CN114733554A - Flame-retardant hydrophobic type porous matrix supported noble metal catalyst, preparation method and application thereof - Google Patents

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

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Publication number
CN114733554A
CN114733554A CN202110023611.8A CN202110023611A CN114733554A CN 114733554 A CN114733554 A CN 114733554A CN 202110023611 A CN202110023611 A CN 202110023611A CN 114733554 A CN114733554 A CN 114733554A
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noble metal
flame
mass
porous matrix
combination
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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 noble metal catalyst, a preparation method and application thereof. The preparation method of the flame-retardant hydrophobic type porous matrix supported noble metal catalyst is simple, high in mechanical strength and strong in water and heat resistance, has the advantages of good catalytic performance of volatile organic compounds, long service life and the like in the treatment of VOCs containing moisture, and can be applied to catalytic wet oxidation of wastewater.

Description

Flame-retardant hydrophobic porous matrix supported noble metal catalyst, and preparation method and application thereof
Technical Field
The invention relates to a flame-retardant hydrophobic type porous matrix supported noble metal catalyst. More particularly, the invention relates to a flame-retardant hydrophobic type porous matrix supported noble metal catalyst and a preparation method thereof. The invention also relates to application of the flame-retardant hydrophobic porous matrix supported 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-1The treatment for removing low-concentration volatile organic pollutants in the waste gas at a low space velocity specifically adopts a porous matrix adsorption and interception mode to adsorb high-boiling-point components (more than C5) on the surface or pore channels of the waste gasThe process has almost no chemical reaction, the substrate after adsorption saturation needs regeneration and desorption to obtain the performance of re-adsorption, and the service cycle of the substrate 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 ℃, and 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 combustion temperature, so that 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 CO2And H2O, catalytic Oxidation non-methane Total hydrocarbons in volatile organics suitable for processing are generally above 500mg/m3. The most important part of catalytic oxidation is the catalyst, which is divided into two types of catalysts, namely noble metal and transition metal oxide. 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 good 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 used for 10000-30000 h-1Under the airspeed, the complete oxidation temperatures of the catalysts, namely the toluene and the ethyl acetate, are 180-200 ℃ and 260-280 ℃ respectively, but the catalyst is special for the preparation of the catalystNothing is said about the effect of bromide on catalyst activity and life. 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 then 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 precious 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 containing2The 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.
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 high thermal stability and high strength and has a good effect of supporting an active metal or an active metal oxide as a matrix (carrier).
Attapulgite clay (Attapulgite), also called Palygorskite (Palygorskite), is called Attapulgite for short, is a natural hydrated clay material which has a layered chain structure and is rich in magnesium-aluminum silicate, the basic structural unit is a sandwich structure of two layers of silicon-oxygen tetrahedrons and one layer of magnesium (aluminum) oxygen octahedrons, and the optimal unit cell molecular formula is (Mg)5Si8O20(OH)2(OH2)4·4H2And 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 SiO2、Al2O3Similar 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. However, it is only rarely reported in literature that natural one-dimensional nano-material attapulgite is used as a material of a porous matrix and noble metal is further loaded for VOCs treatment.
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 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 noble metal component and an auxiliary component as catalyst active components on the matrix. The flame-retardant hydrophobic porous matrix supported 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 noble metal catalyst, which is characterized by comprising a flame-retardant hydrophobic porous matrix, noble metal and an auxiliary agent component which are supported on the flame-retardant hydrophobic porous matrix,
wherein the noble metal is at least one element selected from Pt, Pd, Ru, Rh, Au, Ir and Ag, preferably at least one combination selected from the combination of Pt and Pd, the combination of Pt and Ru, the combination of Pt and Au and the combination of Pt and Ir,
the additive component is at least one selected from the group A elements, the additive is preferably selected from at least one combination of Ce and Mo, Ce and Mn, Ce and Co, Ce and Fe, Ce and Ni, Ce and Bi, Ce and Cr, La and Mn, La and Fe, La and Co, La and Ni, La and Bi,
group A: li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce;
based on the total volume of the flame-retardant hydrophobic porous matrix supported noble metal catalyst, the content of noble metal (calculated by noble metal simple substance) is 100-1300 g/m3Preferably 150 to 1000 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200 kg/m3Preferably 15 to 150 kg/m3，
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 type porous matrix supported 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 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 precious 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;
(6) roasting the contact product to obtain the flame-retardant hydrophobic porous matrix supported noble metal catalyst;
alternatively, the first and second electrodes may be,
(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;
(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 precious 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 noble metal catalyst.
The invention also provides application of the flame-retardant hydrophobic porous matrix supported noble metal catalyst in catalytic oxidation of volatile organic compounds.
The invention also provides application of the flame-retardant hydrophobic porous matrix supported noble metal catalyst in catalytic oxidation of wastewater containing high COD.
Technical effects
The preparation method of the flame-retardant hydrophobic porous matrix supported noble metal catalyst is simple, does not need vacuum pugging and microwave heat treatment, and is low in cost.
The flame-retardant hydrophobic porous matrix supported noble metal catalyst has good hydrothermal property, can be used for treating VOCs with high water vapor content and waste water 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, the flame-retardant hydrophobic porous matrix supported catalyst disclosed by the invention has the advantages that due to the porosity, active components can be fully contacted with VOCs, so that the catalytic treatment of the VOCs is facilitated, and in addition, the active components can be fully contacted with high COD substances in wastewater, so that the catalytic wet oxidation is facilitated, and the 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 noble metal catalyst, which is characterized by comprising a flame-retardant hydrophobic porous matrix, noble metal and an auxiliary agent component which are supported on the flame-retardant hydrophobic porous matrix,
wherein the noble metal is at least one element selected from the group consisting of Pt, Pd, Ru, Rh, Au, Ir and Ag, preferably at least one combination selected from the group consisting of a combination of Pt and Pd, a combination of Pt and Ru, a combination of Pt and Au and a combination of Pt and Ir,
the additive component is at least one selected from the group A elements, the additive is preferably selected from at least one combination of Ce and Mo, Ce and Mn, Ce and Co, Ce and Fe, Ce and Ni, Ce and Bi, Ce and Cr, La and Mn, La and Fe, La and Co, La and Ni, La and Bi,
group A: li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce;
based on the total volume of the flame-retardant hydrophobic porous matrix supported noble metal catalyst, the content of noble metal (calculated by noble metal simple substance) is 100-1300 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200 kg/m3，
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 a calcined oxide of the original matrix, the inorganic material, and the hydrophobically modified material. In one embodiment of the invention, the porous matrix consists only of the calcined oxides of the original matrix, the inorganic material and the hydrophobically modified 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, the attapulgite known in the art may be used as the attapulgite, 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 kinds of hydrophobically modified materials known in the art can be used. 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 modification material can be one or a combination of a plurality of materials selected from 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 noble metal catalyst is 100-800 m2·g-1Preferably 110 to 800m2·g-1The most probable pore diameter is 2 to 12nm, preferably 2 to 10nm, and the pore volume is 0.15 to 1.0 ml/g-1Preferably 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 shaped body is 1mm2~80mm2Preferably 1mm2~40mm2. 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 imparting a certain hydrophobicity to the porous matrix, and when the contact angle of water on the surface of the porous matrix is used as an index of hydrophobicity and measured according to a GB/T36086-2018 method, the contact angle of the porous matrix and 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, at least one noble metal supported on the porous matrix, and an adjunct component.
In one embodiment of the invention, the catalyst consists only of a flame-retardant hydrophobic porous matrix, at least one noble metal supported on the porous matrix, and an adjunct component. 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 present invention, the noble metal is at least one element selected from Pt, Pd, Ru, Rh, Au, Ir, and Ag.
In one embodiment of the present invention, the noble metal is at least one selected from the group consisting of a combination of Pt and Pd, a combination of Pt and Ru, a combination of Pt and Au, and a combination of Pt and Ir, and the mass ratio of the two elements (the former to the latter) (in terms of the simple substance of the element) in each combination is preferably 0.2 to 5, and more preferably 0.4 to 4.
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, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce.
In one embodiment of the present invention, the auxiliary 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 Co, a combination of Ce and Fe, a combination of Ce and Ni, a combination of Ce and Bi, a combination of Ce and Cr, a combination of La and Mn, a combination of La and Fe, a combination of La and Co, a combination of La and Ni, and a combination of La and Bi, and the mass ratio of the two elements (the former to the latter) (in terms of the element) in each combination is preferably 0.1 to 10, preferably 0.5 to 5.
In one embodiment of the invention, the content of the noble metal (calculated by the simple noble metal) is 100-1300 g/m based on the total volume of the flame-retardant hydrophobic porous matrix supported noble metal catalyst3Preferably 150 to 1000 g/m3。
In one embodiment of the invention, the content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200 kg/m based on the total volume of the noble metal catalyst supported by the flame-retardant hydrophobic porous matrix3Preferably 15 to 150 kg/m3。
In one embodiment of the invention, in the flame-retardant hydrophobic porous matrix-supported noble metal catalyst, the mass ratio of the noble metal Pt to other noble metals is 0.7: 1-8: 1.
The invention also provides a preparation method of the flame-retardant hydrophobic type porous matrix supported 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 precious 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;
(6) roasting the contact product to obtain the flame-retardant hydrophobic porous matrix supported noble metal catalyst;
alternatively, the first and second electrodes may be,
(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 precious 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;
(6) and roasting the contact product to obtain the flame-retardant hydrophobic porous matrix supported noble metal catalyst.
In one embodiment of the present invention, in the steps (1) and (1') of the above preparation method, the 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 groups2-20Examples of the alkane include oxalic acid, succinic acid, and adipic acid. The polycarboxylic acid may include C optionally having one or more hydroxyl groups (for example, 1 to 6) and 1 to 10 (preferably 3 to 6) carboxyl groups2-20Alkanes, for exampleMalic acid, tartaric acid, citric acid, stearic acid, and the like. Alternatively, the polycarboxylic acid may be one represented by formula C2-20Examples 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 group1-20Examples 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 groups2-20Examples 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 C2-20Examples 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 carboxylic acid salt, 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 substrate (or modified original substrate) 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 equipment and conditions for the molding process are not particularly limited, and those known in the art may be used.
In the steps (2) and (3'), during molding, an extruder can be used for 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.
In the step (3), the roasted mixed contact body or the roasted porous matrix blank is contacted with a solution containing a hydrophobic modifier in a ratio of 1/5-1/30 relative to the mass of the solution containing the hydrophobic modifier.
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 a combination of several 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 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 baking temperature in the steps (4) and (4') is not particularly limited, and the temperature is 200 to 580 ℃, preferably 200 to 550 ℃, and more preferably 300 to 550 ℃. The calcination may be performed in an air atmosphere or in 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'), there is no particular limitation on the manner in which the contacting step is carried out, as long as sufficient mixing contact 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, there is no particular limitation on the manner of carrying out the contact of steps (3) and (1'), 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 also not particularly limited.
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 the step (5), the noble metal is at least one element selected from the group consisting of Pt, Pd, Ru, Rh, Au, Ir, and Ag. The noble metal is preferably at least one combination selected from the group consisting of a combination of Pt and Pd, a combination of Pt and Ru, a combination of Pt and Au, and a combination of Pt and Ir, and the mass ratio of the two elements (the former to the latter) (in terms of the simple substance of the element) in each combination is preferably 0.2 to 5, and more preferably 0.4 to 4.
In step (5), the auxiliary component comprises at least one element selected from group a: li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce. Preferably, the auxiliary agent is at least one combination 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 Co, a combination of Ce and Ni, a combination of Ce and Bi, a combination of Ce and Cr, a combination of La and Mn, a combination of La and Fe, a combination of La and Co, a combination of La and Ni, and a combination of La and Bi, and preferably, the mass ratio of the two elements (the former to the latter) (in terms of the elements) in each combination is 0.1 to 10, preferably 0.5 to 5.
In the present invention, the precursor of the noble metal component is a precursor of a noble metal commonly used in the art, for example, the precursor of the noble metal may be preferably a soluble salt and/or an acid of the noble metal, and further preferably a chloride, a nitrate, an acetate, a sulfate, an ammonia salt, and the like, but is not limited thereto. For example, the palladium metal precursor may be selected from palladium chloride, palladium nitrate, palladium acetate, palladium dichlorodiammine, etc., and the platinum metal precursor may be selected from chloroplatinic acid, platinum chloride, dinitrosopropylamine, platinum dichlorotetrammine, etc.
In the present invention, the precursor of the auxiliary component is a precursor of an auxiliary metal commonly used in the art, for example, the precursor of the auxiliary metal may be preferably a soluble salt of the auxiliary component, and further preferably a chloride salt, a nitrate, an acetate, a sulfate, an ammonia salt, or a phosphate. 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 noble 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 noble metal component and the precursor of the auxiliary component can be dissolved or suspended and the effect of the present invention is 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 may 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 noble 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 10 to 300 g/L.
In the present invention, various additives, for example, a complexing agent, a stabilizer, and a pH adjuster, may be further added as necessary when preparing a solution or suspension of a precursor of the noble metal component and/or when preparing a solution or suspension of a precursor of the auxiliary component.
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 may be used. The stabilizer preferably comprises one or more barium and/or strontium oxides.
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 at least one noble metal component and the solution or suspension of the precursor of 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 noble 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 noble metal component may be contacted with the porous substrate first, and then the solution or suspension of the precursor of the auxiliary component may be contacted with the porous substrate, or the order may be changed. Or after respectively preparing a solution or suspension of a precursor of the noble 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 contacting steps, a heat treatment step such as drying and baking may be optionally performed, for example, at 50 to 180 ℃, preferably at 60 to 150 ℃, and more preferably at 70 to 120 ℃, followed by drying, air-drying, and air-drying.
In addition, in the invention, a precursor of the noble 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 noble 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, so long as the content of the noble metal (in terms of the simple noble metal) in the finally prepared catalyst is 100 to 1300g/m based on the total volume of the catalyst3Preferably 150 to 1000 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200 kg/m3Preferably 15 to 150 kg/m3And (4) finishing.
In the step (5), when the solution or suspension of the precursor of the noble metal component, the solution or suspension of the precursor of the auxiliary component and the flame-retardant hydrophobic porous matrix are contacted, the concentration of the solution or suspension of the precursor of the noble metal component, the concentration of the solution or suspension of the precursor of the auxiliary 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 content of the noble metal (calculated by the simple substance of the noble metal) in the finally prepared catalyst is 100-1300 g/m based on the total volume of the catalyst3Preferably 150 to 1000 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200 kg/m3Preferably 15 to 150 kg/m3And (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 noble metal 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 noble metal catalyst or the flame-retardant hydrophobic porous matrix supported noble metal 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-1And contacting the porous matrix with a noble metal catalyst at 150-450 ℃ to remove volatile organic gas by catalytic oxidation.
The flame-retardant hydrophobic porous matrix supported noble metal catalyst or the flame-retardant hydrophobic porous matrix supported noble metal catalyst prepared by the preparation method can be used for catalytic oxidation of wastewater, particularly high-COD wastewater.
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-1The pressure is 2-8MPa, the reaction temperature is 200-280 ℃, and the noble metal catalyst is loaded on the porous matrix 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, the content of each metal element is calculated as a simple substance unless otherwise specified.
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 from the 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 cellular macroscopic pore canal has an irregular shape, 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 section area = [ (the longest diameter (or the longest diagonal length) + the shortest diameter (or the shortest diagonal length))/4]2π. 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 body2Roasting 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 embryo body to ethanol with the mass concentration of ethyl silicate of 1 percentSoaking in the solution for 1 hr, taking out, and calcining at 400 deg.C for 4 hr to obtain flame-retardant hydrophobic honeycomb matrix A with contact angle of 53 deg. The Pt content in each cubic flame-retardant hydrophobic honeycomb substrate is 400g/m3The Ru content is 120g/m3The mass ratio of oxalic acid to chloroplatinic acid is 3:1, and the Ce content in each cubic flame-retardant hydrophobic honeycomb matrix is 20kg/m3Sn content of 18kg/m3Preparing aqueous solution of cerium nitrate and stannous chloride according to the proportion, firstly dipping Pt and Ru solution in a flame-retardant hydrophobic honeycomb matrix A, drying for 4 hours at the temperature of 150 ℃, then further dipping Ce and Sn solution, drying again for 2 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 noble metal A1 with the surface area of 141m2·g-1The most probable pore diameter is 5.5nm, and the pore volume is 0.38 ml/g-1The cross section of the honeycomb holes is 9.2mm2。
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 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 container2Roasting 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 Pt content per cubic honeycomb substrate is 500g/m3The Pd content is 120g/m3Preparing a chloroplatinic acid solution and an oxalic acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of oxalic acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic honeycomb matrix is 40kg/m3Mn content of 18kg/m3Proportional arrangement ofThe method comprises the steps of firstly soaking Pt and Pd solutions in a water solution of cerium nitrate and manganese nitrate on a honeycomb substrate, drying for 4 hours at the temperature of 150 ℃, then further soaking in Ce and Mn solutions, drying for 2 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 noble metal catalyst B1 with the surface area of 137m2·g-1The most probable pore diameter was 5.8nm, and the pore volume was 0.31 ml/g-1The cross section of the honeycomb holes is 9mm2。
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 container2Roasting for 2 hours at 300 ℃, cooling to room temperature, and mixing the cooled blank 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. The Pt content per cubic honeycomb substrate is 500g/m3Au content of 150g/m3Preparing a chloroplatinic acid solution and an oxalic acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of oxalic acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic honeycomb matrix is 40kg/m3And the Co content is 18kg/m3Preparing aqueous solution of cerous nitrate and cobalt nitrate according to the proportion, firstly dipping Pt and Au solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further dipping Ce and 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 substrate supported noble metal catalyst C1 with the surface area of 347m2·g-1The most probable pore diameter is 6.8nm, and the pore volume is 0.54ml g-1The cross section of the honeycomb holes is 8.1mm2。
Example 4
Uniformly stirring attapulgite, kaolin, a 5A molecular sieve, 65 mass percent nitric acid, hydroxymethyl propyl cellulose and glycerol in a kneading machine 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 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 length and the height of four bottom sides of the square honeycomb hole blank are respectively 80cm and 100cm, and the honeycomb blank is placed in an N-shaped honeycomb hole2Roasting 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 the contact angle of 61 degrees. The Pt content per cubic honeycomb substrate is 500g/m3The Ir content is 210g/m3The mass ratio of citric acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic honeycomb matrix is 40kg/m3The Fe content is 8kg/m3Preparing aqueous solution of cerium nitrate and ferric nitrate, firstly dipping Pt and Ir solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further dipping Ce 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 noble metal catalyst D1 with the surface area of 188m2·g-1The most probable pore diameter is 5.5nm, and the pore volume is 0.45 ml/g-1The cross section of the honeycomb holes is 8.1mm2。
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: 0.03, adding appropriate amount of water, kneading to obtain plastic mixed contact body, placing the contact body into an extruder, extruding under the conditions of pressure of 7MPa and temperature of 25 deg.C, and making into the final productForming a blank body of square honeycomb holes, wherein the four bottom side lengths and the heights of the blank body of the square honeycomb holes are respectively 80cm and 100cm, and the honeycomb blank body is arranged at N2Roasting for 2 hours at 200 ℃, cooling to room temperature, and then mixing the cooled blank body with the modified solution according to the mass ratio of 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 Pt content per cubic honeycomb substrate is 500g/m3The Pd content is 210g/m3The weight ratio of citric acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic honeycomb matrix is 40kg/m3Ni content of 11kg/m3Preparing aqueous solution of cerium nitrate and nickel nitrate, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking Ce and Ni 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 noble metal catalyst E1 with the surface area of 182m2·g-1The most probable pore diameter was 5.4nm, and the pore volume was 0.43 ml/g-1The cross section of the honeycomb holes is 7.9mm2。
Example 6
The flame-retardant hydrophobic honeycomb substrate E of example 5 was taken. The Pt content per cubic honeycomb substrate is 500g/m3The Pd content is 200g/m3The mass ratio of citric acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic honeycomb matrix is 80kg/m3The Bi content is 11kg/m3Preparing aqueous solution of cerium nitrate and bismuth nitrate, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking Ce and Bi solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 8 hours at the temperature of 500 ℃ to obtain the flame-retardant hydrophobic porous substrate supported noble metal catalyst F1 with the surface area of 176m2·g-1The most probable pore diameter was 5.7nm, and the pore volume was 0.42ml g-1Cross sectional area of honeycomb holesIs 8.6mm2。
Example 7
The flame-retardant hydrophobic honeycomb substrate E of example 5 was taken. The Pt content per cubic honeycomb substrate is 500g/m3Pd content of 150g/m3The mass ratio of citric acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic honeycomb matrix is 80kg/m3The Cr content is 20kg/m3Preparing aqueous solution of cerous nitrate and chromic nitrate according to the proportion, firstly dipping Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further dipping Ce and Cr 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 noble metal catalyst G1 with the surface area of 192m2·g-1The most probable pore diameter is 4.8nm, and the pore volume is 0.40 ml/g-1The cross section of the honeycomb holes is 7.5mm2。
Example 8
The flame-retardant hydrophobic honeycomb substrate E of example 5 was taken. The Pt content per cubic honeycomb substrate is 500g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the La content of each cubic honeycomb matrix is 80kg/m3Mn content of 20kg/m3Preparing aqueous solution of lanthanum nitrate and manganese nitrate, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking La and Mn 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 noble metal catalyst H1 with the surface area of 158m2·g-1The most probable pore diameter is 6.1nm, and the pore volume is 0.38 ml/g-1The cross section of the honeycomb holes is 6.8mm2。
Example 9
The flame-retardant hydrophobic honeycomb substrate E of example 5 was taken. The Pt content per cubic honeycomb substrate is 500g/m3The Pd content is 200g/m3The chloroplatinic acid solution and the hydrochloric acid aqueous solution of palladium chloride are prepared according to the proportionWherein the mass ratio of the hydrochloric acid to the chloroplatinic acid is 3:1, and the La content of each cubic honeycomb matrix is 80kg/m3Co content of 30kg/m3Preparing aqueous solution of lanthanum nitrate and cobalt nitrate, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking La and 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 substrate supported noble metal catalyst I1 with the surface area of 147m2·g-1The most probable pore diameter was 6.8nm, and the pore volume was 0.36 ml/g-1The cross section of the honeycomb holes is 7.3mm2。
Example 10
The flame-retardant hydrophobic honeycomb substrate E of example 5 was taken. The Pt content of each cubic honeycomb substrate is 500g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the La content of each cubic honeycomb matrix is 90kg/m3The Fe content is 18kg/m3Preparing aqueous solution of lanthanum nitrate and ferric nitrate, firstly soaking Pt and Pd solution on a honeycomb substrate, 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 noble metal catalyst J1 with the surface area of 147m2·g-1The most probable pore diameter was 6.8nm, and the pore volume was 0.36 ml/g-1The cross section of the honeycomb holes is 8.2mm2。
Example 11
The flame-retardant hydrophobic honeycomb substrate E of example 5 was taken. The Pt content per cubic honeycomb substrate is 500g/m3Pd content of 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the La content of each cubic honeycomb matrix is 90kg/m3Ni content of 20kg/m3Preparing aqueous solution of lanthanum nitrate and nickel nitrate, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, and then further soaking La and Ni, drying the solution at 150 ℃ for 3 hours again, and roasting the solution at 490 ℃ for 5 hours to obtain the flame-retardant hydrophobic porous matrix supported noble metal catalyst K1 with the surface area of 153m2·g-1The most probable pore diameter was 6.1nm, and the pore volume was 0.39 ml. multidot.g-1The cross section of the honeycomb holes is 8.2mm2。
Example 12
The flame-retardant hydrophobic honeycomb substrate E of example 5 was taken. The Pt content per cubic honeycomb substrate is 500g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the La content of each cubic honeycomb matrix is 90kg/m3And a Bi content of 20kg/m3Preparing aqueous solution of lanthanum nitrate and bismuth nitrate, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking La and Bi solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 490 ℃ to obtain the flame-retardant hydrophobic porous substrate supported noble metal catalyst L1 with the surface area of 158m2·g-1The most probable pore diameter is 6.0nm, and the pore volume is 0.39 ml/g-1The cross section of the honeycomb holes is 8.2mm2。
Example 13
The flame-retardant hydrophobic honeycomb substrate E of example 5 was taken. The Pt content per cubic honeycomb substrate is 500g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the La content of each cubic honeycomb matrix is 90kg/m3The method comprises the steps of preparing a lanthanum nitrate aqueous solution, firstly soaking Pt and Pd solutions on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking the La solution, drying for 3 hours again at the temperature of 180 ℃, and roasting for 5 hours at the temperature of 450 ℃ to obtain the flame-retardant hydrophobic porous substrate supported noble metal catalyst M1 with the surface area of 173M2·g-1The most probable pore diameter was 5.7nm, and the pore volume was 0.43 ml/g-1The cross section of the honeycomb holes is 8.2mm2。
Example 14
The flame-retardant hydrophobic honeycomb substrate E of example 5 was taken. The Pt content per cubic honeycomb substrate is 500g/m3Pd content of 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic honeycomb matrix is 90kg/m3Preparing a cerous nitrate aqueous solution according to the proportion, firstly dipping Pt and Pd solutions on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further dipping the Ce solution, drying for 3 hours at the temperature of 180 ℃, and roasting for 2 hours at the temperature of 500 ℃ to obtain the flame-retardant hydrophobic porous substrate supported noble metal catalyst N1 with the surface area of 157m2·g-1The most probable pore diameter was 6.3nm, and the pore volume was 0.40 ml/g-1The cross section area of the honeycomb holes is 8.2mm2。
Example 15
The flame-retardant hydrophobic honeycomb substrate E of example 5 was taken. The Pt content per cubic honeycomb substrate is 500g/m3The Pd content is 150g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the Cr content of each cubic honeycomb matrix is 90kg/m3Mo content of 20kg/m3Preparing aqueous solution of chromium nitrate and ammonium molybdate according to the proportion, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking Cr and Mo solution, drying for 3 hours again at the temperature of 180 ℃, and roasting for 4 hours at the temperature of 550 ℃ to obtain the flame-retardant hydrophobic porous substrate supported noble metal catalyst O1 with the surface area of 119m2·g-1The most probable pore diameter is 8.3nm, and the pore volume is 0.23 ml/g-1The cross section area of the honeycomb holes is 8.2mm2。
Example 16
The flame-retardant hydrophobic honeycomb substrate E of example 5 was taken. The Pt content per cubic honeycomb substrate is 500g/m3The Pd content is 150g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the content of K in each cubic honeycomb matrix is 10kg/m3Re content of 30kg/m3W is containingThe amount is 20kg/m3Preparing aqueous solution of potassium nitrate, rhenium chloride and ammonium tungstate, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking solution of K, Re and W, drying again for 3 hours at the temperature of 180 ℃, and roasting for 4 hours at the temperature of 480 ℃ to obtain the flame-retardant hydrophobic porous substrate supported noble metal catalyst P1 with the surface area of 131m2·g-1The most probable pore diameter was 6.9nm, and the pore volume was 0.33 ml/g-1The cross section area of the honeycomb holes is 8.2mm2。
Example 17
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, 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 blank of square honeycomb holes, wherein the side length and the height of four bottom edges of the blank of the square honeycomb holes are 80cm and 100cm respectively, and the honeycomb blank is prepared by mixing N, N and N2Roasting 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, soaking the cooled blank body in an ethanol solution with the mass concentration of ethyl silicate of 1 percent for 1 hour, taking out, roasting for 4 hours at 450 ℃, and obtaining the flame-retardant hydrophobic honeycomb matrix Q with a contact angle of 51 degrees. The Pt content per cubic honeycomb substrate is 420g/m3The Pd content is 120g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the Mn content of each cubic honeycomb matrix is 10kg/m3Ce content of 20kg/m3Preparing aqueous solution of manganese nitrate and ammonium ceric nitrate, firstly dipping Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further dipping Mn and Ce solution, drying for 3 hours again at the temperature of 180 ℃, and roasting for 4 hours at the temperature of 480 ℃ to obtain the flame-retardant hydrophobic porous substrate supported noble metal catalyst Q1 with the surface area of 145m2·g-1The most probable pore diameter is 6.1nm, and the pore volume is 0.38 ml/g-1Honeycomb structureThe cross-sectional area of the hole is 8.6mm2。
Example 18
Mixing attapulgite, silicon dioxide, 65% nitric acid, hydroxymethyl propyl cellulose and glycerol according to a mass ratio of 10: 5: 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 molding2Roasting 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 16: 1, soaking the cooled blank body in an ethanol solution with the mass concentration of ethyl silicate of 1 percent for 1 hour, taking out, roasting for 4 hours at 450 ℃, and obtaining the flame-retardant hydrophobic honeycomb matrix S with a contact angle of 62 degrees. The Pt content of each cubic honeycomb substrate is 400g/m3The Pd content is 120g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the Mn content of each cubic honeycomb matrix is 40kg/m3Ce content of 30kg/m3Preparing aqueous solution of manganese nitrate and ammonium ceric nitrate, firstly dipping Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further dipping Mn and Ce solution, drying for 3 hours again at the temperature of 180 ℃, and roasting for 4 hours at the temperature of 480 ℃ to obtain the flame-retardant hydrophobic porous substrate supported noble metal catalyst S1 with the surface area of 158m2·g-1The most probable pore diameter is 6.8nm, and the pore volume is 0.36 ml/g-1The cross section area of the honeycomb holes is 8.3mm2。
Example 19
Mixing attapulgite, alumina, titanium oxide, 65% nitric acid, hydroxymethyl propyl cellulose and glycerol according to a mass ratio of 10: 3: 1: 0.02:0.2: 0.001, stirring 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, and making into cubeThe four bottom side lengths and the heights of the green body of the square honeycomb holes are respectively 80cm and 100cm, and the green body of the honeycomb is N2Roasting 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, soaking the cooled blank body in an ethanol solution with the mass concentration of ethyl silicate of 1 percent for 1 hour, taking out, roasting for 4 hours at 400 ℃, and obtaining the flame-retardant hydrophobic honeycomb matrix T with a contact angle of 49 degrees. The Pt content per cubic honeycomb substrate is 340g/m3The Ru content is 150g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the Mn content of each cubic honeycomb matrix is 40kg/m3La content of 30kg/m3Preparing aqueous solution of manganese nitrate and lanthanum chloride according to the proportion, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking Mn and La solution, drying for 3 hours again at the temperature of 180 ℃, and roasting for 4 hours at the temperature of 480 ℃ to obtain the flame-retardant hydrophobic porous substrate supported noble metal catalyst T1 with the surface area of 125m2·g-1The most probable pore diameter is 6.9nm, and the pore volume is 0.30 ml/g-1The cross section of the honeycomb holes is 8.1mm2。
Comparative example 1
Unlike the hydrophobic flame retardant honeycomb substrate preparation of example 18. Mixing attapulgite, silicon dioxide, 65% nitric acid, hydroxymethyl propyl cellulose and glycerol according to a mass ratio of 10: 5: 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 25 ℃ and 5MPa to prepare 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 molding2Roasting for 4 hours at 450 ℃ under the condition to obtain the flame-retardant non-hydrophobic honeycomb matrix R', the contact angle of which is 18 degrees. The Pt content per cubic honeycomb substrate is 400g/m3Pd content of 120g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass of the hydrochloric acid and the chloroplatinic acidThe ratio is 3:1, and the Mn content per cubic honeycomb matrix is 40kg/m3Ce content of 30kg/m3Preparing aqueous solution of manganese nitrate and ammonium ceric nitrate, firstly soaking Pt and Pd solution on a honeycomb substrate, drying for 4 hours at the temperature of 130 ℃, then further soaking Mn and Ce solution, drying for 3 hours again at the temperature of 180 ℃, and roasting for 4 hours at the temperature of 480 ℃ to obtain the flame-retardant porous substrate supported noble metal catalyst R1 with the surface area of 178m2·g-1The most probable pore diameter is 8.7nm, and the pore volume is 0.52 ml/g-1The area of the honeycomb holes is 8.9mm2。
Example 20
The flame-retardant hydrophobic catalysts of examples 1 to 19 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 methane3The VOCs gas (typical components of the gas are dimethylbenzene, hexane and propane, the volume fraction is 2:1:1, and the rest is air) at the reaction temperature of 350 ℃ and the space velocity of 10000h-1The 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 is3) The reaction time is 500h, and the concentration (mg/m) of VOCs at the outlet is3) The reaction is carried out for 1000h, and the concentration (mg/m) of VOCs at the outlet is3)
A1 13.5 14.4 15.1
B1 3.4 3.6 4.2
C1 5.4 5.5 6.3
D1 7.2 7.4 8.6
E1 7.0 7.3 8.2
F1 6.9 7.1 7.5
G1 6.8 7.5 8.3
H1 7.4 7.8 8.4
I1 9.3 9.8 10.8
J1 9.4 10.1 10.8
K1 8.4 8.7 9.1
L1 7.9 8.2 8.7
M1 28.2 31.2 33.7
N1 30.2 31.7 35.1
O1 32.1 34.4 38.7
P1 33.3 36.8 39.8
Q1 9.8 10.3 10.5
S1 5.7 6.3 6.4
T1 10.4 10.7 11.0
R1 6.4 7.2 7.9
As can be seen from table 1, the noble metal-supported porous substrate 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 21
The catalyst in example 18 and the catalyst in comparative example 1 were subjected to elemental analysis of metals, and the catalyst after 1000 hours of the above reaction to treat the VOCs gas was 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 flame-retardant hydrophobic catalyst
Figure 411480DEST_PATH_IMAGE001
。
As is clear from table 2, in the noble metal-supported porous substrate catalyst of the present invention, the noble metal component and the auxiliary component are firmly supported on the porous substrate, and the active metal is hard to fall off even after long-term use.
Example 22
The flame-retardant hydrophobic catalyst of example 2 is loaded into a fixed bed reactor, acrylic acid-containing wastewater with COD of 35000mg/L is introduced, and the airspeed of the wastewater is 0.5h-1The reaction temperature is 260 ℃ and the pressure is 5 MPa. After the reaction is carried out for 100 hours, the COD of the waste water at the reaction outlet is 2750 mg/L. 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 reaction results of catalytic oxidation of wastewater by flame-retardant hydrophobic catalyst
Figure 515571DEST_PATH_IMAGE002
。
The results show that the catalyst with the noble metal supported on the porous matrix has excellent catalytic oxidation performance for wastewater treatment. In addition, the noble metal component and the auxiliary component are firmly supported on the porous substrate, and the active metal is difficult to fall off even if washed away by 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 (18)

1. A noble metal catalyst loaded on a flame-retardant hydrophobic porous matrix is characterized by comprising the flame-retardant hydrophobic porous matrix, noble metal and an auxiliary agent component loaded on the flame-retardant hydrophobic porous matrix,
wherein the noble metal is at least one element selected from Pt, Pd, Ru, Rh, Au, Ir and Ag, preferably at least one combination selected from the combination of Pt and Pd, the combination of Pt and Ru, the combination of Pt and Au and the combination of Pt and Ir,
the additive component is at least one selected from the group A elements, the additive is preferably selected from at least one combination of Ce and Mo, Ce and Mn, Ce and Co, Ce and Fe, Ce and Ni, Ce and Bi, Ce and Cr, La and Mn, La and Fe, La and Co, La and Ni, La and Bi,
group A: li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce;
based on the total volume of the flame-retardant hydrophobic porous matrix supported noble metal catalyst, the content of noble metal (calculated by noble metal simple substance) is 100-1300 g/m3Preferably 150 to 1000 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200 kg/m3Preferably 15 to 150 kg/m3，
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 a flame retardant hydrophobic porous matrix, at least one noble metal supported on the porous matrix and an adjunct component, preferably the catalyst consists only of a flame retardant hydrophobic porous matrix, at least one noble metal supported on the porous matrix and an adjunct component.
3. According to claim1 or 2, wherein the BET specific surface area of the catalyst is 100-800 m2·g-1Preferably 110 to 800m2·g-1The most probable pore diameter is 2 to 12nm, preferably 2 to 10nm, and the pore volume is 0.15 to 1.0 ml/g-1Preferably 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 1mm2~80mm2Preferably 1mm2~40mm2The 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. The catalyst according to any one of claims 1 to 6, wherein the mass ratio of the noble metal Pt to the other noble metal is 0.7:1 to 8: 1.
8. A preparation method of a flame-retardant hydrophobic type porous matrix supported 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 to prepare a flame-retardant hydrophobic porous matrix;
(5) contacting a solution or suspension of a precursor of at least one precious 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;
(6) roasting the contact product to obtain the flame-retardant hydrophobic porous matrix supported noble metal catalyst;
alternatively, the first and second electrodes may be,
(1') subjecting at least one original matrix selected from the group consisting of attapulgite and kaolin and at least one inorganic material selected from the group consisting of inorganic porous solids, preferably at least one selected from the group consisting of silica, alumina, magnesia, silica-alumina, magnesia-alumina, titania-silica, molecular sieves and montmorillonite, to calcination after each contact with a solution containing a hydrophobic modifier;
(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 precious 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;
(6) and roasting the contact product to obtain the flame-retardant hydrophobic porous matrix supported noble metal catalyst.
9. The production method according to claim 8, 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 carboxylates, 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.
10. The production method according to claim 8 or 9, 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.
11. The production method according to any one of claims 8 to 10, 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 ℃.
12. The production method according to any one of claims 8 to 11, further comprising, before at least one of the above-mentioned firing of step (3), the firing of step (4), the firing of step (1'), and the 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 ℃.
13. The production method according to any one of claims 8 to 12, wherein the auxiliary component is at least one selected from the group A elements, the auxiliary 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 Co, a combination of Ce and Fe, a combination of Ce and Ni, a combination of Ce and Bi, a combination of Ce and Cr, a combination of La and Mn, a combination of La and Fe, a combination of La and Co, a combination of La and Ni, a combination of La and Bi,
group A: li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce,
the noble metal is at least one selected from Pt, Pd, Ru, Rh, Au, Ir and Ag, preferably at least one selected from Pt and Pd combination, Pt and Ru combination, Pt and Au combination and Pt and Ir combination,
the precursor of the noble metal is soluble salt and/or acid of the noble metal, preferably at least one selected from chloride, nitrate, acetate, sulfate and ammonium salt, and further preferably at least one selected from palladium chloride, palladium nitrate, palladium acetate, dichlorodiammine palladium, chloroplatinic acid, platinum chloride, dinitrosoprodam platinum and dichlorotetraammonium;
the precursor of the auxiliary component is at least one of chloride, nitrate, acetate, sulfate, ammonia salt and phosphate of the auxiliary component,
in the obtained catalyst, based on the total volume of the catalyst, the content of the noble metal (calculated by a noble metal simple substance) is 100-1300 g/m3Preferably 150 to 1000 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200 kg/m3Preferably 15 to 150 kg/m3。
14. The production method according to any one of claims 8 to 13, wherein at least one of a complexing agent, a stabilizer, and a pH adjuster may be added to the solution or suspension of the precursor of the noble metal component and/or the solution or suspension of the precursor of the auxiliary component.
15. Use of a noble metal-supported catalyst with a flame-retardant hydrophobic porous matrix according to any one of claims 1 to 7 or prepared by the preparation method according to any one of claims 8 to 14 for catalytic oxidation of volatile organic compounds.
16. Use according to claim 15, 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-1And contacting the porous matrix at 150-450 ℃ to load the noble metal catalyst.
17. Use of the flame-retardant hydrophobic porous matrix supported noble metal catalyst according to any one of claims 1 to 7 or prepared by the preparation method according to any one of claims 8 to 14 for catalytically oxidizing wastewater to reduce COD.
18. Use according to claim 17, wherein said conditions are: the space velocity of the liquid volume of the wastewater is 0.2 to 3h-1The pressure is 2-8MPa, and the reaction temperature is 200-280 ℃, and the noble metal catalyst is loaded on the porous matrix.
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CN115646511B (en) * 2022-11-29 2024-04-05 厦门大学 Catalytic wet oxidation catalyst and preparation method and application thereof

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