CN114797953A - Flame-retardant hydrophobic porous matrix supported non-noble metal catalyst, preparation method and application thereof - Google Patents

Flame-retardant hydrophobic porous matrix supported non-noble metal catalyst, preparation method and application thereof Download PDF

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CN114797953A
CN114797953A CN202110086468.7A CN202110086468A CN114797953A CN 114797953 A CN114797953 A CN 114797953A CN 202110086468 A CN202110086468 A CN 202110086468A CN 114797953 A CN114797953 A CN 114797953A
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flame
mass
catalyst
porous matrix
modified
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刘经伟
朱伟
孟杰
李泽壮
徐骏
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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Abstract

The invention relates to a flame-retardant hydrophobic porous matrix supported non-noble metal catalyst, a preparation method and application thereof. The preparation method of the flame-retardant hydrophobic porous matrix supported non-noble metal catalyst is simple, high in mechanical strength and strong in water-resistant thermal stability, has the advantages of good catalytic performance of volatile organic compounds, long service life and the like in the treatment of moisture-containing VOCs, and can be applied to catalytic wet oxidation of wastewater.

Description

Flame-retardant hydrophobic porous matrix supported non-noble metal catalyst, preparation method and application thereof
Technical Field
The invention relates to a flame-retardant hydrophobic porous matrix supported non-noble metal catalyst. More particularly, the invention relates to a flame-retardant hydrophobic porous matrix supported non-noble metal catalyst and a preparation method thereof. The invention also relates to application of the flame-retardant hydrophobic porous matrix supported non-noble metal catalyst in catalytic oxidation treatment of volatile organic compounds (VOCs or VOC) and high Chemical Oxygen Demand (COD) wastewater.
Background
With the increasing national requirements for environmental protection in recent years, recovery technologies such as adsorption, absorption, condensation, membrane separation, high-temperature incineration, and catalytic oxidation have been widely used for recovery/treatment of various waste gases containing Volatile Organic Compounds (VOCs). Wherein the adsorption method is suitable for 500-3000 h -1 Removing low concentration volatile organic pollutant in waste gas at low space velocityAnd (2) treating, specifically, adsorbing high-boiling-point components (more than C5) on the surface or pore channels of the porous matrix in an adsorption and interception mode, wherein the process hardly generates chemical reaction, the matrix after adsorption saturation needs to be regenerated and desorbed to obtain the re-adsorption performance, and the service cycle of the matrix is treated as dangerous solid waste after 1-2 years. The absorption method is based on the principle of similar phase and adopts a high-boiling point solvent (such as low-temperature diesel oil) to absorb high-boiling point components in VOCs to form a rich solution, and the rich solution is desorbed and then returns to a system for absorption again. The condensation method is a process of condensing organic substances into liquid by cooling and/or pressurizing according to different saturated vapor pressures of the organic substances at different temperatures, and removing and purifying the liquid from a gas phase. The membrane separation process can adopt organic polymeric membranes, inorganic membranes and biological membranes, but the membrane materials have the defects of low flux, poor selectivity, unsuitability for high space velocity treatment and the like. The high-temperature incineration has high requirement on the temperature, generally exceeds 800 ℃, although the high-temperature incineration can reach the standard for treatment, a large amount of auxiliary inflammable gas such as natural gas needs to be supplemented to keep the temperature of combustion, and the energy consumption is high.
Compared with the above methods, the catalytic oxidation method causes the organic waste gas to generate flameless combustion under the action of the catalyst, has the advantages of high selectivity, low reaction temperature and the like, the reaction temperature is generally lower than 500 ℃, and the product is nontoxic CO 2 And H 2 O, catalytic Oxidation non-methane Total hydrocarbons in volatile organics suitable for processing are generally above 500mg/m 3 . The most central of catalytic oxidation is a catalyst, which is divided into a noble metal catalyst and a transition metal oxide catalyst. Noble metal catalysts have the advantages of high activity, low light-off temperature, good stability, long service life and the like, but are expensive and not suitable for treating organic gases containing sulfur. The non-noble metal mainly takes transition metal oxide as a main component, and has better anti-poisoning performance and oxidation activity, but the catalyst has the defects of short service life, low activity, high ignition temperature and the like. ZL200510060542.9 discloses a preparation method of a rare earth composite porous alumina supported palladium catalyst, which takes honeycomb matrix ceramic as a carrier, adopts a sol dip coating method to coat hydrated alumina, a thermal adsorption method to support cerium-zirconium oxide and a supported metal palladium active component, and is in the range of 10000-30000h -1 Under the space velocity, the complete oxidation temperatures of the catalyst for toluene and ethyl acetate are 180-200 ℃ and 260-280 ℃, respectively, but the patent does not mention the influence of bromide on the activity and the service life of the catalyst. US4983366 discloses a process for the catalytic conversion of exhaust gases containing hydrocarbons and carbon monoxide and a related purification unit by passing the exhaust gases over a zeolite containing alumina, silica and/or oxides or barium, manganese, copper, chromium and nickel and over a catalyst containing platinum and/or palladium or rhodium, which is particularly suitable for treating the exhaust gases from vinyl chloride production units, but which does not mention the effect of a high strength substrate on the life of the noble metal catalyst. CN95197182.4 discloses a catalyst and a method for treating a gas containing halogenated organic compounds, non-halogenated organic compounds, carbon monoxide or a mixture thereof, the catalyst being characterized by containing at least one platinum group metal, zirconium oxide and at least one oxide of manganese, cerium or cobalt. CN200610047791.9 provides a method for purifying organic waste gas, especially for purifying organic waste gas containing acetaldehyde, ethylene glycol and PTA dust, such as polyester waste gas treatment method, wherein catalytic combustion adopts platinum, palladium or CuO, MnO containing 2 The honeycomb catalyst of (1). The clariant corporation in CN201810125199.9 discloses low cost ruthenium oxide based catalysts for VOC and halogenated VOC emission control, which catalysts include noble metals platinum based metals such as ruthenium and platinum, cerium zirconium solid solution, and tin oxide and silicon oxide, among other components. According to reports, the Envicat VOC catalyst developed by Craine has high efficiency of removing harmful Volatile Organic Compounds (VOCs) and carbon monoxide (CO), and simultaneously, the thermal energy consumption can be saved by 40 percent. CN201410455174.7 describes a catalyst comprising iron oxide, cobaltosic oxide, nickel oxide, copper oxide, vanadium oxide, chromium oxide, manganese dioxide or cerium oxide as non-noble metal oxide components, which are coated on a carrier to prepare a catalytic combustion catalyst for methane and other VOC gases. ZL201710256841.2 describes the method of loading more than two metals of Mg, Ti, Mn, Co, Cu, La, Ce and Zr on attapulgite, kneading and extruding after roasting, however, the metal loading of the catalyst is large, the cost is high, and the treatment of VOCs is usually carried outThe surface reacts rapidly and the active component inside the catalyst cannot function. CN201911113364.X introduces a catalyst which takes cordierite porous ceramic as a substrate and is coated with a Cu-Mn-Ce composite oxide coating, wherein the Cu-Mn-Ce composite oxide is prepared by taking ethylenediamine as a precipitator through a hydrothermal method.
In the above patent publications, alumina and titania are used as primary coating components in the catalyst coating process, and then active metal or active metal oxide is loaded, the stability of the coating not only affects the service life of the catalyst, but also the pressure drop of the fixed bed layer is increased and uncontrollable reaction factors are increased due to pulverization of the cracked and fallen coating. Therefore, much attention has been paid to the development of a catalyst which has good thermal stability, high strength and good effect of supporting an active metal or an active metal oxide as a matrix (carrier).
Attapulgite clay (Attapulgite), also called Palygorskite (Palygorskite), is Attapulgite for short, is a natural hydrated clay material with a layered chain structure and rich in magnesium aluminum silicate, the basic structural unit is a sandwich structure of two layers of silicon-oxygen tetrahedron and one layer of magnesium (aluminum) oxygen octahedron, and the most ideal unit cell molecular formula is (Mg) 5 Si 8 O 20 (OH) 2 (OH 2 ) 4 ·4H 2 And O. The attapulgite clay has higher specific surface area, open meso-microporous composite pore canals and good thermal stability, and is mixed with molecular sieve and SiO 2 、Al 2 O 3 Similar to other materials, the materials all belong to inorganic mineral materials, have good adhesion performance and play a good role in enhancing and toughening organic and inorganic materials.
Disclosure of Invention
In view of the technical problems in the prior art, the present inventors have assiduously studied on the basis of the prior art, and as a result, have found that a flame-retardant hydrophobic porous matrix-supported non-noble metal catalyst (hereinafter, sometimes also referred to simply as "flame-retardant hydrophobic porous matrix-supported catalyst" or "catalyst of the present invention" or "catalyst") according to the present invention can be prepared by using at least one selected from the group consisting of attapulgite and kaolin as an original matrix, further compounding an appropriate inorganic porous solid, and treating the original matrix with a hydrophobic modifier, and further supporting a cobalt metal component and an auxiliary component as catalyst active components on the matrix. The flame-retardant hydrophobic porous matrix supported non-noble metal catalyst has good VOCs catalytic performance and high COD wastewater degradation performance, thereby completing the invention.
Specifically, the invention provides a flame-retardant hydrophobic porous matrix supported non-noble metal catalyst, which is characterized by comprising a flame-retardant hydrophobic porous matrix, a Co component and an auxiliary agent component which are supported on the flame-retardant hydrophobic porous matrix,
wherein the auxiliary component is at least one selected from the group A elements, the auxiliary is preferably selected from at least one 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, La and Bi, further preferably selected from 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, La and Mn and Bi, the mass ratio (in terms of the highest oxidation state oxide of the metal) of each element in each combination is 0.1 to 10, preferably 0.2 to 5,
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;
based on the total volume of the porous matrix supported non-noble metal catalyst, the content of Co metal (calculated by cobaltosic oxide) is 50-500 kg/m 3 Preferably 50 to 430kg/m 3 The content of the auxiliary component (calculated by the oxide in the highest oxidation state of the auxiliary component) is 10-180 kg/m 3 Preferably 10 to 150kg/m 3 ，
The porous matrix contains at least one original matrix selected from attapulgite and kaolin, at least one inorganic material selected from inorganic porous solids, and a roasted oxide of a hydrophobic modified material, wherein the content of the original matrix is 10-99.5 mass%, preferably 20-99 mass%, the content of the roasted oxide of the hydrophobic modified material is 0.05-1 mass%, preferably 0.05-0.5 mass%, the content of the inorganic material is 0.5-90 mass%, preferably 1-80 mass%, more preferably 5-80 mass%, further preferably 8-70 mass%, and further preferably the balance, and the contact angle of the porous matrix and water is 40-90 °, preferably 45-70 °.
The invention also provides a preparation method of the flame-retardant hydrophobic porous matrix supported non-noble metal catalyst, which is characterized by comprising the following steps of:
(1) mixing and contacting at least one original matrix selected from attapulgite and kaolin, at least one inorganic material selected from inorganic porous solids, peptizing agent and water to prepare a plastic mixed contact body; wherein the content of the original matrix is 10 to 99.5 mass%, preferably 20 to 99 mass%, and the content of the inorganic material is 0.5 to 90 mass%, preferably 1 to 80 mass%, more preferably 5 to 80 mass%, further preferably 8 to 70 mass%, and further preferably the balance, with respect to the total amount of the original matrix and the inorganic material;
(2) optionally, molding the plastic mixed contact body to obtain a porous matrix blank;
(3) roasting the mixed contact body in the step (1) or the porous matrix blank in the step (2) in inert gas, and then further contacting with a solution containing a hydrophobic modifier to obtain a modified blank;
(4) further roasting the modified blank body to prepare 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 the flame-retardant hydrophobic porous matrix to obtain a contact product; and
(6) roasting the contact product to obtain the flame-retardant hydrophobic porous matrix supported catalyst;
or,
(1') 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, respectively, and then calcining the resulting mixture to obtain a modified original matrix and a modified inorganic material;
(2') mixing and contacting the modified original matrix and the modified inorganic material with a peptizing agent and water to prepare a plastic mixed modified contact body; wherein the content of the modified original matrix is 10 to 99.5 mass%, preferably 20 to 99 mass%, and the content of the inorganic material is 0.5 to 90 mass%, preferably 1 to 80 mass%, more preferably 5 to 80 mass%, further preferably 8 to 70 mass%, and further preferably the balance, with respect to the total amount of the modified original matrix and the modified inorganic material;
(3') optionally carrying out molding processing on the plastic mixed modified contact body to obtain a porous matrix modified green body;
(4') further roasting the mixed modified contact body in the step (2') or the modified blank body in the step (3') to prepare 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 the flame-retardant hydrophobic porous matrix to obtain a contact product; and
(6) and roasting the contact product to obtain the flame-retardant hydrophobic porous matrix supported catalyst.
The invention also provides application of the flame-retardant hydrophobic porous matrix supported catalyst in catalytic oxidation of volatile organic compounds.
The invention also provides application of the flame-retardant hydrophobic porous matrix supported catalyst in catalytic oxidation of wastewater containing high COD.
Technical effects
The preparation method of the flame-retardant hydrophobic porous matrix supported catalyst is simple, does not need vacuum pugging and microwave heat treatment, and is low in cost.
The flame-retardant hydrophobic porous matrix supported catalyst has good hydrothermal property, can be used for treating VOCs with high water vapor content and wastewater with high COD (chemical oxygen demand), and keeps excellent stability.
In the flame-retardant hydrophobic porous matrix supported catalyst, the supported metal and the porous matrix have strong interaction, so that coating loading on the porous matrix is not needed, metal components are not easy to fall off, and the service life of the catalyst is long.
In addition, due to the porosity of the flame-retardant hydrophobic porous matrix supported catalyst, active components can be in full contact with VOCs, so that catalytic treatment of the VOCs is facilitated, in addition, the catalyst can be in full contact with high-COD substances in wastewater, so that catalytic wet oxidation is facilitated, and COD is reduced.
Detailed Description
Embodiments of the present invention will be described in more detail below with reference to specific embodiments, but those skilled in the art will understand that the following description of the embodiments is only for illustrating the present invention and should not be construed as limiting the scope of the present invention. On the contrary, the invention is intended to cover all alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims.
Unless otherwise specified, the embodiments of the present invention may be combined in any manner, and the resulting changes, modifications, and alterations of the technical solutions are also included in the scope of the present invention, and do not exceed the scope of the present invention.
The invention provides a flame-retardant hydrophobic porous matrix supported non-noble metal catalyst, which is characterized by comprising a flame-retardant hydrophobic porous matrix, a Co component and an auxiliary agent component which are supported on the flame-retardant hydrophobic porous matrix,
wherein the auxiliary component is at least one selected from the group A elements, the auxiliary is preferably selected from at least one 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, La and Bi, further preferably 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, La and Mn and Bi,
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;
based on the total volume of the non-noble metal supported porous matrix catalyst,
the content of Co metal (calculated by cobaltosic oxide) is 50-500 kg/m 3 Preferably 50 to 430kg/m 3 The content of the auxiliary component (calculated by the oxide in the highest oxidation state of the auxiliary component) is 10-180 kg/m 3 Preferably 10 to 150kg/m 3 ，
The porous matrix contains at least one original matrix selected from attapulgite and kaolin, at least one inorganic material selected from inorganic porous solids, and a roasted oxide of a hydrophobic modified material, wherein the content of the original matrix is 10-99.5 mass%, preferably 20-99 mass%, the content of the roasted oxide of the hydrophobic modified material is 0.05-1 mass%, preferably 0.05-0.5 mass%, the content of the inorganic material is 0.5-90 mass%, preferably 1-80 mass%, more preferably 5-80 mass%, further preferably 8-70 mass%, and further preferably the balance, and the contact angle of the porous matrix and water is 40-90 °, preferably 45-70 °.
In one embodiment of the invention, the porous matrix consists essentially of the original matrix, the calcined oxide of the hydrophobically modified material, and the inorganic material. In one embodiment of the invention, the porous matrix consists only of the original matrix, the calcined oxide of the hydrophobically modified material, and the inorganic material.
In one embodiment of the present invention, the content of the original matrix is 10 to 99.5 mass%, preferably 20 to 99 mass%, based on the total mass of the porous matrix.
In one embodiment of the present invention, the content of the calcined oxide of the hydrophobically modified material is 0.05 to 1 mass%, preferably 0.05 to 0.5 mass%, based on the total mass of the porous matrix.
In one embodiment of the present invention, the inorganic material is contained in an amount of 0.5 to 90 mass%, preferably 1 to 80 mass%, more preferably 5 to 80 mass%, further preferably 8 to 70 mass%, and further preferably the balance, based on the total mass of the porous substrate.
In the present invention, as the attapulgite, known attapulgite in the art may be used, and commercially available attapulgite may be used. The kaolin may be kaolin known in the art, which may be commercially available.
In the present invention, the inorganic porous solid may be a refractory oxide of a metal of group IIA, IIIA, IVA or IVB of the periodic table of elements (for example, silica (also referred to as silica or silica gel), alumina, magnesia, titania, zirconia, thoria, or the like), or any refractory composite oxide of these metals (for example, silica alumina, magnesia-alumina, titania-silica, titania-magnesium, titania-alumina, or the like), clay, molecular sieve, mica, montmorillonite, bentonite, diatomaceous earth, or the like.
In one embodiment of the present invention, the inorganic porous solid is preferably at least one selected from the group consisting of silica, alumina, magnesia, silica alumina, magnesia alumina, titania silica, titania, a molecular sieve, and montmorillonite.
In the present invention, the molecular sieve may use a molecular sieve known in the art, for example, the molecular sieve may be selected from one or a combination of two or more of a type a molecular sieve, a type X molecular sieve, a type Y molecular sieve, a ZSM series, SAPO, AIPO, mordenite molecular sieve, SBA, MCM.
In the present invention, various inorganic materials known in the art can be used for silica, alumina, magnesia, silica-alumina, magnesia-alumina, titania-silica, titania, a molecular sieve and montmorillonite, and they can be produced by a known method or any commercially available product.
In the present invention, various hydrophobically modified materials known in the art can be used as the hydrophobically modified material. In the present invention, the hydrophobic modification material is preferably a silicon source modification material or a metal compound modification material. Wherein, the silicon source modified material can be one or a combination of a plurality of methyl silicate, ethyl silicate, propyl silicate, butyl silicate, (tetra) silicon chloride and sodium silicate.
The metal compound-modifying material may be selected from a titanium source-modifying material and/or an aluminum source-modifying material. The titanium source modified material can be titanate or titanium halide, and can be selected from one or more of methyl titanate, ethyl titanate, propyl titanate, butyl titanate and titanium chloride. The aluminum source modified material can be aluminate or aluminum halide, and can be one or more of methyl aluminate, ethyl aluminate, propyl aluminate, butyl aluminate and aluminum chloride.
In one embodiment of the invention, the BET specific surface area of the flame-retardant hydrophobic porous matrix supported catalyst is 100-800 m 2 ·g -1 Preferably 110 to 800m 2 ·g -1 The most probable pore diameter is 2 to 12 nm, preferably 2 to 10nm, and the pore volume is 0.15 to 1.0 ml/g -1 Preferably 0.2 to 1.0 ml/g -1 。
In one embodiment of the present invention, the catalyst may be molded into a macroscopic catalyst molded body having an appearance of a sphere, a cube, a cuboid, a cylinder, a raschig ring, or the like.
In one embodiment of the present invention, when the catalyst molded body is molded, the catalyst molded body may have macro pores thereon, and the macro pores may have one or more pore structures of a circular, square, triangular, hexagonal or rhombic shape. The arrangement of these macroscopic channels on the catalyst shaped body can be ordered or disordered, preferably uniformly ordered, honeycomb channels. In general, to reduce the adsorption resistance, the macroscopic pores of the catalyst molded body are open.
In one embodiment of the present invention, the cross-sectional area of the macropores in the catalyst molded body is 1mm 2 ~80mm 2 Preferably 1mm 2 ~40mm 2 . The thickness of the hole wall is 1-4 mm, preferably 1-2.5 mm.
In one embodiment of the present invention, the catalyst has a positive pressure strength of 2 to 8MPa, preferably 2 to 6MPa, and a side pressure strength of 0.1 to 2MPa, preferably 0.2 to 2MPa, measured according to the GB/T5072-2008 standard method.
The porous matrix may optionally further contain other auxiliary agents without impairing the effects of the present invention, and examples of the auxiliary agents include various metal oxides other than the above-mentioned inorganic materials, various inert organic porous solids, and the like. The amount of the adjuvant used is 5 to 30% of the total mass of the porous matrix.
In the present invention, without being bound by any theory, the inventors believe that after all the raw material components of the porous matrix are made into a green body, a hydrophobic modification treatment is performed with a hydrophobic modification material immediately before firing to make the final porous matrix; or after all raw material components of the porous matrix are subjected to hydrophobic modification treatment by using a hydrophobic modification material, a modified blank is prepared, and then roasting is carried out, so that a roasted oxide (hydrophobic layer) of the hydrophobic modification material is formed on the surface of the finally prepared porous matrix, and a certain hydrophobicity is given to the porous matrix.
In addition, in the present invention, since the hydrophobic layer is a very thin layer, the weight of the hydrophobic layer is low relative to the porous substrate itself, and the content of the baked oxide of the hydrophobic modification material is usually 0.05 to 1 mass%, preferably 0.05 to 0.5 mass%, based on the total mass of the porous substrate.
In the invention, the flame-retardant hydrophobic porous matrix is subjected to hydrophobic modification treatment so that the content of a calcined oxide in the hydrophobic modified material is 0.05-1 mass%, preferably 0.05-0.5 mass%, thereby endowing the porous matrix with certain hydrophobicity, and when the contact angle of water on the surface of the porous matrix is used as an index of hydrophobicity and is measured according to a GB/T36086-2018 method, the contact angle of the porous matrix and the water is 40-90 degrees, preferably 45-70 degrees.
In one embodiment of the invention, the catalyst consists essentially of a flame-retardant hydrophobic porous matrix, a Co component supported on the porous matrix, and an auxiliary agent.
In one embodiment of the present invention, the catalyst consists of only a flame-retardant hydrophobic porous substrate, a Co component supported on the porous substrate, and an auxiliary. In one embodiment of the invention, the catalyst does not contain carbonaceous materials (including but not limited to activated carbon, carbon fibers, etc.).
In one embodiment of the invention, the adjuvant component is at least one selected from the group consisting of group a elements, 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.
In one embodiment of the present invention, the auxiliary agent is preferably at least one selected from the group consisting of a combination of Ce and Mo, a combination of Ce and Mn, a combination of Ce and Fe, a combination of Ce and Ni, a combination of Ce and Bi, a combination of Ce and Ti, a combination of Ce and Cr, a combination of Ce and V, a combination of La and Mn, a combination of La and Fe, a combination of La and Ni, and a combination of La and Bi, and further preferably at least one selected from the group consisting of a combination of Ce and Mn and Ti, a combination of Ce and Mn and V, a combination of Ce and Mn and Bi, a combination of Ce and Mn and Cr, a combination of La and Mn and Ti, a combination of La and Mn and V, and a combination of La and Mn and Bi. In one embodiment of the present invention, the mass ratio of the elements in each combination is 0.1 to 10, preferably 0.2 to 5, in terms of the oxide in the highest oxidation state of the metal, from the former to the latter (or from the former to the latter).
In one embodiment of the present invention, the content of Co metal (calculated as cobaltosic oxide) is 50 to 500kg/m based on the total volume of the non-noble metal catalyst supported on the porous substrate 3 Preferably 50 to 430kg/m 3 。
In one embodiment of the invention, the content of the auxiliary component (calculated by the oxide in the highest oxidation state of the auxiliary component) is 10-180 kg/m based on the total volume of the non-noble metal catalyst supported by the porous matrix 3 Preferably 10 to 150kg/m 3 。
The invention also provides a preparation method of the flame-retardant hydrophobic porous matrix supported non-noble metal catalyst, which is characterized by comprising the following steps of:
(1) mixing and contacting at least one original matrix selected from attapulgite and kaolin, at least one inorganic material selected from inorganic porous solids, peptizing agent and water to prepare a plastic mixed contact body; wherein the content of the original matrix is 10 to 99.5 mass%, preferably 20 to 99 mass%, and the content of the inorganic material is 0.5 to 90 mass%, preferably 1 to 80 mass%, more preferably 5 to 80 mass%, further preferably 8 to 70 mass%, and further preferably the balance, with respect to the total amount of the original matrix and the inorganic material;
(2) optionally, molding the plastic mixed contact body to obtain a porous matrix blank;
(3) roasting the mixed contact body in the step (1) or the porous matrix blank in the step (2) in inert gas, and then further contacting with a solution containing a hydrophobic modifier to obtain a modified blank;
(4) further roasting the modified blank body to prepare 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 the flame-retardant hydrophobic porous matrix to obtain a contact product; and
(6) roasting the contact product to obtain the flame-retardant hydrophobic porous matrix supported catalyst;
or,
(1') 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, respectively, and then calcining the resulting mixture to obtain a modified original matrix and a modified inorganic material;
(2') mixing and contacting the modified original matrix and the modified inorganic material with a peptizing agent and water to prepare a plastic mixed modified contact body; wherein the modified original matrix is contained in an amount of 10 to 99.5 mass%, preferably 20 to 99 mass%, and the modified inorganic material is contained in an amount of 0.5 to 90 mass%, preferably 1 to 80 mass%, more preferably 5 to 80 mass%, further preferably 8 to 70 mass%, and further preferably the balance, with respect to the total amount of the modified original matrix and the modified inorganic material;
(3') optionally carrying out molding processing on the plastic mixed modified contact body to obtain a porous matrix modified green body; and
(4') further roasting the mixed modified contact body in the step (2') or the modified blank body in the step (3') to prepare 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 the flame-retardant hydrophobic porous matrix to obtain a contact product; and
(6) and roasting the contact product to obtain the flame-retardant hydrophobic porous matrix supported catalyst.
In one embodiment of the present invention, in the steps (1) and (1') of the above-mentioned preparation method, at least one original matrix selected from the group consisting of attapulgite and kaolin is not subjected to any pretreatment.
In the preparation method of the present invention, the attapulgite known in the art may be used, and may be a commercially available attapulgite. The kaolin may be kaolin known in the art, which may be commercially available.
In the preparation method of the present invention, in the above steps (1) and (1'), the inorganic porous solid may be a refractory oxide of a metal of group IIA, IIIA, IVA or IVB of the periodic table of elements (for example, silica (also referred to as silica gel or silica gel), alumina, magnesia, titania, zirconia, thoria, or the like), or any refractory composite oxide of these metals (for example, silica alumina, magnesia alumina, titania silica, titania magnesium, titania alumina, or the like), clay, molecular sieve, mica, montmorillonite, bentonite, diatomaceous earth, or the like.
In one embodiment of the present invention, the inorganic porous solid is preferably at least one selected from the group consisting of silica, alumina, magnesia, silica alumina, magnesia alumina, titania silica, titania, a molecular sieve, and montmorillonite.
The molecular sieve may use a molecular sieve known in the art, for example, the molecular sieve may be selected from one or a combination of two or more of a type a molecular sieve, a type X molecular sieve, a type Y molecular sieve, a ZSM series, a SAPO, an AIPO, a mordenite molecular sieve, an SBA, and an MCM. Silica, alumina, magnesia, silica alumina, magnesia-alumina, titania-silica, molecular sieves and montmorillonite can be made of various materials known in the art by known methods, or any commercially available product.
In the step (1'), the original substrate and the inorganic material after being brought into contact with the hydrophobic modifier are calcined. The roasting temperature is 200-550 ℃, preferably 200-500 ℃, and further preferably 250-500 ℃. The firing may be performed in air. Preferably, the firing is performed under an inert gas atmosphere. Examples of the inert gas include nitrogen gas and a rare gas, and nitrogen gas is preferable. The baking time is not particularly limited, and may be 2 to 20 hours, preferably 4 to 16 hours.
In the production method of the present invention, in the steps (1) and (2'), the peptizing agent may be an organic or inorganic substance as long as it can disperse the original base (or modified original base) and the inorganic material (or modified inorganic material), and examples thereof include inorganic acids, inorganic bases, polycarboxylic acids, monohydric alcohols, polyhydric alcohols, polyamines, cellulose derivatives, and carboxylates. These peptizers may be used alone or in combination of two or more. The amount of the peptizing agent is not particularly limited, and may be adjusted according to the total amount of the original base (or modified original base) and the inorganic material (or modified inorganic material), and is preferably 1 to 20 parts by mass, preferably 1.2 to 10 parts by mass, and more preferably 1.5 to 5 parts by mass, based on 100 parts by mass of the total amount of the original base (or modified original base) and the inorganic material (or modified inorganic material).
As the inorganic acid, various types of inorganic acids known in the art can be used, and for example, one or a combination of two or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and perchloric acid can be cited.
The inorganic base may be an alkali metal hydroxide or an alkaline earth metal hydroxide, and examples thereof include one or a combination of two or more of sodium hydroxide, calcium hydroxide, potassium hydroxide, magnesium hydroxide, and lithium hydroxide.
As the polycarboxylic acid, various polycarboxylic acids known in the art can be used, and examples thereof include C having 2 to 10 (preferably 3 to 6) carboxyl groups 2-20 Examples of the alkane include oxalic acid, succinic acid, and adipic acid. As the polycarboxylic acid, there may be mentionedTo give C optionally having one or more hydroxyl groups (for example, 1 to 6) and 1 to 10 (preferably 3 to 6) carboxyl groups 2-20 Examples of the alkane include malic acid, tartaric acid, citric acid, and stearic acid. Alternatively, the polycarboxylic acid may be one represented by the formula C 2-20 Examples of the polycarboxyalkyl (poly) amine obtained by inserting one or more N atoms into an alkane chain include nitrilotriacetic acid and ethylenediaminetetraacetic acid.
As the monohydric alcohol, various monohydric alcohols known in the art can be used, and examples thereof include C having 1 hydroxyl group 1-20 Examples of the alkane include methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol.
As the polyol, various polyols known in the art can be used, and examples thereof include C having 2 to 10 (preferably 3 to 6) hydroxyl groups 2-20 Examples of the alkane include ethylene glycol, diethylene glycol, propylene glycol, glycerin and pentaerythritol, and examples of the polymer of the polyhydric alcohol include polyethylene glycol and polyvinyl alcohol, and the alkane may be at C 2-20 Examples of the polyhydroxyalkyl (poly) amine obtained by inserting one or more N atoms into an alkane chain include monoethanolamine and triethanolamine.
As the polyamine, various polyamines known in the art can be used, and examples thereof include ethylenediamine, diethylenetriamine, triethylenetetramine, and hexamethylenediamine.
As the cellulose derivative, those known in the art can be used, and examples thereof include methyl cellulose, hydroxymethyl propyl cellulose, carboxymethyl cellulose and the like.
As the carboxylate, those known in the art can be used, and examples thereof include magnesium stearate, sodium stearate, and the like.
In the steps (1) and (2'), the amount of water to be added is not particularly limited as long as the original base (or modified original base) and the inorganic material (or modified inorganic material) can be dispersed. The amount of water is preferably 20 to 120 parts by mass based on 100 parts by mass of the total amount of the original substrate (or modified original substrate) and the inorganic material (or modified inorganic material). In steps (1) and (2'), a contact body can be prepared by stirring using a kneader.
In the steps (2) and (3'), the plastic mixed contact body (plastic mixed modified contact body) is molded to obtain a porous matrix blank body (porous matrix modified blank body). The apparatus and conditions of the molding process are not particularly limited, and those known in the art may be used.
In the steps (2) and (3'), an extruder can be used for molding during molding, the pressure in the charging barrel reaches 0.5-8 MPa, preferably 1-6 MPa, and the extrusion temperature of the charging barrel is 20-80 ℃.
The blank can be molded into various shapes according to requirements, such as a sphere, a cube, a cuboid, a cylinder and a raschig ring. The embryo body can have circular, square, triangular, hexagonal or rhombic macroscopic pores. The macro-cells are preferably uniform ordered through-cell channels.
In the step (3), the porous matrix body is roasted in inert gas. The roasting temperature is 200-580 ℃, and preferably 300-500 ℃. Examples of the inert gas include nitrogen gas and a rare gas, and nitrogen gas is preferable. The baking time is not particularly limited, and may be 2 to 20 hours, preferably 4 to 16 hours.
And (3) contacting the roasted mixed contact body or the roasted porous matrix blank with a solution containing a hydrophobic modifier in a proportion of 1/5-1/30 relative to the mass of the roasted mixed contact body or the roasted porous matrix blank.
In the step (1'), the solution containing the hydrophobic modifier is contacted with the solution containing the hydrophobic modifier in a proportion of 1/5-1/30 relative to the mass of the original matrix and at least one inorganic material selected from inorganic porous solids.
In steps (3) and (1'), the hydrophobic modifier may use various hydrophobic modifiers known in the art. In the present invention, the hydrophobic modifier is preferably a silicon source modifier or a metal compound modifier. Wherein, the silicon source modifier can be one or a combination of a plurality of methyl silicate, ethyl silicate, propyl silicate, butyl silicate, (tetra) silicon chloride and sodium silicate.
The metal compound modifier may be selected from a titanium source modifier and/or an aluminum source modifier. The titanium source modifier can be titanate or titanium halide, and can be selected from one or more of methyl titanate, ethyl titanate, propyl titanate, butyl titanate and titanium chloride. The aluminum source modifier can be aluminate or aluminum halide, and can be selected from one or more of methyl aluminate, ethyl aluminate, propyl aluminate, butyl aluminate and aluminum chloride.
As a solvent for preparing the solution containing the hydrophobic modifier, various organic non-aqueous solvents commonly used in the art may be used, and for example, the solvent may be selected from one or a combination of several of methanol, ethanol, propanol, butanol, benzene, toluene, xylene, long-chain alcohols having 8 to 12 carbons, and N, N-dimethylformamide. Preferably an organic solvent which is completely miscible with the silicon source modifier, the titanium source modifier and the aluminum source modifier.
In the solution containing the hydrophobic modifier, the concentration of the hydrophobic modifier can be adjusted according to needs, and the mass concentration of the hydrophobic modifier can be 0.5-40%, and preferably 0.8-30%. The hydrophobic layer is formed on the surface of the finally obtained porous substrate, so that the contact angle of water on the surface of the porous substrate is 40-90 degrees, preferably 45-70 degrees.
In the steps (4) and (4'), the modified blank is roasted to prepare the flame-retardant hydrophobic porous matrix.
The calcination temperature in the steps (4) and (4') is not particularly limited, and is 200 to 580 ℃, preferably 200 to 550 ℃, and more preferably 300 to 550 ℃. The calcination may be performed in an air atmosphere or an inert gas atmosphere. The baking time is not particularly limited, and may be 1 to 20 hours, preferably 2 to 20 hours, and more preferably 4 to 16 hours.
In the production method of the present invention, the step (2) is an optional step, and in the case where the step (2) is not provided, the plastic mixed contact body in the step (1) is subjected to a firing treatment in the step (3). The firing conditions are the same as described above.
In the production method of the present invention, the above-mentioned step (3') is an optional step, and in the case where the step (3') is not provided, the mixed modified contact body in the step (2') is subjected to a baking treatment in the step (4'). The firing conditions are the same as described above.
According to the present invention, in the contacting step of said steps (1) and (2'), the order of contacting the respective 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 peptizing agent, water, or modified original matrix, modified inorganic material and peptizing agent, and water) is not particularly limited.
According to the present invention, in the steps (1) and (2'), the contacting step is not particularly limited in the manner of carrying out, as long as sufficient mixing and contacting of the respective raw material components can be achieved to form a uniform contact product. For example, the raw material components may be mixed (with additional stirring, if necessary) to homogeneity in any manner known in the art. In steps (1) and (2'), the contacting step may be carried out at any temperature of 0 ℃ to 150 ℃, for example, at room temperature.
According to the present invention, the manner of carrying out the contact of the steps (3) and (1') is not particularly limited as long as the solution containing the hydrophobic modifier is brought into contact with the fired porous base body; or contacting the solution containing the hydrophobic modifier with the original matrix and the inorganic material. The contacting may be performed, for example, by dipping. In steps (3) and (1'), the contacting step may be carried out at any temperature between 0 ℃ and the boiling point of the solvent used for the solution containing the hydrophobic modifier, for example at room temperature. The contact time is not particularly limited, and may be such that a hydrophobic layer is formed on the surface of the porous substrate to be finally obtained and the contact angle of water on the surface of the porous substrate is 40 to 90 °, preferably 45 to 70 °.
In the above method of the present invention, before the firing (for example, the firing of the above step (3), the firing of the step (4), the firing of the step (1'), and the firing of the step (4')) is performed, a heat treatment may be performed to remove moisture in the material to be fired by performing a heat treatment step such as drying, airing, and air-drying, and the heat treatment may be performed at 20 to 150 ℃, preferably 30 to 120 ℃, and more preferably 50 to 100 ℃.
In step (5), the auxiliary component is at least one element selected from group a, 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.
In the step (5), the auxiliary agent is preferably at least one selected from the group consisting of a combination of Ce and Mo, a combination of Ce and Mn, a combination of Ce and Fe, a combination of Ce and Ni, a combination of Ce and Bi, a combination of Ce and Ti, a combination of Ce and Cr, a combination of Ce and V, a combination of La and Mn, a combination of La and Fe, a combination of La and Ni, and a combination of La and Bi, and further preferably at least one selected from the group consisting of a combination of Ce and Mn and Ti, a combination of Ce and Mn and V, a combination of Ce and Mn and Bi, a combination of La and Mn and Ti, a combination of La and Mn and V, and a combination of La and Mn and Bi. In one embodiment of the present invention, the mass ratio of the elements in each combination is 0.1 to 10, preferably 0.2 to 5, in terms of the oxide in the highest oxidation state of the metal, from the former to the latter (or from the former to the latter).
In the present invention, the precursor of the cobalt metal component is a cobalt metal precursor commonly used in the art, for example, the cobalt metal precursor may preferably be a soluble salt or other soluble complex, and further preferably be a chloride salt, a nitrate salt, an acetate salt, or an ammonia salt.
In the present invention, the precursor of the auxiliary component is a precursor of an auxiliary commonly used in the art, for example, the precursor of the auxiliary may be preferably a soluble salt of the auxiliary component, and further preferably a chloride salt, a nitrate salt, an acetate salt, a sulfate salt, an ammonia salt, or a phosphate salt. For example, cerium nitrate, cerium chloride, cerium ammonium nitrate, and the like can be selected as the cerium precursor.
In the present invention, the solvent used for preparing the solution or suspension of the precursor of the cobalt metal component and the solution or suspension of the precursor of the auxiliary component is not particularly limited, and various solvents known in the art may be used as long as the precursor of the cobalt metal component and the precursor of the auxiliary component can be dissolved or suspended and the effects of the present invention are not impaired. It can be various organic solvents or water, preferably deionized water. To the solvent, various kinds of inorganic acids (e.g., hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.), organic acids (e.g., formic acid, acetic acid, propionic acid, oxalic acid, etc.), and the like can be optionally added. The inorganic acid and the organic acid can function as a complexing agent, a stabilizer, and a pH adjuster as described below.
In the present invention, when the precursor of the cobalt metal component and the precursor of the auxiliary component are prepared as a solution or a suspension, the concentration of the solution or the suspension is not particularly limited, and may be usually 5 to 300 g/L.
In the present invention, when a solution or suspension of a precursor of the cobalt metal component and/or a solution or suspension of a precursor of the auxiliary component are prepared, various additives such as a complexing agent, a stabilizer, and a pH adjuster may be further added as necessary.
Examples of the complexing agent include polycarboxylic acids, monohydric alcohols, polyhydric alcohols, and polyamines. These complexing agents may be used alone or in combination of two or more, as required. Examples of the polycarboxylic acid include C2-20 alkanes having 2 to 10 (preferably 3 to 6) carboxyl groups, and examples thereof include oxalic acid, succinic acid, and adipic acid. The polycarboxylic acid may be a C2-20 alkane having one or more hydroxyl groups (for example, 1 to 6) and 2 to 10 (preferably 3 to 6) carboxyl groups, and examples thereof include malic acid, tartaric acid, and citric acid. Alternatively, the polycarboxylic acid may be a polycarboxyalkyl (poly) amine obtained by inserting one or more N atoms into the C2-20 alkane chain, and examples thereof include nitrilotriacetic acid and ethylenediaminetetraacetic acid. Examples of the monohydric alcohol include C1-20 alkanes having 1 hydroxyl group, and examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol. Examples of the polyhydric alcohol include C2-20 alkanes having 2 to 10 (preferably 3 to 6) hydroxyl groups, such as ethylene glycol and glycerol, and polymers of the polyhydric alcohol, such as polyethylene glycol, and polyhydroxyalkyl (poly) amines obtained by inserting one or more N atoms into the hydrocarbon chain of the C2-20 alkane, such as monoethanolamine and triethanolamine. Examples of the polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine, and the like.
As the stabilizer, various stabilizers known in the art may be used, and for example, oxides of metals selected from barium, calcium, magnesium, strontium, and mixtures thereof, methyl (meth) acrylate may be used. The stabilizer preferably comprises one or more barium and/or strontium oxides, methyl (meth) acrylate.
As the pH adjuster, various pH adjusters known in the art can be used, and examples thereof include various water-soluble acids and water-soluble bases, such as hydroxy monocarboxylic acid, polyhydroxy monocarboxylic acid, hydroxy polycarboxylic acid, polyhydroxy polycarboxylic acid, and monocarboxylic acid; and alkaline substances such as ethylenediamine and ammonia water.
When the complexing agent having acidity or basicity is used, it can also function as a pH adjuster.
In the step (5) of bringing the solution or suspension of the precursor of the cobalt metal component and the solution or suspension of the precursor of the at least one auxiliary component into contact with the flame-retardant hydrophobic porous substrate, the order of contacting the solution or suspension of the precursor of the cobalt metal component and the solution or suspension of the precursor of the auxiliary component with the porous substrate is not limited at all. The solution or suspension of the precursor of the cobalt metal component may be contacted with the porous matrix first, and then the solution or suspension of the precursor of the additive component may be contacted with the porous matrix, or the order may be reversed. Or after respectively preparing a solution or suspension of a precursor of the cobalt metal component and a solution or suspension of a precursor of the auxiliary component, mixing the two solutions or suspensions, and simultaneously contacting the two solutions or suspensions with the flame-retardant hydrophobic porous matrix. In addition, between the two contact steps, a heat treatment step such as drying may be optionally interposed, for example, drying, airing, and air-drying at 50 to 180 ℃, preferably 60 to 150 ℃, and more preferably 70 to 120 ℃.
In addition, in the invention, a precursor of the cobalt metal component and a precursor of the auxiliary agent component can be prepared into a solution or suspension together, and then the solution or suspension is contacted with the flame-retardant hydrophobic porous matrix. That is, in this case, "a solution or suspension of a precursor of the cobalt metal component" and "a solution or suspension of a precursor of the auxiliary component" mean the same solution or suspension.
In the step (5) of the present invention, the contact with the flame-retardant hydrophobic porous substrate may be performed by spraying or showering the solution or suspension onto the flame-retardant hydrophobic porous substrate, or may be performed by immersing the flame-retardant hydrophobic porous substrate in the solution or suspension. Preferably by impregnation. The contacting may be carried out at any temperature, for example at room temperature. The contact time is not particularly limited as long as the content of cobalt metal (in terms of tricobalt tetraoxide) in the finally prepared catalyst is 50 to 500kg/m based on the total volume of the catalyst 3 Preferably 50 to 430kg/m 3 The content of the auxiliary agent (calculated by the oxide in the highest oxidation state of the auxiliary agent component) is 10-180 kg/m 3 Preferably 10 to 150kg/m 3 And (4) finishing.
In the step (5), when the solution or suspension of the precursor of the cobalt metal component, the solution or suspension of the precursor of the assistant component, and the flame-retardant hydrophobic porous matrix are contacted, the concentration of the solution or suspension of the precursor of the cobalt metal component, the concentration of the solution or suspension of the precursor of the assistant component, and the contact time of the porous matrix and the solution or suspension of the porous matrix and the flame-retardant hydrophobic porous matrix can be adjusted, so that the cobalt metal content (calculated as cobaltosic oxide) in the finally prepared catalyst is 50-500 kg/m based on the total volume of the catalyst 3 Preferably 50 to 430kg/m 3 The content of the auxiliary agent (calculated by the oxide in the highest oxidation state of the auxiliary agent component) is 10-180 kg/m 3 Preferably 10 to 150kg/m 3 And (4) finishing.
In one embodiment of the present invention, after the contacting step in each step, the resulting contact product may be directly used in the next step.
In one embodiment of the present invention, after the contacting step in each step, the obtained contact product may be further subjected to drying or the like, especially when the contact product is in slurry, by any means known in the art, for example, drying, airing, and air drying at 50 to 180 ℃, preferably 60 to 150 ℃, and more preferably 70 to 120 ℃ to remove any dispersion medium (such as water) that may be introduced during the preparation thereof. According to the invention, the dried contact product is also referred to as contact product.
In the invention, in the step (6), the contact product obtained in the step (5) is roasted to obtain the flame-retardant hydrophobic porous matrix supported catalyst.
In the step (6), the roasting temperature is 200-550 ℃, preferably 200-500 ℃, and further preferably 250-500 ℃. The calcination may be performed in an air atmosphere or an inert gas atmosphere. The heat treatment time is not particularly limited, and may be 2 to 20 hours, preferably 4 to 16 hours.
The flame-retardant hydrophobic porous matrix supported catalyst or the flame-retardant hydrophobic porous matrix supported catalyst prepared by the preparation method can be used for catalytic oxidation treatment of volatile organic compounds.
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 enabled to have a gas volume space velocity of 4000-25000 h -1 And contacting the porous matrix supported catalyst at the temperature of 150-450 ℃ to remove volatile organic gas by catalytic oxidation.
The flame-retardant hydrophobic porous matrix supported catalyst or the flame-retardant hydrophobic porous matrix supported catalyst prepared by the preparation method can be used for catalytic oxidation of wastewater, particularly wastewater containing high COD.
In one embodiment of the present invention, the conditions for the catalytic oxidation treatment of wastewater are: the space velocity of the liquid volume of the wastewater is 0.2 to 3h -1 The pressure is 2-8MPa, the reaction temperature is 200-280 ℃, and the porous matrix is contacted with the catalyst to implement catalytic oxidation.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples. In the present invention, unless otherwise specified, the content of the Co metal is calculated as cobaltosic oxide, and the content of the auxiliary component is calculated as the oxide in the highest oxidation state of the auxiliary component.
In the present invention, the surface area is measured by the BET specific surface area measurement method.
The pore volume was determined by the BJH (Barrett-Joyner-Halenda) method.
The mode pore size was determined by BJH.
The cross-sectional area of individual honeycomb macrocells (also referred to simply as honeycomb cells) is calculated according to a specific shape.
Specifically, when the cellular macroscopic pore canal is circular, square, triangular, hexagonal or rhombic, the sectional area can be calculated according to a conventional area calculation method; when the macroscopic pore canal of the honeycomb is irregularly shaped, the longest diameter (or the longest diagonal length) and the shortest diameter (or the shortest diagonal length) of the shape are measured, and the cross-sectional area = (longest diameter (or the longest diagonal length) + the shortest diameter (or the shortest diagonal length))/4] 2 π. The sectional area of 10 honeycomb holes was calculated, and the average value thereof was taken as the sectional area of a single honeycomb hole.
Contact Angle the contact angle with water was determined according to the method GB/T36086-2018.
The positive pressure strength and the lateral pressure strength are measured by a GB/T5072-2008 national standard method.
Example 1
Mixing attapulgite, a 13X molecular sieve, 65% nitric acid, methylcellulose and magnesium stearate in a mass ratio of 10: 3: 0.02:0.2: 0.001, adding a proper amount of water, kneading into a plastic mixed contact body, putting the contact body into an extruder, extruding and molding under the conditions of 5MPa of pressure and 25 ℃ to prepare a square honeycomb hole blank, wherein the side lengths and the heights of four bottom edges of the square honeycomb hole blank are respectively 80cm and 100cm, and the honeycomb blank is placed in a kneader and stirred uniformly, and the proper amount of water is added to be kneaded into the plastic mixed contact body 2 Roasting for 2 hours at 300 ℃, cooling to room temperature, and then, according to the mass ratio of the cooled blank body to the modified solution being 20: 1 ratio of the amount of the solution to be cooledAnd transferring the blank body to an ethanol solution with the mass concentration of ethyl silicate of 1 percent, soaking for 1 hour, taking out, roasting for 4 hours at 400 ℃, and obtaining the flame-retardant hydrophobic honeycomb matrix A with a contact angle of 53 degrees. The Co content per cubic honeycomb substrate A is 150kg/m 3 Preparing a polyethylene glycol-400 aqueous solution of cobalt nitrate according to the proportion, wherein the mass ratio of the polyethylene glycol to the cobalt nitrate is 0.1:1, and the Ce content on each cubic honeycomb matrix A is 20kg/m 3 Mo content of 18kg/m 3 Preparing aqueous solution of cerium nitrate and ammonium molybdate, dipping Ce and Mo solution on A substrate, drying for 3 hours at 150 ℃, further dipping Co solution, drying for 2 hours at 150 ℃, and roasting for 5 hours at 500 ℃ to obtain the flame-retardant hydrophobic porous substrate supported non-noble metal catalyst A1 with the surface area of 161m 2 ·g -1 The most probable pore diameter is 5.1nm, and the pore volume is 0.42 ml/g -1 The cross section of the honeycomb holes is 9.2mm 2 。
Example 2
Mixing attapulgite, kaolin, a Y molecular sieve, 65% nitric acid, methylcellulose and magnesium stearate in a mass ratio of 8: 2: 2: 0.02:0.2: stirring 0.03 in a kneader, adding appropriate amount of water, kneading to obtain plastic mixed contact body, placing the contact body into an extruder, extruding at 25 deg.C under 5MPa to obtain square honeycomb blank with four bottom edges of 80cm and 100cm respectively, and placing the honeycomb blank in a N-shaped container 2 Roasting for 2 hours at 300 ℃, cooling to room temperature, and then mixing the cooled blank body with the modified solution according to the mass ratio of 30: 1, transferring the cooled blank into a toluene solution with the mass concentration of silicon tetrachloride of 1 percent, soaking for 1 hour, taking out, and roasting for 4 hours at 400 ℃ to obtain the flame-retardant hydrophobic honeycomb matrix B with the contact angle of 58 degrees. The Co content per cubic honeycomb substrate B was 150kg/m 3 Preparing a citric acid aqueous solution of cobalt nitrate according to the proportion, wherein the mass ratio of citric acid to cobalt nitrate is 0.1:1, and the Ce content on each cubic honeycomb matrix B is 35kg/m 3 Mn content of 23kg/m 3 Preparing aqueous solution of cerium nitrate and manganese nitrate, and soaking Ce and Mn solution in advanceDrying the substrate B for 4 hours at the temperature of 150 ℃, further soaking the substrate B in a Co solution, drying the substrate B for 3 hours at the temperature of 150 ℃, and roasting the substrate B for 5 hours at the temperature of 500 ℃ to obtain the flame-retardant hydrophobic porous substrate supported non-noble metal catalyst B1 with the surface area of 144m 2 ·g -1 The most probable pore diameter is 5.8nm, and the pore volume is 0.34 ml/g -1 The cross section of the honeycomb holes is 9mm 2 。
Example 3
Mixing attapulgite, kaolin, an SBA-15 molecular sieve, 65 mass percent nitric acid, methylcellulose and magnesium stearate in a mass ratio of 7:3: 4:0.02:0.2: stirring 0.03 in a kneader, adding appropriate amount of water, kneading to obtain plastic mixed contact body, placing the contact body into an extruder, extruding under the condition of pressure of 5MPa and temperature of 25 deg.C to obtain blank with square honeycomb holes, wherein the length and height of four bottom edges of the blank are 80cm and 100cm respectively, and the blank is placed in a N-shaped container 2 Roasting for 2 hours at 300 ℃, cooling to room temperature, and then mixing the cooled blank body with the modified solution according to the mass ratio of 18: 1, transferring the cooled blank into a butanol solution with the mass concentration of ethyl titanate of 1 percent, soaking for 1 hour, taking out, roasting for 4 hours at 400 ℃, and obtaining the flame-retardant hydrophobic honeycomb matrix C with a contact angle of 61 degrees. According to the Co content of 300kg/m on the flame-retardant hydrophobic honeycomb substrate C 3 Preparing a glycerin aqueous solution of cobalt chloride according to the proportion, wherein the mass ratio of the glycerin to the cobalt chloride is 0.2:1, and the Ce content on the flame-retardant hydrophobic honeycomb substrate C is 70kg/m 3 The Fe content is 21kg/m 3 Preparing aqueous solution of cerium nitrate and ferric nitrate, simultaneously soaking the solution of Ce, Fe and Co on a honeycomb substrate C, drying for 4 hours at the temperature of 150 ℃, and then roasting for 5 hours at the temperature of 500 ℃ to obtain the flame-retardant hydrophobic porous substrate supported non-noble metal catalyst C1 with the surface area of 353m 2 ·g -1 The most probable pore diameter was 7.2nm, and the pore volume was 0.51 ml/g -1 The cross section of the honeycomb holes is 8.2mm 2 。
Example 4
Mixing attapulgite, kaolin, 5A molecular sieve, and 65% by mass of sodium nitrateUniformly stirring acid, hydroxymethyl propyl cellulose and glycerol in a kneader according to the mass ratio of 7:3:1.4:0.02:0.2:0.03, adding a proper amount of water, kneading into a plastic mixed contact body, putting the plastic mixed contact body into an extruder, extruding and molding under the conditions of 5MPa and 25 ℃ to prepare a square honeycomb hole blank, wherein the four bottom side lengths and the heights of the square honeycomb hole blank are 80cm and 100cm respectively, and the honeycomb blank is placed in an N-shaped honeycomb hole 2 Roasting for 2 hours at 300 ℃, cooling to room temperature, and then, according to the mass ratio of the cooled blank body to the modified solution being 20: 1, transferring the cooled blank into an ethanol solution with the mass concentration of 1 percent of aluminum chloride, soaking for 1 hour, taking out, roasting for 4 hours at 350 ℃, and obtaining the flame-retardant hydrophobic honeycomb matrix D with a contact angle of 57 degrees. According to the condition that the Co content on the flame-retardant hydrophobic honeycomb substrate D is 320kg/m 3 Preparing a glycerin aqueous solution of cobalt chloride according to the proportion, wherein the mass ratio of the glycerin to the cobalt chloride is 0.3:1, and the Ce content on each cubic flame-retardant hydrophobic honeycomb substrate D is 50kg/m 3 Ni content of 40kg/m 3 Preparing aqueous solution of cerium nitrate and nickel nitrate, firstly soaking Ce and Ni solution on a honeycomb substrate D, drying for 4 hours at the temperature of 150 ℃, then further soaking Co solution, drying for 3 hours at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 480 ℃ to obtain the flame-retardant hydrophobic porous substrate supported non-noble metal catalyst D1, wherein the surface area is 204m 2 ·g -1 The most probable pore diameter is 8.4nm, and the pore volume is 0.38 ml/g -1 The cross section of the honeycomb holes is 27mm 2 。
Example 5
Mixing attapulgite, kaolin, an SAPO molecular sieve, 65 mass percent nitric acid, hydroxymethyl propyl cellulose, hexamethylene diamine and magnesium stearate according to a mass ratio of 7:3:1.4:0.02:0.2: 0.01: stirring 0.03 in a kneader, adding appropriate amount of water, kneading to obtain plastic mixed contact body, extruding the contact body in an extruder at 25 deg.C under 7MPa to obtain square honeycomb blank with four bottom edges of 80cm and 100cm, and placing the blank in a N-shaped container 2 Roasting at 200 deg.C for 2 hr, coolingAfter the temperature is reduced to room temperature, the mass ratio of the cooled blank body to the modified solution is 19: 1, transferring the cooled blank into an ethanol solution with the mass concentration of ethyl silicate of 2 percent, soaking for 1 hour, taking out, roasting for 3 hours at 300 ℃, and obtaining the flame-retardant hydrophobic honeycomb matrix E with a contact angle of 49 degrees. The Co content on each cubic flame-retardant hydrophobic honeycomb substrate E is 280kg/m 3 Preparing a glycerin aqueous solution of cobalt chloride according to the proportion, wherein the mass ratio of the glycerin to the cobalt chloride is 0.3:1, and the Ce content on each cubic flame-retardant hydrophobic honeycomb substrate E is 60kg/m 3 And a Bi content of 20kg/m 3 Preparing aqueous solution of cerium nitrate and bismuth nitrate, firstly dipping Ce and Bi solution on a honeycomb substrate E, drying for 4 hours at the temperature of 150 ℃, then further loading Co solution, drying again for 3 hours at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 500 ℃ to obtain the flame-retardant hydrophobic porous substrate loaded non-noble metal catalyst forming body E1 with the surface area of 172m 2 ·g -1 The most probable pore diameter is 5.9nm, and the pore volume is 0.40 ml/g -1 The cross section of the honeycomb holes is 26mm 2 。
Example 6
Kaolin, a 13X molecular sieve, 65% mass concentration nitric acid, methylcellulose and magnesium stearate are mixed according to the mass ratio of 10: 4:0.02:0.2: 0.001, adding a proper amount of water, kneading into a plastic mixed contact body, putting the contact body into an extruder, extruding and molding under the conditions of 5MPa of pressure and 25 ℃ to prepare a square honeycomb hole blank, wherein the side lengths and the heights of four bottom edges of the square honeycomb hole blank are respectively 80cm and 100cm, and the honeycomb blank is placed in a kneader to be evenly stirred, and the proper amount of water is added to be kneaded into the plastic mixed contact body 2 Roasting for 2 hours at 300 ℃, cooling to room temperature, and then, according to the mass ratio of the cooled blank body to the modified solution being 20: 1, transferring the cooled blank into an ethanol solution with the mass concentration of ethyl silicate of 1 percent, soaking for 1 hour, taking out, roasting for 4 hours at 450 ℃, and obtaining the flame-retardant hydrophobic honeycomb matrix F with a contact angle of 51 degrees. The Co content per cubic honeycomb matrix F is 350kg/m 3 Preparing a glycerin aqueous solution of cobalt chloride according to the proportion, wherein the mass ratio of the glycerin to the cobalt chloride is 0.3:1, and the Ce content on each cubic honeycomb matrix F is 58kg/m 3 The Cr content is 33kg/m 3 Preparing aqueous solution of cerium nitrate and chromium nitrate, firstly dipping Ce and Cr solution on a honeycomb substrate F, drying for 4 hours at the temperature of 150 ℃, then further dipping Co solution, drying again for 3 hours at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 500 ℃ to obtain the flame-retardant hydrophobic porous substrate supported non-noble metal catalyst F1 with the surface area of 138m 2 ·g -1 The most probable pore diameter is 6.8nm, and the pore volume is 0.34 ml/g -1 The area of the honeycomb holes is 10mm 2 。
Example 7
Mixing attapulgite, silicon dioxide, 65% nitric acid, hydroxymethyl propyl cellulose and glycerol according to a mass ratio of 10: 4:0.02:0.2: 0.001, stirring uniformly in a kneading machine, adding a proper amount of water, kneading into a plastic mixed contact body, putting the contact body into an extruder, extruding and molding under the conditions of 5MPa of pressure and 25 ℃, preparing a billet of square honeycomb holes, wherein the side length and the height of four bottom edges of the billet of the square honeycomb holes are 80cm and 100cm respectively, and the honeycomb billet is subjected to N-shaped extrusion molding 2 Roasting for 2 hours at 300 ℃, cooling to room temperature, and mixing the cooled blank with the modified solution according to the mass ratio of 30: 1, transferring the cooled blank into an ethanol solution with the mass concentration of ethyl silicate of 1 percent, soaking for 1 hour, taking out, roasting for 4 hours at 450 ℃, and obtaining the flame-retardant hydrophobic honeycomb matrix G with a contact angle of 61 degrees. According to the condition that the Co content on the flame-retardant hydrophobic honeycomb matrix G is 350kg/m 3 Preparing a glycerin aqueous solution of cobalt chloride according to the proportion, wherein the mass ratio of the glycerin to the cobalt chloride is 0.3:1, and the Ce content on each cubic flame-retardant hydrophobic honeycomb matrix G is 42kg/m 3 The V content is 17kg/m 3 Preparing oxalic acid aqueous solution of cerous nitrate and ammonium metavanadate according to the proportion, firstly dipping the Ce and V solution on G, drying for 4 hours at the temperature of 150 ℃, then further dipping the Co solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 500 ℃ to obtain the flame-retardant hydrophobic porous matrix supported non-noble metal catalyst G1 with the surface area of 201m 2 ·g -1 The most probable pore diameter was 7.3 nm, and the pore volume was 0.47ml g -1 The area of the honeycomb holes is8.8mm 2 。
Example 8
The flame-retardant hydrophobic honeycomb substrate G of example 7 was taken. The Co content per cubic flame-retardant hydrophobic honeycomb matrix G is 350kg/m 3 Preparing a glycerin aqueous solution of cobalt chloride according to the proportion, wherein the mass ratio of the glycerin to the cobalt chloride is 0.3:1, and the La content on each cubic flame-retardant hydrophobic honeycomb matrix G is 52kg/m 3 Mn content of 17kg/m 3 Preparing acetic acid aqueous solution of lanthanum nitrate and manganese nitrate, firstly dipping La and Mn solution on G, drying for 4 hours at the temperature of 150 ℃, then further dipping Co solution, drying again for 3 hours at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 480 ℃ to obtain the flame-retardant hydrophobic porous matrix supported non-noble metal catalyst H1 with the surface area of 211m 2 ·g -1 The most probable pore diameter is 7nm, and the pore volume is 0.52 ml/g -1 The area of the honeycomb holes is 9.1mm 2 。
Example 9
The flame-retardant hydrophobic honeycomb substrate G of example 7 was taken. The Co content per cubic flame-retardant hydrophobic honeycomb matrix G is 350kg/m 3 Preparing a glycerin aqueous solution of cobalt chloride according to the proportion, wherein the mass ratio of the glycerin to the cobalt chloride is 0.3:1, and the La content on each cubic flame-retardant hydrophobic honeycomb matrix G is 80kg/m 3 Fe content of 20kg/m 3 Preparing aqueous solution of lanthanum nitrate and ferric nitrate, firstly soaking Co solution on a honeycomb substrate G, drying for 4 hours at the temperature of 130 ℃, then further soaking La and Fe solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 500 ℃ to obtain the flame-retardant hydrophobic porous substrate supported non-noble metal catalyst I1 with the surface area of 187m 2 ·g -1 The most probable pore diameter is 8.7nm, and the pore volume is 0.42 ml/g -1 The area of the honeycomb holes is 8.6mm 2 。
Example 10
The flame-retardant hydrophobic honeycomb substrate G of example 7 was taken. The Co content per cubic flame-retardant hydrophobic honeycomb matrix G is 350kg/m 3 Preparing a stearic acid aqueous solution of cobalt chloride according to the proportion, wherein the mass ratio of stearic acid to cobalt chloride is 0.2:1, and each cubic resistivityThe La content on the hydrophobic honeycomb substrate G was 84kg/m 3 Ni content of 10kg/m 3 Preparing aqueous solution of lanthanum nitrate and nickel nitrate, firstly soaking Co solution on a honeycomb substrate G, drying for 4 hours at the temperature of 130 ℃, then further soaking La and Ni solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 500 ℃ to obtain the flame-retardant hydrophobic porous substrate supported non-noble metal catalyst J1 with the surface area of 170m 2 ·g -1 The most probable pore diameter is 8.9nm, and the pore volume is 0.40 ml/g -1 The area of the honeycomb holes is 8.3mm 2 。
Example 11
The flame-retardant hydrophobic honeycomb substrate G of example 7 was taken. The Co content per cubic flame-retardant hydrophobic honeycomb matrix G is 290kg/m 3 Preparing an aqueous solution of methyl methacrylate according to the proportion, wherein the mass ratio of the methyl methacrylate to the cobalt chloride is 0.3:1, and the La content on each cubic flame-retardant hydrophobic honeycomb matrix G is 80kg/m 3 And a Bi content of 20kg/m 3 Preparing aqueous solution of lanthanum nitrate and bismuth nitrate, firstly dipping Co solution on G, drying for 4 hours at the temperature of 130 ℃, then further dipping La and Bi solution, drying again for 3 hours at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 500 ℃ to obtain the flame-retardant hydrophobic porous matrix supported non-noble metal catalyst K1 with the surface area of 183m 2 ·g -1 The most probable pore diameter is 8.2nm, and the pore volume is 0.44 ml/g -1 The area of the honeycomb holes is 8.5mm 2 。
Example 12
The flame-retardant hydrophobic honeycomb substrate G of example 7 was taken. The Co content per cubic flame-retardant hydrophobic honeycomb matrix G is 400kg/m 3 Preparing an aqueous solution of methyl methacrylate according to the proportion, wherein the mass ratio of the methyl methacrylate to the cobalt chloride is 0.3:1, and the Ce content on each cubic flame-retardant hydrophobic honeycomb matrix G is 40kg/m 3 Mn content of 30kg/m 3 Ti content of 20kg/m 3 Preparing aqueous solution of cerium nitrate, manganese nitrate and titanium sulfate, soaking Co solution on G, drying at 130 deg.C for 4 hr, and further soaking in solution of Ce, Mn and TiDrying the solution at 150 ℃ for 3 hours again, and roasting the solution at 500 ℃ for 5 hours to obtain the flame-retardant hydrophobic porous matrix supported non-noble metal catalyst L1 with the surface area of 135m 2 ·g -1 The most probable pore diameter was 11.1nm, and the pore volume was 0.32 ml/g -1 The area of the honeycomb holes is 7.8mm 2 。
Example 13
The flame-retardant hydrophobic honeycomb substrate G of example 7 was taken. The Co content of each cubic flame-retardant hydrophobic honeycomb matrix G is 430kg/m 3 Preparing an aqueous solution of methyl methacrylate according to the proportion, wherein the mass ratio of the methyl methacrylate to the cobalt chloride is 0.3:1, and the Ce content on each cubic flame-retardant hydrophobic honeycomb matrix G is 50kg/m 3 Mn content of 20kg/m 3 The V content is 20kg/m 3 Preparing aqueous solution of cerous nitrate, manganese nitrate and vanadyl sulfate, soaking Co solution on G, drying at 130 ℃ for 4 hours, further soaking solution of Ce, Mn and V, drying at 150 ℃ for 3 hours, and roasting at 500 ℃ for 4 hours to obtain the flame-retardant hydrophobic porous matrix supported non-noble metal catalyst M1 with the surface area of 143M 2 ·g -1 The most probable pore diameter is 9.4nm, and the pore volume is 0.36 ml/g -1 The area of the honeycomb holes is 8.2mm 2 。
Example 14
The flame-retardant hydrophobic honeycomb substrate G of example 7 was taken. According to the proportion that the Co content on each cubic flame-retardant hydrophobic honeycomb substrate G is 430kg/m 3 Preparing an aqueous solution of methyl methacrylate according to the proportion, wherein the mass ratio of the methyl methacrylate to the cobalt chloride is 0.3:1, and the Ce content on each cubic flame-retardant hydrophobic honeycomb matrix G is 50kg/m 3 Mn content of 20kg/m 3 And a Bi content of 20kg/m 3 Preparing aqueous solution of cerium nitrate, manganese nitrate and bismuth nitrate, firstly dipping the solution of Ce, Mn and Bi on G, drying for 4 hours at the temperature of 130 ℃, then further dipping the solution of Co, drying for 3 hours again at the temperature of 150 ℃, and roasting for 4 hours at the temperature of 500 ℃ to obtain the flame-retardant hydrophobic porous matrix supported non-noble metal catalyst N1 with the surface area of 148m 2 ·g -1 Most probable pore diameter of9.3nm, pore volume of 0.36ml g -1 The area of the honeycomb holes is 8.2mm 2 。
Example 15
The flame-retardant hydrophobic honeycomb substrate G of example 7 was taken. The Co content of each cubic flame-retardant hydrophobic honeycomb matrix G is 430kg/m 3 Preparing an aqueous solution of methyl methacrylate according to the proportion, wherein the mass ratio of the methyl methacrylate to the cobalt chloride is 0.3:1, and the Ce content on each cubic flame-retardant hydrophobic honeycomb matrix G is 48kg/m 3 Mn content of 30kg/m 3 The Cr content is 10kg/m 3 Preparing aqueous solution of cerium nitrate, manganese nitrate and chromium nitrate, soaking the solution of Ce, Mn and Cr on G, drying at 130 ℃ for 4 hours, further soaking in Co solution, drying at 150 ℃ for 3 hours, and roasting at 500 ℃ for 4 hours to obtain the flame-retardant hydrophobic porous matrix supported non-noble metal catalyst O1 with the surface area of 151m 2 ·g -1 The most probable pore diameter is 9.1nm, and the pore volume is 0.39 ml/g -1 The area of the honeycomb holes is 8.2mm 2 。
Example 16
The flame-retardant hydrophobic honeycomb substrate G of example 7 was taken. The Co content of each cubic flame-retardant hydrophobic honeycomb matrix G is 280kg/m 3 Preparing an aqueous solution of methyl methacrylate according to the proportion, wherein the mass ratio of the methyl methacrylate to the cobalt chloride is 0.3:1, and the La content on each cubic flame-retardant hydrophobic honeycomb matrix G is 79kg/m 3 Mn content of 20kg/m 3 The V content is 15kg/m 3 Preparing aqueous solution of lanthanum nitrate, manganese nitrate and ammonium metavanadate according to the proportion, firstly dipping the solution of La, Mn and V on G, drying for 4 hours at the temperature of 130 ℃, then further dipping the solution of Co, drying again for 3 hours at the temperature of 150 ℃, and roasting for 4 hours at the temperature of 500 ℃ to obtain the flame-retardant hydrophobic porous matrix supported non-noble metal catalyst P1 with the surface area of 162m 2 ·g -1 The most probable pore diameter was 8.9nm, and the pore volume was 0.46 ml. multidot.g -1 The area of the honeycomb holes is 8.6mm 2 。
Example 17
Mixing attapulgite, alumina, titanium oxide, 65% of the totalThe nitric acid, the hydroxymethyl propyl cellulose and the glycerol with the mass concentration are 10: 3: 1: 0.02:0.2: 0.001, adding a proper amount of water, kneading into a plastic mixed contact body, putting the contact body into an extruder, extruding and molding under the conditions that the temperature is 25 ℃ and the pressure is 5MPa to prepare a square honeycomb hole blank, wherein the side lengths and the heights of four bottom edges of the square honeycomb hole blank are respectively 80cm and 100cm, and the honeycomb blank is placed in a kneader and stirred uniformly 2 Roasting for 2 hours at 300 ℃, cooling to room temperature, and then mixing the cooled blank body with the modified solution according to the mass ratio of 15: 1, transferring the cooled blank into an ethanol solution with the mass concentration of ethyl silicate of 1 percent, soaking for 1 hour, taking out, roasting for 4 hours at 400 ℃, and obtaining the flame-retardant hydrophobic honeycomb matrix Q with a contact angle of 49 degrees. Co content on each cubic flame-retardant hydrophobic honeycomb substrate Q is 280kg/m 3 Preparing an aqueous solution of methyl methacrylate according to the proportion, wherein the mass ratio of the methyl methacrylate to the cobalt chloride is 0.3:1, and the La content on each cubic flame-retardant hydrophobic honeycomb matrix H is 79kg/m 3 Mn content of 20kg/m 3 The V content is 15kg/m 3 Preparing aqueous solution of lanthanum nitrate, manganese nitrate and ammonium metavanadate according to the proportion, firstly dipping the solution of La, Mn and V on Q, drying for 4 hours at the temperature of 130 ℃, then further dipping the solution of Co, drying again for 3 hours at the temperature of 150 ℃, and roasting for 4 hours at the temperature of 500 ℃ to obtain the flame-retardant hydrophobic porous matrix supported non-noble metal catalyst Q1 with the surface area of 152m 2 ·g -1 The most probable pore diameter is 8.4nm, and the pore volume is 0.40 ml/g -1 The area of the honeycomb holes is 8.2mm 2 。
Comparative example 1
Unlike the hydrophobic flame retardant honeycomb substrate preparation of example 7. Mixing attapulgite, silicon dioxide, 65% nitric acid, hydroxymethyl propyl cellulose and glycerol according to a mass ratio of 10: 4:0.02:0.2: 0.001, adding proper amount of water, kneading to obtain plastic mixed contact body, extruding at 25 deg.C and 5MPa in an extruder, and making into square honeycomb blank or square honeycomb blankThe four bottom edge lengths and the heights of the honeycomb body are respectively 80cm and 100cm, and the honeycomb body is arranged at N 2 Roasting for 4 hours at 450 ℃ under the condition to obtain the flame-retardant non-hydrophobic honeycomb matrix G' with a contact angle of 17 degrees. The Co content of each cubic flame-retardant non-hydrophobic honeycomb matrix G' is 280kg/m 3 Preparing an aqueous solution of methyl methacrylate at a mass ratio of 0.3:1, wherein the La content on each cubic flame-retardant non-hydrophobic honeycomb substrate G' is 79kg/m 3 Mn content of 20kg/m 3 The V content is 15kg/m 3 Preparing aqueous solution of lanthanum nitrate, manganese nitrate and ammonium metavanadate according to the proportion, firstly dipping the solution of La, Mn and V on G', drying for 4 hours at the temperature of 130 ℃, then further dipping the solution of Co, drying again for 3 hours at the temperature of 150 ℃, and roasting for 4 hours at the temperature of 500 ℃ to obtain the flame-retardant non-hydrophobic porous matrix supported non-noble metal catalyst R1 with the surface area of 169m 2 ·g -1 The most probable pore diameter is 8.2nm, and the pore volume is 0.48 ml/g -1 The area of the honeycomb holes is 8.7mm 2 。
Example 18
The flame-retardant hydrophobic catalysts of examples 1 to 17 and the flame-retardant catalyst of comparative example 1 were placed in a fixed bed reactor and introduced into a reactor with a total hydrocarbon content of 1200mg/m other than methane 3 VOCs gas (water content 20 mg/m) 3 ) At a reaction temperature of 380 ℃ and a space velocity of 10000h -1 The reaction was carried out under the conditions described above, and the results of the detection of VOCs at the outlet by gas chromatography are shown in Table 1.
TABLE 1 comparison of reactivity of flame-retardant hydrophobic catalysts
Catalyst and process for preparing same The reaction time is 1h, and the concentration (mg/m) of VOCs at the outlet is 3 ) Reaction for 500hConcentration of VOCs (mg/m) 3 ) The reaction time is 1000h, and the concentration (mg/m) of VOCs at the outlet is 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
As can be seen from table 1, the flame-retardant hydrophobic porous matrix-supported non-noble metal catalyst of the present invention exhibits excellent catalytic oxidation performance for VOCs and can maintain excellent catalytic activity even after long-term use. In contrast, in the case of the catalyst not of the present invention, the catalytic activity decreases rapidly when used for a long time.
Example 19
The catalysts of example 16 and comparative example 1 were subjected to elemental analysis of metals, and the catalysts after 1000 hours of reaction of the above-mentioned treated VOCs gases were subjected to elemental analysis, in terms of the metal content per volume of the porous substrate, as shown in table 2.
TABLE 2 analysis of key elements after catalytic reaction of porous matrix supported catalyst
Figure 941433DEST_PATH_IMAGE001
。
As is clear from table 2, in the catalyst supported on a porous substrate of the present invention, the active metal component is firmly supported on the porous substrate, and the active metal is hardly dropped even when used for a long time.
Example 20
The catalysts in example 16 and comparative example 1 are respectively loaded into a fixed bed reactor, acrylic acid-containing wastewater with COD of 35000mg/L is introduced, air oxidation is carried out, and the airspeed of the wastewater is 0.5h -1 The reaction temperature was 270 ℃ and the pressure was 5.5 MPa. Elemental analysis was performed on the catalyst before and after the reaction, and the results are shown in table 3, in terms of the metal content per unit volume of the porous substrate.
TABLE 3 analysis of key elements after catalytic reaction of porous matrix supported catalyst
Figure 327415DEST_PATH_IMAGE002
。
As can be seen from table 3, the porous matrix-supported catalyst of the present invention exhibited excellent catalytic oxidation performance for wastewater. In the porous substrate-supported catalyst of the present invention, the active metal component is firmly supported on the porous substrate, and the active metal component is hard to fall off even if it is washed with water for a long time.
Although the invention is described in detail herein with reference to exemplary embodiments, it should be understood that the invention is not limited to the described embodiments. Those having ordinary skill in the art and access to the teachings herein will recognize additional variations, modifications, and embodiments within the scope thereof. Accordingly, the invention is to be broadly construed, consistent with the claims which are appended hereto.

Claims (17)

1. A flame-retardant hydrophobic porous matrix supported non-noble metal catalyst is characterized by comprising a flame-retardant hydrophobic porous matrix, a Co component and an auxiliary agent component which are supported on the flame-retardant hydrophobic porous matrix,
wherein the auxiliary component is at least one selected from the group A elements, the auxiliary is preferably selected from at least one 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, La and Bi, further preferably selected from 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, La and Mn and Bi, the mass ratio (in terms of the highest oxidation state oxide of the metal) of each element in each combination is 0.1 to 10, preferably 0.2 to 5,
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;
based on the total volume of the porous matrix supported non-noble metal catalyst, the content of Co metal (calculated by cobaltosic oxide) is 50-500 kg/m 3 Preferably 50 to 430kg/m 3 The content of the auxiliary component (calculated by the oxide in the highest oxidation state of the auxiliary component) is 10-180 kg/m 3 Preferably 10 to 150kg/m 3 ，
The porous matrix contains at least one original matrix selected from attapulgite and kaolin, at least one inorganic material selected from inorganic porous solids, and a roasted oxide of a hydrophobic modified material, wherein the content of the original matrix is 10-99.5 mass%, preferably 20-99 mass%, the content of the roasted oxide of the hydrophobic modified material is 0.05-1 mass%, preferably 0.05-0.5 mass%, the content of the inorganic material is 0.5-90 mass%, preferably 1-80 mass%, more preferably 5-80 mass%, further preferably 8-70 mass%, and further preferably the balance, and the contact angle of the porous matrix and water is 40-90 °, preferably 45-70 °.
2. The catalyst according to claim 1, wherein the catalyst consists essentially of the flame-retardant hydrophobic porous substrate, the Co component supported on the porous substrate and the auxiliary component, preferably the catalyst consists of only the flame-retardant hydrophobic porous substrate, the Co component supported on the porous substrate and the auxiliary component.
3. The catalyst according to claim 1 or 2, wherein the BET specific surface area of the catalyst is 100 to 800m 2 ·g -1 Preferably 110 to 800m 2 ·g -1 The most probable pore diameter is 2 to 12 nm, preferably 2 to 10nm, and the pore volume is 0.15 to 1.0 ml/g -1 Preferably 0.2 to 1.0 ml/g -1 。
4. The catalyst according to any one of claims 1 to 3, wherein the hydrophobic modification material is a silicon source modification material or a metal compound modification material, preferably at least one selected from the group consisting of methyl silicate, ethyl silicate, propyl silicate, butyl silicate, (tetra) silicon chloride, sodium silicate, methyl titanate, ethyl titanate, propyl titanate, butyl titanate, titanium chloride, methyl aluminate, ethyl aluminate, propyl aluminate, butyl aluminate, aluminum chloride.
5. Catalyst according to any of claims 1 to 4, shaped as catalyst shaped bodies having the appearance of spheres, cubes, cuboids, cylinders or raschig rings, preferably having one or more of a circular, square, triangular, hexagonal or rhombic macro-channel structure, preferably having a cross-sectional area of 1mm 2 ~80mm 2 Preferably 1mm 2 ~40mm 2 The thickness of the hole wall is 1-4 mm, preferably 1-2.5 mm.
6. The catalyst according to any one of claims 1 to 5, wherein the positive pressure strength of the catalyst is 2 to 8MPa, preferably 2 to 6MPa, and the side pressure strength is 0.1 to 2MPa, preferably 0.2 to 2 MPa.
7. A preparation method of a flame-retardant hydrophobic porous matrix supported non-noble metal catalyst is characterized by comprising the following steps:
(1) mixing and contacting at least one original matrix selected from attapulgite and kaolin, at least one inorganic material selected from inorganic porous solids, peptizing agent and water to prepare a plastic mixed contact body; wherein the content of the original matrix is 10 to 99.5 mass%, preferably 20 to 99 mass%, and the content of the inorganic material is 0.5 to 90 mass%, preferably 1 to 80 mass%, more preferably 5 to 80 mass%, further preferably 8 to 70 mass%, and further preferably the balance, with respect to the total amount of the original matrix and the inorganic material;
(2) optionally, molding the plastic mixed contact body to obtain a porous matrix blank;
(3) roasting the mixed contact body in the step (1) or the porous matrix blank in the step (2) in inert gas, and then further contacting with a solution containing a hydrophobic modifier to obtain a modified blank;
(4) further roasting the modified blank body to prepare 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 the flame-retardant hydrophobic porous matrix to obtain a contact product; and
(6) roasting the contact product to obtain the flame-retardant hydrophobic porous matrix supported catalyst;
or,
(1') 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, respectively, and then calcining to obtain a modified original matrix and a modified inorganic material;
(2') mixing and contacting the modified original matrix and the modified inorganic material with a peptizing agent and water to prepare a plastic mixed modified contact body; wherein the modified original matrix is contained in an amount of 10 to 99.5 mass%, preferably 20 to 99 mass%, and the modified inorganic material is contained in an amount of 0.5 to 90 mass%, preferably 1 to 80 mass%, more preferably 5 to 80 mass%, further preferably 8 to 70 mass%, and further preferably the balance, with respect to the total amount of the modified original matrix and the modified inorganic material;
(3') optionally carrying out molding processing on the plastic mixed modified contact body to obtain a porous matrix modified green body; and
(4') further roasting the mixed modified contact body in the step (2') or the modified blank body in the step (3') to prepare 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 the flame-retardant hydrophobic porous matrix to obtain a contact product; and
(6) and roasting the contact product to obtain the flame-retardant hydrophobic porous matrix supported catalyst.
8. The production method according to claim 7, wherein the peptizing agent is at least one selected from the group consisting of inorganic acids, inorganic bases, polycarboxylic acids, monohydric alcohols, polyhydric alcohols, polyamines, cellulose derivatives, and carboxylic acid salts, preferably at least one selected from the group consisting 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.
9. The production method according to claim 7 or 8, wherein the hydrophobic modifier is a silicon source modifier or a metal compound modifier, preferably at least one selected from the group consisting of methyl silicate, ethyl silicate, propyl silicate, butyl silicate, (tetra) silicon chloride, sodium silicate, methyl titanate, ethyl titanate, propyl titanate, butyl titanate, titanium chloride, methyl aluminate, ethyl aluminate, propyl aluminate, butyl aluminate, and aluminum chloride.
10. The production method according to any one of claims 7 to 9, wherein in the step (1'), the calcination is performed in an inert gas at a temperature of 200 to 550 ℃, preferably 200 to 500 ℃, and more preferably 250 to 500 ℃; in the step (3), roasting is carried out in inert gas, the roasting temperature is 200-580 ℃, preferably 300-500 ℃, and in the steps (4) and (4'), the temperature can be 200-580 ℃, preferably 200-550 ℃, and further preferably 300-550 ℃; in the step (6), the roasting temperature is 200-550 ℃, preferably 200-500 ℃, and further preferably 250-500 ℃.
11. The production method according to any one of claims 7 to 10, further comprising, before at least one of the above-described firing of step (3), firing of step (4), firing of step (1'), and firing of step (4'), performing a heat treatment step on the material to be fired, preferably the heat treatment is performed at 20 to 150 ℃, preferably 30 to 120 ℃, more preferably 50 to 100 ℃.
12. The production method according to any one of claims 7 to 11, wherein the auxiliary component is at least one selected from group A elements, the auxiliary is preferably at least one selected from the group consisting 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, La and Bi, further preferably at least one selected from the group consisting 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, La and Mn and Bi, and La and Mn and Bi, the mass ratio (in terms of the highest oxidation state oxide of the metal) of each element in each combination being 0.1 to 10, preferably 0.2 to 5,
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,
the precursor of the auxiliary component is at least one selected from chloride, nitrate, acetate, sulfate, ammonia salt and phosphate;
the precursor of the cobalt metal is at least one of chloride, nitrate, acetate and ammonia salt of the cobalt metal,
in the obtained catalyst, the content of Co metal (calculated by cobaltosic oxide) is 50-500 kg/m based on the total volume of the catalyst 3 Preferably 50 to 430kg/m 3 The content of the auxiliary component (calculated by the oxide in the highest oxidation state of the auxiliary component) is 10-180 kg/m 3 Preferably 10 to 150kg/m 3 。
13. The production method according to any one of claims 7 to 12, wherein at least one of a complexing agent, a stabilizer, and a pH adjuster may be added to the solution or suspension of the cobalt metal component precursor and/or the solution or suspension of the auxiliary component precursor.
14. Use of a flame retardant hydrophobic porous matrix supported catalyst according to any one of claims 1 to 6 or prepared according to the preparation method of any one of claims 7 to 13 for the catalytic oxidation of volatile organic compounds.
15. Use according to claim 14, wherein the conditions for the catalytic oxidation of volatile organic compounds are: the gas containing volatile organic compounds is enabled to have a gas volume space velocity of 4000-25000 h -1 And contacting the porous matrix supported catalyst at the temperature of 150-450 ℃.
16. Use of the flame retardant hydrophobic porous matrix supported catalyst according to any one of claims 1 to 6 or prepared according to the preparation method of any one of claims 7 to 13 for catalytic oxidation of wastewater to reduce COD.
17. Use according to claim 16, wherein said conditions are: the space velocity of the liquid volume of the wastewater is 0.2 to 3h -1 The pressure is 2-8MPa, and the reaction temperature is 200-280 ℃.
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CN116083043A (en) * 2023-02-22 2023-05-09 广州辉鹏新材料科技有限公司 High-performance sealant and preparation method and application thereof
CN116083043B (en) * 2023-02-22 2023-09-29 宁波东烁新材料科技有限公司 High-performance sealant and preparation method and application thereof

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