A non-noble metal catalyst supported on a flame-retardant porous matrix, a preparation method and applications thereof

Abstract

The application relates to a flame-retardant porous matrix loaded non-noble metal catalyst, a preparation method and application thereof. The preparation method of the flame-retardant porous matrix loaded non-noble metal catalyst is simple, the mechanical strength is high, the hydrothermal stability is strong, the catalyst has good volatile organic compound catalytic performance in VOCs treatment, and the service life is long, and the catalyst can also be applied to catalytic wet oxidation of waste water.

Description

Technical Field

[0001] This invention relates to a flame-retardant porous matrix supported non-precious metal catalyst. More specifically, this invention relates to a flame-retardant porous matrix supported non-precious metal catalyst and its preparation method. This invention also relates to the application of the flame-retardant porous matrix supported non-precious metal catalyst in the catalytic oxidation treatment of volatile organic compounds (VOCs) and high chemical oxygen demand (COD) wastewater. Background Technology

[0002] In recent years, with the increasing stringent environmental protection requirements of the state, 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 auxiliary flammable gas, 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 cracking and flaking of the coating can lead to increased pressure drop in the fixed bed and more uncontrollable factors in the reaction. Therefore, the development of catalysts with good thermal stability, high strength, and good performance as a substrate (support) for loading active metals or active metal oxides has attracted 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 molecular formula is (Mg)₅Si₈O. 20 (OH)2(OH2)4·4H2O. Attapulgite clay exhibits a high specific surface area, open mesoporous and microporous composite channels, and good thermal stability. Moreover, similar to materials such as molecular sieves, SiO2, and Al2O3, it belongs to inorganic mineral materials, has good adhesion properties, and plays a good role in reinforcing and toughening organic and inorganic materials. 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 using at least one selected from attapulgite and kaolin as the original matrix, and further combining it with a suitable inorganic porous solid, a flame-retardant porous matrix can be prepared. Further loading a cobalt metal component and an auxiliary component as the catalyst active component onto this matrix can prepare the flame-retardant porous matrix supported non-precious metal catalyst of the present invention (hereinafter sometimes simply referred to as "flame-retardant porous matrix supported catalyst," "the catalyst of the present invention," or "catalyst"). The flame-retardant porous matrix supported non-precious metal catalyst of the present invention exhibits excellent VOCs catalytic performance and high COD wastewater degradation performance, thus completing the present invention.

[0007] Specifically, this invention provides a flame-retardant porous matrix supported non-precious metal catalyst, characterized in that it contains a flame-retardant porous matrix, a Co component supported on the flame-retardant porous matrix, and an auxiliary component.

[0008] The auxiliary component is selected from at least one element in 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.

[0009] 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;

[0010] Based on the total volume of the non-precious metal catalyst supported on the porous matrix, the Co metal content (calculated as cobalt tetroxide) is 50~500 kg / m³. 3 Preferred weight is 50~430 kg / m³. 3 The content of the auxiliary component (based on the highest oxidation state of the oxide of the auxiliary component) is 10-180 kg / m³. 3 Preferred weight: 10~150 kg / m 3 ,

[0011] The flame-retardant porous matrix contains at least one primary matrix selected from attapulgite and kaolin, and at least one inorganic material selected from inorganic porous solids. Based on the total mass of the porous matrix, the content of the primary matrix is ​​10-99.5% by mass, preferably 20-99% by mass, and the content of the inorganic material is 0.5-90% by mass, preferably 1-80% by mass, more preferably 5-80% by mass, even more preferably 8-70% by mass, and even more preferably the balance.

[0012] This invention also provides a method for preparing a flame-retardant porous matrix supported non-precious metal catalyst, characterized by comprising the following steps:

[0013] (1) A plastic mixed contact body is prepared by mixing and contacting at least one original matrix selected from attapulgite and kaolin, at least one inorganic material selected from inorganic porous solids, a binder, and water; wherein, relative to the total amount of the original matrix and the inorganic material, the content of the original matrix is ​​10 to 99.5% by mass, preferably 20 to 99% by mass, and the content of the inorganic material is 0.5 to 90% by mass, preferably 1 to 80% by mass, more preferably 5 to 80% by mass, further preferably 8 to 70% by mass, and even more preferably the balance;

[0014] (2) Optionally, the plastic mixed contact body is molded to obtain a porous matrix preform;

[0015] (3) The mixed contact body of step (1) or the porous matrix preform of step (2) is calcined to obtain a flame-retardant porous matrix.

[0016] (4) Contacting a solution or suspension of a precursor of at least one cobalt metal component and a solution or suspension of a precursor of at least one auxiliary component with a flame-retardant porous matrix to obtain a contact product; and

[0017] (5) Calcining the contact product to obtain the flame-retardant porous matrix supported catalyst.

[0018] The present invention also provides the application of the flame-retardant porous matrix supported catalyst in the catalytic oxidation of volatile organic compounds.

[0019] The present invention also provides the application of the flame-retardant porous matrix supported catalyst in the catalytic oxidation of high COD wastewater.

[0020] Technical effect

[0021] The preparation method of the flame-retardant porous matrix supported catalyst of the present invention is simple, does not require vacuum slurrying and microwave heat treatment, and is inexpensive.

[0022] The flame-retardant porous matrix supported catalyst of the present invention has good hydrothermal properties, can be used to treat VOCs with high water vapor content, and can also be used to treat wastewater with high COD, while maintaining excellent stability.

[0023] In the flame-retardant porous matrix supported catalyst of the present invention, the supported metal has a strong interaction with the porous matrix. Therefore, there is no need to coat the porous matrix, the metal component is not easy to fall off, and the catalyst has a long service life.

[0024] In addition, the flame-retardant porous matrix supported catalyst of the present invention, due to its porosity, allows the active component to fully contact VOCs, which is beneficial for the catalytic treatment of VOCs. Furthermore, the catalyst of the present invention can allow the active component to fully contact the high COD substances in the wastewater, which is beneficial for catalytic wet oxidation to reduce COD. Detailed Implementation

[0025] 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.

[0026] 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.

[0027] This invention provides a flame-retardant porous matrix supported non-precious metal catalyst, characterized in that it contains a flame-retardant porous matrix, a Co component supported on the flame-retardant porous matrix, and an auxiliary component.

[0028] The auxiliary component is selected from at least one element in 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.

[0029] 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;

[0030] Based on the total volume of the non-precious metal catalyst supported on the porous matrix.

[0031] The Co metal content (calculated as cobalt tetroxide) is 50~500 kg / m³. 3 Preferred weight is 50~430 kg / m³. 3 The content of the auxiliary component (based on the highest oxidation state of the oxide of the auxiliary component) is 10~180 kg / m³. 3 Preferred weight: 10~150 kg / m 3 ,

[0032] The flame-retardant porous matrix contains at least one primary matrix selected from attapulgite and kaolin, and at least one inorganic material selected from inorganic porous solids. Based on the total mass of the porous matrix, the content of the primary matrix is ​​10-99.5% by mass, preferably 20-99% by mass, and the content of the inorganic material is 0.5-90% by mass, preferably 1-80% by mass, more preferably 5-80% by mass, even more preferably 8-70% by mass, and even more preferably the balance.

[0033] In one embodiment of the invention, the porous matrix is ​​substantially composed of the original matrix and the inorganic material. In another embodiment of the invention, the porous matrix is ​​composed only of the original matrix and the inorganic material.

[0034] In one embodiment of the present invention, based on the total mass of the porous matrix, the content of the original matrix is ​​10 to 99.5% by mass, preferably 20 to 99% by mass.

[0035] In one embodiment of the present invention, based on the total mass of the porous matrix, the content of the inorganic material is 0.5-90% by mass, preferably 1-80% by mass, more preferably 5-80% by mass, even more preferably 8-70% by mass, and even more preferably the balance.

[0036] In this invention, the attapulgite clay can be any type of attapulgite clay known in the art, and it can be a commercially available product. The kaolin clay can also be any type of kaolin clay known in the art, and it can be a commercially available product.

[0037] In this invention, the inorganic porous solids can include refractory oxides of metals from Groups IIA, IIIA, IVA, or IVB of the periodic table (such as silicon dioxide, aluminum oxide, magnesium oxide, titanium oxide, zirconium oxide, or thorium oxide), or any refractory composite oxide of these metals (such as aluminum silicate, aluminum magnesium oxide, silicon titanium oxide, magnesium titanium oxide, and aluminum titanium oxide), as well as clay, molecular sieves, mica, montmorillonite, bentonite, and diatomaceous earth.

[0038] In one embodiment of the present invention, the inorganic porous solid is preferably selected from at least one of silicon dioxide, aluminum oxide, magnesium oxide, aluminum silicate, aluminum magnesium oxide, silicon dioxide, titanium dioxide, molecular sieve and montmorillonite.

[0039] In this invention, the molecular sieve can be any molecular sieve known in the art. For example, the molecular sieve can be selected from one or more combinations of type A molecular sieve, type X molecular sieve, type Y molecular sieve, ZSM series, SAPO, AIPO, mordenite molecular sieve, SBA, and MCM.

[0040] In this invention, silicon dioxide, aluminum oxide, magnesium oxide, aluminum silicate, aluminum magnesium oxide, silicon titanium dioxide, titanium dioxide, molecular sieves, and montmorillonite can be any inorganic material known in the art, can be manufactured by known methods, or can be any commercially available product.

[0041] In one embodiment of the present invention, the BET specific surface area of ​​the flame-retardant porous matrix supported catalyst is 100~800 m². 2 ·g -1 Preferred depth: 110~800m2 ·g -1 The most probable pore size is 2~16nm, 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 .

[0042] In one embodiment of the present invention, the flame-retardant porous matrix supported catalyst can be shaped into macroscopic shapes such as spheres, cubes, cuboids, cylinders, Raschig rings, etc.

[0043] In one embodiment of the present invention, when the flame-retardant porous matrix supported catalyst is formed, the flame-retardant porous matrix supported catalyst may have macroscopic channels, which may be one or more of the following pore structures: circular, square, triangular, hexagonal, or rhombic. These macroscopic channels on the flame-retardant porous matrix supported catalyst may be arranged in an ordered or disordered manner, preferably as uniformly ordered honeycomb channels. Generally, to reduce adsorption resistance, the macroscopic channels on the flame-retardant porous matrix supported catalyst are permeable.

[0044] In one embodiment of the present invention, on a macroscopically flame-retardant porous matrix supported catalyst, the cross-sectional area of ​​a single macroscopic pore is 1 mm². 2 ~80mm 2 Preferably 1mm 2 ~35mm 2 The hole wall thickness is 1~4mm, preferably 1~2.5mm.

[0045] In one embodiment of the present invention, the flame-retardant porous matrix supported catalyst has a positive pressure strength of 2 to 8 MPa, preferably 3 to 6 MPa, as determined by the standard method of GB / T 5072-2008, and a lateral pressure strength of 0.1 to 2 MPa, preferably 0.25 to 1.5 MPa.

[0046] Without impairing the effects of the present invention, the porous matrix may optionally contain other auxiliary agents. Examples of such auxiliary agents include various metal oxides and various inert organic porous solids, in addition to the inorganic materials described above. The amount of such auxiliary agent used is 5% to 30% relative to the total mass of the porous matrix.

[0047] In one embodiment of the present invention, the catalyst is basically composed of a flame-retardant porous matrix, a Co component supported on the porous matrix, and an auxiliary component.

[0048] In one embodiment of the present invention, the catalyst consists only of a flame-retardant porous matrix, a Co component supported on the porous matrix, and an additive component. In another embodiment of the present invention, the catalyst does not contain carbonaceous materials (the carbonaceous materials include, but are not limited to, activated carbon, carbon fibers, etc.).

[0049] In one embodiment of the present invention, 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.

[0050] In one embodiment of the invention, 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 oxide), is 0.1 to 10, preferably 0.2 to 5.

[0051] In one embodiment of the present invention, based on the total volume of the non-precious metal catalyst supported on the porous matrix, the Co metal content (calculated as cobalt tetroxide) is 50~500 kg / m³. 3 The preferred value is 50~430 kg / m³. 3 .

[0052] In one embodiment of the present invention, based on the total volume of the non-noble metal catalyst supported on the porous matrix, the content of the auxiliary component (calculated based on the oxide of the highest oxidation state of the auxiliary component) is 10~180 kg / m³. 3 The preferred value is 10~150kg / m 3 .

[0053] This invention also provides a method for preparing a flame-retardant porous matrix supported non-precious metal catalyst, characterized by comprising the following steps:

[0054] (1) A plastic mixed contact body is prepared by mixing and contacting at least one original matrix selected from attapulgite and kaolin, at least one inorganic material selected from inorganic porous solids, a binder, and water; wherein, relative to the total amount of the original matrix and the inorganic material, the content of the original matrix is ​​10 to 99.5% by mass, preferably 20 to 99% by mass, and the content of the inorganic material is 0.5 to 90% by mass, preferably 1 to 80% by mass, more preferably 5 to 80% by mass, even more preferably 8 to 70% by mass, and even more preferably the balance;

[0055] (2) Optionally, the plastic mixed contact body is molded to obtain a porous matrix preform;

[0056] (3) The mixed contact body of step (1) or the porous matrix preform of step (2) is calcined to obtain a flame-retardant porous matrix.

[0057] (4) Contacting a solution or suspension of a precursor of at least one cobalt metal component and a solution or suspension of a precursor of at least one auxiliary component with a flame-retardant porous matrix to obtain a contact product; and

[0058] (5) Calcining the contact product to obtain the flame-retardant porous matrix supported catalyst.

[0059] In one embodiment of the present invention, in step (1) of the above preparation method, no pretreatment is performed on at least one original matrix selected from attapulgite and kaolin.

[0060] 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.

[0061] In the preparation method of the present invention, in step (1) above, the inorganic porous solid can be refractory oxides of metals of Group IIA, IIIA, IVA or IVB of the periodic table (such as silicon dioxide (also known as silicon oxide or silica gel), aluminum oxide, magnesium oxide, titanium oxide, zirconium oxide or thorium oxide, etc.), or any refractory composite oxide of these metals (such as aluminum silicate, aluminum magnesium oxide, silicon titanium oxide, magnesium titanium oxide and aluminum titanium oxide, etc.), as well as clay, molecular sieve, mica, montmorillonite, bentonite and diatomaceous earth, etc.

[0062] In one embodiment of the present invention, the inorganic porous solid is preferably selected from at least one of silicon dioxide, aluminum oxide, magnesium oxide, aluminum silicate, aluminum magnesium oxide, silicon dioxide, titanium dioxide, molecular sieve and montmorillonite.

[0063] Molecular sieves may be those known in the art, such as those selected from type A molecular sieves, type X molecular sieves, type Y molecular sieves, ZSM series, SAPO, AIPO, mordenite molecular sieves, SBA, and MCM, or a combination of two or more of these. Silica, alumina, magnesium oxide, silica-alumina, magnesium-alumina, titanium dioxide-silicon, titanium dioxide, molecular sieves, and montmorillonite may be any materials known in the art, manufactured by known methods, or any commercially available product.

[0064] In the preparation method of this invention, in step (1) above, the adhesive solvent only needs to be able to disperse the original matrix and the inorganic material. It can be an organic or inorganic substance, such as inorganic acids, inorganic bases, polycarboxylic acids, monohydric alcohols, polyhydric alcohols, polyamines, cellulose derivatives, carboxylates, etc. These adhesive solvents can be used alone 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 original matrix and inorganic material. Preferably, the amount of adhesive solvent is 1 to 20 parts by mass relative to 100 parts by mass of the total amount of the original matrix and inorganic material, preferably 1.2 to 10 parts by mass, and more preferably 1.5 to 5 parts by mass.

[0065] 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.

[0066] 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.

[0067] As the polycarboxylic 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. 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.

[0068] 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.

[0069] 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.

[0070] As the polyamine, various polyamines known in the art can be used, such as ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, etc.

[0071] As the cellulose derivatives mentioned above, those known in the art can be used, such as methylcellulose, hydroxymethylcellulose, hydroxymethylpropylcellulose, carboxymethylcellulose, etc.

[0072] As the carboxylate, those carboxylate salts known in the art can be used, such as magnesium stearate, sodium stearate, etc.

[0073] In step (1), the amount of water added is not particularly limited, as long as it is sufficient to disperse the original matrix and inorganic materials. Preferably, the amount of water is 20 to 120 parts by mass relative to 100 parts by mass of the total amount of the original matrix and inorganic materials. In step (1), a kneader can be used for stirring to prepare the contact body.

[0074] In step (2), the plastic mixed contact body is molded to obtain a porous matrix preform. The equipment and conditions for molding are not particularly limited and can be those known in the art.

[0075] In step (2), during molding, an extruder can be used for molding. At this time, the pressure inside the barrel reaches 0.5-8 MPa, preferably 1-6 MPa, and the extrusion temperature of the barrel is 20-80℃.

[0076] It can be molded into various shapes as needed, such as spheres, cubes, cuboids, cylinders, and Raschig rings. These preforms can have macroscopic channels such as circles, squares, triangles, hexagons, or rhombuses. These macroscopic channels are preferably uniformly ordered, transparent honeycomb channels.

[0077] In step (3), the porous matrix preform is calcined to obtain a flame-retardant porous matrix.

[0078] The calcination temperature in step (3) is not particularly limited, but can be 200~580℃, preferably 200~550℃, and more preferably 300~550℃. The calcination time can be 1~20 hours, preferably 2~20 hours, and more preferably 4~16 hours. The calcination can be carried out in air or in an inert gas atmosphere. Examples of inert gases include nitrogen or rare gases, with nitrogen being preferred.

[0079] In the preparation method of the present invention, step (2) is an optional step. In the absence of step (2), in step (3), the plastic mixed contact body in step (1) is calcined. The calcination conditions are the same as those described above.

[0080] Prior to step (3) of the present invention, heat treatment may optionally be performed, such as drying, air drying, or air drying, to remove moisture from the plastic mixed contact body in step (1) or the porous matrix preform in step (2). The heat treatment is performed at 20 to 150°C, preferably at 30 to 120°C, and more preferably at 50 to 100°C.

[0081] According to the present invention, in the contact step of step (1), there is no particular limitation on the contact order of the raw material components (i.e., at least one original matrix selected from attapulgite and kaolin, at least one inorganic material selected from inorganic porous solids, and adhesive solvent and water).

[0082] According to the present invention, there are no particular limitations on the manner in which the contacting step is performed in step (1), as long as sufficient mixing and contact of the raw material components can be achieved to form a uniform contact product. For example, the raw material components can be mixed (with auxiliary stirring if necessary) in any manner known in the art until uniform. In step (1), the contacting step can be performed at any temperature from 0°C to 150°C, for example at room temperature.

[0083] In step (4), 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.

[0084] In step (4), 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 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. 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) (based on the highest oxidation state of the metal), is 0.1 to 10, preferably 0.2 to 5.

[0085] 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.

[0086] In this invention, the precursor of the auxiliary metal 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.

[0087] 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.

[0088] 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.

[0089] In this invention, when preparing solutions or suspensions of cobalt metal components and / or solutions or suspensions of precursors of auxiliary components, various additives may be added as needed, such as complexing agents, stabilizers, and pH adjusters.

[0090] 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.

[0091] 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.

[0092] 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 hydroxy monocarboxylic acids, polyhydroxy monocarboxylic acids, hydroxy polycarboxylic acids, polyhydroxy polycarboxylic acids, monocarboxylic acids, etc.; alkaline substances such as ethylenediamine and ammonia.

[0093] 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.

[0094] In this invention, in step (4), where 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 contacted with a flame-retardant porous matrix, the contact order between the cobalt metal component precursor solution or suspension and the auxiliary component precursor solution or suspension and the porous matrix is ​​not limited. The cobalt metal component precursor solution or suspension can be contacted with the porous matrix first, and then the auxiliary component precursor solution or suspension can be contacted with the porous matrix, or the order can be reversed. Alternatively, after separately preparing the cobalt metal component precursor solution or suspension and the auxiliary component precursor solution or suspension, the two solutions or suspensions can be mixed and simultaneously contacted with the flame-retardant porous matrix. 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.

[0095] In addition, in this invention, the precursors of the cobalt metal component and the additive component can be formulated together into a solution or suspension and then contacted with a flame-retardant porous matrix. That is, in this case, "the solution or suspension of the precursor of the cobalt metal component" and "the solution or suspension of the precursor of the additive component" refer to the same solution or suspension.

[0096] In step (4) of this invention, contact with the flame-retardant porous matrix can be achieved by spraying or sprinkling the solution or suspension onto the flame-retardant porous matrix, or by immersing the flame-retardant porous matrix 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) in the final catalyst is 50-500 kg / m³ based on the total volume of the catalyst. 3 Preferred weight 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 Preferred weight: 10~150 kg / m 3 That's all.

[0097] In step (4) of this invention, when the solution or suspension of the cobalt metal component precursor and the solution or suspension of the additive component precursor are brought into contact with the flame-retardant porous matrix, the concentration of the cobalt metal component precursor solution or suspension, the concentration of the additive component precursor solution or suspension, and the contact time between the porous matrix 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 based on the total volume of the catalyst. 3The 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.

[0098] In one embodiment of the present invention, after the contact step in each step, the resulting contact product can be directly used in the next step.

[0099] In one embodiment of the present invention, after the contacting step in each step, the resulting contact product may be subjected to drying or other treatments, especially when the contact product contains slurry. Drying can be performed by any method 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 referred to as the contact product.

[0100] In this invention, in step (5), the contact product obtained in step (4) is calcined to obtain the flame-retardant porous matrix supported catalyst of this invention.

[0101] In step (5), the calcination temperature is 200~550℃, preferably 200~500℃, and more preferably 250~500℃. 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.

[0102] The flame-retardant porous matrix supported catalyst of the present invention, or the flame-retardant porous matrix supported catalyst prepared according to the preparation method of the present invention, can be used for catalytic oxidation treatment of volatile organic compounds.

[0103] In one embodiment of the present invention, the conditions for catalytic oxidation treatment of volatile organic compounds are: the gas containing volatile organic compounds is subjected to a gas volume hourly space velocity (VHSV) of 4000-25000 h⁻¹. -1 The catalyst is contacted with a porous matrix at 150~450℃ to catalytically oxidize and remove volatile organic compounds.

[0104] The flame-retardant porous matrix supported catalyst of the present invention or the flame-retardant porous matrix supported catalyst prepared according to the preparation method of the present invention can be used for catalytic oxidation of wastewater, especially wastewater with high COD.

[0105] In one embodiment of the present invention, the conditions for catalytic oxidation treatment of wastewater are: the wastewater has a liquid hourly space velocity (LHSV) of 0.2-3 h⁻¹. -1Catalytic oxidation is carried out by contacting a porous matrix supported catalyst under conditions of 2-8 MPa pressure and 200-280℃ reaction temperature. Example

[0106] The present invention is further illustrated in detail below with reference to examples, but the present invention is not limited to these examples. It should be noted that, unless otherwise specified, in the present invention, 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.

[0107] In this invention, the surface area is determined by the BET specific surface area measurement method.

[0108] The pore volume was determined using the BJH (Barrett-Joyner-Halenda) method.

[0109] The most probable pore size was determined by BJH.

[0110] The cross-sectional area of ​​a single honeycomb macroscopic channel (also referred to as a honeycomb cell) is calculated based on its specific shape.

[0111] Specifically, when the macroscopic channels of the honeycomb are circular, square, triangular, hexagonal, or rhomboid, the cross-sectional area can be calculated using conventional area calculation methods. When the macroscopic channels of the honeycomb are irregular in shape, the longest diameter (or longest diagonal length) and the shortest diameter (or shortest diagonal length) of the shape are measured, and the cross-sectional area is calculated as: [(longest diameter (or longest diagonal length) + shortest diameter (or shortest diagonal length)) / 4] 2 ·π. Calculate the cross-sectional area of ​​10 honeycomb cells, and use their average value as the cross-sectional area of ​​a single honeycomb cell.

[0112] The methods for determining the positive pressure strength and lateral pressure strength are in accordance with the national standard method GB / T 5072-2008.

[0113] Example 1

[0114] Attapulgite clay, 13X molecular sieve, 65% nitric acid, methylcellulose, and magnesium stearate were mixed evenly in a kneader at a mass ratio of 10:4:0.02:0.2:0.001. A suitable amount of water was added, and the mixture was kneaded to form a plastic composite. This composite was then loaded into an extruder and extruded at 25°C and 5MPa to produce a square honeycomb preform. The four base sides and height of the preform were 80cm and 100cm respectively. The preform was then calcined at 300°C in air for 2 hours to obtain flame-retardant honeycomb matrix A. The Co content in each cubic meter of honeycomb matrix A was 160kg / m³. 3A polyethylene glycol-400 aqueous solution of cobalt nitrate was prepared in a ratio of 0.1:1 (polyethylene glycol to cobalt nitrate by mass). The Ce content on each cubic meter of honeycomb substrate A was 30 kg / m³. 3 The Mo content is 15 kg / m³. 3 An aqueous solution of cerium nitrate and ammonium molybdate was prepared in a specific ratio. The Ce and Mo solutions were first impregnated onto matrix A and dried at 150°C for 3 hours. Then, a Co solution was further impregnated, and the matrix was dried again at 150°C for 2 hours. Finally, the matrix was calcined at 500°C for 5 hours to obtain a flame-retardant porous matrix-supported non-precious metal catalyst Al with a surface area of ​​178 m². 2 ·g -1 The most probable pore size is 5.5 nm, and the pore volume is 0.45 ml·g. -1 The cross-sectional area of ​​the honeycomb cells is 9.2 mm². 2 .

[0115] Example 2

[0116] Attapulgite, kaolin, Y-type molecular sieve, 65% nitric acid, methylcellulose, and magnesium stearate were mixed evenly in a kneader at a mass ratio of 8:2:2:0.02:0.2:0.03. A suitable amount of water was added, and the mixture was kneaded into a plastic composite. This composite was then loaded into an extruder and extruded at 25°C and 5MPa to form a square honeycomb preform. The four base sides and height of the preform were 80cm and 100cm respectively. The preform was then calcined at 500°C in air for 2 hours to obtain flame-retardant honeycomb matrix B. The Co content per cubic meter of honeycomb matrix B was 130kg / m³. 3 A citric acid aqueous solution of cobalt nitrate was prepared in a ratio of 0.1:1 by mass of citric acid to cobalt nitrate, based on a Ce content of 40 kg / m³ on each cubic meter of honeycomb substrate B. 3 The Mn content is 29 kg / m³. 3 An aqueous solution of cerium nitrate and manganese nitrate was prepared in a specific ratio. The Ce and Mn solutions were first impregnated onto the B matrix and dried at 150°C for 4 hours. Then, a Co solution was further impregnated, and the matrix was dried again at 150°C for 3 hours. Finally, the matrix was calcined at 500°C for 5 hours to obtain a flame-retardant porous matrix-supported non-precious metal catalyst B1 with a surface area of ​​148 m². 2 ·g -1 The most probable pore size is 5.7 nm, and the pore volume is 0.38 ml·g. -1 The cross-sectional area of ​​the honeycomb cells is 9.1 mm². 2 .

[0117] Example 3

[0118] Attapulgite, kaolin, SBA-15 molecular sieve, 65% nitric acid, methylcellulose, and magnesium stearate were mixed evenly in a kneader at a mass ratio of 7:3:4:0.02:0.2:0.03. A suitable amount of water was added, and the mixture was kneaded into a plastic composite. This composite was then loaded into an extruder and extruded at 30℃ and 5MPa to form a square honeycomb preform. The four base sides and height of the preform were 80cm and 100cm respectively. The preform was then calcined at 520℃ in air for 2 hours to obtain the flame-retardant honeycomb matrix C. The Co content of the flame-retardant honeycomb matrix C was 280kg / m³. 3 A glycerol-cobalt chloride aqueous solution was prepared in a ratio of 0.2:1 (glycerol to cobalt chloride by mass). The Ce content on the flame-retardant honeycomb matrix C was 80 kg / m². 3 The Fe content is 30 kg / m³ 3 An aqueous solution of cerium nitrate and ferric nitrate was prepared in a specific ratio. A solution of Ce, Fe, and Co was simultaneously impregnated onto a honeycomb substrate C. After drying at 150°C for 4 hours, and then calcining at 500°C for 5 hours, a flame-retardant porous substrate-supported non-precious metal catalyst C1 was obtained, with a surface area of ​​349 m². 2 ·g -1 The most probable pore size is 7.6 nm, and the pore volume is 0.49 ml·g. -1 The cross-sectional area of ​​the honeycomb cells is 8.2 mm. 2 .

[0119] Example 4

[0120] Attapulgite, kaolin, 5A molecular sieve, 65% nitric acid, hydroxymethylpropyl cellulose, and glycerol were mixed evenly in a kneader at a mass ratio of 7:3:1.4:0.02:0.2:0.03. A suitable amount of water was added, and the mixture was kneaded into a plastic composite. This composite was then loaded into an extruder and extruded at 30℃ and 5MPa to form a square honeycomb preform. The four base sides and height of the preform were 80cm and 100cm respectively. The preform was then calcined at 480℃ for 2 hours in air to obtain the flame-retardant honeycomb matrix D. The Co content of the flame-retardant honeycomb matrix D was 300kg / m³. 3 A glycerol-cobalt chloride aqueous solution was prepared in a ratio of 0.3:1 (glycerol to cobalt chloride by mass). The Ce content on each cubic meter of flame-retardant honeycomb substrate D was 60 kg / m³. 3 The Ni content is 40 kg / m 3An aqueous solution of cerium nitrate and nickel nitrate was prepared in a specific ratio. The Ce and Ni solutions were first impregnated onto a honeycomb substrate D and dried at 150°C for 4 hours. Then, a Co solution was further impregnated, and the substrate was dried again at 150°C for 3 hours. After calcination at 480°C for 5 hours, a flame-retardant porous substrate-supported non-noble metal catalyst D1 was obtained, with a measured surface area of ​​218 m². 2 ·g -1 The most probable pore size is 8.3 nm, and the pore volume is 0.41 ml·g. -1 The cross-sectional area of ​​the honeycomb cells is 27mm². 2 .

[0121] Example 5

[0122] Attapulgite, kaolin, SAPO molecular sieve, 65% nitric acid, hydroxymethylpropyl cellulose, hexamethylenediamine, and magnesium stearate were mixed evenly in a kneader at a mass ratio of 7:3:1.4:0.02:0.2:0.01:0.03. A suitable amount of water was added, and the mixture was kneaded to form a plastic composite. This composite was then loaded into an extruder and extruded at 25°C and 7MPa to produce a square honeycomb preform. The four base sides and height of the preform were 80cm and 100cm respectively. The preform was then calcined at 500°C for 2 hours in air to obtain the flame-retardant honeycomb matrix E. The Co content of each cubic meter of flame-retardant honeycomb matrix E was 280kg / m³. 3 A glycerol-cobalt chloride aqueous solution was prepared in a ratio of 0.3:1 (glycerol to cobalt chloride by mass). The Ce content on each cubic meter of flame-retardant honeycomb substrate E was 70 kg / m³. 3 Bi content is 20 kg / m 3 An aqueous solution of cerium nitrate and bismuth nitrate was prepared in a specific ratio. The Ce and Bi solution was first impregnated onto a honeycomb substrate E and dried at 150°C for 4 hours. Then, a Co solution was further impregnated, and the substrate was dried again at 150°C for 3 hours. Finally, the substrate was calcined at 500°C for 5 hours to obtain a flame-retardant porous substrate supported non-noble metal catalyst E1 with a surface area of ​​185 m². 2 ·g -1 The most probable pore size is 6.0 nm, and the pore volume is 0.43 ml·g. -1 The cross-sectional area of ​​the honeycomb cells is 26mm. 2 .

[0123] Example 6

[0124] Kaolin, 13X molecular sieve, 65% nitric acid, methylcellulose, and magnesium stearate were mixed evenly in a kneader at a mass ratio of 10:4:0.02:0.2:0.001. A suitable amount of water was added, and the mixture was kneaded to form a plastic composite. This composite was then loaded into an extruder and extruded at 25℃ and 5MPa to form a square honeycomb preform. The four base sides and height of the preform were 80cm and 100cm respectively. The preform was then calcined at 500℃ for 4 hours in air to obtain the flame-retardant honeycomb matrix F. The Co content per cubic meter of honeycomb matrix F was 330kg / m³. 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 Ce content of 70 kg / m³ on each cubic meter of honeycomb substrate F. 3 The Cr content is 35 kg / m³. 3 An aqueous solution of cerium nitrate and chromium nitrate was prepared in a specific ratio. The Ce and Cr solutions were first impregnated onto a honeycomb substrate F and dried at 150°C for 4 hours. Then, a Co solution was further impregnated, and the substrate was dried again at 150°C for 3 hours. Finally, the substrate was calcined at 500°C for 5 hours to obtain a flame-retardant porous substrate-supported non-precious metal catalyst F1 with a surface area of ​​145 m². 2 ·g -1 The most probable pore size is 6.5 nm, and the pore volume is 0.38 ml·g. -1 The area of ​​the honeycomb holes is 10mm. 2 .

[0125] Example 7

[0126] Attapulgite clay, silica, 65% nitric acid, hydroxymethylpropyl cellulose, and glycerol were mixed evenly in a kneader at a mass ratio of 10:4:0.02:0.2:0.001. A suitable amount of water was added, and the mixture was kneaded to form a plastic composite. This composite was then loaded into an extruder and extruded at 25°C and 5 MPa to produce a square honeycomb preform. The four base sides and height of the preform were 80 cm and 100 cm, respectively. The preform was then calcined in air at 500°C for 2 hours to obtain the flame-retardant honeycomb matrix G. The Co content of the flame-retardant honeycomb matrix G was 360 kg / m³. 3 A glycerol-cobalt chloride aqueous solution was prepared in a ratio of 0.3:1 (glycerol to cobalt chloride by mass). The Ce content on each cubic meter of flame-retardant honeycomb substrate G was 50 kg / m³. 3 The vitamin C content is 25 kg / m³. 3An aqueous solution of cerium nitrate and ammonium metavanadate in oxalic acid was prepared in a specific ratio. The Ce and V solutions were first impregnated onto G, and then dried at 150°C for 4 hours. A Co solution was then further impregnated, and the mixture was dried again at 150°C for 3 hours. Finally, the mixture was calcined at 500°C for 5 hours to obtain a flame-retardant porous matrix-supported non-precious metal catalyst G1 with a surface area of ​​210 m². 2 ·g -1 The most probable pore size is 6.8 nm, and the pore volume is 0.51 ml·g. -1 The area of ​​the honeycomb cells is 9.0 mm. 2 .

[0127] Example 8

[0128] Take the flame-retardant honeycomb substrate G from Example 7. The Co content on each cubic meter of flame-retardant honeycomb substrate G is 360 kg / m³. 3 A glycerol-cobalt chloride aqueous solution was prepared in a ratio of 0.3:1 (glycerol to cobalt chloride by mass). The La content on each cubic meter of flame-retardant honeycomb substrate G was 60 kg / m³. 3 The Mn content is 30 kg / m³. 3 A lanthanum nitrate and manganese nitrate aqueous solution in acetic acid was prepared in a specific ratio. The La and Mn solutions were first impregnated onto G, and then dried at 150°C for 4 hours. A Co solution was then further impregnated, and the mixture was dried again at 150°C for 3 hours. Finally, the mixture was calcined at 480°C for 5 hours to obtain a flame-retardant porous matrix-supported non-noble metal catalyst H1 with a surface area of ​​219 m². 2 ·g -1 The most probable pore size is 6.9 nm, and the pore volume is 0.55 ml·g. -1 The area of ​​the honeycomb cells is 9.2 mm. 2 .

[0129] Example 9

[0130] Take the flame-retardant honeycomb substrate G from Example 7. The Co content on each cubic meter of flame-retardant honeycomb substrate G is 350 kg / m³. 3 A glycerol-cobalt chloride aqueous solution was prepared in a ratio of 0.3:1 (glycerol to cobalt chloride by mass). The La content on each cubic meter of flame-retardant honeycomb substrate G was 80 kg / m³. 3 The Fe content is 20 kg / m³ 3 Aqueous solutions of lanthanum nitrate and ferric nitrate were prepared in a specific ratio. The Co solution was first impregnated onto a honeycomb substrate G and dried at 130°C for 4 hours. Then, a solution of La and Fe was further impregnated, and the substrate was dried again at 150°C for 3 hours. Finally, the substrate was calcined at 500°C for 5 hours to obtain a flame-retardant porous substrate-supported non-precious metal catalyst I1 with a surface area of ​​193 m². 2 ·g -1The most probable pore size is 7.8 nm, and the pore volume is 0.47 ml·g. -1 The area of ​​the honeycomb cells is 8.8 mm. 2 .

[0131] Example 10

[0132] Take the flame-retardant honeycomb substrate G from Example 7. The Co content on each cubic meter of flame-retardant honeycomb substrate G is 350 kg / m³. 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). The La content on each cubic meter of flame-retardant honeycomb substrate G was 84 kg / m³. 3 The Ni content is 30 kg / m 3 An aqueous solution of lanthanum nitrate and nickel nitrate was prepared in a specific ratio. The Co solution was first impregnated onto a honeycomb substrate G and dried at 130°C for 4 hours. Then, a solution of La and Ni was further impregnated, and the substrate was dried again at 150°C for 3 hours. Finally, the substrate was calcined at 500°C for 5 hours to obtain a flame-retardant porous substrate-supported non-noble metal catalyst J1 with a surface area of ​​176 m². 2 ·g -1 The most probable pore size is 8.5 nm, and the pore volume is 0.42 ml·g. -1 The area of ​​the honeycomb cells is 8.3 mm. 2 .

[0133] Example 11

[0134] Take the flame-retardant honeycomb substrate G from Example 7. The Co content on each cubic meter of flame-retardant honeycomb substrate G is 300 kg / m³. 3 An aqueous solution of methyl methacrylate was prepared in a ratio of 0.3:1 (mass ratio of methyl methacrylate to cobalt chloride). The La content on each cubic meter of flame-retardant honeycomb substrate G was 80 kg / m³. 3 Bi content is 20 kg / m 3 An aqueous solution of lanthanum nitrate and bismuth nitrate was prepared in a specific ratio. Co solution was first impregnated onto G, and then dried at 130°C for 4 hours. Then, a solution of La and Bi was further impregnated, and the mixture was dried again at 150°C for 3 hours. Finally, it was calcined at 500°C for 5 hours to obtain a flame-retardant porous matrix supported non-noble metal catalyst K1 with a surface area of ​​188 m². 2 ·g -1 The most probable pore size is 8.0 nm, and the pore volume is 0.46 ml·g. -1 The area of ​​the honeycomb holes is 8.5mm. 2 .

[0135] Example 12

[0136] Take the flame-retardant honeycomb substrate G from Example 7. The Co content on each cubic meter of flame-retardant honeycomb substrate G is 360 kg / m³. 3 An aqueous solution of methyl methacrylate was prepared in a ratio of 0.3:1 (mass ratio of methyl methacrylate to cobalt chloride). The Ce content on each cubic meter of flame-retardant honeycomb substrate G was 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 specific ratio. Co solution was first impregnated onto G, and then dried at 130°C for 4 hours. Subsequently, a solution of Ce, Mn, and Ti was further impregnated, and the mixture was dried again at 150°C for 3 hours. After calcination at 500°C for 5 hours, a flame-retardant porous matrix supported non-noble metal catalyst L1 with a surface area of ​​139 m² was obtained. 2 ·g -1 The most probable pore size is 10.7 nm, and the pore volume is 0.34 ml·g. -1 The area of ​​the honeycomb cells is 7.8 mm. 2 .

[0137] Example 13

[0138] Take the flame-retardant honeycomb substrate G from Example 7. The Co content on each cubic meter of flame-retardant honeycomb substrate G is 420 kg / m³. 3 An aqueous solution of methyl methacrylate was prepared in a ratio of 0.3:1 (mass ratio of methyl methacrylate to cobalt chloride). The Ce content on each cubic meter of flame-retardant honeycomb substrate G was 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. Co solution was first impregnated onto G, and then dried at 130°C for 4 hours. Subsequently, a solution of Ce, Mn, and V was further impregnated, and the mixture was dried again at 150°C for 3 hours. After calcination at 500°C for 4 hours, a flame-retardant porous matrix supported non-precious metal catalyst M1 with a surface area of ​​151 m² was obtained. 2 ·g -1 The most probable pore size is 9.1 nm, and the pore volume is 0.38 ml·g. -1 The area of ​​the honeycomb cells is 8.2 mm. 2 .

[0139] Example 14

[0140] Take the flame-retardant honeycomb substrate G from Example 7. The Co content on each cubic meter of flame-retardant honeycomb substrate G is 400 kg / m³. 3An aqueous solution of methyl methacrylate was prepared in a ratio of 0.3:1 (mass ratio of methyl methacrylate to cobalt chloride). The Ce content on each cubic meter of flame-retardant honeycomb substrate G was 60 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 Ce, Mn, and Bi solution was first impregnated onto G, and then dried at 130°C for 4 hours. Subsequently, a Co solution was further impregnated, and the mixture was dried again at 150°C for 3 hours. Finally, the mixture was calcined at 500°C for 4 hours to obtain a flame-retardant porous matrix-supported non-noble metal catalyst N1 with a surface area of ​​153 m². 2 ·g -1 The most probable pore size is 9.1 nm, and the pore volume is 0.39 ml·g. -1 The area of ​​the honeycomb cells is 8.2 mm. 2 .

[0141] Example 15

[0142] Take the flame-retardant honeycomb substrate G from Example 7. The Co content on each cubic meter of flame-retardant honeycomb substrate G is 400 kg / m³. 3 An aqueous solution of methyl methacrylate was prepared in a ratio of 0.3:1 (mass ratio of methyl methacrylate to cobalt chloride). The Ce content on each cubic meter of flame-retardant honeycomb substrate G was 50 kg / m³. 3 The Mn content is 30 kg / m³. 3 The Cr content is 10 kg / m³ 3 An aqueous solution of cerium nitrate, manganese nitrate, and chromium nitrate was prepared in a specific ratio. The solution of Ce, Mn, and Cr was first impregnated onto G, and then dried at 130°C for 4 hours. Subsequently, a Co solution was further impregnated, and the mixture was dried again at 150°C for 3 hours. Finally, the mixture was calcined at 500°C for 4 hours to obtain a flame-retardant porous matrix-supported non-noble metal catalyst O1 with a surface area of ​​157 m². 2 ·g -1 The most probable pore size is 9.0 nm, and the pore volume is 0.40 ml·g. -1 The area of ​​the honeycomb cells is 8.2 mm. 2 .

[0143] Example 16

[0144] Take the flame-retardant honeycomb substrate G from Example 7. The Co content on each cubic meter of flame-retardant honeycomb substrate G is 300 kg / m³. 3 An aqueous solution of methyl methacrylate was prepared in a ratio of 0.3:1 (mass ratio of methyl methacrylate to cobalt chloride). The La content on each cubic meter of flame-retardant honeycomb substrate G was 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 specific ratio. The solution of La, Mn, and V was first impregnated onto G, and then dried at 130°C for 4 hours. Subsequently, a Co solution was further impregnated, and the mixture was dried again at 150°C for 3 hours. Finally, the mixture was calcined at 500°C for 4 hours to obtain a flame-retardant porous matrix-supported non-noble metal catalyst P1 with a surface area of ​​170 m². 2 ·g -1 The most probable pore size is 8.6 nm, and the pore volume is 0.48 ml·g. -1 The area of ​​the honeycomb cells is 8.6 mm. 2 .

[0145] Example 17

[0146] Attapulgite clay, alumina, titanium dioxide, 65% nitric acid, hydroxymethylpropyl cellulose, and glycerol were mixed evenly in a kneader at a mass ratio of 10:3:1:0.02:0.2:0.001. A suitable amount of water was added, and the mixture was kneaded to form a plastic composite. This composite was then loaded into an extruder and extruded at 25°C and 5 MPa to produce a square honeycomb preform. The four base sides and height of the preform were 80 cm and 100 cm, respectively. The preform was then calcined in air at 500°C for 2 hours to obtain the flame-retardant honeycomb matrix Q. The Co content in each cubic meter of flame-retardant honeycomb matrix Q was 230 kg / m³. 3 An aqueous solution of methyl methacrylate was prepared in a ratio of 0.3:1 to cobalt chloride. The La content on each cubic meter of flame-retardant honeycomb substrate Q was 60 kg / m³. 3 The Mn content is 30 kg / m³. 3 The vitamin C content is 20 kg / m³. 3 An aqueous solution of lanthanum nitrate, manganese nitrate, and ammonium metavanadate was prepared in a specific ratio. The solution of La, Mn, and V was first impregnated onto Q, and then dried at 130°C for 4 hours. Subsequently, a Co solution was further impregnated, and the mixture was dried again at 150°C for 3 hours. Finally, it was calcined at 500°C for 4 hours to obtain a flame-retardant porous matrix supported non-precious metal catalyst Q1 with a surface area of ​​157 m². 2 ·g -1 The most probable pore size is 8.1 nm, and the pore volume is 0.41 ml·g. -1 The area of ​​the honeycomb holes is 8.5mm. 2 .

[0147] Comparative Example 1

[0148] Alumina, titanium dioxide, 65% nitric acid, hydroxymethylpropyl cellulose, and glycerol were mixed evenly in a kneader at a mass ratio of 3:1:0.02:0.2:0.001. A suitable amount of water was added, and the mixture was kneaded to form a plastic composite. This composite was then loaded into an extruder and extruded at 25°C and 5 MPa to produce a square honeycomb preform. The four base sides and height of the preform were 80 cm and 100 cm, respectively. The preform was then calcined in air at 500°C for 2 hours to obtain the flame-retardant honeycomb matrix R. The Co content in each cubic meter of flame-retardant honeycomb matrix R was 230 kg / m³. 3 An aqueous solution of methyl methacrylate was prepared in a ratio of 0.3:1 (mass ratio of methyl methacrylate to cobalt chloride). The La content on each cubic meter of flame-retardant honeycomb substrate R was 60 kg / m³. 3 The Mn content is 30 kg / m³. 3 The vitamin C content is 20 kg / m³. 3 An aqueous solution of lanthanum nitrate, manganese nitrate, and ammonium metavanadate was prepared in a specific ratio. The solution of La, Mn, and V was first impregnated onto R, and then dried at 130°C for 4 hours. Subsequently, a Co solution was further impregnated, and the mixture was dried again at 150°C for 3 hours. Finally, it was calcined at 500°C for 4 hours to obtain a flame-retardant porous matrix supported non-noble metal catalyst R1 with a surface area of ​​132 m². 2 ·g -1 The most probable pore size is 5.1 nm, and the pore volume is 0.41 ml·g. -1 The area of ​​the honeycomb cells is 8.6 mm. 2 .

[0149] Example 18

[0150] The flame-retardant catalysts of Examples 1-17 and Comparative Example 1 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 380℃ and a volume hourly 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.

[0151] Table 1 Comparison of Reaction Performance of Flame-Retardant Catalysts

[0152] catalyst <![CDATA[Concentration of VOCs at the outlet after 1-hour reaction (mg / m 3 )]]> <![CDATA[VOCs concentration at the outlet after 500h of reaction (mg / m 3 )]]> <![CDATA[VOCs concentration at the outlet after 1000 h of reaction (mg / m 3 )]]> A1 13.5 13.9 14.9 B1 19.7 20.1 21.2 C1 21.5 22.1 22.7 D1 22.6 23.4 23.8 E1 21.8 22.1 22.8 F1 18.5 19.1 20.0 G1 15.2 15.5 16.3 H1 13.1 13.8 14.7 I1 19.7 20.3 21.1 J1 15.7 16.1 16.7 K1 9.4 9.7 10.3 L1 5.3 5.5 5.9 M1 4.5 4.7 4.7 N1 5.6 5.9 6.1 O1 6.1 6.3 6.9 P1 5.8 6.2 6.6 Q1 6.7 6.8 7.0 R1 43.2 48.1 50.4

[0153] As shown in Table 1, the flame-retardant porous matrix-supported non-precious metal catalyst of the present invention exhibits excellent catalytic oxidation performance for VOCs, and maintains excellent catalytic activity even after prolonged use. In contrast, the catalytic activity of catalysts not of the present invention significantly decreases with prolonged use.

[0154] Example 19

[0155] The catalyst in Example 16 was subjected to metal element analysis, and the catalyst after 1000 hours of reaction to treat VOCs gas was also subjected to elemental analysis. The metal content per unit porous matrix volume is shown in Table 2.

[0156] Table 2 Key element analysis after catalytic reaction of flame-retardant catalyst

[0157]

[0158] As shown in Table 2, in the porous matrix supported catalyst of the present invention, the active metal component is firmly supported on the porous matrix, and the active metal is difficult to fall off even after long-term use. Moreover, the positive pressure and lateral pressure strength of the catalyst are well maintained.

[0159] Example 20

[0160] The catalysts from Example 17 and Comparative Example 1 were respectively loaded into fixed-bed reactors, and acrylic acid-containing wastewater with a COD of 35000 mg / L was introduced for air oxidation at a wastewater volume hourly space velocity of 0.5 h⁻¹. -1 The reaction temperature was 270℃ and the pressure was 5.5MPa. Elemental analysis was performed on the catalyst before and after the reaction, and the metal content was converted to a unit porous matrix volume. The results are shown in Table 3.

[0161] Table 3 Key element analysis after catalytic reaction of flame-retardant catalyst

[0162]

[0163] As shown in Table 3, the porous matrix supported catalyst of the present invention exhibits excellent catalytic oxidation performance for wastewater. In the porous matrix supported catalyst of the present invention, the active metal component is firmly supported on the porous matrix, and the active metal is difficult to detach even after prolonged rinsing by water.

[0164] 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 flame-retardant porous matrix supported non-precious metal catalyst, characterized in that, The catalyst contains a flame-retardant porous matrix, a Co component supported on the flame-retardant porous matrix, and an additive component. The auxiliary component is selected from at least one of the following combinations: 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; or is selected from combinations of La, Mn, and V. In each combination, the mass ratio of each element, based on the highest oxidation state of the metal oxide, is either the former to the latter or the former to the sum of the masses of the latter two, and is 0.1 to 10. Based on the total volume of the non-noble metal catalyst supported on the porous matrix, the Co metal content, calculated as cobalt tetroxide, is 50~500 Kg / m³. 3 The content of the auxiliary component, calculated based on the highest oxidation state of the oxide of the auxiliary component, is 10~180 Kg / m. 3 , The flame-retardant porous matrix contains an initial matrix of attapulgite and kaolin, and a molecular sieve as an inorganic material. The molecular sieve is selected from any one of Y-type molecular sieve, SBA-15 molecular sieve, 5A molecular sieve, and SAPO molecular sieve. Based on the total mass of the porous matrix, the content of the initial matrix is ​​10-99.5% by mass, the content of the inorganic material is 0.5-90% by mass, and the BET specific surface area of ​​the catalyst is 100-800 m². 2 ·g -1 The most probable pore size is 2~16 nm, and the pore volume is 0.15~1.0 mL·g. -1 .

2. The catalyst according to claim 1, wherein, The catalyst consists of a flame-retardant porous matrix, a Co component supported on the flame-retardant porous matrix, and an additive component.

3. The catalyst according to claim 1 or 2, wherein, The catalyst has a BET specific surface area of ​​110~800 m². 2 ·g -1 The most probable pore size is 4~12 nm, and the pore volume is 0.2~1.0 mL·g. -1 .

4. The catalyst according to claim 1 or 2, wherein, The additive components are selected from at least one of the following combinations: Ce and Mn with Ti, Ce and Mn with V, Ce and Mn with Bi, Ce and Mn with Cr, and La and Mn with Bi. In each combination, the mass ratio of each element is 0.2 to 5, calculated based on the highest oxidation state of the metal oxide and the ratio of the former to the sum of the masses of the latter two.

5. The catalyst according to claim 1 or 2, wherein the catalyst is shaped into a sphere, cube, cuboid, cylinder, or Raschig ring, the shaped body having one or more macroscopic channel structures selected from circles, squares, triangles, hexagons, or rhombuses, and the cross-sectional area of ​​a single macroscopic channel is 1 mm². 2 ~80mm 2 The hole wall thickness is 1~4mm.

6. The catalyst according to claim 1 or 2, wherein, The catalyst has a positive pressure strength of 2-8 MPa and a lateral pressure strength of 0.1-2 MPa.

7. The catalyst according to claim 1 or 2, wherein, It meets at least one of the following characteristics: 1) Based on the total volume of the non-precious metal catalyst supported on the porous matrix, the Co metal content, calculated as cobalt tetroxide, is 50~430 Kg / m³. 3 The content of the auxiliary component, calculated based on the highest oxidation state of the oxide of the auxiliary component, is 10~150 Kg / m. 3 ; 2) Based on the total mass of the porous matrix, the content of the original matrix is ​​20-99% by mass, and the content of the inorganic material is 1-80% by mass. 3) The catalyst is shaped into a sphere, cube, cuboid, cylinder, or Raschig ring, and the shaped body has one or more macroscopic channel structures selected from circles, squares, triangles, hexagons, or rhombuses, with a cross-sectional area of ​​1 mm² for each macroscopic channel. 2 ~35mm 2 The hole wall thickness is 1~2.5mm; 4) The catalyst has a positive pressure strength of 2~6MPa and a lateral pressure strength of 0.2~2MPa.

8. A method for preparing a flame-retardant porous matrix supported non-precious metal catalyst as described in claim 1, characterized in that, Includes the following steps: (1) A plastic mixed contact body is prepared by mixing and contacting the original matrix of attapulgite and kaolin, a molecular sieve as an inorganic material, a colloidal solvent, and water; wherein, relative to the total amount of the original matrix and the inorganic material, the content of the original matrix is ​​10~99.5% by mass, the content of the inorganic material is 0.5~90% by mass, and the molecular sieve is selected from any one of Y molecular sieve, SBA-15 molecular sieve, 5A molecular sieve, and SAPO molecular sieve; (2) Optionally, the plastic mixed contact body is molded to obtain a porous matrix preform; (3) The plastic mixed contact body of step (1) or the porous matrix preform of step (2) is calcined to obtain a flame-retardant porous matrix. (4) Contact a flame-retardant porous matrix with a solution or suspension of at least one cobalt metal component and a solution or suspension of at least one auxiliary component to obtain a contact product; and (5) Calcining the contact product to obtain the flame-retardant porous matrix supported non-precious metal catalyst. The additive components are selected from at least one of the following combinations: 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, or are selected from combinations of La and Mn and V.

9. The preparation method according to claim 8, wherein, The adhesive solvent is selected from at least one of inorganic acids, inorganic bases, polycarboxylic acids, monohydric alcohols, polyhydric alcohols, polyamines, cellulose derivatives, and carboxylates.

10. The preparation method according to claim 8 or 9, wherein, In step (2), the molding process is carried out under a pressure of 0.5 to 8 MPa and a temperature of 20 to 80°C.

11. The preparation method according to claim 8 or 9, wherein, The roasting temperature in step (3) is 200~580℃.

12. The preparation method according to claim 8 or 9, further comprising, prior to step (3), heat-treating the plastic mixed contact body in step (1) or the porous matrix preform in step (2), wherein the heat treatment temperature is 20 to 150°C.

13. The preparation method according to claim 8 or 9, wherein, The auxiliary component 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, and La and Mn with Bi. In each combination, the mass ratio of each element, based on the highest oxidation state of the metal oxide and the ratio of the former to the sum of the latter two, is 0.2 to 5. The precursor of the adjuvant component is selected from at least one of chloride, nitrate, acetate, sulfate, ammonium salt and phosphate; The cobalt metal precursor is selected from at least one of the following: cobalt metal chloride, nitrate, acetate, and ammonium salt.

14. The preparation method according to claim 8 or 9, wherein, It meets at least one of the following characteristics: 1) At least one of a complexing agent, a stabilizer, and a pH adjuster is added to the solution or suspension of the cobalt metal component precursor and / or the solution or suspension of the auxiliary agent component precursor. 2) Relative to the total amount of the original matrix and the inorganic material, the content of the original matrix is ​​20-99% by mass, and the content of the inorganic material is 1-80% by mass. 3) 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, methylcellulose, hydroxymethylcellulose, hydroxymethylpropylcellulose, carboxymethylcellulose, magnesium stearate, and sodium stearate; 4) In step (2), the molding process is carried out under a pressure of 1 to 6 MPa and a temperature of 20 to 80°C; 5) The roasting temperature in step (3) is 300~550℃; 6) Before step (3), a heat treatment step is performed on the plastic mixed contact body in step (1) or the porous matrix preform in step (2), wherein the heat treatment temperature is 50~100℃; 7) In the auxiliary components, the mass ratio of each element is 0.2 to 5, based on the highest oxidation state of the metal oxide, either the former to the latter or the former to the sum of the masses of the latter two. 8) In the obtained catalyst, based on the total volume of the catalyst, the Co metal content, calculated as cobalt tetroxide, is 50~430 kg / m³. 3 The content of the auxiliary component, calculated based on the highest oxidation state of the oxide of the auxiliary component, is 10~150 Kg / m. 3 .

15. The flame-retardant porous matrix supported non-precious metal catalyst according to any one of claims 1-7 or the flame-retardant porous matrix supported non-precious metal catalyst prepared by the preparation method according to any one of claims 8-14 is used for the catalytic oxidation of volatile organic compounds.

16. The application according to claim 15, wherein, The conditions for catalytic oxidation of volatile organic compounds are: the gas containing volatile organic compounds is at a gas hourly space velocity (VHSV) of 4000–25000 h⁻¹. -1 Non-precious metal catalysts are contacted in a flame-retardant porous matrix supported at 150~450℃.

17. The flame-retardant porous matrix supported non-precious metal catalyst according to any one of claims 1-7 or the flame-retardant porous matrix supported non-precious metal catalyst prepared by the preparation method according to any one of claims 8-14 is used for the catalytic oxidation of wastewater to reduce chemical oxygen demand (COD).

18. The application according to claim 17, wherein, The conditions for catalytic oxidation of wastewater are: a liquid hourly space velocity (LHSV) of 0.2-3 h⁻¹. -1 Under conditions of pressure of 2-8 MPa and reaction temperature of 200-280℃, a non-precious metal catalyst supported on a flame-retardant porous matrix is ​​contacted.

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