CN114797844B - Integrated catalyst for catalytic combustion of volatile organic waste gas and preparation method and application thereof - Google Patents

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

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CN114797844B
CN114797844B CN202210331381.6A CN202210331381A CN114797844B CN 114797844 B CN114797844 B CN 114797844B CN 202210331381 A CN202210331381 A CN 202210331381A CN 114797844 B CN114797844 B CN 114797844B
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cordierite
volatile organic
catalyst
waste gas
organic waste
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CN114797844A (en
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吴东方
鲍磊
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Southeast University
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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
    • 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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • 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
    • B01J23/34—Manganese
    • 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
    • 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
    • B01J23/42—Platinum
    • 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
    • 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
    • B01J23/54—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
    • 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
    • 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
    • B01J23/83—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
    • 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
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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 catalyst for catalyzing and burning volatile organic waste gas and a preparation method and application thereof, wherein the catalyst comprises 70-85 wt% of cordierite and SiO 2 10 to 25 weight percent and 1 to 10 weight percent of CM, wherein the 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 The cordierite carrier is coated and uniformly attached on the surface of the cordierite carrier, and is prepared by roasting. SiO in the catalyst 2 Gaps are formed between the layers and the CM, so that reactants can be effectively enriched, and the conversion rate of the reactants under the condition of high airspeed is improved; the core-shell structure of the catalyst can effectively inhibit sintering of active components, 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

Integrated catalyst for catalytic combustion of volatile organic waste gas and preparation method and application thereof
Technical Field
The invention relates to a catalyst for catalyzing and burning volatile organic waste gas and a preparation method and application thereof, belonging to the fields of catalyst technology and industrial catalysis.
Background
Volatile organic waste gases generally refer to volatile organic compounds that have a melting point below room temperature and a boiling point between 50 and 260 ℃ under standard conditions. Over the past few decades, with the rapid development of industrialization and economies, the annual emissions of volatile organic waste gases have increased dramatically. Among them, industrial processes, particularly petrochemical, chemical, paint and printing industries, account for 43% of the man-made sources of volatile organic waste gases in China in the current year. The volatile organic waste gas has the characteristics of easy diffusion, easy toxicity, easy volatility and the like, is released into the environment, is easy to cause air pollution, and seriously threatens ecological environment and human health. Catalytic combustion is considered to be a method for eliminating volatile organic waste gas with high efficiency and wide application because of the advantages of high energy efficiency, low running cost, secondary pollution and the like. The ceramic-based monolithic catalyst has the advantages of reduced bed lamination, high mass transfer efficiency and easy separation, and is widely applied to waste gas treatment research. Among them, monolithic catalysts using platinum group metals as active components are relatively mature catalysts and are the most widely used catalysts in industry, but the increasing consumption of platinum group metals and their high cost, easy poisoning limit their 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 waste gas treatment. The honeycomb ceramic monolith catalysts reported heretofore are typically prepared by coating a porous support oxide followed by impregnation with a soluble salt of the active metal. The active components are agglomerated on the surface of the coating in the preparation process of the method and are exposed to the air for a long time, so that the service life of the catalyst is reduced; in addition, the catalyst is difficult to be efficiently used for catalytic combustion of 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 silicon-aluminum coating, a composite coating and active components to prepare an integral catalyst by a traditional preparation method, and the catalyst is characterized by good antitoxic property and activity; CN112657525a discloses an integral cordierite carrier hydrodechlorination catalyst, a preparation method and application thereof, which is characterized in that a nitrogen-doped carbon-coated cordierite carrier is immersed into a first metal solution and a second metal solution in sequence to generate a core-shell structure with the second metal wrapping the first metal, and the catalyst has high activity and stability. However, the above two patents do not consider the problem of enrichment of volatile organic waste gases. Therefore, it is important to develop a novel catalyst which has high activity and high stability and can enrich volatile organic waste gas.
Disclosure of Invention
The invention aims to: the invention aims to provide the catalyst for catalyzing and burning the volatile organic waste gas, which has high activity and strong stability and can enrich the volatile organic waste gas; the second object of the invention is to provide a method for preparing the catalyst for catalytic combustion of the volatile organic waste gas; the third object of the invention is to provide the application of the monolithic catalyst for catalytic combustion of volatile organic waste gas in catalytic combustion reaction of alkane, alkene, alcohol, ether, halohydrocarbon, aromatic hydrocarbon and derivatives thereof.
The technical scheme is as follows: the invention relates to a catalyst for catalyzing and burning 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 to 25 weight percent of CM 1 to 10 weight percent; wherein the 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 the above SiO 2 There is a gap with the CM.
Wherein the cordierite is honeycomb ceramic cordierite, and the SiO is a ceramic material 2 Is porous SiO 2 。
CM@blank@SiO according to the invention 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 CM to the surface of a cordierite carrier, and roasting.
Wherein the CM@blank@SiO 2 The preparation method of the cordierite monolithic catalyst comprises the following steps:
(1) Acid pretreatment is carried out on cordierite, washing, drying and roasting are carried out, and pretreated cordierite is obtained;
(2) Grinding CM into CM particles, adding the CM particles into glucose solution, stirring, aging, centrifuging, washing and drying to obtain CM@C;
(3) Mixing CM@C with tetrabutyl orthosilicate, absolute ethyl alcohol and ammonia water, grinding into slurry, immersing pretreated cordierite in the slurry, taking out, and drying to obtain CM@C@SiO 2 Cordierite;
(4) Cm@c@sio 2 Roasting/cordierite to obtain CM@blank@SiO 2 Cordierite monolith catalyst.
In the step (1), the acid pretreatment is to soak cordierite in 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 h.
Wherein in the step (1), the roasting temperature is 300-500 ℃, and the roasting time is 2-4 h.
Wherein in the step (2), the diameter of the CM particles is 1-10 mu m, 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.
Wherein in the step (2), the stirring temperature is 20-60 ℃, the stirring rotating speed is 350-600 rpm, and the stirring time is 1-4 h.
Wherein in the step (2), the aging time is 12-24 hours, the rotational speed of the centrifugation is 4000-8000 rpm, and the centrifugation time is 1-2 minutes.
Wherein in the step (2), the drying temperature is 60-120 ℃, and the drying time is 3-6 h.
In the step (3), the mass ratio of the CM@C, the tetrabutyl orthosilicate, the ammonia water and the absolute ethyl alcohol is (3-10): (6-15): (5-15): (65-80).
In the step (3), the mass ratio of the cordierite to the slurry is 1:15-1:30, the drying temperature is 80-150 ℃, and the drying time is 2-6 h.
Wherein in the step (4), the roasting temperature is 300-600 ℃, and the roasting time is 3-5 h.
The invention also comprises the application of the catalyst in catalytic combustion reaction of alkane, alkene, alcohol, ether, halohydrocarbon, aromatic hydrocarbon and derivative volatile organic waste gas.
The invention relates to a catalytic combustion reaction mechanism of a high-efficiency volatile organic waste gas catalytic combustion monolithic catalyst, which comprises the following steps: as shown in fig. 1, a gap exists between the porous silica in the catalyst and the active component CM, so that 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 piece of 'coat' to prevent the active component CMAgglomeration occurs, and the sintering resistance is improved. The method has good research value and application prospect in the field of purifying volatile organic compounds such as alkane, alkene, alcohol, ether, halohydrocarbon, aromatic hydrocarbon and derivatives thereof under the condition of high airspeed.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
(1) The CM@blank@SiO provided by the invention 2 The cordierite monolithic catalyst is prepared from porous SiO 2 The carbon coating is used for coating the active components on the surface of the cordierite, and a gap exists between the silicon dioxide and the active components after high-temperature roasting, so that the gap is favorable for enriching reactants, and the conversion rate of the reactants under the high airspeed condition is increased; and prevents aggregation deactivation of the metal active component during the reaction.
(2) The CM@blank@SiO provided by the invention 2 The cordierite monolithic catalyst has high specific surface area and stable configuration, and the dispersity of the active component is high, so that the ignition 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 CM@blank@SiO provided by the invention 2 The preparation method of the cordierite monolithic catalyst has simple process, low-cost and easily-obtained raw materials, and is beneficial to large-scale production.
Drawings
FIG. 1 shows a catalytic combustion monolithic catalyst CM@blank@SiO for volatile organic exhaust gas according to the invention 2 A mechanism diagram of catalytic combustion reaction of cordierite.
Detailed Description
The technical scheme is further described below with reference to the accompanying drawings.
Example 1
1. Preparation of a monolithic catalyst for catalytic combustion of volatile organic waste gas:
1) Soaking commercial honeycomb ceramic cordierite in 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, weighing 0.6832g, and obtaining pretreated cordierite for later use;
2) 0.5g Pd/Al 2 O 3 Ball milling with ball mill, collecting sample to obtain Pd/Al 2 O 3 Powder is reserved for standby;
3) 15g of glucose was dissolved in 20mL of deionized water and stirred for 0.5h to form a glucose solution; pd/Al is then added 2 O 3 Adding the powder into glucose solution, stirring at 25deg.C for 2 hr, and aging for 12 hr; centrifuging at 4000rpm for 2min, washing with deionized water for three times, and drying the washed centrifugal product in a drying oven at 120deg.C for 3 hr to obtain Pd/Al 2 O 3 @C；
4) 0.5g of Pd/Al 2 O 3 Mixing and ball grinding the @ C and 1.5ml of tetrabutyl orthosilicate, 12.5ml of absolute ethyl alcohol and 2ml of ammonia water into slurry; immersing pretreated cordierite in the slurry for 2min, taking out and removing excessive suspension in the channel under weak air flow, drying at 80deg.C for 6 hr, repeating the above coating process for 3 times to obtain Pd/Al 2 O 3 @C@SiO 2 Cordierite;
5) Pd/Al 2 O 3 @C@SiO 2 Roasting cordierite at 300 deg.c for 5 hr, and natural cooling to obtain Pd/Al catalyst for catalyzing and burning volatile organic waste gas 2 O 3 @blank@SiO 2 Cordierite.
2. The catalyst Pd/Al is used for catalyzing and burning the volatile organic waste gas prepared in the embodiment 2 O 3 @blank@SiO 2 Cordierite is used for catalytic combustion of volatile organic exhaust gases:
the catalytic combustion activity of o-xylene was evaluated in an atmospheric quartz tube reactor (inner diameter: 10 mm), the reaction atmosphere was a mixture of o-xylene and air, the o-xylene concentration was 1000ppm, and the volume space velocity (GHSV) was about 30000h -1 . The prepared volatile organic waste gas is catalyzed to burn the monolithic catalyst Pd/Al 2 O 3 @blank@SiO 2 The cordierite sample was activated in an air atmosphere at 450 ℃ for 1 hour and then cooled naturally to 100 ℃ to initiate the catalytic combustion reaction. Detecting the generated product on line by a gas chromatograph to obtain the ignition temperature T 50 (the conversion rate reaches 50%) 162℃and the complete conversion temperature T 90 (the conversion reached 90% of the temperature) was 212 ℃.
Example 2
1. Preparation of a monolithic catalyst for catalytic combustion of volatile organic waste gas:
1) Soaking commercial honeycomb ceramic cordierite in 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, weighing 0.6764g, and obtaining pretreated cordierite for later use;
2) 1g of Pt/gamma-Al 2 O 3 Ball milling with ball mill, collecting sample to obtain Pt/gamma-Al 2 O 3 Powder is reserved for standby;
3) 25g of glucose was dissolved in 20ml of deionized water and stirred 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 25deg.C for 1 hr, and aging for 24 hr; centrifuging at 6000rpm for 1.5min, washing with deionized water for three times, and drying at 80deg.C for 5 hr to obtain Pt/gamma-Al 2 O 3 @C；
4) 1g of Pt/gamma-Al 2 O 3 Mixing and ball-milling the @ C and 2.5ml of tetrabutyl orthosilicate, 20ml of absolute ethyl alcohol and 3ml of ammonia water into slurry; immersing the pretreated cordierite in the slurry for 2min, taking out and removing the redundant suspension in the channel under weak air flow, drying at 120deg.C for 4h, repeating the above coating process for 3 times to obtain Pt/gamma-Al 2 O 3 @C@SiO 2 Cordierite;
5) Pt/gamma-Al 2 O 3 @C@SiO 2 Roasting cordierite at 400 ℃ for 4 hours, naturally cooling to obtain the monolithic catalyst Pt/gamma-Al for catalytic combustion of volatile organic waste gas 2 O 3 @blank@SiO 2 Cordierite.
2. The catalyst Pt/gamma-Al is used for catalyzing and burning the volatile organic waste gas prepared in the embodiment 2 O 3 @blank@SiO 2 Cordierite is used for catalytic combustion of volatile organic exhaust gases:
toluene catalytic combustion was carried out in an atmospheric quartz tube reactor (inner diameter: 10 mm)Evaluation of firing Activity, the reaction atmosphere was a mixture of toluene and air, the toluene concentration was 1000ppm, and the volume space velocity (GHSV) was about 30000h -1 . The prepared volatile organic waste gas is catalyzed and combusted to form the monolithic catalyst Pt/gamma-Al 2 O 3 @blank@SiO 2 The cordierite sample was activated in an air atmosphere at 450 ℃ for 1 hour and then cooled naturally to 100 ℃ to initiate the catalytic combustion reaction. Detecting the generated product on line by a gas chromatograph to obtain the ignition temperature T 50 (the conversion rate reaches 50%) at 143℃and the complete conversion temperature T 90 (the temperature at which the conversion reached 90%) was 208 ℃.
Example 3
1. Preparation of a monolithic catalyst for catalytic combustion of volatile organic waste gas:
1) Soaking commercial honeycomb ceramic cordierite in 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, weighing 0.6542g, and obtaining pretreated cordierite for later use;
2) 1g Au/CeO 2 Ball milling with ball mill, collecting sample to obtain Au/CeO 2 Powder is reserved for standby;
3) 15g of glucose was dissolved in 30ml of deionized water and stirred for 0.5h to form a glucose solution; then Au/CeO is added 2 Adding the powder into glucose solution, stirring at 20deg.C for 1 hr, and aging for 18 hr; centrifuging at 8000rpm for 1min, washing with deionized water for three times, placing the washed centrifugal product into a drying oven, and drying at 100deg.C for 4 hr to obtain Au/CeO 2 @C；
4) 1g of Au/CeO 2 Mixing and ball-milling the @ C and 4ml of tetrabutyl orthosilicate, 20ml of absolute ethyl alcohol and 4.5ml of ammonia water into slurry; immersing the pretreated cordierite into the slurry for 2min, taking out and removing the redundant suspension in the channel under weak air flow, drying at 100deg.C for 5h, repeating the above coating process for 3 times to obtain Au/CeO 2 @C@SiO 2 Cordierite;
5) Au/CeO 2 @C@SiO 2 Roasting cordierite at 500 ℃ for 3 hours, naturally cooling to obtain the catalyst Au </u > -for catalyzing and burning the volatile organic waste gasCeO 2 @blank@SiO 2 Cordierite.
2. The catalyst Au/CeO prepared in this example is used for catalytic combustion of the volatile organic waste gas 2 @blank@SiO 2 Cordierite is used for catalytic combustion of volatile organic exhaust gases:
n-butanol catalytic combustion activity was evaluated in an atmospheric quartz tube reactor (inner diameter: 10 mm), in which the reaction atmosphere was a mixture of n-butanol and air, the n-butanol concentration was 1000ppm, and the volume space velocity (GHSV) was about 30000h -1 . The prepared monolithic catalyst sample was activated in an air atmosphere at 450 ℃ for 1 hour, and then cooled naturally to 100 ℃ to start the catalytic combustion reaction. Detecting the generated product on line by a gas chromatograph to obtain the ignition temperature T 50 (the conversion rate reached 50%) was 151℃and the complete conversion temperature T 90 (the conversion reached 90% of the temperature) was 196 ℃.
Example 4
1. Preparation of a monolithic catalyst for catalytic combustion of volatile organic waste gas:
1) Soaking commercial honeycomb ceramic cordierite in 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, weighing 0.6341g, and obtaining pretreated cordierite for later use;
2) 1g CuMnO is added to 2 Ball milling with ball mill, collecting sample to obtain CuMnO 2 Powder is reserved for standby;
3) 15g of glucose was dissolved in 25ml of deionized water and stirred for 0.5h to form a glucose solution; then CuMnO is added 2 Adding the powder into glucose solution, stirring at 20deg.C for 1 hr, and aging for 12 hr; centrifuging at 8000rpm for 1min, washing with deionized water for three times, and drying the washed centrifugal product in a drying oven at 120deg.C for 3 hr to obtain CuMnO 2 @C；
4) 0.5g of CuMnO 2 Mixing and ball grinding @ C and 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 the excess suspension in the channels was removed under a weak air flow, dried at 80 ℃ for 6h, and the weight was increased to achieve the desired loadingThe coating process is carried out for 3 times to obtain CuMnO 2 @C@SiO 2 Cordierite;
5) CuMnO is added to 2 @C@SiO 2 Roasting cordierite at 300 deg.c for 5 hr, and naturally cooling to obtain the integral catalyst CuMnO for catalytic combustion of volatile organic waste gas 2 @blank@SiO 2 Cordierite.
2. The volatile organic waste gas prepared in the embodiment is catalyzed and combusted to form the integral catalyst CuMnO 2 @blank@SiO 2 Cordierite is used for catalytic combustion of volatile organic exhaust gases:
the catalytic combustion activity of styrene was evaluated in an atmospheric quartz tube reactor (inner diameter: 10 mm), the reaction atmosphere was a mixture of styrene and air, the styrene concentration was 1000ppm, and the volume space velocity (GHSV) was about 30000h -1 . The prepared monolithic catalyst sample was activated in an air atmosphere at 450 ℃ for 1 hour, and then cooled naturally to 100 ℃ to start the catalytic combustion reaction. Detecting the generated product on line by a gas chromatograph to obtain the ignition temperature T 50 (the conversion reached 50% at 163 ℃ C.) and the complete conversion temperature T 90 (the temperature at which the conversion reached 90%) was 218 ℃.
Example 5
1. Preparation of a monolithic catalyst for catalytic combustion of volatile organic waste gas:
1) Soaking commercial honeycomb ceramic cordierite in 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, weighing 0.6428g, and obtaining pretreated cordierite for later use;
2) 1g of Ni/CeO 2 Ball milling with ball mill, collecting sample to obtain Ni/CeO 2 Powder is reserved for standby;
3) 25g of glucose was dissolved in 20ml of deionized water and stirred for 0.5h to form a glucose solution; then Ni/CeO is obtained 2 Adding the powder into glucose solution, stirring at 25deg.C for 1 hr, and aging for 24 hr; centrifuging at 6000rpm for 1.5min, washing with deionized water for three times, placing the washed centrifugal product into a drying oven, and drying at 80deg.C for 5 hr to obtain Ni/CeO 2 @C；
4) 1g ofNi/CeO 2 Mixing and ball grinding the @ C and 3ml of tetrabutyl orthosilicate, 18ml of absolute ethyl alcohol and 3ml of ammonia water into slurry; immersing the pretreated cordierite into the slurry for 2min, taking out and removing the redundant suspension in the channel under weak air flow, drying at 120 ℃ for 4h, repeating the coating process for 3 times to obtain Ni/CeO 2 @C@SiO 2 Cordierite;
5) Ni/CeO 2 @C@SiO 2 Roasting cordierite at 400 ℃ for 4 hours, naturally cooling to obtain the Ni/CeO catalyst for catalyzing and burning the volatile organic waste gas 2 @blank@SiO 2 Cordierite.
2. The catalyst Ni/CeO prepared in this example is used for catalytic combustion of the volatile organic waste gas 2 @blank@SiO 2 Cordierite is used for catalytic combustion of volatile organic exhaust gases:
the catalytic combustion activity of toluene was evaluated in an atmospheric quartz tube reactor (inner diameter: 10 mm), the reaction atmosphere was a mixture of toluene and air, the toluene concentration was 1000ppm, and the volume space velocity (GHSV) was about 30000h -1 . The prepared volatile organic waste gas is catalyzed and combusted to integrally catalyze Ni/CeO 2 @blank@SiO 2 The cordierite sample was activated in an air atmosphere at 450 ℃ for 1 hour and then cooled naturally to 100 ℃ to initiate the catalytic combustion reaction. Detecting the generated product on line by a gas chromatograph to obtain the ignition temperature T 50 (the conversion rate reaches 50%) at 154℃and the complete conversion temperature T 90 (the temperature at which the conversion reached 90%) was 227 ℃.
Example 6
1. Preparation of a monolithic catalyst for catalytic combustion of volatile organic waste gas:
1) Soaking commercial honeycomb ceramic cordierite in 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, weighing 0.6943g, and obtaining pretreated cordierite for later use;
2) 1g LaMnO is added 3 Ball milling with ball mill, collecting sample to obtain LaMnO 3 Powder is reserved for standby;
3) 15g glucose was dissolved in 15ml deionized water and stirredForming a glucose solution for 0.5 h; then LaMnO is obtained 3 Adding the powder into glucose solution, stirring at 25deg.C for 1 hr, and aging for 20 hr; centrifuging at 4000rpm for 2min, washing with deionized water for three times, and drying the washed centrifugal product in a drying oven at 80deg.C for 5 hr to obtain LaMnO 3 @C；
4) 1g of LaMnO 3 Mixing and ball-milling the mixture of @ C and 2.5ml of tetrabutyl orthosilicate, 12ml of absolute ethyl alcohol and 2.5ml of ammonia water into slurry; immersing the pretreated cordierite into the slurry for 2min, taking out and removing the redundant suspension in the channel under weak air flow, drying at 100deg.C for 5h, repeating the above coating process for 3 times to obtain LaMnO 3 @C@SiO 2 Cordierite;
5) LaMnO is added to 3 @C@SiO 2 Roasting cordierite at 500 deg.c for 3 hr, and natural cooling to obtain LaMnO as one integral catalyst for catalytic combustion of volatile organic waste gas 3 @blank@SiO 2 Cordierite.
2. The volatile organic waste gas prepared in the embodiment is catalyzed and combusted to form the monolithic catalyst LaMnO 3 @blank@SiO 2 Cordierite is used for catalytic combustion of volatile organic exhaust gases:
the catalytic combustion activity of o-xylene was evaluated in an atmospheric quartz tube reactor (inner diameter: 10 mm), the reaction atmosphere was a mixture of o-xylene and air, the o-xylene concentration was 1000ppm, and the volume space velocity (GHSV) was about 30000h -1 . The prepared volatile organic waste gas is catalyzed and combusted to integrally catalyze LaMnO 3 @blank@SiO 2 The cordierite sample was activated in an air atmosphere at 450 ℃ for 1 hour and then cooled naturally to 100 ℃ to initiate the catalytic combustion reaction. Detecting the generated product on line by a gas chromatograph to obtain the ignition temperature T 50 (the conversion reaches 50%) at 178℃and the complete conversion temperature T 90 (the conversion reached 90% of the temperature) was 236 ℃.
Comparative example 1
The difference from example 6 is the synthesis procedure of the monolithic catalyst.
1. Preparation of a monolithic catalyst for catalytic combustion of volatile organic waste gas:
1) Soaking commercial honeycomb ceramic cordierite in 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, weighing 0.6943g, and obtaining pretreated cordierite for later use;
2) Adding 5ml of tetrabutyl orthosilicate and 20ml of absolute ethyl alcohol into a three-necked flask, adjusting the pH value to 3 in a water bath at 80 ℃, and vigorously stirring for 2 hours to form silica sol;
3) 1g LaMnO is added 3 Ball milling with ball mill, adding into the silica sol prepared in 2), mixing uniformly to form coating solution, immersing pretreated cordierite in the coating solution for 2min, taking out and removing excessive suspension in the channel under weak air flow, drying at 100deg.C for 5h, and roasting at 500deg.C for 3h to obtain LaMnO 3 /SiO 2 Cordierite.
2. The volatile organic waste gas prepared in the embodiment is catalyzed and combusted to form the monolithic catalyst LaMnO 3 /SiO 2 Cordierite is used for catalytic combustion of volatile organic exhaust gases:
the catalytic combustion activity of o-xylene was evaluated in an atmospheric quartz tube reactor (inner diameter: 10 mm), the reaction atmosphere was a mixture of o-xylene and air, the o-xylene concentration was 1000ppm, and the volume space velocity (GHSV) was about 30000h -1 . The prepared volatile organic waste gas is catalyzed and combusted to integrally catalyze LaMnO 3 /SiO 2 The cordierite sample was activated in an air atmosphere at 450 ℃ for 1 hour and then cooled naturally to 100 ℃ to initiate the catalytic combustion reaction. Detecting the generated product on line by a gas chromatograph to obtain the ignition temperature T 50 (the conversion rate reached 50%) was 213℃and the complete conversion temperature T 90 (the temperature at which the conversion reached 90%) was 285 ℃.
As can be seen from the experimental results of example 6 and comparative example 1, the present invention provides LaMnO 3 @blank@SiO 2 The reaction activity of the cordierite monolithic catalyst under the high space velocity o-xylene is superior to that of LaMnO prepared by a conventional method 3 /SiO 2 The cordierite monolithic catalyst has better industrial application prospect.

Claims (9)

1. The catalyst for catalyzing and burning the volatile organic waste gas is characterized by comprising the following components in percentage by mass: 70-85 wt% of cordierite, 10-25 wt% of SiO2 and 1-10 wt% of CM; wherein the CM is any one of Pd/Al2O3, pt/gamma-Al 2O3, au/CeO2, cuMnO2, ni/CeO2 and LaMnO3, a gap is reserved between the SiO2 and the CM, the whole catalyst is prepared by wrapping the CM by glucose, wrapping the CM by porous silica, uniformly attaching the CM on the surface of a cordierite carrier and roasting.
2. The method for preparing the monolithic catalyst for catalytic combustion of volatile organic exhaust gas as claimed in claim 1, comprising the steps of:
(1) Acid pretreatment is carried out on the honeycomb ceramic cordierite, and the pretreated cordierite is obtained after washing, drying and roasting;
(2) Grinding CM into CM particles, adding the CM particles into glucose solution, stirring, aging, centrifuging, washing and drying to obtain CM@C;
(3) Mixing CM@C with 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@SiO2/cordierite;
(4) And roasting the CM@C@SiO2/cordierite to obtain the volatile organic waste gas catalytic combustion monolithic catalyst, namely the CM@blank@SiO2/cordierite monolithic catalyst.
3. The method for preparing the monolithic catalyst for catalytic combustion of volatile organic waste gas according to claim 2, wherein in the step (1), the acid pretreatment of the honeycomb ceramic cordierite is performed by immersing 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.
4. The method for preparing a catalyst for catalytic combustion of volatile organic waste gas as claimed in claim 2, wherein 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.
5. The method for preparing a catalyst for catalytic combustion of volatile organic waste gas according to claim 2, 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 hours, the aging time is 12-24 hours, the centrifugation rotation speed is 4000-8000 rpm, the centrifugation time is 1-2 minutes, the drying temperature is 60-120 ℃, and the drying time is 3-6 hours.
6. The preparation method of the monolithic catalyst for catalytic combustion of volatile organic waste gas according to claim 2, wherein in the step (3), the mass ratio of cm@c, tetrabutyl orthosilicate, ammonia water and absolute ethyl alcohol is 3-10: 6-15: 5-15: 65-80.
7. The method for preparing a catalyst for catalytic combustion of volatile organic waste gas as claimed in claim 2, 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 hours.
8. The method for preparing a catalyst for catalytic combustion of volatile organic waste gas as claimed in claim 2, wherein in the step (4), the roasting temperature is 300-600 ℃ and the roasting time is 3-5 hours.
9. The use of the monolithic catalyst for catalytic combustion of volatile organic waste gas according to claim 1 in catalytic combustion reactions of volatile organic waste gas of alkanes, alkenes, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons and derivatives thereof.
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