Bimetal water-resistant catalyst for catalytic oxidation of VOCs at normal temperature in cooperation with ozone and preparation method thereof

Abstract

The invention belongs to the field of catalysts, and particularly relates to a bimetallic water-resistant catalyst for normal-temperature synergistic ozone catalytic oxidation of VOCs (volatile organic compounds) and a preparation method of the bimetallic water-resistant catalyst. The water-resistant catalyst comprises a multi-element active component which is loaded on a zeolite carrier, wherein the multi-element active component comprises Mn2O3 and auxiliary metal M (M is Fe, Co, Ni, Ce and Cu). The water-resistant catalyst provided by the invention can cooperate with ozone at room temperature to realize efficient catalytic oxidation of VOCs, and can efficiently remove toluene and realize complete decomposition of ozone. Meanwhile, the poisoning effect of water molecules in the environment on active substances in the actual industrial application process can be effectively relieved, the water resistance of the catalyst is remarkably improved, the conversion rate of catalyzing ozone to oxidize toluene in a water-containing atmosphere can reach 90% or above, attenuation is weak compared with that in a dry environment, and the application prospect is wide.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalysts, and specifically relates to room temperature synergistic ozone catalytic oxidation VOCs Bimetallic water-resistant catalyst and preparation method thereof. Background Art

[0002] With the acceleration of the world's industrialization process, volatile organic compounds ( VOCs ) are released into the environment, causing serious impacts and harm to human health, and have become a focus of global air pollution control. Therefore, there is an urgent need for a means to degrade volatile organic compounds to reduce their presence in the environment and minimize their impact on the environment. VOCs It is a complex system that can be divided into hydrocarbons, oxygen-containing organic compounds, halogenated organic compounds, sulfur-containing / nitrogen-containing organic compounds and other substances according to their chemical structure, such as phenols, indoles, ethers, etc. The main sources of volatile organic compounds include two parts, anthropogenic sources and natural sources. Anthropogenic sources mainly include exhaust emissions from industry, agriculture, automobiles, airplanes and other transportation vehicles, interior decoration, fossil fuel combustion, daily cooking, etc. Uncontrolled emission of volatile organic compounds will cause great damage to the environment. For example, volatile organic compounds (VOCs) emitted into the air VOCs ) will react with nitrogen oxides and hydroxyl radicals under ultraviolet radiation to produce ozone, secondary aerosols, photochemical smog and other substances that have serious impacts on humans and the environment. PM 2.5 , peroxyacetyl nitrate ( PAN ) and other common precursors of pollutants, its teratogenicity, carcinogenicity, mutagenicity and other effects on the human body are also well known. VOCs Governance is an important way to reduce ozone pollution and improve ambient air.

[0003] Currently, common governance VOCs The technologies used include adsorption, photocatalysis, catalytic oxidation, non-thermal plasma, catalytic ozonation, etc. Among the above methods, the adsorption method faces the problem of complex by-products, and non-thermal plasma and photocatalysis have high requirements for electrical energy and light energy. Compared with other methods, the catalytic oxidation method has lower energy consumption and can directly VOCs Mineralization CO x Compared with catalytic oxidation, the advantage of catalytic ozone oxidation is that the addition of ozone can achieve room temperature treatment. VOCs , can improve oxygen utilization, save energy and achieve efficient treatment VOCs .

[0004] For this technology, the key to deep oxidation is an efficient catalyst. There are two main types of catalysts currently used, supported precious metals and transition metal catalysts. Among supported precious metal catalysts, Pt 、 Pd It has high low-temperature activity, but it is not suitable for industrial use due to its high price. Transition metal catalysts have problems such as residual organic by-products, incomplete ozone decomposition, and low mineralization rate during the reaction. Therefore, dual-active component catalysts have also been developed, and their performance is better than that of single transition metal catalysts. Dual-active component catalysts often use precious metal components such as platinum, palladium, ruthenium, and silver. Even if the amount of precious metals is reduced by optimizing the preparation method, there are still disadvantages of high cost and difficulty in commercial promotion. At the same time, in the actual application process, the environment H 2 O It will compete with ozone for adsorption on the active sites of the catalyst, leading to catalyst deactivation, which is also a problem that cannot be ignored. Therefore, it is urgent to develop a high-efficiency, water-resistant and low-cost catalyst.

[0005] Public Account CN 114160184 A The invented synthetic silver nanoparticles are used to prepare silver-cerium catalysts. Silver and cerium have strong interactions, achieving high CO 2. Selectivity and good stability. However, the preparation process involves multiple steps, including silver nanoparticle synthesis, molecular sieve treatment and loading, and the reaction conditions of each step, such as solution ratio, reaction temperature, and time, must be strictly controlled. The conditions are relatively harsh, increasing the difficulty and cost of preparation.

[0006] CN 115555018 A Publicly available Mn 2 O 3 is carrier loading Pt and Ce The catalyst can remove toluene at a rate of 95% at room temperature, but it ignores the effect of humidity on the catalyst and is difficult to be directly used in complex waste gas treatment scenarios. Summary of the Invention

[0007] Purpose of the invention: The first purpose of the present invention is to overcome the shortcomings of existing catalysts such as high cost, low pollutant conversion rate, and poor water resistance, and to develop a room temperature high efficiency catalytic ozone oxidation VOCs A water-resistant catalyst; a second object of the present invention is to provide a method for preparing the catalyst.

[0008] Technical solution: Room temperature synergistic ozone catalytic oxidation VOCs A bimetallic water-resistant catalyst comprises: a carrier, a first active component and a second active component; The carrier and the first active component are constructed to obtain Mn / MOR Catalyst, the Mn / MOR The catalyst is modified with a second active component Mn - M / MOR Bimetallic water-resistant catalyst, wherein M Indicates additive metal.

[0009] In a further embodiment, the carrier is zeolite MOR , the first active component is a transition metal oxide MnOx , x Represents the stoichiometric ratio of oxygen atoms to manganese atoms.

[0010] In a further embodiment, the second active ingredient is a promoter metal M , the auxiliary metal M for Fe 、 Co 、 Ni 、 Ce or Cu At least one of .

[0011] In a further embodiment, Mn - M / MOR In bimetallic water-resistant catalysts, Mn The percentage of the element in the total mass of the catalyst is 0.5~10 wt .%; additive metal M The element accounts for 0.5~5% of the total mass of the catalyst wt .%.

[0012] In a further embodiment, the bimetallic water-resistant catalyst has a toluene removal rate of 90-100% at room temperature.

[0013] In a further embodiment, the bimetallic water-resistant catalyst is used in the ozone-catalyzed oxidation of low-concentration toluene.

[0014] A preparation method for preparing the above-mentioned room temperature synergistic ozone catalytic oxidation VOCs The bimetallic water-resistant catalyst comprises the following steps: Step 1: Zeolite MOR Place in a beaker, mix with deionized water to make a suspension, and place in an ultrasonic tank to obtain a solution. A ; Step 2: The solution obtained in step 1 A Place on a magnetic stirrer and add the manganese solution dropwise to the solution A After uniform mixing and drying, the Mn / MOR powder; Step 3: Add the auxiliary metal M The nitrate solution was dissolved in deionized water and added Mn / MOR The powder is dispersed in an ultrasonic bath, dried, calcined and tableted. Mn - M / MOR Bimetallic water-resistant catalyst.

[0015] In a further embodiment, the ultrasonic dispersion time in step 1 and step 3 is 60 to 120 seconds. min .

[0016] In a further embodiment, the stirring rate of the magnetic stirrer in step 2 is 400 rpm / min, stirring time is 6 h .

[0017] In a further embodiment, the calcination temperature in step 3 is 500-600°C; the calcination time is 3-6 h ; The heating rate of calcination is 5~10℃ / min .

[0018] Beneficial effects of the present invention: The present invention uses zeolite MOR Molecular sieves, with their large surface area, high adsorption capacity, and high thermal and hydrothermal stability, can regulate the humidity within the crystals and facilitate the formation of crystals within the pores. Furthermore, their microporous structure, with its well-controlled shape, enhances the adsorption performance of molecular sieves.

[0019] The manganese salt and iron salt of the present invention function to decompose ozone into active oxygen atoms and efficiently remove toluene through a redox reaction during the activity evaluation process. The manganese-based catalyst exhibits strong low-temperature activity due to its multiple oxidation states and high dispersibility.

[0020] The doping of additive metals promotes MnOx The interaction with the carrier is more conducive to Mn 3+ The formation of more oxygen vacancies induces Mn - M ( M = Fe 、 Co 、 Ni 、 Ce 、 Cu One or more of the above) / MOR It showed excellent ozone decomposition ability and toluene removal rate. Mn and M The modification alleviates the hydrophilicity of the zeolite material, thereby exhibiting certain water resistance.

[0021] The present invention adopts the impregnation method to uniformly load the manganese oxide on the zeolite carrier, and then uses ultrasonic dispersion to M Scattered Mn / zeolite. This method promotes the interaction between manganese oxide and the carrier by doping auxiliary metals, strengthens the interfacial electron transfer ability, decomposes ozone into active oxygen atoms, and at the same time cooperates with the large specific surface area of zeolite. VOCs Provide sufficient adsorption sites.

[0022] Compared with the prior art, the present invention has the following significant advantages: (1) The catalyst prepared by the method of the present invention is simple to prepare, and the raw materials are easy to obtain, which is conducive to industrialization; (2) The carrier selected by the present invention has a large specific surface area and excellent adsorption capacity, which helps the active components to be highly dispersed on the carrier; (3) The active components of the present invention are introduced into the catalyst. Mn and additives M As an active component, it exhibits synergistic effects with ozone at room temperature. VOCs High conversion rate of oxidation; (4) The catalyst prepared by the present invention, the auxiliary metal M Select as Fe When the catalyst has better water resistance; (5) the catalyst prepared by the present invention Mn - Fe / MOR The catalyst has good stability and can still maintain good toluene degradation performance during long-term reaction in a water-containing atmosphere. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a graph showing the activity test results of the catalyst in Example 2 under dry atmosphere and water-containing atmosphere.

[0024] Figure 2 This is a graph showing the activity test results of the catalyst in comparative example 1 under dry atmosphere and water-containing atmosphere.

[0025] Figure 3 The results of the activity test of the catalyst in Example 3 under dry atmosphere and water-containing atmosphere are shown.

[0026] Figure 4 The results of the activity test of the catalyst in Example 4 under dry atmosphere and water-containing atmosphere are shown.

[0027] Figure 5 The results of the activity test of the catalyst in Example 5 under dry atmosphere and water-containing atmosphere are shown.

[0028] Figure 6 Activity test results of the catalyst in Example 6 under dry atmosphere and water-containing atmosphere. DETAILED DESCRIPTION

[0029] The technical solution of the present invention will be further described below in conjunction with the embodiments and the accompanying drawings.

[0030] Example 1 This embodiment discloses the room temperature synergistic ozone catalytic oxidation VOCs The bimetallic water-resistant catalyst comprises: a carrier, a first active component and a second active component. Mn / MOR Catalyst, the Mn / MOR The catalyst is modified with a second active component Mn - M / MOR Bimetallic water-resistant catalyst, wherein M Indicates additive metal.

[0031] In this embodiment, the carrier is zeolite MOR , the first active component is a transition metal oxide MnOx , x Represents the stoichiometric ratio of oxygen atoms to manganese atoms.

[0032] The second active ingredient is an auxiliary metal M , the auxiliary metal M for Fe 、 Co 、 Ni 、 Ce or Cu At least one of .

[0033] Mn - M / MOR In bimetallic water-resistant catalysts, Mn The percentage of the element in the total mass of the catalyst is 0.5~10 wt .%; additive metal M The element accounts for 0.5~5% of the total mass of the catalyst wt .%.

[0034] The prepared Mn - M / MOR Bimetallic water-resistant catalysts are used in the ozone catalytic oxidation of low-concentration toluene.

[0035] Example 2 This embodiment discloses a Mn - M / MOR The preparation method of the bimetallic water-resistant catalyst comprises the following steps: (1) First weigh 8 g of H -MOR Molecular sieve powder is dissolved in 20 mL Ultrasonic dispersion in deionized water for 10 min , and obtain a solution A ; (2) Measure 0.52 g of Mn ( NO 3)2(Sinopharm, AR ) solution is evenly dispersed in 20 mL In deionized water, the solution B Then, while stirring, B Add dropwise into the solution A The stirring rate was 400 rpm ; Set at 60 kHz Ultrasonic dispersion 90 min , and then stirred in a magnetic stirrer for 6 h The mixture was then dried in an oven at 80°C for 12 h , crushed thoroughly in an agate mortar to obtain a manganese loading of 1 wt .% of 1 Mn / MOR sample.

[0036] (3) Weigh 0.58 g of Fe ( NO 3)3∙9 H 2 O (National Medicine, AR ) dissolved in 20 mL In high-purity water, a solution was obtained C ; Weigh 8.081 g 1 Mn / MOR Samples and 60 mL Mix with deionized water to obtain a solution D ; Under stirring conditions, the solution C Add dropwise to the solution D Middle; set at 60 Hz Ultrasonic dispersion 90 min , and then stirred in a magnetic stirrer for 6 h The mixture was then dried in an oven at 80°C for 12 h , crushed thoroughly in an agate mortar, and spun in air at 10°C / min Heat to 550℃ and calcine for 3 hours h , compacted and crushed by tablet press, screened to 40-60 mesh size, tablet press pressure 10 Mpa ,get Fe Load is 1 wt .% of 1Mn -1 Fe / MOR Catalyst samples.

[0037] Example 3 This embodiment discloses a Mn - M / MOR The preparation method of the bimetallic water-resistant catalyst comprises the following steps: (1) First weigh 8 g of H - MOR Molecular sieve powder is dissolved in 20 mL Ultrasonic dispersion in deionized water for 10 min , and obtain a solution A ; (2) Measure 0.52 g of Mn ( NO 3)2(Sinopharm, AR ) solution is evenly dispersed in 20 mL In deionized water, the solution B Then, while stirring, B Add dropwise into the solution A The stirring rate was 400 rpm ; Set at 60 kHz Ultrasonic dispersion 90 min , and then stirred in a magnetic stirrer for 6 h The mixture was then dried in an oven at 80°C for 12 h , crushed thoroughly in an agate mortar to obtain a manganese loading of 1 wt .% of 1 Mn / MOR sample.

[0038] (3) Weigh 0.41 g of Co ( NO 3) 2∙6 H 2 O (National Medicine, AR ) dissolved in 20 mL In high-purity water, a solution was obtained C ; Weigh 8.081 g 1 Mn / MOR Samples and 60 mL Mix with deionized water to obtain a solution D ; Under stirring conditions, the solution C Add dropwise to the solution D Middle; set at 60 Hz Ultrasonic dispersion 90 min, and then stirred in a magnetic stirrer for 6 h The mixture was then dried in an oven at 80°C for 12 h , crushed thoroughly in an agate mortar, and spun in air at 10°C / min Heat to 550℃ and calcine for 3 hours h , compacted and crushed by tablet press, screened to 40-60 mesh size, tablet press pressure 8 Mpa ,get Co Load is 1 wt .% of 1 Mn -1 Co / MOR Catalyst samples.

[0039] Example 4 This embodiment discloses a Mn - M / MOR The preparation method of the bimetallic water-resistant catalyst comprises the following steps: (1) First weigh 8 g of H - MOR Molecular sieve powder is dissolved in 20 mL Ultrasonic dispersion in deionized water for 10 min , and obtain a solution A ; (2) Measure 0.52 g of Mn ( NO 3)2(Sinopharm, AR ) solution is evenly dispersed in 20 mL In deionized water, the solution B Then, while stirring, B Add dropwise into the solution A The stirring rate was 400 rpm ; Set at 60 kHz Ultrasonic dispersion 90 min , and then stirred in a magnetic stirrer for 6 h The mixture was then dried in an oven at 80°C for 12 h , crushed thoroughly in an agate mortar to obtain a manganese loading of 1 wt .% of 1 Mn / MOR sample.

[0040] (3) Weigh 0.41 g of Ni ( NO 3) 2∙6 H 2 O (National Medicine, AR ) dissolved in 20 mLIn high-purity water, a solution was obtained C ; Weigh 8.081 g 1 Mn / MOR Samples and 60 mL Mix with deionized water to obtain a solution D ; Under stirring conditions, the solution C Add dropwise to the solution D Middle; set at 60 Hz Ultrasonic dispersion 90 min , and then stirred in a magnetic stirrer for 6 h The mixture was then dried in an oven at 80°C for 12 h , crushed thoroughly in an agate mortar, and spun in air at 10°C / min Heat to 550℃ and calcine for 3 hours h , compacted and crushed by tablet press, screened to 40-60 mesh size, tablet press pressure 8 Mpa ,get Ni Load is 1 wt .% of 1 Mn -1 Ni / MOR Catalyst samples.

[0041] Example 5 This embodiment discloses a Mn - M / MOR The preparation method of the bimetallic water-resistant catalyst comprises the following steps: (1) First weigh 8 g of H - MOR Molecular sieve powder is dissolved in 20 mL Ultrasonic dispersion in deionized water for 10 min , and obtain a solution A ; (2) Measure 0.52 g of Mn ( NO 3)2(Sinopharm, AR ) solution is evenly dispersed in 20 mL In deionized water, the solution B Then, while stirring, B Add dropwise into the solution A The stirring rate was 400 rpm ; Set at 60 kHz Ultrasonic dispersion 90 min , and then stirred in a magnetic stirrer for 6 h The mixture was then dried in an oven at 80°C for 12 h, crushed thoroughly in an agate mortar to obtain a manganese loading of 1 wt .% of 1 Mn / MOR sample.

[0042] (3) Weigh 0.26 g of Ce ( NO 3)3∙6 H 2 O (National Medicine, AR ) dissolved in 20 mL In high-purity water, a solution was obtained C ; Weigh 8.081 g 1 Mn / MOR Samples and 60 mL Mix with deionized water to obtain a solution D ; Under stirring conditions, the solution C Add dropwise to the solution D Middle; set at 60 Hz Ultrasonic dispersion 90 min , and then stirred in a magnetic stirrer for 6 h The mixture was then dried in an oven at 80°C for 12 h , crushed thoroughly in an agate mortar, and spun in air at 10°C / min Heat to 550℃ and calcine for 3 hours h , compacted and crushed by tablet press, screened to 40-60 mesh size, tablet press pressure 8 Mpa ,get Ce Load is 1 wt .% of 1 Mn -1 Ce / MOR Catalyst samples.

[0043] Example 6 This embodiment discloses a Mn - M / MOR The preparation method of the bimetallic water-resistant catalyst comprises the following steps: (1) First weigh 8 g of H - MOR Molecular sieve powder is dissolved in 20 mL Ultrasonic dispersion in deionized water for 10 min , and obtain a solution A ; (2) Measure 0.52 g of Mn ( NO 3)2(Sinopharm, AR ) solution is evenly dispersed in 20mL In deionized water, the solution B Then, while stirring, B Add dropwise into the solution A The stirring rate was 400 rpm ; Set at 60 kHz Ultrasonic dispersion 90 min , and then stirred in a magnetic stirrer for 6 h The mixture was then dried in an oven at 80°C for 12 h , crushed thoroughly in an agate mortar to obtain a manganese loading of 1 wt .% of 1 Mn / MOR sample.

[0044] (3) Weigh 0.31 g of Cu ( NO 3)3∙3 H 2 O (National Medicine, AR ) dissolved in 20 mL In high-purity water, a solution was obtained C ; Weigh 8.081 g 1 Mn / MOR Samples and 60 mL Mix with deionized water to obtain a solution D ; Under stirring conditions, the solution C Add dropwise to the solution D Middle; set at 60 Hz Ultrasonic dispersion 90 min , and then stirred in a magnetic stirrer for 6 h The mixture was then dried in an oven at 80°C for 12 h , crushed thoroughly in an agate mortar, and spun in air at 10°C / min Heat to 550℃ and calcine for 3 hours h , compacted and crushed by tablet press, screened to 40-60 mesh size, tablet press pressure 8 Mpa ,get Cu Load is 1 wt .% of 1 Mn -1 Cu / MOR Catalyst samples.

[0045] Comparative Example 1 This example provides a conventional preparation method, the steps are as follows: (1) First weigh 8 g of H - MOR Molecular sieve powder is dissolved in 20mL Ultrasonic dispersion in deionized water for 10 min , and obtain a solution A ; (2) Measure 0.52 g of Mn ( NO 3)2(Sinopharm, AR ) solution is evenly dispersed in 20 mL In deionized water, the solution B Then, while stirring, B Add dropwise into the solution A The stirring rate was 400 rpm ; Set at 60 Hz Ultrasonic dispersion 90 min , and then stirred in a magnetic stirrer for 6 h The mixture was then dried in an oven at 80°C for 12 h , crushed thoroughly in an agate mortar, and spun in air at 10°C / min Heat to 550℃ and calcine for 3 hours h , compacted and crushed by tablet press, screened to 40-60 mesh size, tablet press pressure 8 Mpa , and get 1 Mn / MOR catalyst.

[0046] Catalyst activity test Examples 2-6 and Comparative Example 1 were used for catalyst activity test, and 3 mL The 40~60 mesh catalyst was placed in the catalyst activity evaluation device for testing. The initial concentrations of toluene and ozone were 20 ppm and 300 ppm , balance gas N 2. Gas flow rate 1400 mL / min The water-containing atmosphere is heated and vaporized by a certain flow of deionized water through the vaporization chamber (temperature is 80℃) at the front end of the reactor, and N 2. Purge is achieved. The gas at the outlet of the catalytic reactor is analyzed by gas chromatograph to determine CO 、 CO The concentrations of 2 and toluene were measured, and the residual ozone was quantified by iodine titration. Before the activity evaluation, the catalyst was first saturated by toluene adsorption, and then ozone was injected into the simulated flue gas. The reaction activity was measured by toluene conversion, ozone decomposition rate and CO 2. Mineralization rate expression.

[0047] According to the above test conditions, the toluene removal rate, ozone decomposition rate and CO2 Mineralization rate Figures 1 - 6 shown. Figures 1 - 6 The two dotted lines indicate that 1 vol .% water vapor, the gas composition at this time is toluene + ozone + nitrogen + water vapor, and the rest of the time period is toluene + ozone + nitrogen.

[0048] Depend on Figure 1 It can be seen that: (1) Fe The modified catalyst has the best water resistance. The conversion rate of toluene in catalytic ozone oxidation in a water-containing atmosphere can reach more than 90%, which is slightly weaker than that in a dry environment. (2) When the water vapor is stopped, the toluene removal rate, ozone decomposition rate and CO 2The mineralization rate returns to the original level.

[0049] Figure 2 The test results of the catalyst performance without adding additives show that: (1) Comparative Example 1 shows the most serious competitive adsorption between ozone and water vapor. It is immediately deactivated after the introduction of water vapor, and the toluene removal rate drops sharply. It is difficult to recover after the water vapor is stopped, indicating that water vapor causes irreversible deactivation of the catalyst; (2) Only the ozone decomposition rate of Comparative Example 1 is lower than 100%. This may be because the catalyst without adding additives does not have sufficient active sites to provide for ozone adsorption and decomposition into active oxygen atoms.

[0050] Depend on Figures 3 - 6 It can be seen that adding other additives does not significantly improve the water resistance of the catalyst.

[0051] Based on this, the present invention has developed a kind of strong reducing and multiple oxidation states Mn and Fe 、 Co 、 Ni 、 Ce 、 Cu Elements are loaded on zeolites with abundant acidic sites ( MOR ) bimetallic catalyst. After high temperature calcination, the catalyst shows Mn - O - M The strong interaction between the two species has excellent electron transfer ability, showing excellent synergistic ozone catalytic oxidation performance of toluene and water resistance.

Claims

1. Room temperature synergistic ozone catalytic oxidation VOCs The bimetallic water-resistant catalyst is characterized in that include: a carrier, a first active ingredient, and a second active ingredient; The carrier and the first active component are constructed to obtain Mn / MOR Catalyst, the Mn / MOR The catalyst is modified with a second active component Mn - M / MOR Bimetallic water-resistant catalyst, wherein M Indicates additive metal.

2. The room temperature collaborative ozone catalytic oxidation according to claim 1 VOCs The bimetallic water-resistant catalyst is characterized in that The carrier is zeolite MOR , the first active component is a transition metal oxide MnOx , x Represents the stoichiometric ratio of oxygen atoms to manganese atoms.

3. The room temperature collaborative ozone catalytic oxidation according to claim 1 VOCs The bimetallic water-resistant catalyst is characterized in that The second active ingredient is an auxiliary metal M , the auxiliary metal M for Fe 、 Co 、 Ni 、 Ce or Cu At least one of .

4. The room temperature collaborative ozone catalytic oxidation according to claim 1 VOCs The bimetallic water-resistant catalyst is characterized in that Mn - M / MOR In bimetallic water-resistant catalysts, Mn The percentage of the element in the total mass of the catalyst is 0.5~10 wt .%; additive metal M The element accounts for 0.5~5% of the total mass of the catalyst wt .%.

5. The room temperature collaborative ozone catalytic oxidation according to claim 1 VOCs The bimetallic water-resistant catalyst is characterized in that The toluene removal rate of the bimetallic water-resistant catalyst at room temperature is 90-100%.

6. The room temperature synergistic ozone catalytic oxidation according to any one of claims 1 to 5 VOCs The bimetallic water-resistant catalyst is characterized in that The bimetallic water-resistant catalyst is used in the ozone catalytic oxidation of low-concentration toluene.

7. A preparation method for preparing the room temperature synergistic ozone catalytic oxidation according to any one of claims 1 to 5 VOCs The bimetallic water-resistant catalyst is characterized in that The following steps are involved: Step 1: Zeolite MOR Place in a beaker, mix with deionized water to make a suspension, and place in an ultrasonic tank to obtain a solution. A ; Step 2: The solution obtained in step 1 A Place on a magnetic stirrer and add the manganese solution dropwise to the solution A After ultrasonic mixing and drying, the Mn / MOR powder; Step 3: Add the auxiliary metal M The nitrate solution was dissolved in deionized water and added Mn / MOR The powder is dispersed in an ultrasonic bath, dried, calcined and tableted. Mn - M / MOR Bimetallic water-resistant catalyst.

8. A preparation method according to claim 7, characterized in that, The ultrasonic dispersion time in step 2 and step 3 is 60-120 min .

9. A preparation method according to claim 7, characterized in that, The stirring rate of the magnetic stirrer in step 2 is 400 rpm / min, stirring time is 6 h .

10. A preparation method according to claim 7, characterized in that: The calcination temperature in step 3 is 500-600°C; the calcination time is 3-6 h ; The heating rate of calcination is 5~10℃ / min .

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