A non-precious metal coating-supported catalyst, its preparation method and its application

Abstract

This invention provides a catalyst coated with a non-precious metal coating on a support and its preparation method. The invention also relates to the application of this non-precious metal coated-supported catalyst in the catalytic oxidation treatment of volatile organic compounds (VOCs). The catalyst of this invention has high mechanical strength, good coating wear resistance, and is not easily detached. Furthermore, the catalyst exhibits strong hydrothermal stability, good catalytic degradation performance of volatile organic compounds, and a long service life, making it particularly suitable for the treatment of VOCs containing sulfides.

Description

Technical Field

[0001] This invention relates to a non-precious metal coated-supported catalyst. More specifically, this invention relates to a catalyst coated with a non-precious metal coating on a support and a method for preparing the same. This invention also relates to the application of this non-precious metal coated-supported catalyst in the catalytic oxidation treatment of volatile organic compounds (VOCs). Background Technology

[0002] In recent years, with the increasing stringent national environmental protection requirements, recovery technologies such as adsorption, absorption, condensation, membrane separation, high-temperature incineration, and catalytic oxidation have been widely applied to the recovery / treatment of various waste gases containing volatile organic compounds (VOCs). Among them, adsorption is suitable for 500-3000 h⁻¹. -1 Treatment for removing low concentrations of volatile organic pollutants (VOCs) from exhaust gas at relatively low space velocities involves adsorption using a porous matrix to adsorb high-boiling-point components (C5 and above) onto its surface or pores. This process involves almost no chemical reaction. After adsorption saturation, the matrix needs to be regenerated and desorbed to regain its adsorption capacity. The matrix's service life is 1-2 years before it is disposed of as hazardous solid waste. Absorption methods, based on the principle of "like dissolves like," use high-boiling-point solvents (such as low-temperature diesel) to absorb high-boiling-point components from VOCs, forming a rich solution. This rich solution is then desorbed and returned to the system for reuse. Condensation methods utilize the different saturated vapor pressures of organic matter at different temperatures. By cooling and / or pressurizing, organic matter is condensed into a liquid and removed from the gas phase for purification. Membrane separation processes can use organic polymer membranes, inorganic membranes, and biomembranes; however, these membrane materials have drawbacks such as low flux, poor selectivity, and unsuitability for high-space-velocity processing. High-temperature incineration requires very high temperatures, generally exceeding 800℃. Although it can achieve the treatment standard, it requires the addition of a large amount of additives and flammable gases such as natural gas to maintain the combustion temperature, resulting in high energy consumption.

[0003] Compared with the methods mentioned above, catalytic oxidation involves flameless combustion of organic waste gas under the action of a catalyst. It has advantages such as high selectivity and low reaction temperature, typically below 500℃. The products are non-toxic CO2 and H2O. Catalytic oxidation is suitable for treating volatile organic compounds with non-methane total hydrocarbons usually exceeding 500 mg / m³. 3The most crucial element in catalytic oxidation is the catalyst, which is divided into two categories: noble metal catalysts and transition metal oxide catalysts. Noble metal catalysts have advantages such as high activity, low ignition temperature, good stability, and long service life, but they are expensive and unsuitable for treating organic gases containing sulfur. Non-noble metal catalysts are mainly transition metal oxides, which have good resistance to poisoning and oxidation activity, but they suffer from disadvantages such as short lifespan, low activity, and high ignition temperature. ZL200510060542.9 discloses a method for preparing a rare earth composite porous alumina-supported palladium catalyst. This catalyst uses a honeycomb ceramic substrate as a support, employs a sol-coating method to coat hydrated alumina, a thermal adsorption method to support cerium-zirconium oxide, and a supported palladium active component, with an operating time of 10,000–30,000 h. -1At space velocity, the complete oxidation temperatures of toluene and ethyl acetate by the catalyst are 180~200℃ and 260~280℃, respectively, but this patent does not mention the effect of bromides on catalyst activity and lifetime. US4983366 discloses a method and related purification device for the catalytic conversion of waste gas containing hydrocarbons and carbon monoxide. The method involves passing the waste gas through zeolite containing alumina, silica, and / or oxides or barium, manganese, copper, chromium, and nickel, and then through a catalyst containing platinum and / or palladium or rhodium. This catalyst is particularly suitable for treating waste gas generated from vinyl chloride production plants. However, this catalyst does not mention the effect of a high-strength matrix on the lifetime of noble metal catalysts. CN95197182.4 discloses a catalyst and method for treating gases containing halogenated organic compounds, non-halogenated organic compounds, carbon monoxide, or mixtures thereof. The catalyst is characterized by containing at least one platinum group metal, zirconium oxide, and at least one oxide of manganese, cerium, or cobalt. CN200610047791.9 discloses a method for purifying organic waste gas, particularly a method for purifying organic waste gas containing acetaldehyde, ethylene glycol, and PTA dust, such as a method for treating polyester waste gas. The method involves catalytic combustion using a honeycomb catalyst containing platinum, palladium, or CuO and MnO2. Clariant disclosed a low-cost ruthenium oxide catalyst for controlling VOC and halogenated VOC emissions in CN201810125199.9. This catalyst includes precious platinum group metals such as ruthenium and platinum, cerium-zirconium solid solutions, and components such as tin oxide and silicon oxide. According to reports, Clariant's EnviCat VOC catalyst is highly efficient at removing harmful volatile organic compounds (VOCs) and carbon monoxide (CO), while simultaneously saving up to 40% in thermal energy consumption. CN201410455174.7 describes a catalyst comprising non-precious metal oxide components such as iron oxide, cobalt tetroxide, nickel oxide, copper oxide, vanadium oxide, chromium oxide, manganese dioxide, or cerium oxide. This catalyst component is coated onto a support to prepare a catalytic combustion catalyst for methane and other VOC gases. ZL201710256841.2 describes a method of loading two or more metals (Mg, Ti, Mn, Co, Cu, La, Ce, Zr) onto attapulgite clay, followed by calcination and extrusion molding. However, this catalyst has a high metal loading and high cost, and VOCs treatment typically involves rapid surface reactions, leaving the active components inside the catalyst ineffective. CN201911113364.X describes a catalyst using cordierite porous ceramic as a matrix coated with a Cu-Mn-Ce composite oxide coating. The Cu-Mn-Ce composite oxide is prepared via a hydrothermal method using ethylenediamine as a precipitant.

[0004] In the above-disclosed patents, alumina and titanium dioxide are used as primary coating components in the catalyst coating process, followed by the loading of active metals or active metal oxides. The stability of the coating not only affects the catalyst's lifespan, but also the pulverization of the coating due to cracking and flaking can increase the pressure drop in the fixed bed and increase uncontrollable factors in the reaction. Therefore, the development of coated catalysts with good thermal stability, high erosion resistance, and good bonding with the substrate has received more attention.

[0005] Attapulgite, also known as palygorskite, is a natural hydrated clay material rich in magnesium aluminum silicate with a layered chain structure. Its basic structural unit is a sandwich structure consisting of two layers of silicon-oxygen tetrahedra and one layer of magnesium (aluminum)-oxygen octahedra. The ideal unit cell formula is (Mg)₅Si₈O. 20 (OH)₂(OH₂)₄·4H₂O. After modification, attapulgite clay possesses a high specific surface area, open mesoporous-microporous composite channels, and good thermal stability. Furthermore, as it belongs to inorganic mineral materials such as molecular sieves, SiO₂, and Al₂O₃, it exhibits good adhesion properties and provides excellent reinforcement and toughening effects in both organic and inorganic materials. However, there are few literature reports on the use of natural one-dimensional nanomaterial attapulgite as an inner coating material for honeycomb carriers, further loading non-precious metals for VOCs treatment. Summary of the Invention

[0006] In view of the technical problems in the prior art, the inventors, through diligent research based on the prior art, discovered that by coating a support with a coating containing a Co component and an auxiliary component, wherein the coating substrate is at least one selected from attapulgite, kaolin, and montmorillonite, a non-precious metal coating-support catalyst (hereinafter referred to as "the catalyst of this invention" or "catalyst") is prepared. The catalyst of this invention exhibits good VOCs catalytic oxidation conversion performance, thermal stability, and sulfur poisoning resistance, thus completing this invention.

[0007] Specifically, the present invention relates to the following aspects.

[0008] A non-precious metal coated-supported catalyst, characterized in that it comprises a support and a coating covering the support, the coating comprising a coating component and an active metal component, the active metal component comprising a Co metal component and an additive component, and the coating component comprising at least one substrate selected from attapulgite, kaolinite and montmorillonite.

[0009] The auxiliary component is at least one element selected from group A. Preferably, the auxiliary component is selected from at least one group selected from combinations of Ce and Mo, Ce and Mn, Ce and Fe, Ce and Ni, Ce and Bi, Ce and Ti, Ce and Cr, Ce and V, La and Mn, La and Fe, La and Ni, and La and Bi. More preferably, it is selected from at least one group selected from combinations of Ce and Mn with Ti, Ce and Mn with V, Ce and Mn with Bi, Ce and Mn with Cr, La and Mn with Ti, La and Mn with V, and La and Mn with Bi.

[0010] Group A: Li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce;

[0011] Based on the total volume of the non-noble metal coating-supported catalyst, the Co metal content (calculated as cobalt tetroxide) is 50~500 kg / m³. 3 Preferred weight: 50~430 kg / m 3 The content of the auxiliary component (based on the highest oxidation state of the auxiliary component) is 10~180 kg / m³. 3 Preferred weight: 10~150 kg / m 3 The content of coating components is 30-200 kg / m³. 3 The preferred value is 60~200 kg / m 3 .

[0012] This invention also provides a method for preparing a non-precious metal coating-supported catalyst, which includes the following steps:

[0013] (1) A coating component slurry is prepared by contacting at least one substrate selected from attapulgite, kaolin and montmorillonite, a binder and water.

[0014] (2) The step of contacting the coating component slurry, a solution or suspension of at least one cobalt metal component precursor, and a solution or suspension of at least one auxiliary component precursor with a carrier to obtain a contact product, and

[0015] (3) The step of calcining the contact product to obtain the non-precious metal coating-supported catalyst.

[0016] The present invention also provides the application of the above-described non-precious metal coating-supported catalyst in the catalytic oxidation treatment of volatile organic compounds.

[0017] Invention Effects

[0018] Compared with existing coated catalysts, the non-precious metal coating-supported catalyst of the present invention has high mechanical strength, good coating wear resistance, and is not easy to fall off. In addition, the catalyst has strong hydrothermal stability, good catalytic degradation performance of volatile organic compounds, and long service life, and is especially suitable for the treatment of VOCs containing sulfides.

[0019] In addition, the preparation method of the non-precious metal coating-supported catalyst of the present invention is simple, and the amount of active metal component contained in the coating can be adjusted as needed to adjust the activity of the catalyst. Detailed Implementation

[0020] The embodiments of the present invention will be described in more detail below with reference to specific examples. However, those skilled in the art will understand that the specific embodiments described below are for illustrative purposes only and should not be considered as limiting the scope of protection of the present invention. Rather, the present invention is intended to cover all alternatives, modifications, and equivalents that may be included within the scope of the present invention as defined by the claims.

[0021] Unless otherwise specified, the various embodiments of the present invention can be combined in any way, and the resulting transformations, modifications, and alterations of the technical solutions are also included within the scope of the present invention and do not exceed the scope of the present invention.

[0022] The present invention provides a non-precious metal coating-supported catalyst, characterized in that it includes a support and a coating covering the support, the coating comprising a coating component and an active metal component, the active metal component comprising a Co metal component and an additive component, and the coating component comprising at least one substrate selected from attapulgite, kaolinite and montmorillonite.

[0023] The auxiliary component is at least one element selected from group A. Preferably, the auxiliary component is selected from at least one group selected from combinations of Ce and Mo, Ce and Mn, Ce and Fe, Ce and Ni, Ce and Bi, Ce and Ti, Ce and Cr, Ce and V, La and Mn, La and Fe, La and Ni, and La and Bi. More preferably, it is selected from at least one group selected from combinations of Ce and Mn with Ti, Ce and Mn with V, Ce and Mn with Bi, Ce and Mn with Cr, La and Mn with Ti, La and Mn with V, and La and Mn with Bi.

[0024] Group A: Li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce;

[0025] Based on the total volume of the non-noble metal coating-supported catalyst, the Co metal content (calculated as cobalt tetroxide) is 50~500 kg / m³. 3 The content of the auxiliary component (based on the highest oxidation state of the auxiliary component) is 10~180 kg / m³. 3 The content of coating components is 30-200 kg / m³. 3 .

[0026] In one embodiment of the present invention, the catalyst is substantially composed of a support, a coating component, and an active metal component. In another embodiment of the present invention, the catalyst consists only of a support, a coating component, and an active metal component. In yet another embodiment of the present invention, the catalyst does not contain carbonaceous materials (including but not limited to activated carbon, carbon fibers, etc.).

[0027] In this invention, "carrier" refers to a material on which additional compounds and / or elements are carried, preferably composed of an inert material. There are no particular limitations on the carrier in this invention; carriers commonly used in the field can be used, specifically inorganic carriers. For example, as an inorganic carrier, the carrier can be selected from at least one of cordierite, alumina, magnesium oxide, silicon carbide, aluminum titanate, silicon oxide, zirconium oxide, cerium oxide, titanium oxide, zirconium silicate, magnesium silicate, layered silicates, and ceramics, but is not limited thereto. In this invention, the carrier can be porous or non-porous. Non-porous is preferred. The carrier can be composed of particles with regular or irregular shapes. The shape of the carrier can be, for example, spherical, sheet-like, cylindrical, cubic, cuboid, solid or hollow cylinder, annular, star-shaped, Raschig ring, or other shapes.

[0028] In one embodiment of the present invention, the carrier refers to a carrier material (inert carrier) that has no substantial oxidative effect on the distribution of oxidation reaction products, and has a BET specific surface area of ​​0.1~5m². 2 ·g -1 The pore volume is less than 0.02 ml·g -1 .

[0029] In one embodiment of the present invention, the micropore volume of the carrier is almost undetectable in the BJH method for N2 adsorption test at -196°C.

[0030] In one embodiment of the present invention, the carrier preferably has macroscopic channels, which can be one or more of the following shapes: circular, square, triangular, hexagonal, or rhomboid. These macroscopic channels can be arranged in an ordered or disordered manner on the carrier, preferably as uniformly ordered honeycomb channels. Generally, to reduce adsorption resistance, the macroscopic channels on the carrier are permeable.

[0031] In one embodiment of the present invention, the cross-sectional area of ​​the single macroscopic channel on the carrier is 1 mm. 2 ~80mm 2 Preferably 1mm 2 ~35mm 2 The hole wall thickness is 1~4mm, preferably 1~2.5mm.

[0032] In this invention, the coating component comprises at least one substrate selected from attapulgite, kaolin, and montmorillonite.

[0033] In one embodiment of the present invention, the coating component may further include at least one material selected from molecular sieves, alumina, silicon oxide, magnesium oxide, and titanium oxide.

[0034] In one embodiment of the present invention, the coating component preferably comprises attapulgite. In another embodiment of the present invention, the coating component preferably comprises attapulgite and at least one selected from kaolin, montmorillonite, molecular sieve, alumina, silica, magnesium oxide, and titanium oxide, wherein the content of attapulgite relative to the total mass of the coating component is 50%-98%, preferably 60%-95%.

[0035] In one embodiment of the invention, the coating component is substantially composed of at least one substrate selected from attapulgite, kaolin, and montmorillonite, and optionally at least one material selected from molecular sieves, alumina, silica, magnesium oxide, and titanium oxide. In another embodiment of the invention, the coating component is composed only of at least one substrate selected from attapulgite, kaolin, and montmorillonite, and optionally at least one material selected from molecular sieves, alumina, silica, magnesium oxide, and titanium oxide.

[0036] In one embodiment of the invention, the coating component is substantially composed of attapulgite and at least one material optionally selected from kaolin, montmorillonite, molecular sieve, alumina, silica, magnesium oxide, and titanium oxide. In another embodiment of the invention, the coating component is composed only of attapulgite and at least one material optionally selected from kaolin, montmorillonite, molecular sieve, alumina, silica, magnesium oxide, and titanium oxide.

[0037] In one embodiment of the present invention, the substrate selected from at least one of attapulgite, kaolin and montmorillonite in the coating component accounts for 50-100% of the total mass of the coating component, preferably 50-95%, and more preferably 55-90%.

[0038] In one embodiment of the present invention, the content of the coating component is 30~200 kg / m³ based on the total volume of the non-precious metal coating-supported catalyst. 3 Preferred weight: 60~200 kg / m 3 .

[0039] In one embodiment of the present invention, the BET specific surface area of ​​the coating component is 80~600m². 2 ·g -1 Preferred depth: 100~600m 2 ·g -1 The average pore size is 2~12nm, preferably 4~12nm, and the pore volume is 0.15~1.0ml·g. -1 The preferred dosage is 0.2~1.0 ml·g. -1 .

[0040] In this invention, the BET specific surface area, pore size, and pore volume of the coating components are values ​​obtained by uniformly mixing the coating materials and then testing them. For example, when the coating components consist of attapulgite and molecular sieves, the attapulgite and molecular sieves need to be uniformly mixed by ball milling or other dispersion methods before testing to obtain the values.

[0041] In this invention, the active metal component comprises a Co metal component and an auxiliary component.

[0042] In one embodiment of the present invention, the auxiliary component is at least one selected from elements in group A, which includes: Li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Ni, Re, Zn, MnGa, Al, Sn, Pb, Bi, Sb, La, and Ce.

[0043] In one embodiment of the present invention, the auxiliary component is preferably selected from at least one group selected from combinations of Ce and Mo, Ce and Mn, Ce and Fe, Ce and Ni, Ce and Bi, Ce and Ti, Ce and Cr, Ce and V, La and Mn, La and Fe, La and Ni, and La and Bi. More preferably, it is selected from at least one group selected from combinations of Ce and Mn and Ti, Ce and Mn and V, Ce and Mn and Bi, Ce and Mn and Cr, La and Mn and Ti, La and Mn and V, and La and Mn and Bi. In one embodiment of the present invention, in each combination, the mass ratio of each element, the former to the latter (or the former to both of the latter) (based on the highest oxidation state of the metal), is 0.1 to 10, preferably 0.2 to 5.

[0044] In one embodiment of the present invention, based on the total volume of the non-precious metal coating-support catalyst, the Co metal content (calculated as cobalt tetroxide) is 50~500 kg / m³. 3 The preferred value is 50~430 kg / m³. 3 .

[0045] In one embodiment of the present invention, based on the total volume of the non-precious metal coating-supported catalyst, the content of the auxiliary component (calculated as the highest oxidation state oxide of the auxiliary component) is 10~180 kg / m³. 3 The preferred value is 10~150kg / m 3 .

[0046] In one embodiment of the present invention, the molar ratio of Co metal component to auxiliary component in the active metal component is 0.5:1 to 20:1, preferably 0.6:1 to 15:1.

[0047] In this invention, the auxiliary metals may be in their highest oxidation state after high-temperature calcination, but during the reaction process, there may be a process of coexistence of multiple oxidation states and interconversion of multiple oxidation states. This process maintains the activity and stability of the catalyst.

[0048] This invention also provides a method for preparing a non-precious metal coating-supported catalyst, characterized by comprising the following steps:

[0049] (1) A coating component slurry is prepared by contacting at least one substrate selected from attapulgite, kaolin and montmorillonite, a binder and water.

[0050] (2) The step of contacting the coating component slurry, a solution or suspension of at least one cobalt metal component precursor, and a solution or suspension of at least one auxiliary component precursor with a carrier to obtain a contact product, and

[0051] (3) The step of calcining the contact product to obtain the non-precious metal coating-supported catalyst.

[0052] In one embodiment of the present invention, in step (1) of the above preparation method, no pretreatment is performed on at least one substrate selected from attapulgite, kaolin and montmorillonite.

[0053] In one embodiment of the present invention, at least one substrate selected from attapulgite, kaolin, and montmorillonite can be pretreated using an acid or the like. As a pretreatment method, the substrate can be mixed with an inorganic acid for activation treatment. In this case, the mass ratio of the substrate to the solute in the inorganic acid is preferably 1:1 to 10, more preferably 1:3 to 7. The inorganic acid is preferably dilute sulfuric acid, nitric acid, or hydrochloric acid; the mass concentration of the inorganic acid is preferably 1 to 10%, more preferably 4 to 8%. The activation treatment temperature is preferably 20 to 80°C, more preferably 30 to 50°C; the activation treatment time is preferably 1 to 10 hours, more preferably 4 to 8 hours. During the activation treatment, stirring can be performed, and the stirring rate is preferably 200 to 500 r / min. In the present invention, the activation treatment can increase the specific surface area of ​​the substrate and improve its adsorption capacity. After activation treatment, the substrate is calcined to obtain the treated substrate. In the present invention, for convenience, both the pretreated substrate and the untreated substrate will be referred to as substrate in the following text.

[0054] In the preparation method of this invention, the attapulgite can be any attapulgite known in the art, and it can be a commercially available product. The kaolin can be any kaolin known in the art, and it can be a commercially available product. The montmorillonite can be any montmorillonite known in the art, and it can be a commercially available product.

[0055] In the preparation method of this invention, the substrate comprises at least one selected from attapulgite, kaolin, and montmorillonite, accounting for 50-100% of the total mass of the substrate, preferably 50-95%, and more preferably 55-90%. In the preparation method of this invention, the substrate may further include at least one material selected from molecular sieves, alumina, silicon dioxide, magnesium oxide, and titanium dioxide. In one embodiment of this invention, the substrate preferably comprises attapulgite. In one embodiment of this invention, the substrate preferably comprises attapulgite and at least one selected from kaolin, montmorillonite, molecular sieves, alumina, silicon dioxide, magnesium oxide, and titanium dioxide, in which case the content of attapulgite relative to the total mass of the substrate is 50%-98%, preferably 60%-95%. In this invention, the amount of the substrate used is a predetermined amount, such that the content of the substrate relative to the total volume of the carrier is 30-200 kg / m³. 3 Preferred weight: 60~200 kg / m 3 .

[0056] In the preparation method of this invention, in step (1) above, the adhesive solvent only needs to be able to disperse the substrate and can be an organic or inorganic substance, such as inorganic acids, inorganic bases, organic acids, monohydric alcohols, polyhydric alcohols, ethers, organic bases, cellulose derivatives, carboxylates, etc. These adhesive solvents can be used individually or in combination as needed. The amount of adhesive solvent is not particularly limited and can be adjusted according to the total amount of the substrate. Preferably, relative to 100 parts by mass of the total amount of the substrate, the amount of adhesive solvent is 1-20 parts by mass, more preferably 1.2-10 parts by mass, and more preferably 1.5-5 parts by mass.

[0057] As the inorganic acid, various inorganic acids known in the art can be used, such as one or more combinations of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and perchloric acid.

[0058] The inorganic base can be an alkali metal hydroxide or an alkaline earth metal hydroxide, for example, one or more combinations of sodium hydroxide, calcium hydroxide, potassium hydroxide, magnesium hydroxide, and lithium hydroxide.

[0059] As the organic acid, various polycarboxylic acids known in the art can be used, for example, those with 2 to 10 (preferably 3 to 6) carboxyl groups. 2-20 Alkanes, for example, include oxalic acid, succinic acid, and adipic acid. As polycarboxylic acids, examples include C14 groups optionally having one or more hydroxyl groups (e.g., 1 to 6) and simultaneously having 1 to 10 (preferably 3 to 6) carboxyl groups. 2-20 Alkanes, such as malic acid, tartaric acid, citric acid, and stearic acid, can also be used as polycarboxylic acids, specifically those in the C2O2 group. 2-20 Polycarboxylated alkyl (poly)amines are obtained by inserting one or more nitrogen atoms into an alkane chain, such as hypozinotriacetic acid and ethylenediaminetetraacetic acid.

[0060] As the monohydric alcohol, various monohydric alcohols known in the art can be used, such as C16 alcohols with one hydroxyl group. 1-20 Alkanes, for example, include methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol.

[0061] As the polyol, various polyols known in the art can be used, such as those with 2 to 10 (preferably 3 to 6) hydroxyl groups. 2-20 Alkanes, such as ethylene glycol, diethylene glycol, propylene glycol, glycerol, pentaerythritol, or polymers of such polyols, such as polyethylene glycol, polyvinyl alcohol, etc., or may be those contained in the C... 2-20 Polyhydroxyalkyl (poly)amines are obtained by inserting one or more nitrogen atoms into an alkane chain, such as monoethanolamine and triethanolamine.

[0062] The ether can be of the molecular formula RO(CH2CH2O). n Fatty alcohol polyoxyethylene ethers with H (R being a C3-C9 alkyl group and n being an integer from 1 to 12); molecular formula RC6H4O(CH2CH2O). n Alkylphenol polyoxyethylene ethers with the molecular formula C8H (where R is an alkyl group from C3 to C9 and n is an integer from 1 to 12). 17 (CH2CH2O) n Sec-octanol polyoxyethylene ether (H, where n is an integer from 1 to 12).

[0063] As the organic base, various polyamines and nitrogen-containing basic organic compounds known in the art can be used, such as urea, pyridine, ephedrine, ethylenediamine, diethylenetriamine, triethylenetetramine, dopamine, etc.

[0064] As the cellulose derivatives mentioned above, those known in the art can be used, such as methylcellulose, hydroxymethylcellulose, hydroxymethylpropylcellulose, carboxymethylcellulose, etc.

[0065] As the carboxylate, those carboxylate salts known in the art can be used, such as magnesium stearate, sodium stearate, etc.

[0066] In step (1), the amount of water added is not particularly limited, as long as it can disperse the substrate. Preferably, the amount of water used is 20 to 120 parts by weight relative to 100 parts by weight of the total substrate.

[0067] In step (1), a kneader can be used to stir and prepare the contact body, or the substrate can be ball-milled to make a slurry.

[0068] In step (2), there are no particular restrictions on the contact order of the raw material components (i.e., the carrier, coating component, cobalt metal component precursor, and additive component precursor). Furthermore, according to the present invention, there are no particular restrictions on the manner in which the contact step is performed, as long as sufficient contact between the raw material components and the carrier is achieved, and a uniform contact product is formed. For example, the raw material components can be mixed (and stirred if necessary) to homogeneity in any manner known in the art.

[0069] For example, the coating component slurry can first be contacted with the carrier, optionally subjected to heat treatment, and then contacted with the cobalt metal component precursor and the additive component precursor, which are the active metal components. Alternatively, the coating component slurry, the cobalt metal component precursor, and the additive component precursor can be contacted with the carrier simultaneously.

[0070] In one embodiment of the present invention, step (2) may include the following steps:

[0071] (2-1) First, bring the coating component slurry into contact with the carrier; and

[0072] (2-2) Optionally, the contact product of step (2-1) is heat-treated and then contacted with a solution or suspension of at least one cobalt metal component precursor or a solution or suspension of at least one auxiliary component precursor.

[0073] In one embodiment of the present invention, step (2) may include the following steps:

[0074] (2-1') Contacting a solution or suspension of at least one cobalt metal component precursor, a solution or suspension of at least one auxiliary component precursor, with a support; and

[0075] (2-2') The contact product from step (2-1') is optionally heat-treated and then contacted with the coating component slurry.

[0076] In one embodiment of the present invention, step (2) may include the following steps:

[0077] (2') The coating component slurry, a solution or suspension of at least one cobalt metal component precursor, and a solution or suspension of at least one auxiliary component precursor are simultaneously brought into contact with the carrier.

[0078] In step (2), the auxiliary component is at least one element selected from group A, which includes: Li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, and Ce.

[0079] In step (2), the additive is preferably selected from at least one group selected from combinations of Ce and Mo, Ce and Mn, Ce and Fe, Ce and Ni, Ce and Bi, Ce and Ti, Ce and Cr, Ce and V, La and Mn, La and Fe, La and Ni, and La and Bi. More preferably, it is selected from at least one group selected from combinations of Ce and Mn and Ti, Ce and Mn and V, Ce and Mn and Bi, Ce and Mn and Cr, La and Mn and Ti, La and Mn and V, and La and Mn and Bi. In one embodiment of the invention, in each combination, the mass ratio of each element, the former to the latter (or the former to both of the latter) (based on the highest oxidation state of the metal), is 0.1 to 10, preferably 0.2 to 5.

[0080] In this invention, the precursor of the cobalt metal component is a cobalt metal precursor commonly used in the art. For example, the cobalt metal precursor can preferably be a soluble salt or other soluble complex, and more preferably a chloride salt, nitrate salt, acetate salt, or ammonium salt.

[0081] In this invention, the precursor of the auxiliary component is a precursor of an auxiliary metal commonly used in the art. For example, the precursor of the auxiliary metal can preferably be a soluble salt of the auxiliary component, and more preferably a chloride salt, nitrate salt, acetate salt, sulfate salt, ammonium salt, or phosphate salt. For example, for cerium precursors, cerium nitrate, cerium chloride, and cerium ammonium nitrate can be selected.

[0082] In this invention, when preparing a solution or suspension of the precursor of the cobalt metal component and / or a solution or suspension of the precursor of the auxiliary component, the pH can be adjusted using the pH adjuster described below.

[0083] In this invention, the solvents used for preparing the precursor solution or suspension of the cobalt metal component and the precursor solution or suspension of the auxiliary component are not particularly limited. Various solvents known in the art can be used, as long as they can dissolve the precursor of the cobalt metal component or the precursor of the auxiliary component, or suspend it, without affecting the effects of this invention. These solvents can be various organic solvents or water, preferably deionized water. Various inorganic acids (e.g., hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) and organic acids (e.g., formic acid, acetic acid, propionic acid, oxalic acid, etc.) can optionally be added to the solvent. These inorganic and organic acids can function as complexing agents, stabilizers, and pH adjusters as described below.

[0084] In this invention, when the precursor of the cobalt metal component and the precursor of the auxiliary component are prepared into a solution or suspension, the concentration of the solution or suspension is not particularly limited, and can usually be 5 g / L to 300 g / L.

[0085] In this invention, when preparing solutions or suspensions of cobalt metal precursors or solutions or suspensions of auxiliary component precursors, various additives may be added as needed, such as complexing agents, stabilizers, and pH adjusters.

[0086] Examples of complexing agents include polycarboxylic acids, monohydric alcohols, polyols, and polyamines. These complexing agents can be used individually or in combination as needed. Examples of polycarboxylic acids include C2-20 alkanes with 2 to 10 (preferably 3 to 6) carboxyl groups, such as oxalic acid, succinic acid, and adipic acid. Examples of polycarboxylic acids include C2-20 alkanes with one or more hydroxyl groups (e.g., 1 to 6) and 2 to 10 (preferably 3 to 6) carboxyl groups, such as malic acid, tartaric acid, and citric acid. Alternatively, the polycarboxylic acid can also be a polycarboxylated alkyl (poly)amine obtained by inserting one or more nitrogen atoms into the aforementioned C2-20 alkane chain, such as hypozoxytriacetic acid and ethylenediaminetetraacetic acid. Examples of monohydric alcohols include C1-20 alkanes with one hydroxyl group, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol. Examples of polyols include C2-20 alkanes having 2 to 10 (preferably 3 to 6) hydroxyl groups, ethylene glycol, glycerol, or polymers of such polyols, such as polyethylene glycol. Alternatively, polyhydroxyalkyl(poly)amines obtained by inserting one or more nitrogen atoms into the C2-20 alkane chain can be included, such as monoethanolamine and triethanolamine. Examples of polyamines include ethylenediamine, diethylenetriamine, and triethylenetetramine.

[0087] As the stabilizer, various stabilizers known in the art can be used, such as oxides of metals selected from barium, calcium, magnesium, strontium, and mixtures thereof, or methyl methacrylate. The stabilizer preferably comprises one or more oxides of barium and / or strontium, or methyl methacrylate.

[0088] As a pH adjuster, various pH adjusters known in the art can be used, such as various water-soluble acids and water-soluble bases, such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydroxy monocarboxylic acid, polyhydroxy monocarboxylic acid, hydroxy polycarboxylic acid, polyhydroxy polycarboxylic acid, monocarboxylic acid, etc.; and alkaline substances such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ethylenediamine, and ammonia.

[0089] Additionally, it should be noted that when using the above-mentioned complexing agents that are acidic or alkaline, they can also function as pH adjusters.

[0090] In step (2) of this invention, the contact between the coating component slurry and the carrier can be achieved by using conventional coating equipment to coat the carrier with the slurry, or by immersing the carrier in the slurry. The concentration of the coating component slurry, the coating amount, and the contact time between the carrier and the coating component slurry can be adjusted so that the content of the coating component in the final catalyst, relative to the total volume of the catalyst, is 30~200 kg / m³. 3 Preferred weight: 60~200 kg / m 3 .

[0091] In step (2) of this invention, the contact between the solution or suspension of the active metal precursor and the support can be achieved by spraying or sprinkling the solution or suspension onto the support, or by immersing the support in the solution or suspension. Immersion is preferred. The contact can be performed at any temperature, such as room temperature. The contact time is not particularly limited, as long as the cobalt metal content (calculated as cobalt tetroxide) relative to the total volume of the final catalyst is 50-500 kg / m³. 3 Preferred weight: 50~430 kg / m 3 The content of the additives (based on the highest oxidation state of the oxide of the additive component) is 10~180 kg / m³. 3 Preferred weight: 10~150 kg / m 3 That's all.

[0092] In step (2) of this invention, there is no limitation on the contact order between the cobalt metal component precursor solution or suspension, the auxiliary component precursor solution or suspension, and the carrier. The cobalt metal component precursor solution or suspension can be contacted with the carrier first, followed by the auxiliary component precursor solution or suspension, or the order can be reversed. Alternatively, after preparing the cobalt metal component precursor solution or suspension and the auxiliary component precursor solution or suspension separately, the two solutions or suspensions can be mixed and then simultaneously contacted with the carrier. Furthermore, a heat treatment step such as drying can optionally be inserted between the two contact steps, for example, drying, air drying, or sun drying at 50~180°C, preferably 60~150°C, and more preferably 70~120°C.

[0093] In step (2) of this invention, when the solution or suspension of the cobalt metal component precursor and the solution or suspension of the auxiliary component precursor are brought into contact with the support, the concentration of the cobalt metal component precursor solution or suspension, the concentration of the auxiliary component precursor solution or suspension, and the contact time between the support and the solutions or suspensions of the two components can be adjusted so that the cobalt metal content (calculated as cobalt tetroxide) in the final catalyst is 50~500 kg / m³.3 The preferred value is 50~430 kg / m³. 3 The content of the additives (based on the highest oxidation state of the oxide of the additive component) is 10~180 kg / m³. 3 The preferred value is 10~150kg / m 3 That's all.

[0094] In this invention, after contact or immersion treatments are completed, heat treatment steps such as air drying or air drying can be performed within one or two steps. This heat treatment can be carried out at 20~150°C, preferably 30~120°C, and more preferably 50~100°C.

[0095] In this invention, if necessary, for more uniform and sufficient contact, or to facilitate contact, the contact step can also be carried out in the presence of a dispersion medium such as water. The resulting contact product may then be in the form of a slurry or paste-like liquid.

[0096] In this invention, the contact step can be performed at any temperature from 0°C to 150°C, for example, at room temperature. When the temperature is higher than the boiling point of the dispersion medium, it can be performed in a pressure vessel so that the boiling point corresponding to that pressure is higher than the temperature. For convenience, room temperature is preferred, but it is not always limited to this. The contact time is determined by obtaining the desired contact product, generally 0.5 to 5 hours, but it is not limited to this.

[0097] According to the present invention, the contact product, after preparation, especially when the contact product contains a slurry, may sometimes be dried by any means known in the art, such as baking, air drying, or desiccation at 50-180°C, preferably 60-150°C, and more preferably 70-120°C, to remove any dispersion medium (such as water) that may have been introduced during its preparation. According to the present invention, the dried contact product is also simply referred to as the contact product.

[0098] In this invention, in step (3), the contact product obtained in step (2) is calcined to obtain the non-precious metal coating-support catalyst of this invention.

[0099] In step (3), the calcination temperature is 200~580℃, preferably 200~550℃, and more preferably 250~550℃. Calcination can be carried out in an air atmosphere or in an inert gas atmosphere. The calcination time is not particularly limited and can be 2~20 hours, preferably 4~16 hours.

[0100] The present invention also provides the application of a non-precious metal coated-supported catalyst or a non-precious metal coated-supported catalyst prepared according to the preparation method of the present invention in the catalytic oxidation treatment of volatile organic compounds.

[0101] In the application of the non-precious metal coated-supported catalyst of the present invention, a non-precious metal coated-supported catalyst is packed into a reactor, and a gas containing volatile organic compounds is introduced, with a gas hourly space velocity of 4000~25000 h⁻¹. -1 Catalytic oxidation at 150~550℃ removes volatile organic compounds. Example

[0102] The present invention will be further described in detail below with reference to the embodiments, but the present invention is not limited to these embodiments.

[0103] It should be noted that, unless otherwise specified, in the embodiments of the present invention, "parts" refers to "parts by mass". Unless otherwise specified, the content of Co metal is calculated as cobalt tetroxide, and the content of the auxiliary component is calculated as the oxide of the highest oxidation state of the auxiliary component.

[0104] In this invention, the surface area is determined by the BET specific surface area measurement method.

[0105] The pore volume was determined using the BJH (Barrett-Joyner-Halenda) method.

[0106] The average pore size was determined using the BJH method.

[0107] The cordierite used in this embodiment has a single pore cross-sectional area of ​​4.5 mm. 2 The carrier of macroscopic honeycomb pores.

[0108] Example 1

[0109] Ten parts of attapulgite clay, one part of γ-alumina, 0.3 parts of urea, and one part of 65% nitric acid were mixed with an appropriate amount of water and milled into a slurry. This slurry was then coated onto the surface of 100 parts of cordierite (10cm × 10cm × 5cm). After drying at 80℃ for 4 hours, a honeycomb inner coating carrier was obtained. The specific surface area of ​​the coating components was 192 μm. 2 / g, pore volume is 0.26cm 3 / g, average pore size 4.8nm, coating content per unit volume 82kg / m 3 Based on a Co content of 150 kg / m³ for cordierite. 3 A polyethylene glycol-400 aqueous solution of cobalt nitrate was prepared in a ratio of 0.1:1 (polyethylene glycol to cobalt nitrate by mass), based on a cordierite Ce content of 20 kg / m³. 3 The Mo content is 18 kg / m³. 3An aqueous solution of cerium nitrate and ammonium molybdate was prepared in a certain proportion. The Ce and Mo solutions were first impregnated onto the coating support and dried at 150°C for 3 hours. Then, the Co solution was further impregnated and dried again at 150°C for 2 hours. After calcination at 550°C for 5 hours, a non-precious metal coating-support catalyst A was obtained.

[0110] Example 2

[0111] Ten parts of attapulgite clay, one part of γ-alumina, 0.3 parts of hydroxymethyl cellulose, and one part of 65% nitric acid were mixed with an appropriate amount of water and milled into a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained. The specific surface area of ​​the coating components was 192 μm. 2 / g, pore volume is 0.26cm 3 / g, average pore size is 4.8nm, coating content per unit volume is 102kg / m 3 Based on a Co content of 150 kg / m³ for cordierite. 3 A citric acid aqueous solution of cobalt nitrate was prepared in a ratio of 0.1:1 (citric acid to cobalt nitrate by mass), based on a cordierite Ce content of 35 kg / m³. 3 The Mn content is 23 kg / m³. 3 An aqueous solution of cerium nitrate and manganese nitrate was prepared in a certain proportion. The Ce and Mn solution was first impregnated on the coating support and dried at 150°C for 4 hours. Then, the Co solution was further impregnated and dried again at 150°C for 3 hours. After calcination at 550°C for 5 hours, a non-precious metal coating-support catalyst B was obtained.

[0112] Comparative Example 1

[0113] Eleven parts of γ-alumina, 0.3 parts of hydroxymethyl cellulose, and one part of 65% nitric acid were ball-milled with an appropriate amount of water to form a slurry. This slurry was then coated onto the surface of 80 parts of cordierite measuring 10cm × 10cm × 5cm. After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained, with a coating content of 102 kg / m³. 3 Based on a Co content of 150 kg / m³ for cordierite. 3 A citric acid aqueous solution of cobalt nitrate was prepared in a ratio of 0.1:1 (citric acid to cobalt nitrate by mass), based on a cordierite Ce content of 35 kg / m³. 3 The Mn content is 23 kg / m³. 3An aqueous solution of cerium nitrate and manganese nitrate was prepared in a certain proportion. The Ce and Mn solution was first impregnated on the coating support and dried at 150°C for 4 hours. Then, the Co solution was further impregnated and dried again at 150°C for 3 hours. After calcination at 550°C for 5 hours, a non-precious metal coating-support catalyst B1 was obtained.

[0114] Example 3

[0115] Ten parts of attapulgite clay, one part of SiO2, 0.3 parts of hydroxymethyl cellulose, and one part of 65% nitric acid were mixed with an appropriate amount of water and milled into a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained. The specific surface area of ​​the coating components was 205 μm. 2 / g, pore volume is 0.41cm 3 / g, average pore size is 6.2nm, coating content per unit volume is 102kg / m 3 Based on a Co content of 300 kg / m³ of cordierite. 3 A glycerol-cobalt chloride aqueous solution was prepared in a ratio of 0.2:1 (glycerol to cobalt chloride by mass), based on a cordierite Ce content of 70 kg / m³. 3 The Fe content is 21 kg / m³. 3 An aqueous solution of cerium nitrate and ferric nitrate was prepared in a certain proportion. The solutions of Ce, Fe and Co were simultaneously impregnated on the coating support. After drying at 150°C for 4 hours, the solution was then calcined at 550°C for 5 hours to obtain a non-precious metal coating-support catalyst C.

[0116] Comparative Example 2

[0117] Eleven parts SiO2, 0.3 parts hydroxymethyl cellulose, and one part 65% nitric acid were ball-milled with an appropriate amount of water to form a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained. The coating's volume content was 102 kg / m³. 3 Based on a Co content of 300 kg / m³ of cordierite. 3 A glycerol-cobalt chloride aqueous solution was prepared in a ratio of 0.2:1 (glycerol to cobalt chloride by mass), based on a cordierite Ce content of 70 kg / m³. 3 The Fe content is 21 kg / m³. 3 An aqueous solution of cerium nitrate and ferric nitrate was prepared in a certain proportion. The solutions of Ce, Fe and Co were simultaneously impregnated on the coating support. After drying at 150°C for 4 hours, the solution was then calcined at 550°C for 5 hours to obtain a non-precious metal coating-support catalyst C1.

[0118] Example 4

[0119] Ten parts of attapulgite, one part of kaolin, one part of SiO2, 0.3 parts of hydroxymethyl cellulose, and one part of 65% nitric acid were ball-milled with an appropriate amount of water to form a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained. The specific surface area of ​​the coating components was 189 μm. 2 / g, pore volume is 0.39cm 3 / g, average pore size is 8.2nm, coating content per unit volume is 112kg / m 3 Based on a Co content of 320 kg / m³ of cordierite. 3 Prepare a glycerol-cobalt chloride aqueous solution in a ratio of 0.3:1 (glycerol to cobalt chloride by mass), based on a cordierite (Ce) content of 50 kg / m³. 3 The Ni content is 40 kg / m 3 An aqueous solution of cerium nitrate and nickel nitrate was prepared in a certain proportion. The Ce and Ni solutions were first impregnated on the coating support and dried at 150°C for 4 hours. Then, the Co solution was further impregnated and dried again at 150°C for 3 hours. After calcination at 550°C for 5 hours, a non-precious metal coating-support catalyst D was obtained.

[0120] Example 5

[0121] Eleven parts of kaolin, one part of SiO2, 0.3 parts of hydroxymethyl cellulose, and one part of 65% nitric acid were ball-milled with an appropriate amount of water to form a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained. The specific surface area of ​​the coating components was 186 μm. 2 / g, pore volume 0.42cm 3 / g, average pore size is 8.4nm, coating content per unit volume is 112kg / m 3 Based on a Co content of 280 kg / m³ of cordierite. 3 A glycerol-cobalt chloride aqueous solution was prepared in a ratio of 0.3:1 (glycerol to cobalt chloride by mass), based on a cordierite Ce content of 60 kg / m³. 3 Bi content is 20 kg / m 3 An aqueous solution of cerium nitrate and bismuth nitrate was prepared in a certain proportion. The Ce and Bi solutions were first impregnated on the coating support and dried at 150°C for 4 hours. Then, a Co solution was further impregnated and dried again at 150°C for 3 hours. After calcination at 550°C for 5 hours, a non-precious metal coating-support catalyst E was obtained.

[0122] Example 6

[0123] Eleven parts montmorillonite, one part SiO2, 0.3 parts hydroxymethyl cellulose, and one part 65% nitric acid were ball-milled with an appropriate amount of water to form a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained. The specific surface area of ​​the coating components was 193 μm. 2 / g, pore volume 0.40cm 3 / g, average pore size 7.9nm, coating content per unit volume 112kg / m 3 Based on a Co content of 350 kg / m³ of cordierite. 3 A glycerol-cobalt chloride aqueous solution was prepared in a ratio of 0.3:1 (glycerol to cobalt chloride by mass), based on a cordierite Ce content of 58 kg / m³. 3 The Cr content is 33 kg / m³. 3 An aqueous solution of cerium nitrate and chromium nitrate was prepared in a certain proportion. The Ce and Cr solutions were first impregnated on the coating support and dried at 150°C for 4 hours. Then, the Co solution was further impregnated and dried again at 150°C for 3 hours. After calcination at 550°C for 5 hours, a non-precious metal coating-support catalyst F was obtained.

[0124] Example 7

[0125] Ten parts of attapulgite, one part of kaolin, one part of SiO2, 0.3 parts of hydroxymethyl cellulose, and one part of 65% nitric acid were ball-milled with an appropriate amount of water to form a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained. The specific surface area of ​​the coating components was 189 μm. 2 / g, pore volume is 0.39cm 3 / g, average pore size is 8.2nm, coating content per unit volume is 112kg / m 3 Based on a Co content of 350 kg / m³ of cordierite. 3 A glycerol-cobalt chloride aqueous solution was prepared in a ratio of 0.3:1 (glycerol to cobalt chloride by mass), based on a cordierite Ce content of 42 kg / m³. 3 The vitamin C content is 17 kg / m³. 3 An aqueous solution of oxalic acid containing cerium nitrate and ammonium metavanadate was prepared in a specific ratio. The Ce and V solutions were first impregnated onto the coating support and dried at 150°C for 4 hours. Then, a Co solution was further impregnated and dried again at 150°C for 3 hours. Finally, the mixture was calcined at 500°C for 5 hours to obtain a non-precious metal coating-support catalyst G.

[0126] Example 8

[0127] A mixture of 12 parts attapulgite, 2 parts kaolin, 1 part SiO2, 2 parts urea, and 3 parts 65% nitric acid was ball-milled with an appropriate amount of water to form a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). The slurry was dried at 150℃ for 4 hours to obtain the honeycomb inner coating carrier. The specific surface area of ​​the coating components was 145 μm. 2 / g, pore volume 0.33cm 3 / g, average pore size is 8.9nm, coating content per unit volume is 140kg / m 3 Based on a Co content of 350 kg / m³ of cordierite. 3 A glycerol-cobalt chloride aqueous solution was prepared in a ratio of 0.3:1 (glycerol to cobalt chloride by mass), based on a cordierite (La) content of 52 kg / m³. 3 The Mn content is 17 kg / m³. 3 A lanthanum nitrate and manganese nitrate aqueous solution in acetic acid was prepared in a certain proportion. The La and Mn solutions were first impregnated on the coating support and dried at 150°C for 4 hours. Then, the Co solution was further impregnated and dried again at 150°C for 3 hours. After calcination at 520°C for 5 hours, a non-precious metal coating-support catalyst H was obtained.

[0128] Example 9

[0129] Ten parts attapulgite, two parts kaolin, one part SBA-15 molecular sieve, two parts urea, and four parts 65% nitric acid were ball-milled with appropriate amounts of water and triethylene glycol to form a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained. The specific surface area of ​​the coating components was 298 μm. 2 / g, pore volume is 0.43cm 3 / g, average pore size 9.8nm, coating content per unit volume 121 kg / m 3 Based on a Co content of 350 kg / m³ of cordierite. 3 A glycerol-cobalt chloride aqueous solution was prepared in a ratio of 0.3:1 (glycerol to cobalt chloride by mass), based on a cordierite (La) content of 80 kg / m³. 3 The Fe content is 20 kg / m³ 3 A solution of lanthanum nitrate and ferric nitrate was prepared in a certain proportion. The Co solution was first impregnated on the coating support and dried at 130°C for 4 hours. Then, the La and Fe solutions were further impregnated and dried again at 150°C for 3 hours. After calcination at 500°C for 5 hours, a non-precious metal coating-support catalyst I was obtained.

[0130] Example 10

[0131] Ten parts of attapulgite, two parts of kaolin, one part of SBA-15 molecular sieve, two parts of urea, and one part of 65% nitric acid were ball-milled with appropriate amounts of water and triethylene glycol to form a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained. The specific surface area of ​​the coating components was 298 μm. 2 / g, pore volume is 0.43cm 3 / g, average pore size 9.8nm, coating content per unit volume 121 kg / m 3 Based on a Co content of 350 kg / m³ of cordierite. 3 A stearic acid aqueous solution of cobalt chloride was prepared in a ratio of 0.2:1 (mass ratio of stearic acid to cobalt chloride), based on a cordierite (La) content of 84 kg / m³. 3 The Ni content is 10 kg / m 3 A solution of lanthanum nitrate and nickel nitrate was prepared in a certain proportion. The Co solution was first impregnated on the coating support and dried at 130°C for 4 hours. Then, the La and Ni solutions were further impregnated and dried again at 150°C for 3 hours. After calcination at 500°C for 5 hours, a non-precious metal coating-support catalyst J was obtained.

[0132] Example 11

[0133] Ten parts of attapulgite, two parts of kaolin, two parts of SAPO molecular sieve, two parts of urea, and one part of 65% nitric acid were ball-milled with appropriate amounts of water and triethylene glycol to form a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained. The specific surface area of ​​the coating components was 208 μm. 2 / g, pore volume is 0.46cm 3 / g, average pore size 7.1nm, coating content per unit volume 131 kg / m 3 Based on a Co content of 290 kg / m³ of cordierite. 3 An aqueous solution of methyl methacrylate was prepared in a ratio of 0.3:1 to cobalt chloride, based on a cordierite (La) content of 80 kg / m³. 3 Bi content is 20 kg / m 3 Aqueous solutions of lanthanum nitrate and bismuth nitrate were prepared in a specific ratio. The Co solution was first impregnated onto the coating support and dried at 130°C for 4 hours. Then, the La and Bi solutions were further impregnated, dried again at 150°C for 3 hours, and calcined at 500°C for 5 hours to obtain a non-precious metal coating-support catalyst K.

[0134] Example 12

[0135] Ten parts of attapulgite, one part of kaolin, one part of alumina, two parts of urea, and one part of 65% nitric acid were ball-milled with appropriate amounts of water and triethylene glycol to form a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained. The specific surface area of ​​the coating components was 156 μm. 2 / g, pore volume 0.42cm 3 / g, average pore size 7.7nm, coating content per unit volume 112kg / m 3 Based on a Co content of 430 kg / m³ of cordierite. 3 An aqueous solution of methyl methacrylate was prepared in a ratio of 0.3:1 to cobalt chloride, based on a cordierite (Ce) content of 40 kg / m³. 3 The Mn content is 30 kg / m³. 3 Ti content is 20 kg / m 3 An aqueous solution of cerium nitrate, manganese nitrate, and titanium sulfate was prepared in a certain proportion. The Co solution was first impregnated onto the coating support and dried at 130°C for 4 hours. Then, a solution of Ce, Mn, and Ti was further impregnated, dried again at 150°C for 3 hours, and calcined at 540°C for 4 hours to obtain a non-precious metal coating-support catalyst L.

[0136] Example 13

[0137] Ten parts of attapulgite, one part of kaolin, one part of alumina, two parts of urea, and one part of 65% nitric acid were ball-milled with appropriate amounts of water and triethylene glycol to form a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained. The specific surface area of ​​the coating components was 156 μm. 2 / g, pore volume 0.42cm 3 / g, average pore size 7.7nm, coating content per unit volume 112kg / m 3 Based on a Co content of 430 kg / m³ of cordierite. 3 An aqueous solution of methyl methacrylate was prepared in a ratio of 0.3:1 to cobalt chloride, based on a cordierite (Ce) content of 50 kg / m³. 3 The Mn content is 20 kg / m³. 3 The vitamin C content is 20 kg / m³. 3 An aqueous solution of cerium nitrate, manganese nitrate, and vanadium oxysulfate was prepared in a specific ratio. The Co solution was first impregnated onto the coating support and dried at 130°C for 4 hours. Then, a solution of Ce, Mn, and V was further impregnated, dried again at 150°C for 3 hours, and calcined at 550°C for 4 hours to obtain a non-precious metal coating-support catalyst M.

[0138] Example 14

[0139] Ten parts of attapulgite, one part of kaolin, one part of alumina, two parts of urea, and one part of 65% nitric acid were ball-milled with appropriate amounts of water and triethylene glycol to form a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained. The specific surface area of ​​the coating components was 156 μm. 2 / g, pore volume 0.42cm 3 / g, average pore size 7.7nm, coating content per unit volume 112kg / m 3 Based on a Co content of 430 kg / m³ of cordierite. 3 An aqueous solution of methyl methacrylate was prepared in a ratio of 0.3:1 to cobalt chloride, based on a cordierite (Ce) content of 50 kg / m³. 3 The Mn content is 20 kg / m³. 3 Bi content is 20 kg / m 3 An aqueous solution of cerium nitrate, manganese nitrate, and bismuth nitrate was prepared in a specific ratio. The solution of Ce, Mn, and Bi was first impregnated onto the coating support and dried at 130°C for 4 hours. Then, a Co solution was further impregnated, and the solution was dried again at 150°C for 3 hours. Finally, the solution was calcined at 550°C for 4 hours to obtain a non-precious metal coating-support catalyst N.

[0140] Example 15

[0141] Ten parts of attapulgite, one part of kaolin, one part of alumina, two parts of urea, and one part of 65% nitric acid were ball-milled with appropriate amounts of water and triethylene glycol to form a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained. The specific surface area of ​​the coating components was 156 μm. 2 / g, pore volume 0.42cm 3 / g, average pore size 7.7nm, coating content per unit volume 112kg / m 3 Based on a Co content of 430 kg / m³ of cordierite. 3 An aqueous solution of methyl methacrylate was prepared in a ratio of 0.3:1 to cobalt chloride, based on a cordierite (Ce) content of 48 kg / m³. 3 The Mn content is 30 kg / m³. 3 The Cr content is 10 kg / m³ 3An aqueous solution of cerium nitrate, manganese nitrate, and chromium nitrate was prepared in a certain proportion. The solution of Ce, Mn, and Cr was first impregnated on the coating support and dried at 130°C for 4 hours. Then, Co solution was further impregnated, dried again at 150°C for 3 hours, and calcined at 550°C for 4 hours to obtain a non-precious metal coating-support catalyst O.

[0142] Example 16

[0143] Ten parts of attapulgite, one part of kaolin, one part of alumina, two parts of urea, and one part of 65% nitric acid were ball-milled with appropriate amounts of water and triethylene glycol to form a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained. The specific surface area of ​​the coating components was 156 μm. 2 / g, pore volume 0.42cm 3 / g, average pore size 7.7nm, coating content per unit volume 112kg / m 3 Based on a Co content of 280 kg / m³ of cordierite. 3 An aqueous solution of methyl methacrylate was prepared in a ratio of 0.3:1 to cobalt chloride, based on a cordierite (La) content of 75 kg / m³. 3 The Mn content is 20 kg / m³. 3 Ti content is 10 kg / m 3 An aqueous solution of lanthanum nitrate, manganese nitrate, and titanium sulfate was prepared in a certain proportion. The solution of La, Mn, and Ti was first impregnated on the coating support and dried at 130°C for 4 hours. Then, Co solution was further impregnated, dried again at 150°C for 3 hours, and calcined at 550°C for 4 hours to obtain a non-precious metal coating-support catalyst P.

[0144] Example 17

[0145] Ten parts of attapulgite, one part of kaolin, one part of titanium dioxide, two parts of urea, and one part of 65% nitric acid were ball-milled with appropriate amounts of water and triethylene glycol to form a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained. The specific surface area of ​​the coating components was 121 μm. 2 / g, pore volume 0.35cm 3 / g, average pore size is 8.1nm, coating content per unit volume is 112kg / m 3 Based on a Co content of 280 kg / m³ of cordierite. 3 An aqueous solution of methyl methacrylate was prepared in a ratio of 0.3:1 to cobalt chloride, based on a cordierite (La) content of 79 kg / m³.3 The Mn content is 20 kg / m³. 3 The vitamin C content is 15 kg / m³. 3 An aqueous solution of lanthanum nitrate, manganese nitrate, and ammonium metavanadate was prepared in a certain proportion. The solution of La, Mn, and V was first impregnated on the coating support and dried at 130°C for 4 hours. Then, Co solution was further impregnated, dried again at 150°C for 3 hours, and calcined at 550°C for 4 hours to obtain a non-precious metal coating-support catalyst Q.

[0146] Example 18

[0147] Ten parts of attapulgite, one part of kaolin, one part of magnesium oxide, two parts of urea, and one part of 65% nitric acid were ball-milled with appropriate amounts of water and triethylene glycol to form a slurry. This slurry was then coated onto the surface of 80 parts of cordierite (10cm × 10cm × 5cm). After drying at 150℃ for 4 hours, a honeycomb inner coating carrier was obtained. The specific surface area of ​​the coating components was 123 μm. 2 / g, pore volume 0.32cm 3 / g, average pore size is 6.1nm, coating content per unit volume is 112kg / m 3 Based on a Co content of 400 kg / m³ of cordierite. 3 An aqueous solution of methyl methacrylate was prepared in a ratio of 0.3:1 to cobalt chloride, based on a cordierite (La) content of 79 kg / m³. 3 The Mn content is 25 kg / m³. 3 Bi content is 15 kg / m 3 An aqueous solution of lanthanum nitrate, manganese nitrate, and bismuth nitrate was prepared in a specific ratio. The solution of La, Mn, and Bi was first impregnated onto the coating support and dried at 130°C for 4 hours. Then, a Co solution was further impregnated, and the solution was dried again at 150°C for 3 hours. Finally, the solution was calcined at 550°C for 4 hours to obtain a non-precious metal coating-support catalyst R.

[0148] Example 19

[0149] The non-precious metal coated-supported catalysts from Examples 1-18 and Comparative Examples 1-2 were loaded into a fixed-bed reactor, and non-methane total hydrocarbons were introduced at a concentration of 1200 mg / m³. 3 The VOCs gas, at a reaction temperature of 430℃ and a space velocity of 10000 h⁻¹ -1 The reaction was carried out under the specified conditions, and the VOCs at the outlet were detected by gas chromatography. The results are shown in Table 1.

[0150] Table 1 Comparison of catalytic performance of non-precious metal coating-supported catalysts

[0151] catalyst <![CDATA[VOCs concentration at the outlet after 1-hour reaction (mg / m 3 )]]> <![CDATA[VOCs concentration at the outlet after 500h of reaction (mg / m 3 )]]> <![CDATA[Concentration of VOCs at the outlet after 1000 h of reaction (mg / m 3 )]]> A 33.9 34.3 37.0 B 12.3 13.5 14.1 C 15.1 15.4 16.5 D 19.0 19.4 20.8 E 15.3 16.1 16.9 F 18.6 18.9 19.7 G 18.1 19.3 19.8 H 17.7 18.5 19.4 I 19.3 19.8 20.8 J 18.4 19.4 20.2 K 18.9 19.4 20.1 L 9.6 10.2 10.7 M 8.9 9.2 9.7 N 4.8 5.7 6.1 O 8.9 9.1 9.7 P 5.9 6.3 8.1 Q 7.1 7.5 8.2 R 7.6 7.9 8.3 B1 51.4 55.4 57.1 C1 50.2 51.2 53.1

[0152] Example 20

[0153] Metal elemental analysis was performed on the catalysts in Examples 2 and 3, as well as Comparative Examples 1 and 2. Elemental analysis was also performed on samples after 1000 hours of reaction for treating VOCs gas, and the metal content per unit catalyst volume was calculated, as shown in Table 2. The comparison shows that the internally coated catalyst of the present invention exhibits a low rate of active metal component detachment and good stability.

[0154] Table 2 Key element analysis after catalytic reaction of non-precious metal coating-supported catalyst

[0155]

[0156] Although the invention has been described in detail herein with reference to exemplary embodiments, it should be understood that the invention is not limited to the described embodiments. Other variations, modifications, and embodiments within the scope of the invention will be recognized by those skilled in the art and who have access to the teachings herein. Therefore, the invention should be broadly interpreted in accordance with the claims set forth below.

Claims

1. A non-precious metal coating-supported catalyst, characterized in that, The device includes a carrier and a coating covering the carrier. The coating comprises a coating component and an active metal component, the active metal component comprising a Co metal component and an additive component. The coating component is composed of attapulgite, kaolin, and at least one material selected from molecular sieves, alumina, and silica. The auxiliary component is selected from combinations of Ce and Mn with Ti, Ce and Mn with V, Ce and Mn with Bi, Ce and Mn with Cr, La and Mn with Ti, La and Mn with V, or La and Mn with Bi. Based on the total volume of the non-noble metal coating-supported catalyst, the Co metal content, calculated as cobalt tetroxide, is 50~500 kg / m³. 3 The content of the auxiliary component, based on its highest oxidation state, is 10~180 kg / m³. 3 The content of the coating component is 30~200kg / m 3 , The non-noble metal coating-supported catalyst is prepared by a method comprising the following steps: (1) A coating component slurry is prepared by contacting attapulgite, kaolin, and a substrate selected from at least one material chosen from molecular sieves, alumina, and silica, along with a binder and water, wherein the amount of the substrate is such that the content of the substrate relative to the total volume of the carrier is 30~200 kg / m³. 3 ; (2) The step of contacting the coating component slurry, a solution or suspension of at least one cobalt metal component precursor, and a solution or suspension of at least one auxiliary component precursor with a carrier to obtain a contact product, wherein the auxiliary is selected from combinations of Ce and Mn with Ti, Ce and Mn with V, Ce and Mn with Bi, Ce and Mn with Cr, La and Mn with Ti, La and Mn with V, or La and Mn with Bi, and (3) The step of calcining the contact product to obtain the non-precious metal coating-supported catalyst.

2. The non-precious metal coating-supported catalyst according to claim 1, characterized in that, The catalyst is composed of a support, a coating component, and an active metal component.

3. The non-precious metal coating-supported catalyst according to claim 1 or 2, characterized in that, The content of attapulgite is 50%-98% relative to the total mass of the coating components.

4. The non-precious metal coating-supported catalyst according to claim 1 or 2, characterized in that, The attapulgite clay in the coating component accounts for 55-90% of the total mass of the coating component.

5. The non-precious metal coating-supported catalyst according to claim 1 or 2, characterized in that, The molar ratio of Co metal to the auxiliary component is 0.5:1 to 20:

1.

6. The non-precious metal coating-supported catalyst according to claim 1 or 2, characterized in that, The coating component has a BET specific surface area of ​​80~600 m². 2 ·g -1 The average pore size is 2~12 nm, and the pore volume is 0.15~1.0 ml·g. -1 .

7. The non-precious metal coating-supported catalyst according to claim 1 or 2, characterized in that, The carrier is selected from at least one of cordierite, alumina, silicon carbide, aluminum titanate, silicon oxide, zirconium oxide, cerium oxide, zirconium silicate, magnesium silicate, and ceramics.

8. The non-precious metal coating-supported catalyst according to claim 1 or 2, characterized in that, The carrier is formed in at least one of the following shapes: spherical, sheet-like, cube, cuboid, solid or hollow cylinder, ring-shaped, and star-shaped. The carrier has macroscopic channels, which are one or more of the following shapes: circular, square, triangular, hexagonal, or rhomboid. The cross-sectional area of ​​a single macroscopic channel is 1 mm². 2 ~80mm 2 The hole wall thickness is 1~4mm.

9. The non-precious metal coating-supported catalyst according to claim 1 or 2, characterized in that, At least one of the following conditions must be met: Based on the total volume of the non-noble metal coating-supported catalyst, the Co metal content, calculated as cobalt tetroxide, is 50~430 kg / m³. 3 The content of the auxiliary component, based on its highest oxidation state, is 10~150 kg / m³. 3 The content of the coating component is 60~200 kg / m². 3 , The coating component has a BET specific surface area of ​​100~600 m². 2 ·g -1 The average pore size is 4~12 nm, and the pore volume is 0.2~1.0 ml·g. -1 , The BET specific surface area of ​​the carrier is 0.1~5m². 2 ·g -1 The pore volume is less than 0.02 ml·g -1 , The carrier is formed in at least one of the following shapes: spherical, sheet-like, cube, cuboid, solid or hollow cylinder, ring-shaped, and star-shaped. The carrier has macroscopic channels, which are one or more of the following shapes: circular, square, triangular, hexagonal, or rhomboid. The cross-sectional area of ​​a single macroscopic channel is 1 mm². 2 ~35mm 2 The hole wall thickness is 1~2.5mm.

10. The non-precious metal coating-supported catalyst according to claim 1 or 2, characterized in that, The carrier is a layered silicate.

11. A method for preparing a non-precious metal coating-supported catalyst as described in claim 1, characterized in that, Includes the following steps: (1) A coating component slurry is prepared by contacting attapulgite, kaolin, and a substrate selected from at least one material chosen from molecular sieves, alumina, and silica, along with a binder and water, wherein the amount of the substrate is such that the content of the substrate relative to the total volume of the carrier is 30~200 kg / m³. 3 ; (2) The step of contacting the coating component slurry, a solution or suspension of at least one cobalt metal component precursor, and a solution or suspension of at least one auxiliary component precursor with a carrier to obtain a contact product, wherein the auxiliary is selected from combinations of Ce and Mn with Ti, Ce and Mn with V, Ce and Mn with Bi, Ce and Mn with Cr, La and Mn with Ti, La and Mn with V, or La and Mn with Bi, and (3) The step of calcining the contact product to obtain the non-precious metal coating-supported catalyst.

12. The preparation method according to claim 11, characterized in that, The attapulgite clay accounts for 55-90% of the total mass of the substrate.

13. The preparation method according to claim 11 or 12, characterized in that, The adhesive solvent is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, sodium hydroxide, calcium hydroxide, potassium hydroxide, magnesium hydroxide, lithium hydroxide, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, pentaerythritol, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, urea, methylcellulose, hydroxymethylcellulose, hydroxymethylpropylcellulose, carboxymethylcellulose, magnesium stearate, and sodium stearate.

14. The preparation method according to any one of claims 11 or 12, characterized in that, Step (2) includes the following steps: (2-1) First, bring the coating component slurry into contact with the carrier; and (2-2) After heat treatment of the contact product of step (2-1), it is then contacted with a solution or suspension of at least one cobalt metal component precursor and a solution or suspension of at least one auxiliary component precursor. or (2-1') Contacting a solution or suspension of at least one cobalt metal component precursor, a solution or suspension of at least one auxiliary component precursor, with a support; and (2-2') After heat treatment of the contact product in step (2-1'), it is then brought into contact with the coating component slurry; or (2') The coating component slurry, a solution or suspension of at least one cobalt metal component precursor, and a solution or suspension of at least one auxiliary component precursor are simultaneously brought into contact with the carrier.

15. The preparation method according to claim 11 or 12, characterized in that, In each combination of additives, the mass ratio of each element, based on the highest oxidation state of the metal oxide, is 0.1 to 10, which is the ratio of the former to the sum of the latter two. The precursor of the adjuvant component is at least one selected from chloride, nitrate, acetate, sulfate and phosphate. The cobalt metal precursor is at least one selected from cobalt metal chloride, nitrate, and acetate. In the obtained catalyst, the Co metal content, calculated as cobalt tetroxide, is 50~500 kg / m³ relative to the total volume of the catalyst. 3 The content of the auxiliary component, based on its highest oxidation state, is 10~180 kg / m³. 3 .

16. The preparation method according to claim 11 or 12, characterized in that, At least one of a complexing agent, a stabilizer, and a pH adjuster is added to the solution or suspension of the precursor of the cobalt metal component and / or the solution or suspension of the precursor of the auxiliary agent component.

17. The preparation method according to claim 11 or 12, characterized in that, In step (3), the roasting temperature is 200~580℃; the roasting time is 2~20 hours.

18. The preparation method according to claim 11 or 12, characterized in that, At least one of the following conditions must be met: In step (1), the amount of the substrate used is such that the content of the substrate relative to the total volume of the carrier is 60~200 kg / m³. 3 ; In each combination of additives, the mass ratio of each element, based on the highest oxidation state of the metal oxide, is 0.2 to 5 times the sum of the masses of the former and the latter two. In the obtained catalyst, the Co metal content, calculated as cobalt tetroxide, is 50~430 kg / m³ relative to the total volume of the catalyst. 3 The content of the auxiliary component, based on its highest oxidation state, is 10~150 kg / m³. 3 ; In step (3), the roasting temperature is 250~550℃; the roasting time is 4~16 hours.

19. The use of the non-precious metal coated-supported catalyst according to any one of claims 1 to 10 or the non-precious metal coated-supported catalyst prepared according to any one of claims 11 to 18 in the catalytic oxidation of volatile organic compounds.

20. The application of claim 19, characterized in that, The conditions for this application are: the gas containing volatile organic compounds is supplied with a gas volume hourly space velocity (VHSV) of 4000~25000 h⁻¹. -1 The non-precious metal coating-supported catalyst is contacted at 150~550℃.

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