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

Abstract

The present application relates to a kind of non-noble metal catalysts supported on flame-retardant hydrophobic porous matrix, preparation method and application thereof.The preparation method of the non-noble metal catalysts supported on flame-retardant hydrophobic porous matrix is simple, has high mechanical strength, strong hydrothermal stability, has good volatile organic compound catalytic performance in moisture-containing VOCs treatment and long service life, and can also be applied to catalytic wet oxidation of wastewater.

Description

Technical Field

[0001] This invention relates to a flame-retardant, hydrophobic, porous matrix supported non-precious metal catalyst. More specifically, this invention relates to a flame-retardant, hydrophobic, porous matrix supported non-precious metal catalyst and its preparation method. This invention also relates to the application of this flame-retardant, hydrophobic, 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 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, further combining it with a suitable inorganic porous solid, and treating it with a hydrophobic modifier, a flame-retardant hydrophobic porous matrix can be prepared. Further loading cobalt metal components and auxiliary components as the catalyst active component onto this matrix can prepare the flame-retardant hydrophobic porous matrix supported non-precious metal catalyst of the present invention (hereinafter sometimes simply referred to as "flame-retardant hydrophobic porous matrix supported catalyst," "the catalyst of the present invention," or "catalyst"). The flame-retardant hydrophobic 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, the present invention provides a flame-retardant and hydrophobic porous matrix supported non-precious metal catalyst, characterized in that it contains a flame-retardant and hydrophobic porous matrix, a Co component supported on the flame-retardant and hydrophobic 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 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 each combination, the mass ratio of each element (based on the highest oxidation state of the metal oxide) is 0.1 to 10, preferably 0.2 to 5.

[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: 50~430 kg / m 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 porous matrix contains at least one primary matrix selected from attapulgite and kaolin, at least one inorganic material selected from inorganic porous solids, and calcined oxide of a hydrophobic modifying material. 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; the content of the calcined oxide of the hydrophobic modifying material is 0.05-1% by mass, preferably 0.05-0.5% by mass; the content of the inorganic material is 0.5-90% by mass, preferably 1-80% by mass, more preferably 5-80% by mass, further preferably 8-70% by mass, and even more preferably the balance. The contact angle between the porous matrix and water is 40-90°, preferably 45-70°.

[0012] This invention also provides a method for preparing a flame-retardant, hydrophobic, porous matrix supported non-noble 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, even more 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 in step (1) or the porous matrix preform in step (2) is calcined in an inert gas and then further contacted with a solution containing a hydrophobic modifier to obtain a modified preform.

[0016] (4) The modified preform is further calcined to obtain a flame-retardant hydrophobic porous matrix;

[0017] (5) 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 hydrophobic porous matrix to obtain a contact product; and

[0018] (6) Calcining the contact product to obtain the flame-retardant hydrophobic porous matrix supported catalyst;

[0019] or,

[0020] (1') After contacting at least one original matrix selected from attapulgite and kaolin, and at least one inorganic material selected from inorganic porous solids with a solution containing a hydrophobic modifier, calcination is carried out to obtain a modified original matrix and a modified inorganic material.

[0021] (2') The modified original matrix, the modified inorganic material, the adhesive solvent, and water are mixed and brought into contact to form a plastic mixed modified contact body; wherein, relative to the total amount of the modified original matrix and the modified inorganic material, the content of the modified original 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;

[0022] (3') Optionally, the plastic mixed modified contact body is molded to obtain a porous matrix modified preform;

[0023] (4') The mixed modified contact body in step (2') or the modified preform in step (3') is further calcined to obtain a flame-retardant hydrophobic porous matrix;

[0024] (5) 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 hydrophobic porous matrix to obtain a contact product; and

[0025] (6) Calcining the contact product to obtain the flame-retardant hydrophobic porous matrix supported catalyst.

[0026] The present invention also provides the application of the flame-retardant hydrophobic porous matrix supported catalyst in the catalytic oxidation of volatile organic compounds.

[0027] The present invention also provides the application of the flame-retardant hydrophobic porous matrix supported catalyst in the catalytic oxidation of wastewater containing high COD.

[0028] Technical effect

[0029] The preparation method of the flame-retardant hydrophobic porous matrix supported catalyst of the present invention is simple, does not require vacuum slurrying and microwave heat treatment, and is inexpensive.

[0030] The flame-retardant, hydrophobic, 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.

[0031] In the flame-retardant and hydrophobic 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.

[0032] In addition, the flame-retardant hydrophobic 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 substances with high COD in wastewater, which is beneficial for catalytic wet oxidation to reduce COD. Detailed Implementation

[0033] 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.

[0034] 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.

[0035] This invention provides a flame-retardant, hydrophobic porous matrix supported non-precious metal catalyst, characterized in that it contains a flame-retardant, hydrophobic porous matrix, a Co component supported on the flame-retardant, hydrophobic porous matrix, and an additive component.

[0036] 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.

[0037] 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;

[0038] Based on the total volume of the non-precious metal catalyst supported on the porous matrix.

[0039] 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 oxide of the auxiliary component) is 10~180 kg / m³. 3 Preferred weight: 10~150 kg / m 3 ,

[0040] The porous matrix contains at least one primary matrix selected from attapulgite and kaolin, at least one inorganic material selected from inorganic porous solids, and calcined oxide of a hydrophobic modifying material. 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; the content of the calcined oxide of the hydrophobic modifying material is 0.05-1% by mass, preferably 0.05-0.5% by mass; the content of the inorganic material is 0.5-90% by mass, preferably 1-80% by mass, more preferably 5-80% by mass, further preferably 8-70% by mass, and even more preferably the balance. The contact angle between the porous matrix and water is 40-90°, preferably 45-70°.

[0041] In one embodiment of the present invention, the porous matrix is ​​substantially composed of the original matrix, the calcined oxide of the hydrophobic modified material, and the inorganic material. In another embodiment of the present invention, the porous matrix is ​​composed only of the original matrix, the calcined oxide of the hydrophobic modified material, and the inorganic material.

[0042] In one embodiment of the present invention, the content of the original matrix is ​​10 to 99.5% by mass, preferably 20 to 99% by mass, based on the total mass of the porous matrix.

[0043] In one embodiment of the present invention, the content of calcined oxide of the hydrophobic modified material is 0.05 to 1% by mass, preferably 0.05 to 0.5% by mass, based on the total mass of the porous matrix.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] In this invention, various hydrophobic modifying materials known in the art can be used as the hydrophobic modifying materials. Preferably, the hydrophobic modifying materials are silicon-based or metal compound-based. Specifically, the silicon-based modifying material can be selected from one or a combination of several of methyl silicate, ethyl silicate, propyl silicate, butyl silicate, (tetra)silicon chloride, and sodium silicate.

[0051] As a metal compound modifier, it can be selected from titanium-based modifiers and / or aluminum-based modifiers. The titanium-based modifier can be a titanate ester or titanium halide, selected from one or more combinations of methyl titanate, ethyl titanate, propyl titanate, butyl titanate, and titanium chloride. The aluminum-based modifier can be an aluminate ester or aluminum halide, selected from one or more combinations of methyl aluminate, ethyl aluminate, propyl aluminate, butyl aluminate, and aluminum chloride.

[0052] In one embodiment of the present invention, the flame-retardant hydrophobic porous matrix supported catalyst BET has a specific surface area of ​​100~800 m². 2 ·g -1 Preferred depth: 110~800m 2 ·g -1 The most probable pore size is 2~12 nm, preferably 2~10 nm, and the pore volume is 0.15~1.0 ml·g. -1 The preferred dosage is 0.2~1.0 ml·g. -1 .

[0053] In one embodiment of the present invention, the catalyst can be shaped into a macroscopic catalyst body with an appearance of spheres, cubes, cuboids, cylinders, Raschig rings, etc.

[0054] In one embodiment of the present invention, when the catalyst is formed into a molded body, the catalyst molded body may have macroscopic channels, which may be one or more of the following channel structures: circular, square, triangular, hexagonal, or rhombic. The arrangement of these macroscopic channels on the catalyst molded body may be ordered or disordered, preferably uniformly ordered honeycomb channels. Generally, to reduce adsorption resistance, the macroscopic channels on the catalyst molded body are permeable.

[0055] In one embodiment of the present invention, the cross-sectional area of ​​a single pore in the macroscopic channel on the catalyst molding body is 1 mm. 2 ~80mm 2 Preferably 1mm 2 ~40mm 2 The hole wall thickness is 1~4mm, preferably 1~2.5mm.

[0056] In one embodiment of the present invention, the catalyst has a positive pressure strength of 2 to 8 MPa, preferably 2 to 6 MPa, as determined according to the standard method of GB / T 5072-2008, and a lateral pressure strength of 0.1 to 2 MPa, preferably 0.2 to 2 MPa.

[0057] 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.

[0058] In this invention, without any theoretical limitations, the inventors believe that after all the raw material components of the porous matrix are made into a preform, a hydrophobic modification treatment is performed on it before calcination to make the final porous matrix; or, after all the raw material components of the porous matrix are hydrophobically modified with a hydrophobic modification material, a modified preform is made, and then calcination is performed, a calcined oxide (hydrophobic layer) of the hydrophobic modification material is formed on the surface of the finally prepared porous matrix, thus imparting a certain degree of hydrophobicity to the porous matrix.

[0059] In addition, in this invention, since the hydrophobic layer is a very thin layer, the weight of the hydrophobic layer is very low relative to the porous matrix itself. Typically, based on the total mass of the porous matrix, the content of the calcined oxide of the hydrophobic modified material is 0.05 to 1% by mass, preferably 0.05 to 0.5% by mass.

[0060] In this invention, the flame-retardant hydrophobic porous matrix is ​​hydrophobically modified to produce a calcined oxide content of 0.05-1% by mass, preferably 0.05-0.5% by mass, thereby imparting a certain degree of hydrophobicity to the porous matrix. The contact angle of water on the surface of the porous matrix is ​​used as an indicator of hydrophobicity. When measured according to the method of GB / T36086-2018, the contact angle between the porous matrix and water is 40-90°, preferably 45-70°.

[0061] In one embodiment of the present invention, the catalyst is basically composed of a flame-retardant hydrophobic porous matrix, a Co component supported on the porous matrix, and an additive.

[0062] In one embodiment of the present invention, the catalyst consists only of a flame-retardant hydrophobic porous matrix, a Co component supported on the porous matrix, and an additive. 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.).

[0063] 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.

[0064] 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.

[0065] 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 .

[0066] 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 .

[0067] This invention also provides a method for preparing a flame-retardant, hydrophobic, porous matrix supported non-noble metal catalyst, characterized by comprising the following steps:

[0068] (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;

[0069] (2) Optionally, the plastic mixed contact body is molded to obtain a porous matrix preform;

[0070] (3) The mixed contact body in step (1) or the porous matrix preform in step (2) is calcined in an inert gas and then further contacted with a solution containing a hydrophobic modifier to obtain a modified preform.

[0071] (4) The modified preform is further calcined to obtain a flame-retardant hydrophobic porous matrix;

[0072] (5) 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 hydrophobic porous matrix to obtain a contact product; and

[0073] (6) Calcining the contact product to obtain the flame-retardant hydrophobic porous matrix supported catalyst;

[0074] or,

[0075] (1') After contacting at least one original matrix selected from attapulgite and kaolin, and at least one inorganic material selected from inorganic porous solids with a solution containing a hydrophobic modifier, calcination is carried out to obtain a modified original matrix and a modified inorganic material.

[0076] (2') The modified original matrix, the modified inorganic material, the adhesive solvent, and water are mixed and contacted to form a plastic mixed modified contact body; wherein, relative to the total amount of the modified original matrix and the modified inorganic material, the content of the modified original matrix is ​​10~99.5% by mass, preferably 20~99% by mass, and the content of the modified 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;

[0077] (3') Optionally, the plastic mixed-modified contact body is molded to obtain a porous matrix-modified preform; and

[0078] (4') The mixed modified contact body in step (2') or the modified preform in step (3') is further calcined to obtain a flame-retardant hydrophobic porous matrix;

[0079] (5) 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 hydrophobic porous matrix to obtain a contact product; and

[0080] (6) Calcining the contact product to obtain the flame-retardant hydrophobic porous matrix supported catalyst.

[0081] In one embodiment of the present invention, in steps (1) and (1') of the above preparation method, no pretreatment is performed on at least one original matrix selected from attapulgite and kaolin.

[0082] 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.

[0083] In the preparation method of the present invention, in the above steps (1) and (1'), 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.

[0084] 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.

[0085] 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.

[0086] In step (1') above, the original matrix and inorganic material after contact with the hydrophobic modifier are calcined. The calcination temperature is 200~550℃, preferably 200~500℃, and more preferably 250~500℃. Calcination can be carried out in air. Preferably, calcination is carried out in an inert gas atmosphere. Examples of inert gases include nitrogen or rare gases, with nitrogen being preferred. The calcination time is not particularly limited and can be 2~20 hours, preferably 4~16 hours.

[0087] In the preparation method of this invention, in steps (1) and (2') above, the adhesive solvent only needs to be able to disperse the original matrix (or modified original matrix) and the inorganic material (or modified 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 (or modified original matrix) and inorganic material (or modified 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 (or modified original matrix) and inorganic material (or modified inorganic material), preferably 1.2 to 10 parts by mass, and more preferably 1.5 to 5 parts by mass.

[0088] 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.

[0089] 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.

[0090] 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. 2-20Alkanes, 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.

[0091] 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.

[0092] 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.

[0093] As the polyamine, various polyamines known in the art can be used, such as ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, etc.

[0094] As the cellulose derivatives mentioned above, those known in the art can be used, such as methylcellulose, hydroxymethylcellulose, hydroxymethylpropylcellulose, carboxymethylcellulose, etc.

[0095] As the carboxylate, those carboxylate salts known in the art can be used, such as magnesium stearate, sodium stearate, etc.

[0096] In steps (1) and (2'), the amount of water added is not particularly limited, as long as it is sufficient to disperse the original matrix (or modified original matrix) and the inorganic material (or modified inorganic material). 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 (or modified original matrix) and the inorganic material (or modified inorganic material). In steps (1) and (2'), a kneader can be used for stirring to prepare the contact body.

[0097] In steps (2) and (3'), the plastic mixed contact body (plastic mixed modified contact body) is molded to obtain a porous matrix preform (porous matrix modified preform). The equipment and conditions for the molding process are not particularly limited and those known in the art can be used.

[0098] In steps (2) and (3'), during molding, an extruder can be used for molding processing. At this time, the pressure inside the barrel reaches 0.5 to 8 MPa, preferably 1 to 6 MPa, and the extrusion temperature of the barrel is 20 to 80°C.

[0099] 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.

[0100] In step (3), the porous matrix preform is calcined in an inert gas. The calcination temperature is 200~580℃, preferably 300~500℃. Examples of inert gases include nitrogen or rare gases, with nitrogen being preferred. The calcination time is not particularly limited and can be 2~20 hours, preferably 4~16 hours.

[0101] In step (3), the solution containing the hydrophobic modifier is brought into contact with the calcined mixed contact body or porous matrix preform at a ratio of 1 / 5 to 1 / 30 relative to the mass of the calcined mixed contact body or porous matrix preform.

[0102] In step (1'), the solution containing the hydrophobic modifier is contacted with the original matrix at a ratio of 1 / 5 to 1 / 30 of the mass of at least one inorganic material selected from inorganic porous solids.

[0103] In steps (3) and (1'), the hydrophobic modifier can be any of the various hydrophobic modifiers known in the art. In this invention, the hydrophobic modifier is preferably a silicon-based modifier or a metal compound modifier. The silicon-based modifier can be selected from one or a combination of several of methyl silicate, ethyl silicate, propyl silicate, butyl silicate, (tetra)silicon chloride, and sodium silicate.

[0104] As a metal compound modifier, it can be selected from titanium-based modifiers and / or aluminum-based modifiers. The titanium-based modifier can be a titanate ester or titanium halide, and can be selected from one or more combinations of methyl titanate, ethyl titanate, propyl titanate, butyl titanate, and titanium chloride. The aluminum-based modifier can be an aluminate ester or aluminum halide, and can be selected from one or more combinations of methyl aluminate, ethyl aluminate, propyl aluminate, butyl aluminate, and aluminum chloride.

[0105] As a solvent for preparing solutions containing hydrophobic modifiers, various organic non-aqueous solvents commonly used in the art can be used. For example, the solvent can be selected from one or a combination of methanol, ethanol, propanol, butanol, benzene, toluene, xylene, long-chain alcohols having 8-12 carbons, and N,N-dimethylformamide. Preferably, it is an organic solvent that is completely miscible with silicon-based modifiers, titanium-based modifiers, and aluminum-based modifiers.

[0106] In the solution containing the hydrophobic modifier, the concentration of the hydrophobic modifier can be adjusted as needed, and its mass concentration can be 0.5~40%, preferably 0.8~30%. As long as a hydrophobic layer is formed on the surface of the finally obtained porous matrix, such that the contact angle of water on the surface of the porous matrix is ​​40~90°, preferably 45~70°.

[0107] In steps (4) and (4'), the modified preform is calcined to obtain a flame-retardant hydrophobic porous matrix.

[0108] The calcination temperature in steps (4) and (4') is not particularly limited, but can be 200~580℃, preferably 200~550℃, and more preferably 300~550℃. Calcination can be carried out in an air atmosphere or an inert gas atmosphere. The calcination time is not particularly limited, but can be 1~20 hours, preferably 2~20 hours, and more preferably 4~16 hours.

[0109] 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.

[0110] In the preparation method of the present invention, step (3') is optional. In the absence of step (3'), the mixed modified contact body in step (2') is calcined in step (4'). The calcination conditions are the same as those described above.

[0111] According to the present invention, in the contact steps of steps (1) and (2'), 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 a binder, water; or modified original matrix, modified inorganic material and binder, and water).

[0112] According to the present invention, there are no particular limitations on the manner in which the contacting step is performed in steps (1) and (2'), 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 steps (1) and (2'), the contacting step can be performed at any temperature from 0°C to 150°C, for example at room temperature.

[0113] According to the present invention, there are no particular restrictions on the manner in which the contact is performed in steps (3) and (1'), as long as the solution containing the hydrophobic modifier is in contact with the calcined porous matrix preform; or the solution containing the hydrophobic modifier is in contact with the original matrix or inorganic material. For example, contact can be performed by impregnation. In steps (3) and (1'), the contact step can be performed at any temperature between 0°C and the boiling point of the solvent used in the solution containing the hydrophobic modifier, for example, at room temperature. There are no particular restrictions on the contact time, as long as a hydrophobic layer is formed on the surface of the finally obtained porous matrix, such that the contact angle of water on the surface of the porous matrix is ​​40~90°, preferably 45~70°.

[0114] In the above method of the present invention, heat treatment can be performed before roasting (e.g., roasting in step (3), roasting in step (4), roasting in step (1'), and roasting in step (4')). The material to be roasted is subjected to heat treatment steps such as drying, air drying, and air drying to remove moisture. The heat treatment is performed at 20~150°C, preferably at 30~120°C, and more preferably at 50~100°C.

[0115] In step (5), 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.

[0116] In step (5), 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) (based on the highest oxidation state of the metal), is 0.1 to 10, preferably 0.2 to 5.

[0117] 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.

[0118] In this invention, the precursor of the auxiliary component is a precursor commonly used in the art. For example, the precursor of the auxiliary component 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.

[0119] 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.

[0120] 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.

[0121] In this invention, when preparing a solution or suspension of the cobalt metal component precursor and / or a solution or suspension of the auxiliary component precursor, various additives may be added as needed, such as complexing agents, stabilizers, and pH adjusters.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] In this invention, in step (5), 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 hydrophobic 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 hydrophobic 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.

[0127] 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 hydrophobic porous matrix. That is, in this case, "the solution or suspension of the cobalt metal component precursor" and "the solution or suspension of the additive component precursor" refer to the same solution or suspension.

[0128] In step (5) of this invention, contact with the flame-retardant hydrophobic porous matrix can be achieved by spraying or sprinkling the solution or suspension onto the flame-retardant hydrophobic porous matrix, or by immersing the flame-retardant hydrophobic 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 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.

[0129] In step (5) of this invention, when the solution or suspension of the cobalt metal component precursor and the solution or suspension of the additive component precursor come into contact with the flame-retardant hydrophobic 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.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.

[0130] 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.

[0131] 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, 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.

[0132] In this invention, in step (6), the contact product obtained in step (5) is calcined to obtain the flame-retardant hydrophobic porous matrix supported catalyst of this invention.

[0133] In step (6), the calcination temperature is 200~550℃, preferably 200~500℃, and more preferably 250~500℃. Calcination can be carried out in an air atmosphere or an inert gas atmosphere. The heat treatment time is not particularly limited and can be 2~20 hours, preferably 4~16 hours.

[0134] The flame-retardant hydrophobic porous matrix supported catalyst of the present invention, or the flame-retardant hydrophobic 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.

[0135] 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.

[0136] The flame-retardant hydrophobic porous matrix supported catalyst of the present invention, or the flame-retardant hydrophobic porous matrix supported catalyst prepared according to the preparation method of the present invention, can be used for catalytic oxidation of wastewater, especially wastewater containing high COD.

[0137] 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.-1 Catalytic oxidation is carried out by contacting a porous matrix supported catalyst under conditions of 2-8 MPa pressure and 200-280℃ reaction temperature. Example

[0138] 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, the content of Co metal in the present invention 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.

[0139] In this invention, the surface area is determined by the BET specific surface area measurement method.

[0140] The pore volume was determined using the BJH (Barrett-Joyner-Halenda) method.

[0141] The most probable pore size was determined by BJH.

[0142] The cross-sectional area of ​​a single honeycomb macroscopic channel (also referred to as a honeycomb cell) is calculated based on its specific shape.

[0143] 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.

[0144] The contact angle was determined according to the method in GB / T36086-2018.

[0145] The methods for determining the positive pressure strength and lateral pressure strength are in accordance with the national standard method GB / T 5072-2008.

[0146] Example 1

[0147] Attapulgite clay, 13X molecular sieve, 65% nitric acid, methylcellulose, and magnesium stearate were mixed evenly in a kneader at a mass ratio of 10:3:0.02:0.2:0.001. 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 a pressure of 5 MPa and a temperature of 25°C 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 calcined at 300°C under N2 conditions for 2 hours. After cooling to room temperature, the preform was transferred to a 1% ethyl silicate ethanol solution at a mass ratio of 20:1 and immersed for 1 hour. It was then calcined at 400°C for 4 hours to obtain a flame-retardant hydrophobic honeycomb matrix A with a contact angle of 53°. The Co content per cubic meter of honeycomb matrix A was 150 kg / m³. 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). The Ce content on each cubic meter of honeycomb substrate A was 20 kg / m³. 3 The Mo content is 18 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, hydrophobic, porous matrix-supported non-noble metal catalyst Al with a surface area of ​​161 m². 2 ·g -1 The most probable pore size is 5.1 nm, and the pore volume is 0.42 ml·g. -1 The cross-sectional area of ​​the honeycomb cells is 9.2 mm². 2 .

[0148] Example 2

[0149] Attapulgite, kaolin, Y 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 to form a plastic composite. This composite was then loaded into an extruder and extruded at 5 MPa and 25°C 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 calcined at 300°C under N2 conditions for 2 hours. After cooling to room temperature, the preform was transferred to a 1% toluene solution containing silicon tetrachloride at a mass ratio of 30:1 and immersed for 1 hour. It was then calcined at 400°C for 4 hours to obtain flame-retardant hydrophobic honeycomb matrix B with a contact angle of 58°. The Co content per cubic meter of honeycomb matrix B was 150 kg / m³. 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). The Ce content on each cubic meter of honeycomb substrate B was 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 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, hydrophobic, porous matrix-supported non-noble metal catalyst B1 with a surface area of ​​144 m². 2 ·g -1 The most probable pore size is 5.8 nm, and the pore volume is 0.34 ml·g. -1 The cross-sectional area of ​​the honeycomb holes is 9mm. 2 .

[0150] Example 3

[0151] 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 to form a plastic composite. This composite was then loaded into an extruder and extruded at a pressure of 5 MPa and a temperature of 25°C to produce a preform with square honeycomb cells. The four base sides and height of the preform were 80 cm and 100 cm, respectively. The honeycomb preform was calcined at 300°C under N2 conditions for 2 hours. After cooling to room temperature, the preform was transferred to a 1% butanol solution containing ethyl titanate at a mass ratio of 18:1 and immersed for 1 hour. It was then calcined at 400°C for 4 hours to obtain a flame-retardant hydrophobic honeycomb matrix C with a contact angle of 61°. The Co content on the flame-retardant and hydrophobic honeycomb matrix C is 300 kg / 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 hydrophobic honeycomb matrix C was 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 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, hydrophobic, porous substrate-supported non-precious metal catalyst C1 was obtained, with a surface area of ​​353 m². 2 ·g -1 The most probable pore size is 7.2 nm, and the pore volume is 0.51 ml·g. -1 The cross-sectional area of ​​the honeycomb cells is 8.2 mm. 2 .

[0152] Example 4

[0153] 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 to form a plastic composite. This composite was then loaded into an extruder and extruded at 5 MPa and 25°C to form a square honeycomb preform. The four base sides and height of the square honeycomb preform were 80 cm and 100 cm, respectively. The honeycomb preform was calcined at 300°C under N2 conditions for 2 hours. After cooling to room temperature, the preform was transferred to a 1% aluminum chloride ethanol solution at a mass ratio of 20:1 and immersed for 1 hour. It was then calcined at 350°C for 4 hours to obtain a flame-retardant hydrophobic honeycomb matrix D with a contact angle of 57°. The Co content on the flame-retardant and hydrophobic honeycomb matrix D is 320 kg / m².3 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 the flame-retardant hydrophobic honeycomb matrix D was 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 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, hydrophobic, porous substrate-supported non-noble metal catalyst D1 was obtained, with a measured surface area of ​​204 m². 2 ·g -1 The most probable pore size is 8.4 nm, and the pore volume is 0.38 ml·g. -1 The cross-sectional area of ​​the honeycomb cells is 27mm². 2 .

[0154] Example 5

[0155] 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 a pressure of 7 MPa and a temperature of 25°C to produce a square honeycomb preform. The four base sides and height of the square honeycomb preform were 80 cm and 100 cm, respectively. The honeycomb preform was calcined at 200°C under N2 conditions for 2 hours. After cooling to room temperature, the preform was transferred to a 2% ethyl silicate ethanol solution at a mass ratio of 19:1 and immersed for 1 hour. It was then calcined at 300°C for 3 hours to obtain a flame-retardant hydrophobic honeycomb matrix E with a contact angle of 49°. Based on a Co content of 280 kg / m³ on the flame-retardant hydrophobic honeycomb matrix E. 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 the flame-retardant hydrophobic honeycomb substrate E was 60 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 loaded, dried again at 150°C for 3 hours, and calcined at 500°C for 5 hours to obtain a flame-retardant, hydrophobic porous substrate-supported non-precious metal catalyst molded body E1 with a surface area of ​​172 m². 2 ·g -1The most probable pore size is 5.9 nm, and the pore volume is 0.40 ml·g. -1 The cross-sectional area of ​​the honeycomb cells is 26mm². 2 .

[0156] Example 6

[0157] 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 a pressure of 5 MPa and a temperature of 25°C 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 calcined at 300°C under N2 conditions for 2 hours. After cooling to room temperature, the preform was transferred to a 1% ethyl silicate ethanol solution at a mass ratio of 20:1 and immersed for 1 hour. It was then calcined at 450°C for 4 hours to obtain a flame-retardant hydrophobic honeycomb matrix F with a contact angle of 51°. The Co content per cubic meter of honeycomb matrix F was 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), based on a Ce content of 58 kg / m³ on each cubic meter of honeycomb substrate F. 3 The Cr content is 33 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, hydrophobic, porous substrate-supported non-precious metal catalyst F1 with a surface area of ​​138 m². 2 ·g -1 The most probable pore size is 6.8 nm, and the pore volume is 0.34 ml·g. -1 The area of ​​the honeycomb holes is 10mm. 2 .

[0158] Example 7

[0159] 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 a pressure of 5 MPa and a temperature of 25°C to produce a preform with square honeycomb cells. The four base sides of the preform were 80 cm long and the height was 100 cm. The honeycomb preform was calcined at 300°C under N2 conditions for 2 hours. After cooling to room temperature, the preform was transferred to a 1% ethyl silicate ethanol solution at a mass ratio of 30:1 and immersed for 1 hour. It was then calcined at 450°C for 4 hours to obtain a flame-retardant hydrophobic honeycomb matrix G with a contact angle of 61°. The Co content on the flame-retardant and hydrophobic honeycomb matrix G is 350 kg / m². 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 the flame-retardant hydrophobic honeycomb matrix G was 42 kg / m³. 3 The vitamin C content is 17 kg / m³. 3 An 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, hydrophobic, porous matrix-supported non-precious metal catalyst G1 with a surface area of ​​201 m². 2 ·g -1 The most probable pore size is 7.3 nm, and the pore volume is 0.47 ml·g. -1 The area of ​​the honeycomb cells is 8.8 mm. 2 .

[0160] Example 8

[0161] Take the flame-retardant and hydrophobic honeycomb substrate G from Example 7. The Co content on each cubic meter of flame-retardant and hydrophobic 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 the flame-retardant hydrophobic honeycomb matrix G was 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 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, hydrophobic, porous matrix-supported non-precious metal catalyst H1 with a surface area of ​​211 m². 2 ·g-1 The most probable pore size is 7 nm, and the pore volume is 0.52 ml·g. -1 The area of ​​the honeycomb cells is 9.1 mm. 2 .

[0162] Example 9

[0163] Take the flame-retardant and hydrophobic honeycomb substrate G from Example 7. The Co content on each cubic meter of flame-retardant and hydrophobic 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 the flame-retardant hydrophobic honeycomb matrix G was 80 kg / m³. 3 The Fe content is 20 kg / m³ 3 An aqueous solution of lanthanum nitrate and ferric 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 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, hydrophobic, porous substrate-supported non-precious metal catalyst I1 with a surface area of ​​187 m². 2 ·g -1 The most probable pore size is 8.7 nm, and the pore volume is 0.42 ml·g. -1 The area of ​​the honeycomb cells is 8.6 mm. 2 .

[0164] Example 10

[0165] Take the flame-retardant and hydrophobic honeycomb substrate G from Example 7. The Co content on each cubic meter of flame-retardant and hydrophobic 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 the flame-retardant hydrophobic honeycomb matrix G was 84 kg / m³. 3 The Ni content is 10 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, hydrophobic, porous substrate-supported non-noble metal catalyst J1 with a surface area of ​​170 m². 2 ·g -1 The most probable pore size is 8.9 nm, and the pore volume is 0.40 ml·g. -1 The area of ​​the honeycomb cells is 8.3 mm. 2 .

[0166] Example 11

[0167] Take the flame-retardant and hydrophobic honeycomb substrate G from Example 7. The Co content on each cubic meter of flame-retardant and hydrophobic honeycomb substrate G is 290 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 the flame-retardant hydrophobic honeycomb matrix 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, hydrophobic, porous matrix-supported non-noble metal catalyst K1 with a surface area of ​​183 m². 2 ·g -1 The most probable pore size is 8.2 nm, and the pore volume is 0.44 ml·g. -1 The area of ​​the honeycomb holes is 8.5mm. 2 .

[0168] Example 12

[0169] Take the flame-retardant and hydrophobic honeycomb substrate G from Example 7. The Co content on each cubic meter of the flame-retardant and hydrophobic 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 the flame-retardant hydrophobic honeycomb matrix 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, hydrophobic, porous matrix-supported non-noble metal catalyst L1 with a surface area of ​​135 m² was obtained. 2 ·g -1 The most probable pore size is 11.1 nm, and the pore volume is 0.32 ml·g. -1 The area of ​​the honeycomb cells is 7.8 mm. 2 .

[0170] Example 13

[0171] Take the flame-retardant and hydrophobic honeycomb substrate G from Example 7. The Co content on each cubic meter of flame-retardant and hydrophobic honeycomb substrate G is 430 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 the flame-retardant hydrophobic honeycomb matrix 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, hydrophobic, porous matrix-supported non-precious metal catalyst M1 with a surface area of ​​143 m² was obtained. 2 ·g -1 The most probable pore size is 9.4 nm, and the pore volume is 0.36 ml·g. -1 The area of ​​the honeycomb cells is 8.2 mm. 2 .

[0172] Example 14

[0173] Take the flame-retardant and hydrophobic honeycomb substrate G from Example 7. The Co content on each cubic meter of flame-retardant and hydrophobic honeycomb substrate G is 430 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 the flame-retardant hydrophobic honeycomb matrix G was 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 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, hydrophobic, porous matrix-supported non-noble metal catalyst N1 with a surface area of ​​148 m². 2 ·g -1 The most probable pore size is 9.3 nm, and the pore volume is 0.36 ml·g. -1 The area of ​​the honeycomb cells is 8.2 mm. 2 .

[0174] Example 15

[0175] Take the flame-retardant and hydrophobic honeycomb substrate G from Example 7. The Co content on each cubic meter of flame-retardant and hydrophobic honeycomb substrate G is 430 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 the flame-retardant hydrophobic honeycomb matrix G was 48 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, hydrophobic, porous matrix-supported non-noble metal catalyst O1 with a surface area of ​​151 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 .

[0176] Example 16

[0177] Take the flame-retardant and hydrophobic honeycomb substrate G from Example 7. The Co content on each cubic meter of flame-retardant and hydrophobic honeycomb substrate G is 280 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 the flame-retardant hydrophobic honeycomb matrix 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, hydrophobic, porous matrix-supported non-noble metal catalyst P1 with a surface area of ​​162 m². 2 ·g -1 The most probable pore size is 8.9 nm, and the pore volume is 0.46 ml·g. -1 The area of ​​the honeycomb cells is 8.6 mm. 2 .

[0178] Example 17

[0179] 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 5MPa to produce a preform with square honeycomb cells. The four base sides of the preform were 80cm and the height was 100cm. The honeycomb preform was calcined at 300°C under N2 conditions for 2 hours. After cooling to room temperature, the preform was transferred to a 1% ethyl silicate ethanol solution at a mass ratio of 15:1 and immersed for 1 hour. It was then calcined at 400°C for 4 hours to obtain a flame-retardant hydrophobic honeycomb matrix Q with a contact angle of 49°. Based on a Co content of 280 kg / m³ on the flame-retardant hydrophobic honeycomb matrix Q. 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 the flame-retardant hydrophobic honeycomb matrix H 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 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, hydrophobic, porous matrix-supported non-precious metal catalyst Q1 with a surface area of ​​152 m². 2 ·g -1 The most probable pore size is 8.4 nm, and the pore volume is 0.40 ml·g. -1 The area of ​​the honeycomb cells is 8.2 mm. 2 .

[0180] Comparative Example 1

[0181] Unlike the preparation of the hydrophobic and flame-retardant honeycomb matrix in Example 7, 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 into a plastic contact body. This contact body was loaded into an extruder and extruded at 25°C and 5MPa to form a preform with square honeycomb cells. The four base sides and height of the preform were 80cm and 100cm, respectively. The honeycomb preform was calcined at 450°C for 4 hours under N2 conditions to obtain the flame-retardant non-hydrophobic honeycomb matrix G' with a contact angle of 17°. The Co content on each cubic meter of the flame-retardant non-hydrophobic honeycomb matrix G' was 280 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 the flame-retardant non-hydrophobic honeycomb matrix 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. A 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, non-hydrophobic, porous matrix-supported non-precious metal catalyst R1 with a surface area of ​​169 m². 2 ·g -1 The most probable pore size is 8.2 nm, and the pore volume is 0.48 ml·g. -1 The area of ​​the honeycomb cells is 8.7 mm. 2 .

[0182] Example 18

[0183] The flame-retardant hydrophobic catalysts from 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 VOCs gas (water content 20 mg / m³) 3 At a reaction temperature of 380℃ 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.

[0184] Table 1 Comparison of reaction performance of flame-retardant hydrophobic catalysts

[0185] catalyst <![CDATA[Concentration of VOCs at the outlet after 1-hour reaction (mg / m 3 )]]> <![CDATA[Concentration of VOCs at the outlet after 500 h of reaction (mg / m 3 )]]> <![CDATA[VOCs concentration at the outlet after 1000h of reaction (mg / m 3 )]]> A1 14.3 14.5 15.1 B1 21.3 22.1 23.2 C1 22.8 23.5 25.3 D1 23.6 24.4 26.6 E1 22.8 23.3 23.8 F1 19.6 20.1 20.5 G1 17.2 17.5 18.2 H1 14.9 15.8 16.4 I1 21.1 21.8 22.4 J1 16.7 17.1 17.7 K1 10.4 10.7 11.6 L1 6.4 6.5 6.7 M1 5.1 5.5 5.7 N1 6.2 6.7 6.9 O1 7.1 7.6 8.2 P1 6.3 6.3 6.8 Q1 7.0 7.4 8.2 R1 7.1 7.6 8.5

[0186] As shown in Table 1, the flame-retardant, hydrophobic, 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, catalysts not of the present invention show a faster decline in catalytic activity after prolonged use.

[0187] Example 19

[0188] Metal element analysis was performed on the catalysts in Example 16 and Comparative Example 1, and elemental analysis was also performed on the catalysts after 1000 hours of reaction to treat VOCs gas. The metal content per unit porous matrix volume is shown in Table 2.

[0189] Table 2 Key elemental analysis of catalysts supported on porous substrates after catalytic reaction

[0190] .

[0191] 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 detach even after long-term use.

[0192] Example 20

[0193] The catalysts from Example 16 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 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.

[0194] Table 3 Key elemental analysis of catalysts supported on porous substrates after catalytic reaction

[0195] .

[0196] 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.

[0197] 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, hydrophobic, porous matrix supported non-precious metal catalyst, characterized in that, The catalyst contains a flame-retardant hydrophobic porous matrix, a Co component supported on the flame-retardant hydrophobic porous matrix, and an auxiliary 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 / m³. 3 , The porous matrix contains an original matrix of attapulgite and kaolin, a molecular sieve as an inorganic material, and calcined oxide as a hydrophobic modifying material. The molecular sieve is selected from any one of Y 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 original matrix is ​​10~99.5% by mass, the content of the calcined oxide as a hydrophobic modifying material is 0.05~1% by mass, the content of the inorganic material is 0.5~90% by mass, the sum of the masses of all components in the porous matrix is ​​100%, and the contact angle between the porous matrix and water is 40~90°. The hydrophobic modified material is selected from at least one of methyl silicate, ethyl silicate, propyl silicate, butyl silicate, silicon tetrachloride, sodium silicate, methyl titanate, ethyl titanate, propyl titanate, butyl titanate, titanium chloride, methyl aluminate, ethyl aluminate, propyl aluminate, and aluminum chloride.

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

3. The catalyst according to claim 1 or 2, wherein, The catalyst has a BET specific surface area of ​​100~800 m². 2 ·g -1 The most probable pore size is 2~12 nm, and the pore volume is 0.15~1.0 mL·g. -1 .

4. The catalyst according to claim 1 or 2, wherein the catalyst is shaped into a catalyst body with the appearance of 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, the cross-sectional area of ​​the macroscopic channels being 1 mm². 2 ~80mm 2 The hole wall thickness is 1~4mm.

5. 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.

6. The catalyst according to claim 1 or 2, wherein, It must satisfy at least one of the following characteristics: 1) The auxiliary component is 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, based on the highest oxidation state of the oxide of the metal and the ratio of the former to the sum of the masses of the latter two. 2) 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 ; 3) Based on the total mass of the porous matrix, the content of the original matrix is ​​20-99% by mass, the content of the calcined oxide of the hydrophobic modified material is 0.05-0.5% by mass, the content of the inorganic material is 1-80% by mass, and the sum of the masses of all components in the porous matrix is ​​100%. 4) The contact angle between the porous matrix and water is 45~70°. 5) The BET specific surface area of ​​the catalyst is 110~800m². 2 ·g -1 The most probable pore size is 2~10 nm, and the pore volume is 0.2~1.0 mL·g. -1 ; 6) The catalyst is shaped into a catalyst body with the appearance of spheres, cubes, cuboids, cylinders, or Raschig rings. The shaped body has one or more macroscopic channel structures selected from circles, squares, triangles, hexagons, or rhombuses, and the cross-sectional area of ​​the macroscopic channels is 1 mm². 2 ~40mm 2 The hole wall thickness is 1~2.5mm; 7) The catalyst has a positive pressure strength of 2~6MPa and a lateral pressure strength of 0.2~2MPa.

7. A method for preparing the flame-retardant, hydrophobic, 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 in step (1) or the porous matrix preform in step (2) is calcined in an inert gas and then further contacted with a solution containing hydrophobic modifying material to obtain a modified preform. (4) The modified preform is further calcined to obtain a flame-retardant hydrophobic porous matrix; (5) 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 hydrophobic porous matrix to obtain a contact product; and (6) Calcining the contact product to obtain the flame-retardant hydrophobic porous matrix supported non-precious metal catalyst; or, (1') After contacting the original matrix of attapulgite and kaolin, and the molecular sieve as an inorganic material with a solution containing hydrophobic modifying material, respectively, they are calcined to obtain the modified original matrix and the modified inorganic material. (2') The modified original matrix, the modified inorganic material, the adhesive solvent, and water are mixed and brought into contact to form a plastic mixed modified contact body; wherein, relative to the total amount of the modified original matrix and the modified inorganic material, the content of the modified original matrix is ​​10~99.5% by mass, and the content of the modified inorganic material is 0.5~90% by mass. (3') Optionally, the plastic mixed-modified contact body is molded to obtain a porous matrix-modified preform; and (4') The plastic mixed modified contact body in step (2') or the porous matrix modified preform in step (3') is further calcined to obtain a flame-retardant hydrophobic porous matrix; (5') 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 hydrophobic porous matrix to obtain a contact product; and (6') Calcining the contact product to obtain the flame-retardant hydrophobic porous matrix supported non-precious metal catalyst; in: The hydrophobic modifying material is selected from at least one of methyl silicate, ethyl silicate, propyl silicate, butyl silicate, silicon tetrachloride, sodium silicate, methyl titanate, ethyl titanate, propyl titanate, butyl titanate, titanium chloride, methyl aluminate, ethyl aluminate, propyl aluminate, and aluminum chloride. 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 the combination of La and Mn with V.

8. The preparation method according to claim 7, 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.

9. The preparation method according to claim 7 or 8, wherein, In step (1'), calcination is carried out in an inert gas at a temperature of 200~550℃; in step (3), the calcination temperature is 200~580℃; in steps (4) and (4'), the calcination temperature is 200~580℃; in step (6), the calcination temperature is 200~550℃.

10. The preparation method according to claim 7 or 8, further comprising, prior to at least one of the roasting in step (3), step (4), step (1'), and step (4'), a heat treatment step is performed on the material to be roasted, said heat treatment being performed at 20 to 150°C.

11. The preparation method according to claim 7 or 8, 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, is 0.2 to 5, calculated as the ratio of the former to the sum of the latter two. 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.

12. The preparation method according to claim 7 or 8, wherein, 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.

13. The catalyst according to claim 7 or 8, wherein, It must satisfy at least one of the following characteristics: 1) 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 1~80% by mass, and the sum of the mass of the original matrix and the inorganic material is 100%; 2) 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; 3) In step (1'), calcination is carried out in an inert gas at a temperature of 250~500℃; in step (3), the calcination temperature is 300~500℃; in steps (4) and (4'), the calcination temperature is 300~550℃; in step (6), the calcination temperature is 250~500℃. 4) In each combination, the mass ratio of each element is calculated based on the highest oxidation state of the metal oxide, either by the former to the latter or by the former to the sum of the masses of the latter two, and is 0.2 to 5. 5) Before at least one of the roasting in step (3), step (4), step (1'), and step (4'), the material to be roasted is subjected to a heat treatment step, wherein the heat treatment is performed at 50~100°C. 6) 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 .

14. The flame-retardant hydrophobic porous matrix supported non-precious metal catalyst according to any one of claims 1-6 or the flame-retardant hydrophobic porous matrix supported non-precious metal catalyst prepared by any one of claims 7-13 is used for the catalytic oxidation of volatile organic compounds.

15. The application according to claim 14, 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 supported on flame-retardant and hydrophobic porous matrices at temperatures ranging from 150 to 450°C.

16. The flame-retardant hydrophobic porous matrix supported non-precious metal catalyst according to any one of claims 1-6 or the flame-retardant hydrophobic porous matrix supported non-precious metal catalyst prepared by any one of claims 7-13 is used for the catalytic oxidation of wastewater to reduce chemical oxygen demand (COD).

17. The application according to claim 16, 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 flame-retardant hydrophobic porous matrix supported non-precious metal catalyst is contacted.