CN114618517A - Metal honeycomb combustion catalyst with integral structure, preparation method and application - Google Patents
Metal honeycomb combustion catalyst with integral structure, preparation method and application Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0242—Coating followed by impregnation
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
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Abstract
The application discloses a monolithic structure metal honeycomb combustion catalyst, a preparation method and application thereof. The combustion catalyst comprises a metal honeycomb substrate and a catalytic component; the catalytic component is loaded on the surface of the metal honeycomb substrate; the catalytic component comprises an active component and a multi-metal composite oxide; the active component is loaded on the multi-metal composite oxide; the active component comprises at least one of Ru element, Pt element, Pd element and Rh element; the chemical formula of the multi-metal composite oxide is MxM'yO2(ii) a The M is selected from at least one of Co, Mn, Ce, Sn, Ni and Fe; m' is at least one selected from V, Zr, Nb, Cr, Mo, W and LaSeed growing; 0<x<1，0<y<1. The combustion catalyst has the characteristics of quick initiation, excellent combustion activity, high-temperature hydrothermal resistance, simple preparation and high-efficiency removal and purification of VOCs contained in industrial waste gas.
Description
Technical Field
The application relates to a metal honeycomb combustion catalyst with an integral structure, a preparation method and application, and belongs to the technical field of catalytic purification of atmospheric pollutants.
Background
In recent years, the atmospheric pollution of China begins to present the situation of regional and compound pollution, and especially in the industrial production process of chemicals related to the industries such as chemical industry, petroleum industry, paint industry, printing and dyeing industry and the like, the problem of large amount of VOCs emission pollution needs to be solved urgently. The catalytic combustion method is considered to be one of the most promising technologies for VOCs treatment because of its advantages of low ignition temperature, no secondary pollution, high treatment efficiency, etc. The essence of the catalytic combustion method is that the aim of eliminating the VOCs reactant is achieved by reducing the activation energy of the target reaction and promoting the activation, adsorption and reaction of active oxygen and target VOCs reactant molecules on the active site of the catalyst. This in fact places very high demands on the construction and preparation of efficient combustion catalysts.
At present, ceramic honeycombs are adopted as carriers for combustion catalysts with integral structures, which are generally applied in industry, however, due to the characteristics of high heat capacity, low heat conductivity and the like of the ceramic honeycombs, in practical application, the starting time of device equipment is long, the temperature rise rate is slow, a large amount of VOCs gas is discharged into the atmosphere at the initial stage of starting operation to cause environmental pollution, and in addition, a catalyst bed layer can generate a hot spot due to temperature runaway locally in the operation process, so that the catalytic performance is influenced. An effective solution is to use a metal honeycomb substrate to replace a ceramic honeycomb substrate, and compared with the ceramic substrate with an integral structure, the metal substrate has the advantages of thin wall thickness, low heat capacity, high heat transfer coefficient and the like, and has higher mechanical strength and vibration resistance. It should be pointed out that the preparation process of the metal honeycomb substrate combustion catalyst has great technical challenges, especially the problem of the bonding firmness of the carrier coating on the surface of the metal substrate, and the phenomena of uneven coating thickness, coating cracking and the like are easily caused, so that the firmness of the coating is reduced, and the performance and the service life of the catalyst are influenced.
In addition, in an actual application system, multi-component VOCs coexist, and different types of VOCs have competitive adsorption, so that the catalytic combustion performance of the VOCs is influenced. Most of the currently reported researches aim at the catalytic performance of single VOCs, so that the universality of the developed catalyst is greatly limited. Therefore, it is necessary to develop a catalytic combustion system with multiple active sites to improve the universality of the catalyst.
Disclosure of Invention
In view of the above, the invention provides a metal honeycomb combustion catalyst with an integral structure and a preparation method thereof, which constructs the combustion catalyst by taking the synergetic catalytic action of a plurality of active sites of 'noble metal-oxygen defect-acid site' as a core and aims to improve the catalytic performance, high-temperature hydrothermal resistance and long-term use stability of the combustion catalyst; meanwhile, due to the construction of a plurality of active sites, the influence of competitive adsorption when multi-component VOCs coexist on catalytic combustion performance can be avoided, and the performance and the broad spectrum of the catalyst are further improved. The metal honeycomb substrate is used for replacing a conventional ceramic honeycomb substrate, so that the heat conductivity of the combustion catalyst is improved, the starting time of a device is shortened, the emission of toxic and harmful gases is reduced, and the active site of the catalyst is protected, so that the catalytic performance and the long-term use stability of the combustion catalyst are improved; the firmness of the metal composite oxide coating on the surface of the metal matrix is improved by optimizing the slurry property of the oxide coating precursor and the coating loading process.
In order to achieve the purpose, the invention provides the following technical scheme:
a combustion catalyst system comprising a plurality of active sites of "noble metal-oxygen defect-acid sites" is constructed on a monolithic structural metal honeycomb substrate. The combustion catalyst supports an oxide coating containing a plurality of active sites of 'noble metal-oxygen defect-acid sites' and a catalytic active center on a metal honeycomb substrate;
the catalytic active center is composed of precious metals such as Ru, Pt, Pd, Rh and the like;
the oxygen defect and the acid site are both multi-metal composite oxide MxM'yO2Providing; wherein the oxygen defects are formed by redox cycling (M) of a transition metala+→M(a-1)+) Providing a metal compound, wherein M is a transition metal element such as Co, Mn, Ce, Sn, Ni, Fe, etc.; the acid site is formed by a high-valence metal redox cycle (M'b+→M'(b-1)+) Wherein M' is a high-valence metal element such as V, Zr, Nb, Cr, Mo, W, etc.
According to a first aspect of the present application, a monolithic structural metal honeycomb combustion catalyst is provided.
A monolithic structural metal honeycomb combustion catalyst comprising a metal honeycomb substrate and a catalytic component;
the catalytic component is loaded on the surface of the metal honeycomb substrate;
the catalytic component comprises an active component and a multi-metal composite oxide;
the active component is loaded on the multi-metal composite oxide;
the active component comprises at least one of Ru element, Pt element, Pd element and Rh element;
the chemical formula of the multi-metal composite oxide is MxM'yO2；
The M is at least one selected from Co, Mn, Ce, Sn, Ni and Fe;
m' is at least one selected from V, Zr, Nb, Cr, Mo, W and La;
0<x<1，0<y<1。
optionally, the active component includes at least two of Ru element, Pt element, Pd element, Rh element.
Wherein, for the multi-metal composite oxide MxM'yO2The multiple element can be binary, ternary, etc., for example, Ce can be used in case of binary metal composite oxide0.8La0.2O2、Ce0.5Zr0.5O2Etc.; in the case of ternary metal composite oxide, Ce may be used0.4Zr0.4Mn0.2O2、Ce0.45Zr0.45La0.1O2And the like.
Optionally, the mass of the multi-element metal composite oxide is 1% to 40% of the mass of the metal honeycomb substrate.
Optionally, the mass of the multi-element metal composite oxide is a ratio of the mass of the metal honeycomb substrate independently selected from any value of 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or a range value between any two.
Optionally, the mass of the active component is 0.1-10% of the mass of the multi-metal composite oxide.
Optionally, the mass of the active component is a ratio of the mass of the multi-metal composite oxide independently selected from any of 0.1%, 0.2%, 0.5%, 1%, 1.2%, 1.5%, 2%, 4%, 5%, 8%, 10% or a range between any two.
Optionally, the metal honeycomb substrate is stainless steel or an iron-based alloy.
Optionally, the metal honeycomb substrate is a stainless steel or iron-based alloy metal honeycomb with a regular structure.
Optionally, the iron-based alloy is a FeCrAl alloy.
Optionally, the single-hole cross section of the metal honeycomb substrate is polygonal. The metal honeycomb substrate can be round, square, triangular, hexagonal and the like, and the metal honeycomb substrate with the proper shape can be selected according to actual needs.
According to a second aspect of the present application, there is provided a method of making the above monolithic structural metal honeycomb combustion catalyst.
A preparation method of the combustion catalyst comprises the following steps:
(1) obtaining a metal honeycomb substrate;
(2) obtaining precursor slurry containing the multi-element metal composite oxide;
(3) coating the precursor slurry on the surface of a metal honeycomb matrix, drying and roasting to obtain a multi-element metal composite oxide carrier coating intermediate;
(4) and loading the active component on the intermediate of the multi-metal composite oxide carrier coating, drying and roasting to obtain the combustion catalyst.
Wherein, in the step (3), the coating can be carried out once or in multiple times.
Optionally, in the step (2), the precursor slurry has a pH of 2.0 to 5.0, a viscosity of 10 to 200 mPas, and an average particle diameter D of the solid phase particles500.5-20 μm.
Optionally, the pH in the precursor slurry is independently selected from any of 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, or a range between any two.
Alternatively, the viscosity of the precursor slurry is independently selected from any value of 10mPa · s, 20mPa · s, 40mPa · s, 50mPa · s, 60mPa · s, 80mPa · s, 100mPa · s, 120mPa · s, 140mPa · s, 160mPa · s, 180mPa · s, 200mPa · s, or a range value between any two of them.
Optionally, in the precursor slurry, the average particle diameter D of the solid phase particles50Independently selected from any value of 0.5 μm, 1 μm, 3 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm, 14 μm, 15 μm, 18 μm, 20 μm or a range value between any two.
Optionally, step (2) comprises:
and performing ball milling treatment on a mixture containing the multi-element metal composite oxide, inorganic oxide sol, inorganic acid, an organic additive and water to obtain the precursor slurry.
Optionally, the mixture comprises the following components in parts by weight:
20-50 parts by weight of multi-metal composite oxide
1-15 parts by weight of inorganic oxide sol
1 to 10 parts by weight of an inorganic acid
0.1 to 15 parts by weight of an organic additive
20-60 parts of water.
Alternatively, the amount of the multi-component metal composite oxide is independently selected from any of 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, or a range between any two thereof.
Alternatively, the inorganic oxide sol is independently used in an amount selected from any of 1 part by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, or a range between any two thereof.
Alternatively, the amount of the inorganic acid is independently selected from any of 1 part by weight, 2 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, or a range between any two thereof.
Alternatively, the organic additive is used in an amount independently selected from any of 0.1 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 1 part by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, or a range between any two thereof.
Alternatively, the amount of water is independently selected from any of 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, or a range between any two.
Optionally, the inorganic oxide sol is at least one of aluminum sol, silica sol, cerium sol, zirconium sol and cerium-zirconium sol;
the inorganic acid is at least one of nitric acid, sulfuric acid and hydrochloric acid;
the organic additive is at least one of polyalcohol compounds and polyether compounds.
Optionally, the polyalcohol compound is selected from at least one of polyvinyl alcohol (PVA), tween, and polyethylene glycol (PEG).
Optionally, the polyether compound is at least one selected from propylene glycol block polyether compounds.
Specifically, the polyvinyl alcohol is PVA-1750.
Specifically, tween is tween-20.
Preferably, the organic additive is selected from the group consisting of water-soluble polyvinyl alcohol and tween-20.
Optionally, the concentration of the inorganic oxide sol is 10-20%, and the pH value is 2.0-4.5;
the concentration of the inorganic acid is 1M-10M.
Optionally, the concentration of the inorganic oxide sol is independently selected from any of 10%, 12%, 14%, 15%, 16%, 18%, 20%, or a range between any two.
Optionally, the pH of the inorganic oxide sol is independently selected from any of 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, or a range between any two.
Optionally, the concentration of the inorganic acid is independently selected from any of 1M, 2M, 3M, 4M, 5M, 6M, 7M, 8M, 9M, 10M, or a range between any two.
Preferably, the inorganic acid is dilute nitric acid, and the mass concentration of the substance is 1M-10M.
Optionally, the process conditions of the ball milling are as follows: the ball milling time is 2-24 hours, and the rotating speed is 300-500 r/min.
Optionally, step (4) comprises:
and (3) loading the solution containing the active component on the multi-metal composite oxide carrier coating intermediate by adopting an excess impregnation method.
Optionally, in step (3) and step (4), the drying conditions are independently selected from: the temperature is 80-120 ℃, and the time is 1-6 hours.
Optionally, the temperature of drying is independently selected from any of 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ or a range between any two.
Optionally, the time of drying is independently selected from any of 1h, 2h, 3h, 4h, 5h, 6h, or a range of values between any two.
Alternatively, in the step (3) and the step (4), the roasting conditions are as follows: heating to 450-850 ℃ at a heating rate of 1-5 ℃/min, and keeping for 1-6 hours.
Optionally, the temperature of the firing is independently selected from any value of 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃ or a range value between any two.
Alternatively, the time of calcination is independently selected from any of 1h, 2h, 3h, 4h, 5h, 6h, or a range between any two.
Optionally, the temperature rise rate of the firing is independently selected from any of 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, or a range between any two.
Optionally, in the step (3), the metal honeycomb substrate is pretreated before use;
the pretreatment comprises surface cleaning treatment and high-temperature oxidation treatment.
Optionally, the surface cleaning treatment comprises: ultrasonically cleaning the metal honeycomb matrix in an alcohol solvent for 10-60 min, and drying.
Optionally, the high temperature oxidation treatment comprises: and roasting the sample with the surface cleaned for 1-24 h at 800-1100 ℃ in the air atmosphere.
Optionally, the alcoholic solvent is ethanol.
Alternatively, the method for obtaining the active ingredient-containing solution comprises: dissolving simple substances corresponding to active component elements in aqua regia, and adding water to obtain the solution containing the active components.
As a preferred embodiment, comprising:
step 1: obtaining a metal honeycomb substrate with an integral structure;
step 2: obtaining a precursor slurry of a binary or multi-element metal composite oxide coating that provides catalytic components of oxygen defects and acid sites;
and step 3: uniformly coating the precursor slurry of the binary or multi-element composite oxide carrier coating on the surface of the pretreated metal honeycomb substrate with the integral structure at one time or a plurality of times, and drying and roasting to obtain a metal wall carrier coating intermediate sample A;
and 4, step 4: and (3) loading an active component on the carrier coating intermediate sample A obtained in the step (3) by adopting an excess impregnation method, and drying and roasting to obtain a catalyst sample.
According to a third aspect of the application, the monolithic structure metal honeycomb combustion catalyst and the monolithic structure metal honeycomb combustion catalyst prepared by the method are applied to removing and purifying VOCs.
The catalytic combustion catalyst and the combustion catalyst prepared by the method are applied to VOCs gas removal and purification.
The beneficial effects that this application can produce include:
1) the metal honeycomb combustion catalyst with the integral structure provided by the application takes the synergetic catalysis of a plurality of active sites of 'noble metal-oxygen defect-acid site' as a core, and avoids the influence of competitive adsorption on the catalytic purification performance when a plurality of pollutant components coexist. The combustion catalyst is constructed and prepared on the surface of the metal honeycomb substrate, and the catalytic performance, the high-temperature hydrothermal resistance, the long-term use stability and the applicability of the combustion catalyst are improved by adjusting and matching and utilizing the strong interaction between the active center of the catalyst and the carrier.
2) According to the preparation method of the metal honeycomb combustion catalyst with the integral structure, the inorganic oxide sol with the property similar to that of the multi-element composite oxide coating is adopted, and the organic additive is matched for use, so that the property of the precursor slurry of the composite oxide coating is optimized, the distribution state of the surface tension of the coating slurry is improved, the cracking and falling phenomena of the oxide coating on the surface of the metal honeycomb substrate are avoided, the mechanical stability of the catalyst is effectively improved, and the long-term stable use of the combustion catalyst is facilitated.
3) The application of the overall structure metal honeycomb combustion catalyst provided by the application substitutes conventional ceramic honeycomb base body with the metal honeycomb base body, the heat conduction efficiency of the combustion catalyst is obviously improved, the temperature gradient of a catalyst bed layer is reduced, in the practical industrial VOCs treatment application, the start-up time of a device system can be effectively shortened, the emission of toxic and harmful gases is reduced, the local temperature runaway of the catalyst bed layer can be avoided, the active site of the catalyst is effectively protected, and the improvement of the catalytic performance, the high-temperature hydrothermal resistance and the long-term use stability of the combustion catalyst is facilitated.
Drawings
FIG. 1 is a comparison of propane removal performance before and after high temperature hydrothermal aging treatment of catalyst samples of example 3.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified. If not stated, the test method adopts the conventional method, and the instrument setting adopts the setting recommended by the manufacturer.
Example 1:
in this example, binary metal composite oxide Ce is used0.5Zr0.5O2The solid solution is taken as a carrier coating, Pt and Pd are taken as active components, and the combustion catalyst is prepared on the surface of the metal honeycomb substrate in a loading way.
Pretreating an overall structural FeCrAl metal matrix: selecting an approximate cylindrical FeCrAl metal alloy matrix with the pore density of 400cpsi and the size of phi 12 multiplied by 12mm, firstly carrying out ultrasonic cleaning for 30 minutes by using ethanol, then carrying out cleaning by using deionized water, and roasting a dried metal alloy matrix sample for 10 hours at 950 ℃ in an air atmosphere for later use, wherein the mark is J-1.
Ce0.5Zr0.5O2Preparation of precursor slurry for washcoat: quantitatively weighing 30 parts by weight of Ce0.5Zr0.5O2The precursor slurry S-1 is prepared by the following steps of mixing powder, 10 parts by weight of Ce sol (the concentration is 15 wt%, and the pH value is 3.2), 5 parts by weight of dilute nitric acid with the substance concentration of 3M, 5 parts by weight of polyvinyl alcohol (PVA-1750), 5 parts by weight of Tween-20 and 45 parts by weight of water, and then performing ball milling for 6 hours at the rotating speed of 500 revolutions per minute by adopting a mechanical ball milling method to obtain the precursor slurry S-1. The viscosity was 69 mPas, pH 3.37. Measuring Ce in slurry S-1 by adopting Malvern particle sizer0.5Zr0.5O2Average particle diameter D50-13.965 μm.
FeCrAl metal alloy substrate surface Ce0.5Zr0.5O2Preparation of a carrier coating: uniformly coating the slurry S-1 on a metal substrate J-1, drying at 110 ℃ for 2 hours, putting a sample in a muffle furnace, heating to 550 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 2 hours to obtain Ce0.5Zr0.5O2Capacity of capacity25.37 wt% of intermediate carrier sample A-1;
preparing an active component precursor solution: (1) dissolving a quantitative Pt simple substance in aqua regia, and marking as R-a; (2) dissolving a quantitative Pd simple substance in aqua regia, and marking as R-b; (3) and mixing the R-a and the R-b, adding water to a constant volume to obtain a mixed solution labeled as R-1, wherein the concentration of Pt is 10.01mg/mL, and the concentration of Pd is 10.03 mg/mL.
Active component loading preparation: soaking the intermediate carrier sample A-1 in an excessive R-1 solution for 3min, taking out, blowing out the rest liquid on the surface of the carrier by using cold air, drying at 110 ℃ for 2h, putting the sample in a muffle furnace, heating to 650 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 2h, and obtaining a catalyst sample labeled as Example-1, wherein the loading amounts of Pt and Pd are both 0.5 wt%.
Example 2:
the embodiment uses ternary metal composite oxide Ce0.4Zr0.4Mn0.2O2The solid solution is taken as a carrier coating, Pt and Pd are taken as active components, and the combustion catalyst is prepared on the surface of the metal honeycomb substrate in a loading way.
Pretreating an overall structural FeCrAl metal matrix: the resulting metal matrix is labeled J-2 as in example 1.
Ce0.4Zr0.4Mn0.2O2Preparation of precursor slurry for washcoat: quantitatively weighing 30 parts by weight of Ce0.4Zr0.4Mn0.2O2The precursor slurry S-2 is prepared by mixing powder, 10 parts by weight of Ce sol (the concentration is 15 wt%, and the pH value is 3.2), 5 parts by weight of dilute nitric acid with the substance concentration of 3M, 5 parts by weight of polyvinyl alcohol (PVA-1750), 5 parts by weight of Tween-20 and 45 parts by weight of water, and then ball-milling for 6 hours at the rotating speed of 500 revolutions per minute by adopting a mechanical ball milling method. The viscosity was 78 mPas and the pH was 3.19. Measuring Ce in slurry S-2 by adopting Malvern particle sizer0.4Zr0.4Mn0.2O2Average particle diameter D50-23.433 μm.
FeCrAl metal alloy substrate surface Ce0.4Zr0.4Mn0.2O2Preparation of a carrier coating: uniformly applying the slurry S-2 to a metalDrying the substrate J-2 at 110 ℃ for 2 hours, putting the sample in a muffle furnace, heating to 550 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 2 hours to obtain Ce0.4Zr0.4Mn0.2O2Intermediate support sample a-2 at a loading of 25.04 wt%;
preparing an active component precursor solution: as in example 1, the mixed solution was designated R-2.
Active component loading preparation: soaking the intermediate carrier sample A-2 in an excessive R-2 solution for 3min, taking out, blowing out the rest liquid on the surface of the carrier by using cold air, drying at 110 ℃ for 2h, putting the sample in a muffle furnace, heating to 650 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 2h, and obtaining a catalyst sample labeled as Example-2, wherein the loading amounts of Pt and Pd are both 0.5 wt%.
Example 3:
the embodiment uses ternary metal composite oxide Ce0.45Zr0.45La0.1O2The solid solution is taken as a carrier coating, Pt and Pd are taken as active components, and the combustion catalyst is prepared on the surface of the metal honeycomb substrate in a loading way.
Pretreating an overall structural FeCrAl metal matrix: the resulting metal matrix is labeled J-3 as in example 1.
Ce0.45Zr0.45La0.1O2Preparation of precursor slurry for washcoat: quantitatively weighing 30 parts by weight of Ce0.45Zr0.45La0.1O2The precursor slurry S-3 is prepared by the following steps of mixing powder, 10 parts by weight of Ce-Zr sol (the concentration is 15 wt%, and the pH value is 2.4), 5 parts by weight of dilute nitric acid with the substance concentration of 3M, 5 parts by weight of polyvinyl alcohol (PVA-1750), 5 parts by weight of Tween-20 and 45 parts by weight of water, and performing ball milling for 6 hours at the rotating speed of 500 revolutions per minute by adopting a mechanical ball milling method to obtain the precursor slurry S-3. The viscosity was 75 mPas and the pH was 3.13. Measuring Ce in slurry S-3 by adopting Malvern particle sizer0.45Zr0.45La0.1O2Average particle diameter D50-34.087 μm.
FeCrAl metal alloy substrate surface Ce0.45Zr0.45La0.1O2Preparation of a carrier coating: mixing the pulpUniformly coating the liquid S-3 on a metal substrate J-3, drying at 110 ℃ for 2 hours, putting a sample in a muffle furnace, heating to 550 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 2 hours to obtain Ce0.45Zr0.45La0.1O2Intermediate support sample A-3 with a loading of 24.89 wt%;
preparing an active component precursor solution: as in example 1, the mixed solution was designated as R-3.
Active component loading preparation: soaking the intermediate carrier sample A-3 in an excessive R-3 solution for 3min, taking out, blowing out the rest liquid on the surface of the carrier by cold air, drying at 110 ℃ for 2 hours, putting the sample in a muffle furnace, heating to 650 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 2 hours, and obtaining a catalyst sample labeled as Example-3, wherein the loading amounts of Pt and Pd are both 0.5 wt%.
Example 4:
the embodiment uses ternary metal composite oxide Ce0.45Zr0.45La0.1O2The solid solution is a carrier coating, Pt is used as an active component, and a combustion catalyst is prepared on the surface of the metal honeycomb substrate in a loading mode.
Pretreating an overall structural FeCrAl metal matrix: the resulting metal matrix is labeled J-C-1 as in example 1.
Ce0.45Zr0.45La0.1O2Preparation of precursor slurry for washcoat: the same as in example 3.
FeCrAl metal alloy substrate surface Ce0.45Zr0.45La0.1O2Preparation of a carrier coating: the preparation process is the same as that of example 3, except that the intermediate carrier sample Ce is obtained0.45Zr0.45La0.1O2At a loading of 25.73 wt%, labeled A-4;
preparing an active component precursor solution: (1) dissolving a quantitative Pt simple substance in aqua regia; (2) adding water to a constant volume, wherein the Pt concentration is 20.04mg/mL, and the solution is marked as R-4.
Active component loading preparation: soaking the intermediate carrier sample A-4 in an excessive R-4 solution for 3min, taking out, blowing out the rest liquid on the surface of the carrier by using cold air, drying at 110 ℃ for 2h, putting the sample in a muffle furnace, heating to 650 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 2h, and marking the obtained catalyst sample as an Example-4, wherein the Pt loading capacity is 1 wt%.
The catalyst samples prepared in the above examples 1-4 were investigated for activity and stability with the tail gas removal from the industrial acrylic acid production as the target reaction system. The tail gas of the industrial production of acrylic acid contains VOCs gases such as propylene, propane, acrylic acid, acrolein, acetic acid and the like, wherein the most difficult removal is propane. Propane is taken as a target reactant, and the composition of reaction raw material gas is as follows (volume ratio): 0.1% propane, 0.8% CO, 2.5% CO2、6％O2、10％H2O, the balance being N2. The volume space velocity (GHSV) of the reaction mass is 25,000h-1The catalyst activity and stability are shown in Table 1, wherein "T50/. degree.C" and "T95/. degree.C" represent the reaction temperature at the surface of the catalyst bed at 50% and 95% conversion of propane, respectively. The results show that the catalyst samples in the examples all show excellent catalytic activity, and the experimental results after the operation for 48 hours at 600 ℃ show that the catalyst adopting bimetallic collocation as the active center has better stability compared with a single-metal active center, because the presence of the bimetallic active center is more beneficial to the function of a 'noble metal-oxygen defect-acid site' catalytic system constructed on the surface of a metal substrate.
TABLE 1 propane removal Performance of catalysts of the examples of the invention
Taking the catalyst sample Example-3 in Example 3 as an object to be examined, comparing the catalytic performances of the catalyst before and after high-temperature hydrothermal aging, the evaluation conditions of the catalyst are as follows: propane is taken as a target reactant, and the composition of reaction raw material gas is as follows (volume ratio): 0.1% propane, 0.8% CO, 2.5% CO2、6％O2、10％H2O, the balance being N2. The volume space velocity (GHSV) of the reaction mass is 25,000h-1。
The high-temperature hydrothermal aging treatment conditions are as follows:
(1) the composition of the raw material gas for reaction is (volume ratio): 0.1% propane, 0.2% acrylic acid, 0.3% acrolein, 0.8% CO, 2.5% CO2、6％O2、15％H2O, the balance being N2；
(2) The volume space velocity (GHSV) of the reaction mass is 100,000h-1；
(3) The reaction was carried out at 800 ℃ for 24 hours.
As shown in the attached figure 1, after hydrothermal aging, the performance of the sample-3 catalyst is not attenuated, but the activity is slightly improved in a low-temperature range. The reason is that the activity and the high-temperature hydrothermal resistance of the catalyst are improved due to the synergistic catalytic action between the bimetallic active component and the ternary composite oxide carrier coating under the high-temperature hydrothermal condition.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A monolithic structural metal honeycomb combustion catalyst, characterized in that the combustion catalyst comprises a metal honeycomb substrate and a catalytic component;
the catalytic component is loaded on the surface of the metal honeycomb substrate;
the catalytic component comprises an active component and a multi-metal composite oxide;
the active component is loaded on the multi-metal composite oxide;
the active component comprises at least one of Ru element, Pt element, Pd element and Rh element;
the chemical formula of the multi-metal composite oxide is MxM'yO2；
The M is selected from at least one of Co, Mn, Ce, Sn, Ni and Fe;
m' is at least one selected from V, Zr, Nb, Cr, Mo, W and La;
0<x<1，0<y<1。
2. the combustion catalyst as claimed in claim 1, wherein the mass of the multi-metal composite oxide is 1 to 40% of the mass of the metal honeycomb substrate;
preferably, the mass of the active component is 0.1-10% of the mass of the multi-metal composite oxide.
3. The combustion catalyst as claimed in claim 1, wherein the metal honeycomb substrate is stainless steel or an iron-based alloy.
4. A method of preparing a combustion catalyst as claimed in any one of claims 1 to 3, comprising the steps of:
(1) obtaining a metal honeycomb substrate;
(2) obtaining precursor slurry containing the multi-element metal composite oxide;
(3) coating the precursor slurry on the surface of a metal honeycomb matrix, drying and roasting to obtain a multi-element metal composite oxide carrier coating intermediate;
(4) and loading the active component on the intermediate of the multi-metal composite oxide carrier coating, drying and roasting to obtain the combustion catalyst.
5. The method according to claim 4, wherein in the step (2), the precursor slurry has a pH of 2.0 to 5.0, a viscosity of 10 to 200 mPas, and an average particle diameter D of solid-phase particles500.5-20 μm.
6. The method according to claim 4, wherein the step (2) comprises:
performing ball milling treatment on a mixture containing a multi-element metal composite oxide, inorganic oxide sol, inorganic acid, an organic additive and water to obtain precursor slurry;
preferably, the mixture comprises the following components in parts by weight:
20-50 parts by weight of multi-metal composite oxide
1-15 parts by weight of inorganic oxide sol
1-10 parts by weight of inorganic acid
0.1 to 15 parts by weight of an organic additive
20-60 parts by weight of water;
preferably, the inorganic oxide sol is at least one of aluminum sol, silica sol, cerium sol, zirconium sol and cerium-zirconium sol;
the inorganic acid is at least one of nitric acid, sulfuric acid and hydrochloric acid;
the organic additive is at least one of polyalcohol compounds and polyether compounds;
preferably, the concentration of the inorganic oxide sol is 10-20 wt%, and the pH value is 2.0-4.5;
the concentration of the inorganic acid is 1M-10M.
7. The method of claim 4, wherein step (4) comprises:
and (3) loading the solution containing the active component on the multi-metal composite oxide carrier coating intermediate by adopting an excess impregnation method.
8. The method of claim 4, wherein in step (3) and step (4), the drying conditions are independently selected from the group consisting of: the temperature is 80-120 ℃, and the time is 1-6 hours;
preferably, in the step (3) and the step (4), the roasting conditions are as follows: heating to 450-850 ℃ at a heating rate of 1-5 ℃/min, and keeping for 1-6 hours.
9. The method of claim 4, wherein in step (3), the metal honeycomb substrate is pretreated before use;
the pretreatment comprises surface cleaning treatment and high-temperature oxidation treatment.
10. Use of the catalytic combustion catalyst according to any one of claims 1 to 3, of the combustion catalyst prepared according to any one of claims 4 to 9 for the removal and purification of VOCs gases.
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