalytic combustion of volatile organic exhaust gas according to claim 2, comprising the steps of:
(1) carrying out acid pretreatment on cordierite, washing, drying and roasting to obtain pretreated cordierite;
(2) grinding CM into CM particles, adding the CM particles into a glucose solution, stirring, aging, centrifuging, washing and drying to obtain CM @ C;
(3) mixing CM @ C, tetrabutyl orthosilicate, absolute ethyl alcohol and ammonia water, grinding into slurry, immersing pretreated cordierite into the slurry, taking out, and drying to obtain CM @ C @ SiO 2 Cordierite;
(4) prepared from CM @ C @ SiO 2 Roasting cordierite to obtain the monolithic catalyst for catalytic combustion of volatile organic waste gas, namely CM @ blank @ SiO 2 A cordierite monolithic catalyst.
4. The preparation method of the monolithic catalyst for catalytic combustion of volatile organic exhaust gas according to claim 3, wherein in the step (1), the acid pretreatment of the honeycomb ceramic-like cordierite is to soak the cordierite in a 50% acetic acid solution for 30-90 min, the drying temperature is 80-160 ℃, the drying time is 2-4 h, the roasting temperature is 300-500 ℃, and the roasting time is 2-4 h.
5. The method for preparing the monolithic catalyst for catalytic combustion of volatile organic exhaust gas according to claim 3, wherein in the step (2), the diameter of the CM particles is 1 to 10 μm, the mass ratio of the CM particles to the glucose solution is 1:40 to 1:70, and the concentration of the glucose solution is 1 to 10 mol/L.
6. The preparation method of the monolithic catalyst for catalytic combustion of volatile organic exhaust gas according to claim 3, wherein in the step (2), the stirring temperature is 20-60 ℃, the stirring rotation speed is 350-600 rpm, the stirring time is 1-4 h, the aging time is 12-24 h, the centrifuging rotation speed is 4000-8000 rpm, the centrifuging time is 1-2 min, the drying temperature is 60-120 ℃, and the drying time is 3-6 h.
7. The preparation method of the monolithic catalyst for catalytic combustion of volatile organic exhaust gas according to claim 3, wherein in the step (3), the mass ratio of CM @ C to tetrabutyl orthosilicate to the mass ratio of ammonia water to absolute ethyl alcohol is 3-10: 6-15: 5-15: 65-80.
8. The method for preparing the monolithic catalyst for catalytic combustion of volatile organic exhaust gas according to claim 3, wherein in the step (3), the mass ratio of cordierite to slurry is 1: 15-1: 30, the drying temperature is 80-150 ℃, and the drying time is 2-6 h.
9. The method for preparing the monolithic catalyst for catalytic combustion of volatile organic exhaust gas according to claim 3, wherein in the step (4), the roasting temperature is 300-600 ℃ and the roasting time is 3-5 h.
10. The use of the monolithic catalyst for catalytic combustion of volatile organic exhaust gases according to claim 1 in catalytic combustion reactions of volatile organic exhaust gases such as alkanes, alkenes, alcohols, ethers, halogenated hydrocarbons, and aromatic hydrocarbons and their derivatives.
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