Catalyst for catalytic oxidation of vocs and method of making and using same

Abstract

The application relates to the field of catalyst preparation, and discloses a VOCs catalytic oxidation catalyst, a preparation method and application thereof, the method comprising the following steps: mixing a noble metal precursor, a reducing agent, a stabilizer and water to prepare a noble metal colloidal solution; contacting an organic acid salt of cerium with the noble metal colloidal solution, and adjusting the pH of the material to 3-8 to obtain a noble metal-cerium mixed solution; mixing a substrate source, a transition metal oxide and an oxide of a rare earth metal except cerium with the noble metal colloidal solution to obtain a catalyst slurry; loading the catalyst slurry on a carrier, and performing drying and ozone calcination treatment to obtain a VOCs catalytic oxidation catalyst loaded with a catalyst layer. The organic acid salt of cerium is adsorbed on the surface of noble metal particles, and the catalyst is calcined at low temperature by using ozone, so that the organic groups are removed sufficiently, the number of interface sites is retained as much as possible, and the obtained catalyst can realize efficient conversion of VOCs at low temperature.

Description

Technical Field

[0001] This invention relates to the field of catalyst preparation, specifically to a VOCs catalytic oxidation catalyst, its preparation method, and its application in the catalytic oxidation of VOCs. Background Technology

[0002] Volatile organic compounds (VOCs) are the main pollutants emitted during the production and processing of various industries such as petrochemicals, printing, and pharmaceuticals. They have a distinct odor and can irritate or damage human organs. In severe cases, they can cause poisoning or cancer, endangering human health. In addition, VOCs in the atmosphere can also cause problems such as photochemical smog, seriously damaging the ecological environment.

[0003] VOCs pollution control can be categorized into adsorption, incineration, catalytic oxidation, biological methods, and membrane separation. Among these, catalytic oxidation technology is one of the most promising technologies for VOCs removal; and developing high-performance catalytic oxidation catalysts is key to achieving waste gas purification and green production. Currently, most catalytic oxidation catalysts use honeycomb inert materials (such as cordierite) as carriers to load active components with low-temperature oxidation properties to achieve VOCs catalytic oxidation.

[0004] Catalytic oxidation catalysts for VOCs typically employ noble metals such as gold, silver, platinum, and palladium as active components because these metals can simultaneously adsorb and activate VOCs and O2 at low temperatures, with the two adsorbed species reacting on the noble metal surface via the LH mechanism. However, near the ignition temperature, the two reactants compete for adsorption on the noble metal surface, inhibiting oxygen adsorption and activation to some extent, resulting in a lack of available oxygen for the reaction at the ignition temperature. To address this issue, cerium-based materials are often introduced into VOCs catalysts as oxygen storage and release components, providing active lattice oxygen species for VOCs oxidation. In this case, VOCs adsorbed on the noble metal surface react with the lattice oxygen species of the cerium-based material at the interface via the mvK mechanism, avoiding the problem of competitive adsorption between VOCs and O2. For example, CN201811568947 discloses an oxidation catalyst for the catalytic combustion of VOCs and its preparation method, in which a Pt- and CeO2-containing coating is coated on the surface of a cordierite honeycomb ceramic support, and the catalyst can achieve complete toluene conversion below 250℃. However, this conventional preparation method, which involves directly adding the noble metal precursor solution to a mixed slurry containing a matrix, cerium-based oxides, and transition metal oxides, results in low contact efficiency between the noble metal and cerium-based oxides, leading to insufficient low-temperature oxidation performance of the catalyst. Improving slurry preparation technology to promote close coupling between redox components (noble metals) and oxygen storage / release components, thereby enhancing the efficiency of oxygen species transfer and utilization, and providing a VOCs catalyst that fully utilizes its catalytic performance at low temperatures, is a pressing issue in this field. Summary of the Invention

[0005] The purpose of this invention is to provide a VOCs catalyst that can fully exert its catalytic oxidation performance at low temperatures. Specifically, it provides a VOCs catalytic oxidation catalyst, its preparation method, and the application of the catalyst in the catalytic oxidation of VOCs. The method of this invention adsorbs cerium organic acid salts onto the surface of noble metal particles, achieving close coupling between redox components and oxygen storage and release components. The adsorption amount can be controlled by adjusting the pH of the solution. After slurry coating, the catalyst is calcined at low temperature using ozone to fully remove organic groups while retaining as many interfacial sites as possible. The resulting catalyst can achieve efficient conversion of VOCs at low temperatures.

[0006] To achieve the above objectives, the first aspect of the present invention provides a method for preparing a VOCs catalytic oxidation catalyst, the method comprising:

[0007] (1) A noble metal colloidal solution is prepared by mixing a precursor of the noble metal, a reducing agent, a stabilizer and water.

[0008] (2) Contact the organic acid salt of cerium with the colloidal solution of noble metal and adjust the pH of the material to 3-8 to obtain a noble metal-cerium mixture;

[0009] (3) Mix the matrix source, transition metal oxides and rare earth metal oxides other than cerium with the noble metal colloidal solution to obtain a catalyst slurry;

[0010] (4) The catalyst slurry is loaded onto the support and then dried and calcined with ozone to obtain a VOCs catalytic oxidation catalyst with a catalyst layer.

[0011] Preferably, the organic acid salt of cerium is a carboxylate of cerium.

[0012] Preferably, the molar ratio of the cerium organic acid salt to the noble metal is 1-30:1.

[0013] A second aspect of the present invention provides a catalyst prepared according to the method described above.

[0014] A third aspect of the present invention provides a VOCs catalytic oxidation catalyst, the catalyst comprising a support and a catalyst layer supported on the support;

[0015] The catalyst layer contains a catalyst support and an active component. The catalyst support includes cerium oxide, a matrix, transition metal oxides, and rare earth oxides other than cerium. The active component is a noble metal.

[0016] Cerium oxide is coated on the surface of the noble metal.

[0017] The fourth aspect of the present invention relates to the application of the VOCs oxidation catalyst described above in the catalytic oxidation of VOCs.

[0018] In this invention, cerium organic acid salts are contacted with a noble metal colloidal solution, and the pH of the material is adjusted to 3-8, so that the cerium organic acid salts are adsorbed on the surface of the noble metal particles. This achieves tight coupling between the redox components and the oxygen storage and release components, effectively improving the contact efficiency between the redox components and the oxygen storage and release components, promoting oxygen transfer, and improving the low-temperature catalytic oxidation performance of the catalyst. Furthermore, the adsorption amount can be controlled by adjusting the pH of the solution. After slurry coating, the catalyst is calcined at low temperature using ozone. While fully removing organic groups, the number of interfacial sites is preserved as much as possible. The resulting catalyst can achieve efficient conversion of VOCs at low temperatures.

[0019] The preparation method provided in this invention effectively improves the utilization efficiency of active metals by constructing an interface between noble metals and cerium-based oxides, thereby reducing the amount of noble metals and rare earth element oxides used in the catalyst and thus reducing costs.

[0020] The preparation method provided in this invention helps to form a strong metal-support interaction between noble metals and cerium-based oxides, thereby improving the hydrothermal stability of the catalyst.

[0021] The preparation method provided in this invention is simple to operate, suitable for mass production, and is expected to be extended to the preparation of various fixed-bed catalytic materials, showing broad application prospects. Attached Figure Description

[0022] Figure 1 This is a TEM image of the noble metal colloidal particles in Example 1.

[0023] Figure 2 This is a TEM image of the noble metal colloidal particles adsorbing cerium citrate in Example 1. Detailed Implementation

[0024] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0025] The first aspect of this invention provides a method for preparing a VOCs catalytic oxidation catalyst, the method comprising:

[0026] (1) A noble metal colloidal solution is prepared by mixing a precursor of the noble metal, a reducing agent, a stabilizer and water.

[0027] (2) Contact the organic acid salt of cerium with the colloidal solution of noble metal and adjust the pH of the material to 3-8 to obtain a noble metal-cerium mixture;

[0028] (3) Mix the matrix source, transition metal oxides and rare earth metal oxides other than cerium with the noble metal colloidal solution to obtain a catalyst slurry;

[0029] (4) The catalyst slurry is loaded onto the support and then dried and calcined with ozone to obtain a VOCs catalytic oxidation catalyst with a catalyst layer.

[0030] In this invention, the noble metal can be selected from at least one of Au, Ag, Pt, and Pd, preferably Pt. The precursor of the noble metal is preferably a soluble salt of the noble metal, such as at least one of acetate, nitrate, and chloride, preferably a nitrate. For example, if the noble metal is Pt, the precursor of the noble metal is also a precursor of Pt, such as platinum nitrate, platinum tetrachloride, or platinum acetate. Those skilled in the art are familiar with the types of soluble salts of other noble metals, which will not be elaborated here.

[0031] Preferably, the reducing agent is selected from at least one of ascorbic acid, borohydride (such as sodium borohydride or potassium borohydride), and citrate (such as sodium citrate or potassium citrate), more preferably ascorbic acid.

[0032] Preferably, the stabilizer is an organic amine; more preferably, the stabilizer is selected from at least one of diethylamine, triethylamine, and trimethylamine; and even more preferably, diethylamine and / or triethylamine.

[0033] In this invention, the order in which the precious metal precursor, reducing agent, stabilizer, and water are first mixed is not particularly limited, and those skilled in the art can add them in any order. Preferably, the precious metal precursor is mixed with water in the fifth step to obtain a precious metal salt solution; the reducing agent, stabilizer, and water are then mixed in the sixth step to obtain a mixed solution of the reducing agent and stabilizer. The two solutions can then be mixed, for example, the mixed solution of the reducing agent and stabilizer can be added to the precious metal salt solution to obtain a precious metal colloidal solution. In this invention, unless otherwise specified, mixing can be achieved by stirring, ultrasonication, or vibration.

[0034] Preferably, in the noble metal salt solution, the concentration of the noble metal precursor, in terms of the molar amount of the metal element, is 0.5-6 mmol / L, for example, it can be 0.5, 0.6, 0.8, 1, 2, 4, 6 mmol / L or any range between any two values, more preferably 1-4.5 mmol / L.

[0035] Preferably, in the mixed solution of reducing agent and stabilizer, the concentration of reducing agent is 0.5-15 mmol / L, for example, it can be 0.5, 0.6, 0.8, 1, 2, 4, 6, 8, 10, 12, 14, 15 mmol / L and any range between any two values, more preferably 1-10 mmol / L.

[0036] Preferably, in the mixed solution of reducing agent and stabilizer, the concentration of stabilizer is 30-450 mmol / L, for example, it can be 30, 50, 100, 150, 200, 250, 300, 350, 400, 450 mmol / L and any range between any two values, more preferably 50-350 mmol / L.

[0037] Preferably, the amount of the reducing agent compared to 1 mol of precious metal is 0.5-5 mol, for example, it can be 0.5, 0.6, 0.8, 1, 2, 4, 5 mmol / L and any range between any two values, preferably 1-3 mol, and the amount of the stabilizer is 10-100 mol, for example, it can be 10, 20, 40, 60, 80, 100 mmol / L and any range between any two values, more preferably 40-80 mol.

[0038] The volumes of the mixed solution of reducing agent and stabilizer and the noble metal salt solution can be selected within a wide range, such as 0.1-10:1, or any range of 0.1:1, 0.2:1, 0.4:1, 0.6:1, 0.8:1, 1:1, 2:1, 4:1, 6:1, 8:1, 10:1, and any two of these values, preferably 0.5-2:1.

[0039] In this invention, unless otherwise specified, the mixing method is any method conventional in the art that can mix materials, such as stirring, shaking, ultrasonic treatment, etc.

[0040] In step (2), the organic acid salt of cerium is brought into contact with the colloidal solution of noble metals, and the pH of the material is adjusted to 3-8 to obtain a noble metal-cerium mixture.

[0041] Preferably, the organic acid salt of cerium is a carboxylate of cerium, more preferably selected from at least one of cerium citrate, cerium acetate, cerium oxalate, cerium tartrate and cerium succinate, and even more preferably cerium citrate and / or cerium acetate.

[0042] Preferably, the molar ratio of the cerium organic acid salt to the noble metal is 1-30:1, for example, it can be 1:1, 2:1, 4:1, 6:1, 8:1, 10:1, 15:1, 20:1, 25:1, 30:1 and any range between any two values, preferably 5-15:1.

[0043] In this invention, the organic acid salt of cerium can be directly added to the noble metal colloidal solution, or it can be prepared into a solution and then mixed with the noble metal colloidal solution. Preferably, the concentration of the organic acid salt of cerium is 1-10 mmol / L.

[0044] In this invention, a pH adjuster is used to adjust the pH of the material. The noble metal colloidal solution obtained in step (1) is alkaline, so the pH adjuster used to adjust the pH of the material is an acidic adjuster, preferably an inorganic acid, and more preferably selected from hydrochloric acid, nitric acid and sulfuric acid.

[0045] The concentration of the inorganic acid can be selected within a wide range. Preferably, the concentration of the inorganic acid is 0.1-5 mol / L.

[0046] The amount of pH adjuster used is such that the pH of the material is within the range of 3-8, for example, it can be 3, 4, 5, 6, 7, 8, or any range between any two values. Preferably, the amount of pH adjuster used is such that the pH of the material is 4-7. Under these preferred conditions, the catalytic performance of the catalyst is better.

[0047] After adjusting the pH using a pH adjuster, the colloidal double layer property can be used to adsorb cerium organic acid salts onto the surface of noble metal particles, forming a thin film that encapsulates them (see...). Figure 2 After adjusting the pH, stir for a period of time (e.g., 5-40 minutes) to ensure thorough mixing of the materials, thereby allowing the colloidal double layer to fully adsorb cerium salts.

[0048] It is important to understand that while nitrogen complexes in organic amines stabilize the surface of noble metal colloids, they also weaken the adsorption properties of the colloids. The purpose of adding inorganic acids to lower the pH is to protonate the organic amines, causing the lone pair electrons of nitrogen to lose their complexing ability, thus stripping the organic amines from the surface of the noble metal colloid particles. The pKb of organic amines is lower than that of organic acid salts (e.g., triethylamine has a pKb of 3.25, and citrate has a pKb of 7.6), making them more alkaline. Inorganic acids will preferentially react with triethylamine. After organic acid salts are adsorbed into the colloidal double layer, they will also play a role in stabilizing the colloids. In other words, the addition of inorganic acids achieves the replacement of colloidal stabilizers.

[0049] The inventors of this invention have discovered that increasing the amount of inorganic acid increases the adsorption of cerium in the organic acid, while the colloidal particles in the solvent system gradually change from a single-particle dispersed state to a multi-particle aggregated state. However, this aggregation behavior does not damage the stability of the colloidal solution.

[0050] In step (3), the matrix source, transition metal oxide and rare earth metal oxides other than cerium are mixed with the noble metal colloidal solution to obtain the catalyst slurry.

[0051] The matrix source is a substance that can be transformed into a matrix under the ozone roasting conditions in step (4). The matrix can be selected from at least one of alumina, spinel, perovskite, silica-alumina, zeolite, kaolin, diatomite, and perlite, preferably from at least one of alumina, spinel, and perovskite, and more preferably from alumina. For example, boehmite (matrix source) is used, which is roasted to generate alumina (matrix). The matrix source can be, for example, at least one of boehmite, alumina, spinel, perovskite, silica-alumina, zeolite, kaolin, diatomite, hydrotalcite, and perlite.

[0052] Preferably, the transition metal is selected from at least one non-noble metal element in groups VB (e.g., V, Nb, Ta), VIIB (e.g., Mn), and VIII (e.g., Fe, Co, Ni), and is preferably cobalt and / or manganese. Those skilled in the art know the corresponding oxides of transition metals; for example, the oxide of Co is cobalt oxide (Co3O4), and the oxide of manganese is manganese dioxide (MnO2).

[0053] Preferably, the rare earth metal other than cerium is selected from at least one of La, Y, Pr and Nd, more preferably La and / or Y. For example, the oxides of La, Y, Pr and Nd can be lanthanum oxide, yttrium oxide, praseodymium oxide and neodymium oxide, respectively.

[0054] Before mixing the matrix source, transition metal oxides, and rare earth metal oxides (excluding cerium) with the noble metal colloidal solution, the matrix source, transition metal oxides, and rare earth metal oxides (excluding cerium) can be mixed with water and then ground, preferably by ball milling; preferably, the ball milling time is 1-5 hours, and the rotation speed is 500-1500 rpm. A vibratory ball mill (such as the GZM-6 vibratory ball mill from Tianjin Shengyuan Equipment Co., Ltd.) can be used for ball milling. Preferably, the ball milling conditions result in an average particle diameter of less than 15 μm in the mixture. That is, the average particle diameter in the catalyst slurry is less than 15 μm.

[0055] Preferably, the solid content of the catalyst slurry is 5-35% by weight, for example, it can be 5, 10, 15, 20, 25, 30, 35% by weight or any range between any two values.

[0056] In step (4), the catalyst slurry is loaded onto the support and then dried and calcined with ozone to obtain a VOCs catalytic oxidation catalyst with a catalyst layer.

[0057] Preferably, the catalyst slurry loading is such that, based on the volume of the carrier, the loading of the catalyst layer is 10-200 g / L, for example, it can be 10, 20, 40, 60, 80, 100, 120, 140, 160, 180, 200 g / L and any range between any two values, preferably 40-160 g / L.

[0058] Preferably, the amounts of each component are such that, based on the volume of the carrier, the loading of the noble metal is 0.1-1 g / L, for example, it can be 0.1, 0.2, 0.4, 0.6, 0.8, 1 g / L or any range between any two values, preferably 0.2-0.8 g / L; the loading of cerium oxide is 0.5-10 g / L, for example, it can be 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 g / L or any range between any two values, preferably 2-6 g / L; and the loading of the matrix is ​​30-120 g / L, for example, it can be 30, 40, 6... The loading of transition metal oxides is 5-20 g / L, for example, 5, 6, 8, 10, 12, 14, 16, 18, 20 g / L, or any range between any two values, preferably 8-16 g / L; the loading of rare earth metal oxides other than cerium is 5-20 g / L, for example, 5, 6, 8, 10, 12, 14, 16, 18, 20 g / L, or any range between any two values, preferably 8-16 g / L.

[0059] The present invention has a wide range of choices for the carrier, and can be any carrier commonly used in the field. The present invention does not have any particular limitation on this. For example, the carrier can be an inorganic oxide carrier.

[0060] Preferably, the carrier is a carrier with a regular structure. That is, the carrier has a regular structure in appearance, which facilitates assembly, and the pore structure of the carrier can also be regular.

[0061] Preferably, the pore density of the cross-section of the regular structure carrier is 50-400 pores / square inch, for example, it can be 50, 100, 150, 200, 250, 300, 350, 400 pores / square inch or any range between any two values.

[0062] Preferably, the carrier is selected from at least one of cordierite, mullite, diamond, corundum, zirconium corundum, quartz, nepheline, feldspar, alumina, and metal alloys.

[0063] In a preferred embodiment, the cross-sectional area of ​​each hole in the carrier is 0.4-10 square millimeters, preferably 0.4-4 square millimeters.

[0064] In a preferred embodiment, the porosity of the carrier's cross-sectional surface is 20-80%, more preferably 50-80%.

[0065] The holes can be regular or irregular in shape. The shapes of the holes can be the same or different. Each hole can be one of the following: square, equilateral triangle, regular hexagon, circle, and corrugated.

[0066] The support described in this invention can be used in the catalyst bed provided in a fixed-bed reactor. The support can be a monolithic block with an internally formed hollow channel structure. Active components can be distributed on the inner and / or outer walls of the channels, and the channel space can serve as a flow space for fluids. The support can also be a regular support with a honeycomb-like opening in its cross-section (referred to as a honeycomb support).

[0067] In this invention, the catalyst slurry can be uniformly loaded onto the surface of a carrier by spraying, coating, or immersion. After loading, it is dried and calcined to obtain a carrier with catalyst layers loaded on both the inner and outer surfaces. For example, the carrier can be immersed in the catalyst slurry for 5-30 seconds for loading. It should be understood that the catalyst slurry can be loaded onto the carrier through one or more processes.

[0068] In this invention, in step (4), preferably, the drying conditions include: a temperature of 100-140℃ (for example, it can be 100, 110, 120, 130, 140℃ and any range between any two values), and a time of 0.5-4h.

[0069] The conditions for ozone roasting include: a roasting temperature of 150-450℃ (e.g., 150, 180, 200, 220, 250, 300, 350, 400, 450℃, or any range between any two values), preferably 150-250℃, and a roasting time of 1-3 hours. For example, the temperature can be increased to 150-450℃ at a rate of 3-15℃ / min and maintained for 1-3 hours. The ozone atmosphere is achieved using an ozone generator (such as the OZ-004 ozone generator from Qingdao Zhongke Sanyang Co., Ltd.).

[0070] The inventors of this invention discovered that if the catalyst is calcined in an air or oxygen atmosphere, Ce species will migrate and destroy the constructed interface while removing organic groups. Therefore, ozone, which has a stronger oxidizing ability, is selected to reduce the calcination temperature, avoid the migration of cerium species at high temperatures, and remove the organic groups of cerium salts at low temperatures, converting them into oxides that are solidified on the surface of noble metals.

[0071] It should be understood that, in this invention, the preferred conditions are more conducive to improving catalyst performance, reducing catalytic temperature, and improving catalytic effect.

[0072] A second aspect of the present invention provides a catalyst prepared according to the method described above.

[0073] A third aspect of the present invention provides a VOCs catalytic oxidation catalyst, the catalyst comprising a support and a catalyst layer supported on the support;

[0074] The catalyst layer contains a catalyst support and an active component. The catalyst support includes cerium oxide, a matrix, transition metal oxides, and rare earth oxides other than cerium. The active component is a noble metal.

[0075] Cerium oxide is coated on the surface of the noble metal.

[0076] Preferably, based on the volume of the carrier, the total loading of the active components is 10-200 g / L, more preferably 40-160 g / L.

[0077] Preferably, based on the volume of the carrier, the loading of the noble metal is 0.1-1 g / L, for example, it can be 0.1, 0.2, 0.4, 0.6, 0.8, 1 g / L or any range between any two values, more preferably 0.2-0.8 g / L; the loading of cerium oxide is 0.5-10 g / L, for example, it can be 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 g / L or any range between any two values, more preferably 2-6 g / L; the loading of the matrix is ​​30-120 g / L, for example, it can be 30, 40, 60, 80, ... The loading of transition metal oxides is 5-20 g / L, for example, 5, 6, 8, 10, 12, 14, 16, 18, 20 g / L, for example, 5, 6, 8, 10, 12, 14, 16, 18, 20 g / L, for example, 5, 6, 8, 10, 12, 14, 16, 18, 20 g / L, for example, 5, 6, 8, 10, 12, 14, 16, 18, 20 g / L, for example, 5, 6, 8, 10, 12, 14, 16, 18, 20 g / L, for example, 5, 6, 8, 10, 12, 14, 16, 18, 20 g / L, for example, 8-16 g / L.

[0078] The descriptions of each component have already been provided in the first part and will not be repeated here.

[0079] The fourth aspect of the present invention relates to the application of the VOCs oxidation catalyst described above in the catalytic oxidation of VOCs.

[0080] The present invention will be described in detail below through embodiments. The following embodiments will further illustrate the present invention, but are not intended to limit the present invention.

[0081] The average particle diameter in the catalyst slurry was the equivalent volume diameter obtained by laser particle size analysis. Experimental instrument: Malvern Mastersizer 3000.

[0082] The activity evaluation of the toluene catalytic oxidation reaction was performed on a micro fixed-bed reactor designed and manufactured by Tianjin Pengxiang Technology Co., Ltd., equipped with an MKS Multigas 2030 infrared detector. The reaction was carried out at atmospheric pressure, with an initial temperature of 150℃, and a programmed temperature increase at a rate of 3℃ / min until complete toluene conversion. The inlet gas composition was 450ppm C7H8 / 7% O2 / N2, and the space velocity was 12000 h⁻¹. -1 .

[0083] The carrier is a VOC-specific cordierite honeycomb carrier purchased from Pingxiang Guanlin Environmental Protection Technology Co., Ltd. The carrier has a pore density of 300 pores / square inch, a cross-sectional area of ​​1.5 square millimeters per pore, an open porosity of 70%, and a circular shape.

[0084] Example 1

[0085] (1) Preparation of noble metal colloidal solution: Prepare a 1 mmol / L platinum nitrate solution and a mixed solution of 1 mmol / L ascorbic acid and 50 mmol / L triethylamine. The volume ratio of platinum nitrate solution to mixed solution is 1:1. Under stirring conditions, the mixed solution is quickly added to the prepared platinum nitrate solution and stirred continuously for 10 minutes to obtain noble metal colloidal solution.

[0086] (2) Construction of noble metal-cerium interface by adsorbing cerium organic acid salts: Prepare a 5 mmol / L cerium citrate solution, and under stirring conditions, quickly add the cerium citrate solution to the noble metal colloidal solution, add an appropriate amount of 0.5 mol / L nitric acid to adjust the pH to 6, stir for 10 minutes to obtain a noble metal-cerium mixed solution.

[0087] (3) Catalyst slurry preparation and coating: Add appropriate amounts of alumina, manganese dioxide and lanthanum oxide powder to deionized water, and use a vibratory ball mill (Tianjin Shengyuan Equipment Co., Ltd., GZM-6) to fully grind the above mixture. The specific grinding conditions are: ball milling time 2.5h, rotation speed 1000rpm, and the average particle diameter in the mixture after ball milling is 10.3μm. After stirring the ball-milled mixture for 1 hour, add the above precious metal-cerium mixed solution, and continue stirring for 1 hour to obtain the catalyst slurry. Control the solid content of the slurry to be 15% by weight. Then, uniformly coat the catalyst slurry on the surface of a 300-mesh regular structure carrier, so that the total coating amount on each liter of ceramic carrier is 60g. In terms of elements, the platinum content is 0.2g; in terms of oxides, the cerium oxide content is 1g, the alumina content is 45g, the lanthanum oxide content is 7g, and the manganese dioxide content is 6.8g.

[0088] (4) Coating and post-treatment: The carrier coated with catalyst slurry was dried at 140°C for 2 hours, and then subjected to ozone calcination treatment. The temperature was increased to 180°C at a rate of 5°C / min and held for 2 hours to obtain VOCs catalytic oxidation catalyst.

[0089] Example 2

[0090] (1) Preparation of noble metal colloidal solution: Prepare a 3 mmol / L platinum nitrate solution and a mixed solution of 6 mmol / L ascorbic acid and 200 mmol / L diethylamine. The volume ratio of platinum nitrate solution to the mixed solution is 1:1. Under stirring conditions, the mixed solution is quickly added to the prepared platinum nitrate solution and stirred continuously for 20 minutes to obtain the noble metal colloidal solution.

[0091] (2) Construction of noble metal-cerium interface by adsorbing cerium organic acid salts: Prepare a 15 mmol / L cerium acetate solution, and under stirring conditions, quickly add the cerium citrate solution to the noble metal colloidal solution, add an appropriate amount of 1 mol / L nitric acid to adjust the pH to 4, stir for 20 minutes to obtain a noble metal-cerium mixed solution.

[0092] (3) Catalyst slurry preparation and coating: Add appropriate amounts of alumina, manganese dioxide and lanthanum oxide powder to deionized water, and use a vibratory ball mill (Tianjin Shengyuan Equipment Co., Ltd., GZM-6) to fully grind the above mixture. The specific grinding conditions are: ball milling time 3h, rotation speed 800rpm, and the average particle diameter in the mixture after ball milling is 8.5μm. After stirring the ball-milled mixture for 1.5 hours, add the above precious metal-cerium mixed solution, and continue stirring for 1.5 hours to obtain the catalyst slurry. Control the solid content of the slurry to be 20% by weight. Then, uniformly coat the catalyst slurry onto the surface of a 300-mesh regular structure carrier, so that the total coating amount on each liter of ceramic carrier is 100g. In terms of elements, the platinum content is 0.3g; in terms of oxides, the cerium oxide content is 3g, the alumina content is 70g, the lanthanum oxide content is 12g, and the manganese dioxide content is 14.7g.

[0093] (4) Coating and post-treatment: The support coated with catalyst slurry was dried at 120°C for 1.5 h, and then subjected to ozone roasting treatment, with the temperature increased to 200°C at a rate of 3°C / min and held for 1.5 h to obtain VOCs catalytic oxidation catalyst.

[0094] Example 3

[0095] (1) Preparation of noble metal colloidal solution: Prepare a 4 mmol / L platinum nitrate solution and a mixed solution of 10 mmol / L ascorbic acid and 300 mmol / L triethylamine. The volume ratio of platinum nitrate solution to mixed solution is 1:1. Under stirring conditions, the mixed solution is quickly added to the prepared platinum nitrate solution and stirred continuously for 25 minutes to obtain noble metal colloidal solution.

[0096] (2) Construction of noble metal-cerium interface by adsorbing cerium organic acid salts: Prepare a 40 mmol / L cerium citrate solution, and under stirring conditions, quickly add the cerium citrate solution to the noble metal colloidal solution, add an appropriate amount of 1.5 mol / L nitric acid to adjust the pH to 5, stir for 30 minutes to obtain a noble metal-cerium mixed solution.

[0097] (3) Catalyst slurry preparation and coating: Add appropriate amounts of alumina, manganese dioxide and lanthanum oxide powder to deionized water, and use a vibratory ball mill (Tianjin Shengyuan Equipment Co., Ltd., GZM-6) to fully grind the above mixture. The specific grinding conditions are: ball milling time 1.5h, rotation speed 1200rpm, and the average particle diameter in the mixture after ball milling is 12.5μm. After stirring the ball-milled mixture for 2 hours, add the above precious metal-cerium mixed solution, and continue stirring for 2 hours to obtain the catalyst slurry. Control the solid content of the slurry to be 22% by weight. Then, uniformly coat the catalyst slurry on the surface of a 300-mesh regular structure carrier, so that the total coating amount on each liter of ceramic carrier is 120g. In terms of elements, the platinum content is 0.8g; in terms of oxides, the cerium oxide content is 8g, the alumina content is 85g, the lanthanum oxide content is 12g, and the manganese dioxide content is 14.2g.

[0098] (4) Coating and post-treatment: The carrier coated with catalyst slurry was dried at 130°C for 1 hour, and then subjected to ozone calcination treatment. The temperature was increased to 200°C at a rate of 7°C / min and held for 2 hours to obtain VOCs catalytic oxidation catalyst.

[0099] Example 4

[0100] In Example 4, the pH was adjusted to 7 in step (2) to reduce the amount of cerium salt adsorption, while other conditions were the same as in Example 1.

[0101] Example 5

[0102] In Example 5, in step (1), platinum nitrate was replaced with palladium nitrate so that the loading of Pd was the same as that of Pt, and other conditions were the same as in Example 1.

[0103] Example 6

[0104] In Example 6, lanthanum oxide was replaced with an equal mass of yttrium oxide in step (3), and other conditions were the same as in Example 1.

[0105] Example 7

[0106] In Example 7, manganese dioxide was replaced with an equal mass of cobalt tetroxide in step (3), and other conditions were the same as in Example 1.

[0107] Example 8

[0108] In Example 8, a high-temperature ozone calcination treatment was used in step (4), that is, the temperature was increased to 400°C at a rate of 8°C / min and held for 2 hours to obtain a VOCs catalytic oxidation catalyst. Other conditions were the same as in Example 1.

[0109] Comparative Example 1

[0110] Comparative Example 1 did not include cerium organic acid salts, i.e., step (2) was not performed, and other conditions were the same as in Example 1.

[0111] Comparative Example 2

[0112] Comparative Example 2 did not include cerium organic acid salts, i.e., step (2) was not performed. In step (3), 5g of cerium oxide was added together with other oxides to prepare a catalyst slurry, and other conditions were the same as in Example 1.

[0113] Comparative Example 3

[0114] Comparative Example 3 was not roasted in an ozone atmosphere, but in an air atmosphere, with the temperature increased to 500°C at a rate of 6°C / min and held for 2 hours, with other conditions the same as in Example 1.

[0115] Comparative Example 4

[0116] Comparative Example 4 used a custom-made commercial cordierite VOCs catalyst (precious metal content 0.4 g / L) with a single cubic columnar straight channel inside; it was cut into cylinders of the same size as the example (3 cm in diameter at the bottom and 1 cm in height) for activity evaluation.

[0117] Comparative Example 5

[0118] In Comparative Example 5, cerium nitrate of equimolar concentration was used in step (2), and other conditions were the same as in Example 1.

[0119] Comparative Example 6

[0120] In Comparative Example 6, the pH was adjusted to 9.5 in step (2) to reduce the amount of cerium salt adsorption, while other conditions were the same as in Example 1.

[0121] The performance of VOCs catalytic oxidation materials obtained in the examples and comparative examples was evaluated using toluene as a model compound. The T of the freshener was... 50 and T 99 The conversion temperatures are shown in Table 1.

[0122] The catalysts prepared in the examples and comparative examples were subjected to catalyst aging performance tests, respectively. Aging agent T 99 The conversion temperature results are shown in Table 1.

[0123] The catalyst aging conditions were as follows: air atmosphere containing 10% water vapor, temperature 800℃, 10h.

[0124] Table 1. T values ​​of fresh and hydrothermally aged catalyst samples 50 T 99

[0125]

[0126]

[0127] As can be seen from Table 1, the T values ​​of the VOCs catalytic materials obtained in the examples are... 50 and T 99 The conversion temperature of toluene was lower than that of the comparative example, and the stability of the catalyst was better than that of the comparative example in the aging performance test. The VOCs catalytic material prepared by this invention has a higher efficiency in degrading pollutants and is expected to be promoted to the preparation of various fixed-bed catalytic materials, with broad application prospects.

[0128] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing a VOCs catalytic oxidation catalyst, characterized in that, The method includes: (1) A noble metal colloidal solution is prepared by mixing a precursor of the noble metal, a reducing agent, a stabilizer and water; (2) Contact the organic acid salt of cerium with the colloidal solution of noble metal and adjust the pH of the material to 3-8 to obtain a noble metal-cerium mixture; (3) Mix the matrix source, transition metal oxides and rare earth metal oxides other than cerium with a noble metal-cerium mixture to obtain a catalyst slurry; (4) The catalyst slurry is loaded onto the support and then dried and calcined with ozone to obtain a VOCs catalytic oxidation catalyst with a catalyst layer. The stabilizer is an organic amine; The pH adjuster for adjusting the pH of the material is an inorganic acid; The conditions for ozone roasting include a roasting temperature of 150-250℃.

2. The method according to claim 1, wherein, The precious metal is selected from at least one of Au, Ag, Pt, and Pd; and / or The organic acid salt of cerium is selected from at least one of cerium citrate, cerium acetate, cerium oxalate, cerium tartrate, and cerium succinate; and / or The stabilizer is selected from at least one of diethylamine, triethylamine, and trimethylamine; and / or The pH adjuster for adjusting the pH of the material is selected from hydrochloric acid, nitric acid, and sulfuric acid.

3. The method according to claim 1 or 2, wherein, The precursor of the noble metal is a soluble salt of the noble metal; and / or The reducing agent is selected from at least one of ascorbic acid, borohydride, and citrate; and / or The stabilizer is diethylamine and / or triethylamine; and / or Compared to 1 mol of precious metal, the amount of reducing agent used is 0.5-5 mol, and the amount of stabilizer used is 10-100 mol.

4. The method according to claim 3, wherein, The precursor of the noble metal is a nitrate; and / or The reducing agent is ascorbic acid; and / or Compared to 1 mol of precious metal, the amount of reducing agent used is 1-3 mol, and the amount of stabilizer used is 40-80 mol.

5. The method according to any one of claims 1-2 and 4, wherein, The organic acid salts of cerium are cerium carboxylates; and / or The molar ratio of cerium organic acid salts to noble metals is 1-30:

1.

6. The method according to claim 5, wherein, The organic acid salts of cerium are selected from at least one of cerium citrate, cerium acetate, cerium oxalate, cerium tartrate, and cerium succinate.

7. The method according to claim 3, wherein, The organic acid salts of cerium are cerium carboxylates; and / or The molar ratio of cerium organic acid salts to noble metals is 1-30:

1.

8. The method according to claim 7, wherein, The organic acid salts of cerium are selected from at least one of cerium citrate, cerium acetate, cerium oxalate, cerium tartrate, and cerium succinate.

9. The method according to any one of claims 1-2, 4, 6-8, wherein, The matrix source is a substance that can be transformed into a matrix under the ozone roasting conditions in step (4); The matrix is ​​selected from at least one of alumina, spinel, perovskite, silica-alumina, zeolite, kaolin, diatomite, and perlite; and / or The transition metal is selected from at least one non-noble metal element from Groups VB, VIIB, and VIII; and / or The rare earth metals other than cerium are selected from at least one of La, Y, Pr and Nd.

10. The method according to claim 9, wherein, The matrix is ​​selected from at least one of alumina, spinel, and perovskite; and / or The transition metal is one or more of cobalt, copper, iron, and manganese; and / or The rare earth metals other than cerium are La and / or Y.

11. The method according to claim 10, wherein, The matrix is ​​alumina; and / or The transition metal is cobalt and / or manganese.

12. The method according to claim 3, wherein, The matrix source is a substance that can be transformed into a matrix under the ozone roasting conditions in step (4); The matrix is ​​selected from at least one of alumina, spinel, perovskite, silica-alumina, zeolite, kaolin, diatomite, and perlite; and / or The transition metal is selected from at least one non-noble metal element from Groups VB, VIIB, and VIII; and / or The rare earth metals other than cerium are selected from at least one of La, Y, Pr and Nd.

13. The method according to claim 12, wherein, The matrix is ​​selected from at least one of alumina, spinel, and perovskite; and / or The transition metal is one or more of cobalt, copper, iron, and manganese; and / or The rare earth metals other than cerium are La and / or Y.

14. The method according to claim 11, wherein, The matrix is ​​alumina; and / or The transition metal is cobalt and / or manganese.

15. The method according to claim 5, wherein, The matrix source is a substance that can be transformed into a matrix under the ozone roasting conditions in step (4); The matrix is ​​selected from at least one of alumina, spinel, perovskite, silica-alumina, zeolite, kaolin, diatomite, and perlite; and / or The transition metal is selected from at least one non-noble metal element from Groups VB, VIIB, and VIII; and / or The rare earth metals other than cerium are selected from at least one of La, Y, Pr and Nd.

16. The method according to claim 15, wherein, The matrix is ​​selected from at least one of alumina, spinel, and perovskite; and / or The transition metal is one or more of cobalt, copper, iron, and manganese; and / or The rare earth metals other than cerium are La and / or Y.

17. The method according to claim 16, wherein, The matrix is ​​alumina; and / or The transition metal is cobalt and / or manganese.

18. The method according to any one of claims 1-2, 4, 6-8, and 10-17, wherein, The catalyst slurry loading is such that, based on the volume of the carrier, the loading of the catalyst layer is 10-200 g / L.

19. The method of claim 17, wherein, The catalyst slurry loading is such that, based on the volume of the carrier, the loading of the catalyst layer is 40-160 g / L.

20. The method according to claim 3, wherein, The catalyst slurry loading is such that, based on the volume of the carrier, the loading of the catalyst layer is 10-200 g / L.

21. The method according to claim 20, wherein, The catalyst slurry loading is such that, based on the volume of the carrier, the loading of the catalyst layer is 40-160 g / L.

22. The method according to claim 5, wherein, The catalyst slurry loading is such that, based on the volume of the carrier, the loading of the catalyst layer is 10-200 g / L.

23. The method according to claim 22, wherein, The catalyst slurry loading is such that, based on the volume of the carrier, the loading of the catalyst layer is 40-160 g / L.

24. The method according to claim 9, wherein, The catalyst slurry loading is such that, based on the volume of the carrier, the loading of the catalyst layer is 10-200 g / L.

25. The method according to claim 24, wherein, The catalyst slurry loading is such that, based on the volume of the carrier, the loading of the catalyst layer is 40-160 g / L.

26. The method according to any one of claims 1-2, 4, 6-8, 10-17, and 19-25, wherein, The amounts of each component are adjusted based on the volume of the carrier, with the loading of noble metals being 0.1-1 g / L; the loading of cerium oxide being 0.5-10 g / L; the loading of the matrix being 30-120 g / L; the loading of transition metal oxides being 5-20 g / L; and the loading of rare earth metal oxides other than cerium being 5-20 g / L.

27. The method according to claim 26, wherein, The amounts of each component are adjusted based on the volume of the carrier, with the loading of noble metals being 0.2-0.8 g / L; the loading of cerium oxide being 2-6 g / L; the loading of the matrix being 60-95 g / L; the loading of transition metal oxides being 8-16 g / L; and the loading of rare earth metal oxides other than cerium being 8-16 g / L.

28. The method according to claim 3, wherein, The amounts of each component are adjusted based on the volume of the carrier, with the loading of noble metals being 0.1-1 g / L; the loading of cerium oxide being 0.5-10 g / L; the loading of the matrix being 30-120 g / L; the loading of transition metal oxides being 5-20 g / L; and the loading of rare earth metal oxides other than cerium being 5-20 g / L.

29. The method according to claim 28, wherein, The amounts of each component are adjusted based on the volume of the carrier, with the loading of noble metals being 0.2-0.8 g / L; the loading of cerium oxide being 2-6 g / L; the loading of the matrix being 60-95 g / L; the loading of transition metal oxides being 8-16 g / L; and the loading of rare earth metal oxides other than cerium being 8-16 g / L.

30. The method according to claim 5, wherein, The amounts of each component are adjusted based on the volume of the carrier, with the loading of noble metals being 0.1-1 g / L; the loading of cerium oxide being 0.5-10 g / L; the loading of the matrix being 30-120 g / L; the loading of transition metal oxides being 5-20 g / L; and the loading of rare earth metal oxides other than cerium being 5-20 g / L.

31. The method according to claim 30, wherein, The amounts of each component are adjusted based on the volume of the carrier, with the loading of noble metals being 0.2-0.8 g / L; the loading of cerium oxide being 2-6 g / L; the loading of the matrix being 60-95 g / L; the loading of transition metal oxides being 8-16 g / L; and the loading of rare earth metal oxides other than cerium being 8-16 g / L.

32. The method according to claim 9, wherein, The amounts of each component are adjusted based on the volume of the carrier, with the loading of noble metals being 0.1-1 g / L; the loading of cerium oxide being 0.5-10 g / L; the loading of the matrix being 30-120 g / L; the loading of transition metal oxides being 5-20 g / L; and the loading of rare earth metal oxides other than cerium being 5-20 g / L.

33. The method according to claim 32, wherein, The amounts of each component are adjusted based on the volume of the carrier, with the loading of noble metals being 0.2-0.8 g / L; the loading of cerium oxide being 2-6 g / L; the loading of the matrix being 60-95 g / L; the loading of transition metal oxides being 8-16 g / L; and the loading of rare earth metal oxides other than cerium being 8-16 g / L.

34. The method according to claim 18, wherein, The amounts of each component are adjusted based on the volume of the carrier, with the loading of noble metals being 0.1-1 g / L; the loading of cerium oxide being 0.5-10 g / L; the loading of the matrix being 30-120 g / L; the loading of transition metal oxides being 5-20 g / L; and the loading of rare earth metal oxides other than cerium being 5-20 g / L.

35. The method according to claim 34, wherein, The amounts of each component are adjusted based on the volume of the carrier, with the loading of noble metals being 0.2-0.8 g / L; the loading of cerium oxide being 2-6 g / L; the loading of the matrix being 60-95 g / L; the loading of transition metal oxides being 8-16 g / L; and the loading of rare earth metal oxides other than cerium being 8-16 g / L.

36. The method according to any one of claims 1-2, 4, 6-8, 10-17, 19-25, and 27-35, wherein, The carrier is a regular structure carrier.

37. The method according to claim 36, wherein, The carrier has a cross-sectional pore density of 50-400 pores / square inch and an open porosity of 20-80%; and / or The carrier is selected from at least one of cordierite, mullite, diamond, corundum, zirconium corundum, quartz, nepheline, feldspar, alumina, and metal alloys.

38. The method according to claim 3, wherein, The carrier is a regular structure carrier.

39. The method according to claim 38, wherein, The carrier has a cross-sectional pore density of 50-400 pores / square inch and an open porosity of 20-80%; and / or The carrier is selected from at least one of cordierite, mullite, diamond, corundum, zirconium corundum, quartz, nepheline, feldspar, alumina, and metal alloys.

40. The method according to claim 5, wherein, The carrier is a regular structure carrier.

41. The method according to claim 40, wherein, The carrier has a cross-sectional pore density of 50-400 pores / square inch and an open porosity of 20-80%; and / or The carrier is selected from at least one of cordierite, mullite, diamond, corundum, zirconium corundum, quartz, nepheline, feldspar, alumina, and metal alloys.

42. The method according to claim 9, wherein, The carrier is a regular structure carrier.

43. The method according to claim 42, wherein, The carrier has a cross-sectional pore density of 50-400 pores / square inch and an open porosity of 20-80%; and / or The carrier is selected from at least one of cordierite, mullite, diamond, corundum, zirconium corundum, quartz, nepheline, feldspar, alumina, and metal alloys.

44. The method according to claim 18, wherein, The carrier is a regular structure carrier.

45. The method according to claim 44, wherein, The carrier has a cross-sectional pore density of 50-400 pores / square inch and an open porosity of 20-80%; and / or The carrier is selected from at least one of cordierite, mullite, diamond, corundum, zirconium corundum, quartz, nepheline, feldspar, alumina, and metal alloys.

46. ​​The method of claim 26, wherein, The carrier is a regular structure carrier.

47. The method according to claim 46, wherein, The carrier has a cross-sectional pore density of 50-400 pores / square inch and an open porosity of 20-80%; and / or The carrier is selected from at least one of cordierite, mullite, diamond, corundum, zirconium corundum, quartz, nepheline, feldspar, alumina, and metal alloys.

48. The method according to claim 1, wherein, In step (3), the average diameter of the particles in the catalyst slurry is less than 15 μm.

49. The method according to claim 1, wherein, In step (4), the drying conditions include: a temperature of 100-140℃ and a time of 0.5-4h; and / or The conditions for ozone roasting include: roasting temperature of 150-450℃ and time of 1-3h.

50. The VOCs catalytic oxidation catalyst prepared by the method according to any one of claims 1-49.

51. The catalyst according to claim 50, characterized in that, The catalyst comprises a support and a catalyst layer supported on the support; The catalyst layer contains a catalyst support and an active component. The catalyst support includes cerium oxide, a matrix, transition metal oxides, and rare earth oxides other than cerium. The active component is a noble metal. Cerium oxide is coated on the surface of the noble metal.

52. The catalyst according to claim 51, wherein, Based on the volume of the carrier, the total loading of the active components is 10-200 g / L; and / or Based on the volume of the carrier, the loading of noble metals is 0.1-1 g / L; the loading of cerium oxide is 0.5-10 g / L; the loading of the matrix is ​​30-120 g / L; the loading of transition metal oxides is 5-20 g / L; and the loading of rare earth metal oxides other than cerium is 5-20 g / L.

53. The catalyst according to claim 52, wherein, Based on the volume of the carrier, the total loading of the active components is 40-160 g / L; and / or Based on the volume of the carrier, the loading of noble metals is 0.2-0.8 g / L; the loading of cerium oxide is 2-6 g / L; the loading of the matrix is ​​60-95 g / L; the loading of transition metal oxides is 8-16 g / L; and the loading of rare earth metal oxides other than cerium is 8-16 g / L.

54. The catalyst according to any one of claims 51-53, wherein, The precious metal is selected from at least one of Au, Ag, Pt, and Pd; and / or The matrix is ​​selected from at least one of alumina, spinel, perovskite, silica-alumina, zeolite, kaolin, diatomite, and perlite; and / or The transition metal is selected from at least one non-noble metal element from Groups VB, VIIB, and VIII; and / or The rare earth metals other than cerium are selected from at least one of La, Y, Pr, and Nd; and / or The carrier is selected from at least one of cordierite, mullite, diamond, corundum, zirconium corundum, quartz, nepheline, feldspar, alumina, and metal alloys.

55. The catalyst according to claim 54, wherein, The precious metal is selected from at least one of Au, Ag, Pt, and Pd; and / or The matrix is ​​selected from at least one of alumina, spinel, and perovskite; and / or The transition metal is cobalt and / or manganese; and / or The rare earth metals other than cerium are La and / or Y; and / or The carrier is selected from at least one of cordierite, mullite, diamond, corundum, zirconium corundum, quartz, nepheline, feldspar, alumina, and metal alloys.

56. The catalyst according to claim 55, wherein, The matrix is ​​aluminum oxide.

57. The catalyst according to any one of claims 51-53 and 55-56, wherein, The carrier is a regular structure carrier.

58. The catalyst according to claim 57, wherein, The carrier has a cross-sectional pore density of 50-400 pores / square inch and an open porosity of 20-80%.

59. The catalyst according to claim 54, wherein, The carrier is a regular structure carrier.

60. The catalyst according to claim 59, wherein, The carrier has a cross-sectional pore density of 50-400 pores / square inch and an open porosity of 20-80%.

61. The use of the catalyst according to any one of claims 50-60 in the catalytic oxidation of VOCs.

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