CN111001437A - AEI/AFX structure symbiotic composite molecular sieve, preparation method and SCR application thereof - Google Patents

AEI/AFX structure symbiotic composite molecular sieve, preparation method and SCR application thereof Download PDF

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CN111001437A
CN111001437A CN201911287130.7A CN201911287130A CN111001437A CN 111001437 A CN111001437 A CN 111001437A CN 201911287130 A CN201911287130 A CN 201911287130A CN 111001437 A CN111001437 A CN 111001437A
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silicon
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王志光
柳海涛
王炳春
李进
王贤彬
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Abstract

The invention discloses an AEI/AFX topological structure intergrowth composite molecular sieve and a preparation method of an SCR catalyst, wherein the AEI/AFX topological structure intergrowth composite molecular sieve is formed by intergrowth of an AEI molecular sieve and an AFX topological structure molecular sieve, and a characteristic diffraction peak is arranged at a2 theta angle in a phase spectrogram of an X-ray diffraction of the molecular sieve of an intergrowth composite structure; the molar ratio of silicon to aluminum in the intergrowth composite molecular sieve is 10-200. The preparation method comprises the steps of adopting a composite template agent in the preparation process of the symbiotic composite molecular sieve, using an FAU type silicon-aluminum molecular sieve as an aluminum source and a silicon source, forming mixed sol by combining other silicon sources and alkali sources, dynamically crystallizing at different temperatures to synthesize the AEI/AFX symbiotic structure molecular sieve, and then exchanging with soluble metal salt cations to obtain the SCR molecular sieve catalyst. The obtained SSZ-39 with the AEI structure and the SSZ-16 with the AFX structure form a symbiotic composite molecular sieve, so that the molecular sieve has more reasonably distributed acidity and good hydrothermal stability, has good catalytic activity and excellent service life in SCR reaction of NOx-containing gas discharged by a mobile source and a fixed source, and can well meet the standard requirement of tail gas emission.

Description

AEI/AFX structure symbiotic composite molecular sieve, preparation method and SCR application thereof
Technical Field
The invention relates to an AEI/AFX structure intergrowth composite molecular sieve, a preparation method and SCR application thereof, in particular to synthesis of an SSZ-39/SSZ-16 intergrowth composite molecular sieve and preparation of a catalyst thereof, belonging to the fields of chemical synthesis technology and application thereof.
Background
The AEI type molecular sieve has a three-dimensional channel system with large cages, and can form a three-dimensional channel structure through 8-membered rings, wherein the pore size is 0.38nm multiplied by 0.38nm, the framework density is 14.8, and the cage size can reach the diameter
Figure BDA0002318316390000011
A sphere. The AEI molecular sieve structure has two adjacent double 6-membered rings (d6r) connected by 4-membered rings in a spatially mirror symmetric distribution. Ion-exchanged or metal-loaded active components of AEI molecular sieve catalysts exhibit unique selective reduction (SCR) activity and have attracted considerable attention for their excellent performance in the reduction treatment of nitrogen oxides (NOx). The literature (chem.commun.,2012,48,8264) reports that the SCR denitration catalytic reaction using AEI structured Cu-SSZ-39 molecular sieve shows higher hydrothermal stability and catalytic activity compared to commercial 8MR molecular sieve Cu-SSZ-13(CHA topology).
The AFX type molecular sieve is a three-dimensional intersected eight-membered ring channel with relatively small channel size
Figure BDA0002318316390000012
Figure BDA0002318316390000013
The framework density was 14.7 and consisted of elongated, larger aft cages (0.55X 1.35nm) and smaller gme cages (0.33X 0.74nm), with the SSZ-16 molecular sieve belonging to a typical AFX type topology. The Cu-SSZ-16 keeps the NOx conversion rate higher than 90 percent at the high temperature ranging from 400 ℃ to 550 ℃ all the time, and has slightly better high-temperature NOx compound SCR reaction conversion rate than the Cu-SSZ-13 molecular sieve.
Molecular sieves of both AEI and AFX topologies belong to 8-membered ring small pore molecular sieves. While molecular sieves of the AEI structure are used in large quantities for SCR reactions of NOx compounds, while AFX structure molecular sieves have a different pore structure than AEI, many recent documents report their application as exhaust gas denitration treatments, for copper supported AFX or AEI molecular sieve catalysts, the structure of the molecular sieve also has an impact on the distribution of copper species, and the d6r building blocks in small pore cage molecular sieves are considered to be the key to the generation of highly active copper species by their association with activity and also topology. Meanwhile, the existence of pores with proper size can also better reduce the formation of low-activity CuO cluster particles and effectively limit the generation of byproducts, thereby bringing favorable effect on the NH3-SCR process.
Generally, the SCR catalyst is a molecular sieve having a crystal structure prepared by using zeolite as a carrier and loading an SCR active component, wherein the zeolite is an aluminosilicate crystal material having a fairly regular pore size, and patents EP1961933a1, EP1147801a1, EP 2123614a2, US7332148B2, EP1579911a1 and US20030143141a1 disclose X zeolite, Y zeolite, β zeolite, mordenite, ferrierite, a zeolite, erionite, L zeolite, ZSM-5, ZSM-8, ZSM-11 and ZSM-12 zeolite molecular sieves and the like as SCR catalyst carriers, and these zeolites can be exchanged with metals such as Cu, Fe, Mn, Ag, V, Ti and Co, or the zeolite itself contains a part of metals such as Cu and Fe.
FAU-type zeolites contain a double 6-membered ring (D6R) building block in a structure similar to AEI and AFX. The literature shows that the conversion of FAU-type zeolites with similar silica to alumina ratio to AEI molecular sieves, into AEI molecular sieves simultaneously, with high solids yields, is possible with molecular sieves.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defect that the activity of an SCR catalyst for synthesizing a molecular sieve by using supported iron and copper is lower at low temperature through a hydrothermal durability test in the prior art, and provides a copper-based SCR catalyst which still has higher activity at low temperature after the hydrothermal durability test and a preparation method thereof.
The invention aims to provide a metal-loaded SSZ-39/SSZ-16 symbiotic composite molecular sieve catalyst, the two types of molecular sieves belong to AEI and AFX structures respectively, and can be used for catalytic reduction (SCR) treatment of waste gas NOx of internal combustion engines, gas turbines, coal or fuel power generation and the like, and the hydrothermal stability and the initiation activity are improved. In a particular embodiment of the invention, the method is used for treating a NOx-containing exhaust gas of a lean-burn internal combustion engine, such as a diesel engine, a lean-burn gasoline engine or an engine powered by liquid petroleum gas or natural gas, the NOx-containing exhaust gas of which is preferably an exhaust gas stream emitted by a motor vehicle, more preferably an exhaust gas stream obtained from a lean-burn engine, even more preferably a diesel exhaust gas stream.
The molecular sieve catalysts of the present invention can also be used to treat gases from industrial processes such as refining, NOx-containing gases from refining heaters and boilers, furnaces, chemical processing industries, coke ovens, municipal waste treatment plants, and incinerators. Nitrogen oxides (NOx), including various compounds, such as nitrous oxide (N)2O), Nitric Oxide (NO), nitrogen dioxide (NO)2) Dinitrogen trioxide (N)2O3) Dinitrogen tetroxide (N)2O4) And dinitrogen pentoxide (N)2O5) And the like.
The method for treating a gas stream containing NOx, wherein the NOx is metered to 100 wt.% and the NO thereof is added before the catalyst is brought into contact with the gas stream2The content is 80 wt% or less, wherein NO is preferably contained in an amount of 5 to 70 wt%, more preferably 10to 60 wt%, more preferably 15 to 55 wt%, even more preferably 20 to 50 wt%2And (4) content. An oxidation catalyst located upstream of the catalyst oxidizes nitrogen monoxide in the gas to nitrogen dioxide and then mixes the resulting gas with a nitrogenous reductant prior to the mixture being added to the zeolite catalyst, wherein the oxidation catalyst is adapted to produce a gas stream that enters the zeolite catalystSaid gas flow having a flow rate of 4: 1 to 1: 3 NO: NO2Volume ratio.
Reducing agents (urea, NH) are generally used3Etc.), several chemical reactions occur, all of which represent reactions that reduce NOx to elemental nitrogen. In particular, the dominant reaction mechanism at low temperature is represented by formula (1).
4NO+4NH3+O2→4N2+6H2O (1)
Non-selective reaction with competing oxygen, or formation of 2-fold products, or non-productive consumption of NH3. As such a non-selective reaction, for example, NH represented by the formula (2)3Is completely oxidized.
4NH3+5NO2→4NO+6H2O (2)
Furthermore, NO present in NOx2And NH3The reaction of (3) is considered to proceed by means of the reaction formula.
3NO2+4NH3→(7/2)N2+6H2O (3)
And NH3With NO and NO2The reaction between (a) and (b) is represented by the reaction formula (4).
NO+NO2+2NH3→2N2+3H2O (4)
The reaction rates of the reactions (1), (3) and (4) are greatly different depending on the reaction temperature and the kind of the catalyst used, and the rate of the reaction (4) is usually 2 to 10 times the rate of the reactions (1) and (3).
In the SCR catalyst, in order to improve NOx purification ability at low temperature, it is necessary to make the reaction of formula (4) dominant, not the reaction of formula (1). The reaction of formula (4) is dominant at low temperatures, preferably increasing NO2This is obvious.
Therefore, at a low temperature of 150-300 ℃, copper has excellent adsorption capacity to NO and has stronger NO oxidation capacity. The oxidation reaction of NO is represented by formula (5).
NO+1/2O2→NO2(5)
In order to solve the problems, the technical scheme provided by the invention is as follows: the preparation method comprises the steps of taking an intergrowth composite molecular sieve containing an AEI structure molecular sieve and an AFX structure molecular sieve as a main matrix component of the catalyst, and effectively introducing active metal components such as copper, iron and the like to prepare the copper-based or iron-based SCR molecular sieve catalyst.
The invention provides an SCR catalyst for denitration, which adopts the symbiotic composite silicon-aluminum molecular sieve and soluble metal salt solution to carry out ion exchange to obtain the metal-promoted SCR catalyst of the symbiotic composite molecular sieve with an AEI/AFX topological structure.
The invention discloses an intergrowth composite molecular sieve with an AEI/AFX structure, which is characterized in that: the composite material is formed by intergrowth of AEI and AFX topological structure molecular sieves, wherein the AEI structure molecular sieve accounts for 60-99% of the total weight, and the AFX structure molecular sieve accounts for 1.0-40% of the total weight; the molar ratio of silicon to aluminum oxide in the intergrowth composite molecular sieve is 10-200; the molecular sieve X-ray diffraction phase spectrogram of the intergrowth structure has characteristic peaks at the 2 theta angles of 7.42 +/-0.2, 8.64 +/-0.2, 9.48 +/-0.2, 10.60 +/-0.2, 11.56 +/-0.2, 12.86 +/-0.2, 12.90 +/-0.2, 15.50 +/-0.2, 16.06 +/-0.2, 16.85 +/-0.2, 17.16 +/-0.2, 17.78 +/-0.2, 19.64 +/-0.2, 20.20 +/-0.2, 20.70 +/-0.2, 21.34 +/-0.2, 21.62 +/-0.2, 23.90 +/-0.2, 25.88 +/-0.2, 26.26 +/-0.2, 27.82 +/-0.2, 30.32 +/-0.2 and 31.26 +/-0.2.
Further, in the above technical solution, the intergrowth composite molecular sieve having AEI/AFX topology of the present invention is characterized in that: the AEI structure molecular sieve specifically comprises any one or more of SSZ-39, SAPO-18, AlPO-18 and SIZ-8, and is preferably an SSZ-39 silicon-aluminum molecular sieve; the AFX structure molecular sieve specifically comprises any one or more of SAPO-56 and SSZ-16, and preferably is an SSZ-16 silicon-aluminum molecular sieve.
Further, in the above technical solution, the synthesis method of the intergrowth composite silicon-aluminum molecular sieve having AEI/AFX topology of the present invention is characterized in that:
1) uniformly stirring NaOH, a composite template agent and deionized water in an ultrasonic manner, and then adding an FAU type molecular sieve and a silicon source into the mixture to be uniformly mixed into gel; FAU type silicon-aluminum molecular sieve provides aluminum source and partial silicon source, mixed slurryIn the silicon source is SiO2The aluminum source is A12O3The composite template agent is calculated by OSDA, NaOH is calculated by Na2Calculated by O, the molar ratio of the components is nSiO2:nA12O3:nNa2O:nOSDA:nH2O＝1:(0.005～0.1):(0.05～0.5):(0.05～1.0):(10～100)；
2) Stirring the mixture obtained in the step 1), transferring the mixture into a hydrothermal crystallization reaction kettle, performing two-section or multi-section crystallization at the autogenous pressure and the temperature of 120-200 ℃ for 48-168 hours in total, and filtering, washing, drying and roasting the obtained crystallization liquid to obtain SSZ-39/SSZ-16 symbiotic composite silicon-aluminum molecular sieve raw powder;
the composite template agent OSDA in the step 1) comprises organic template agents R1 and R2, wherein the molar ratio of the two organic template agents is nR1, nR2 is 1 (0.05-0.8);
the organic template R1 in the step 1) comprises the following types: n, N-dimethyl-3, 5-dimethylpiperidinium, N-dimethyl-2, 6-dimethylpiperidinium, 1,2,2,6, 6-hexamethylpiperidinium, 1,2,2,6, 6-hexamethyl-4-oxopiperidinium, 1,3, 5-tetramethyl-4-oxopiperidinium, 1-hydroxy-1, 1,2,2,6, 6-hexamethylpiperidinium, 1-dimethyl-4, 4-dipropoxypiperidinium, 3, 5-dimethoxy-1, 1-dimethylpiperidinium, 3, 5-dihydroxy-1, 1-dimethylpiperidinium, 4-ethyl-1, 1-dimethyl-3, one or more of 5-dioxopiperidinium, 1-ethyl-1-methyl-2, 2,6, 6-hexamethylpiperidinium, 1-epoxypropyl-1-methyl-2, 2,6, 6-hexamethylpiperidinium, N-dimethyl-2- (2-hydroxyethyl) piperidinium and N, N-dimethyl-2-ethylpiperidinium;
the organic template R2 in the step 1) is a compound containing a structure of alkane substituted by double six-membered ring or double five-membered heterocyclic group, and comprises the following 11 chemical formulas:
Figure BDA0002318316390000071
Figure BDA0002318316390000072
Figure BDA0002318316390000073
Figure BDA0002318316390000074
Figure BDA0002318316390000075
Figure BDA0002318316390000076
Figure BDA0002318316390000077
Figure BDA0002318316390000078
Figure BDA0002318316390000079
Figure BDA00023183163900000710
Figure BDA00023183163900000711
further, in the above technical solution, the molar ratio of silicon to aluminum in the intergrowth composite molecular sieve is 10to 200, preferably 10to 100, and more preferably 10to 50.
Further, in the above technical solution, the synthesis method of the present invention is characterized in that: the aluminum source is selected from four-coordinate aluminum in FAU type silicon-aluminum zeolite, wherein the FAU type molecular sieve comprises an X molecular sieve, a Y molecular sieve and a USY molecular sieve.
Further, in the above technical solution, the synthesis method of the present invention is characterized in that: the silicon source in the step 1) is selected from one or more of white carbon black, macroporous silica gel, coarse porous silica gel, fine porous silica gel, thin layer chromatography silica gel, B type silica gel, sodium metasilicate, silica sol, water glass, alkyl silicate, diatomite and gas phase method silica gel, and preferably chromatography silica gel, white carbon black, silica sol, water glass and alkyl silicate.
Further, in the above technical solution, the synthesis method of the present invention is characterized in that: the organic template R2 is of the following types: any one or more of 1, 4-bis ([ 4-aza-1-azoniabicyclo [2.2.2]) butane, 1, 4-bis (quinuclidinium) butane, 1, 4-bis (N-methylpiperidinium) butane, 1, 4-bis (N-methylpiperazinium) butane, 1, 4-bis (N-methylmorpholinium) butane, 1, 4-bis (N-methylpiperidinium) butane, 1, 4-bis (N-methylpyrrolidium) butane, 1, 4-bis (N-methylimidazolium) butane, 1, 4-bis (2, 3-dimethylimidazolium) butane and 1, 4-bis (N-methylimidazolium) butane.
Further, in the technical scheme, in the synthesis, the symbiotic composite molecular sieve raw powder obtained in the step 2) and an ammonium salt solution with the concentration of 0.1-5.0 mol/L are mixed according to a solid-liquid mass ratio of 1: (5-50) carrying out ion exchange at 80-120 ℃, wherein each time of exchange is 0.5-6 hours, and repeatedly exchanging the obtained filter cake with a fresh ammonium ion solution for 1-3 times until the Na content in the molecular sieve sample is lower than 500 ppm; then filtering and separating out a solid product, repeatedly washing the solid product with deionized water to be neutral, drying a filter cake at 100-130 ℃ for 12-48 hours, and roasting the filter cake at 400-600 ℃ for 2-8 hours to obtain an H-type symbiotic composite silicon-aluminum molecular sieve;
the ammonium salt is a mixture formed by mixing any one, two or more than two of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium acetate in any proportion.
The invention provides an SCR catalyst for denitration, which is characterized in that the AEI/LEV structure symbiotic composite molecular sieve is subjected to ion exchange with a soluble metal salt solution, then forms slurry with solid content of 25.0-48.0 wt% with a binder and deionized water, and is coated on a carrier of a porous regular material or an integral filter substrate to form a proper coating, so that the metal-promoted SCR catalyst with the AEI/LEV topology symbiotic composite molecular sieve is obtained.
Further, in the above technical solution, the binder is selected from any one or a mixture of several of silica sol, aluminum sol or pseudo-boehmite; SiO in sol2Or Al2O3The mass of the catalyst is 8.0-25.0 wt% of that of the supported metal symbiotic AEI/LEV molecular sieve catalyst.
Further, in the technical scheme, the porous regular material or the monolithic filter base material is prepared from any one of cordierite, α -alumina, silicon carbide, aluminum titanate, silicon nitride, zirconia, mullite, spodumene, alumina-silica-magnesia or zirconium silicate, and the carrier material is preferably a cordierite porous honeycomb flow-through monolith carrier, and the carrying capacity of the carrier material is 170-270 g/L.
The soluble metal salt used in the preparation process of the catalyst is selected from one or a combination of more of soluble salts of copper, iron, cobalt, tungsten, nickel, zinc, molybdenum, vanadium, tin, titanium, zirconium, manganese, chromium, niobium, bismuth, antimony, ruthenium, germanium, palladium, indium, platinum, gold or silver, preferably any one or two of copper salt and iron salt, and further preferably copper salt. The copper salt is one or more of copper nitrate, copper chloride, copper acetate or copper sulfate; the concentration of copper ions in the copper salt aqueous solution is 0.1-0.5 mol/L.
The amount of Cu in the copper-based SCR molecular sieve catalyst of the present invention is 0.03 to 20 wt%, based on the weight of the copper-based SCR catalyst, wherein the amount of Cu is preferably 0.2 to 15 wt%, more preferably 0.5 to 10 wt%, more preferably 1.0 to 8.0 wt%, more preferably 1.5 to 5.0 wt%, more preferably 2.0 to 4.0 wt%, more preferably 2.5 to 3.5 wt%, more preferably 2.7 to 3.3 wt%, more preferably 2.9 to 3.1 wt%.
In embodiments of the invention, the washcoat of the intergrowth composite molecular sieve SCR catalyst is preferably a solution, suspension or slurry that is coated onto a porous structured material (i.e., a honeycomb monolithic catalyst support structure having a plurality of parallel small channels running axially through the entire assembly) or a monolithic filter substrate such as a wall-flow filter or the like, with suitable coatings including a surface coating, a coating that penetrates a portion of the substrate, a coating that penetrates the substrate, or some combination thereof.
The two most common substrate designs to which the SCR catalyst of the invention can be applied are plate and honeycomb. Preferred substrates, particularly for mobile applications, include flow-through monoliths having a so-called honeycomb geometry comprising a plurality of adjacent, parallel channels that are open at both ends and generally extend from an inlet face to an outlet face of the substrate, and that result in a high surface area to volume ratio. For certain applications, the honeycomb flow-through monolith preferably has a high pore density, for example, about 600 to 800 pores per square inch, and/or an average internal wall thickness of about 0.18 to 0.35mm, preferably about 0.20 to 0.25 mm. For certain other applications, the honeycomb flow-through monolith preferably has a low pore density of about 150 to 600 pores per square inch, more preferably about 200 to 400 pores per square inch.
The catalyst in the embodiments of the invention shows that high NOx conversion is obtained in a much wider temperature window. The temperature range for improving the conversion efficiency may be about 150 to 650 ℃, preferably 200 to 500 ℃, more preferably 200 to 450 ℃, or most significantly 200 to 400 ℃. Within these temperature ranges, the conversion efficiency after exposure to a reducing atmosphere, even after exposure to a reducing atmosphere and high temperatures (e.g., up to 850 ℃) can be greater than 55% to 100%, more preferably greater than 90% efficiency, and even more preferably greater than 95% efficiency.
The SCR catalyst prepared by the AEI/AFX structure symbiotic composite molecular sieve provided by the invention has better hydrothermal stability and wider ignition activity window temperature (200-500 ℃), has good low-temperature and high-temperature ignition activity, has a proper pore structure, is beneficial to the diffusion of NOx molecules, enhances the adhesion of metal copper ions, and reduces the possibility of aggregation caused by the hydrothermal effect.
The intergrowth composite zeolite molecular sieve is formed by SSZ-16 with an AFX structure and SSZ-39 with an AEI structure, has two molecular sieve structural characteristics, generates structural particularity, has more reasonably distributed acidity and good hydrothermal stability, overcomes the limitations of components, better meets the requirements of industrial application, and has wide application prospect.
Description of the drawingsthe invention will now be further described with reference to the accompanying drawings and examples:
FIG. 1 is an XRD diffractogram of the intergrown SSZ-39/SSZ-16 molecular sieve synthesized in example 1;
FIG. 2 is an XRD diffractogram of the intergrown SSZ-39/SSZ-16 molecular sieve synthesized in example 2;
FIG. 3 is an XRD diffractogram of the intergrown SSZ-39/SSZ-16 molecular sieve synthesized in example 3;
FIG. 4 is an XRD diffractogram of the intergrown SSZ-39/SSZ-16 molecular sieve synthesized in example 4;
FIG. 5 is an XRD diffractogram of the intergrown SSZ-39/SSZ-16 molecular sieve synthesized in example 5.
Detailed Description
The embodiments and the effects of the present invention are further illustrated by examples and comparative examples, but the scope of the present invention is not limited to the contents listed in the examples.
The intergrowth composite molecular sieve of the present invention is identified by finding the lattice plane spacing (d) from the XRD pattern by the Powder method of X-ray Diffraction (X-ray Diffraction) analysis, and comparing the obtained lattice plane spacing (d) with Data collected from the XRD database of the International society for synthetic zeolites or the PDF (Powder Diffraction File) of ICDD (International centre for Diffraction Data).
Mechanically and uniformly mixing and grinding the SSZ-39 molecular sieve and the SSZ-16 molecular sieve which are pure in phase and have high relative crystallinity according to the mass ratio of 50:50, 60:40, 70:30, 80:20 and 90:10, and determining the XRD characteristic peak area. The SSZ-39 molecular sieve corresponds to the characteristic peaks at 9.48 +/-0.2, 10.60 +/-0.2, 16.06 +/-0.2, 20.70 +/-0.2 and 23.90 +/-0.2 of the 2 theta angle, and the total area of the SSZ-39 molecular sieve is related to the mass percentage of SSZ-39; the five characteristic peaks at the 2 theta angle of 7.42 +/-0.2, 8.64 +/-0.2, 11.56 +/-0.2, 17.78 +/-0.2 and 20.20 +/-0.2 correspond to the SSZ-16 molecular sieve, and the total area of the five characteristic peaks is related to the SSZ-16 mass percentage content. Thereby obtaining a function curve of the SSZ-39/SSZ-16 peak area ratio and the SSZ-39/SSZ-16 molecular sieve mass ratio, and the function curve is used as a reference curve for calculating the relative proportion value of the two molecular sieves in the sample to be measured.
Example 1
A preparation method of an SSZ-39/SSZ-16 symbiotic composite silicon-aluminum molecular sieve and an SCR catalyst comprises the following steps:
1) 13.86g HY (nSiO2/nAl2O3 ═ 5.2, dry basis 78 wt%) molecular sieve and 179.04g deionized water were ultrasonically stirred to form a solution, and then 25.29g water glass (Na) was added2O：7.48wt％，SiO2: 24.61 wt%), 18.34g of silica gel solution (Na)2O：0.23wt％，SiO2: 29.49 wt%), 16.05g of 1,1,2,2,6, 6-hexamethylpiperidinium quaternary ammonium base (25 wt% strength by weight, designated as R1), 4.31g of 1, 4-bis ([ 4-aza-1-azoniabicyclo [ 2.2.2)]) Butane (purity 99 wt%, recorded as R2) is ultrasonically and uniformly mixed, and the molar ratio of the components of the mixed slurry to nSiO is matched2:nA12O3:Na2O:nR1:nR2:nH2O＝1:0.050:0.038:0.085:0.035:25；
2) Stirring the mixture obtained in the step 1), transferring the mixture into a hydrothermal crystallization reaction kettle, stirring the mixture under the autogenous pressure and the speed of 80rpm, crystallizing the mixture for 24 hours at the temperature of 140 ℃, and then heating the mixture to 170 ℃ for crystallizing the mixture for 72 hours. And after complete crystallization, quickly cooling the product, performing suction filtration separation and washing until the pH value is 8.0-9.0, drying at 120 ℃ for 12 hours, and roasting at 540 ℃ for 4 hours to obtain SSZ-39/SSZ-16 symbiotic composite silicon-aluminum molecular sieve raw powder.
Carrying out ion exchange on the symbiotic composite silicon-aluminum molecular sieve raw powder and an ammonium nitrate solution with the concentration of 1.0mol/L for 2 hours at 90 ℃ according to the solid-liquid mass ratio of 1:10, and then repeatedly exchanging the filter cake obtained by filtering with a fresh ammonium nitrate solution twice under the same condition to ensure that the Na ion content in the sample is lower than 500 ppm. The filter cake obtained by subsequent filtration is dried at 110 ℃ overnight to obtain ammonium type molecular sieve NH4And (4) heating to 450 ℃ and roasting for 16 hours to obtain the H-type SSZ-39/SSZ-16 molecular sieve.
3) Adding 50.0g of the H-type SSZ-39/SSZ-16 symbiotic composite silicon-aluminum molecular sieve in the step 2) into a 0.15mol/L copper nitrate aqueous solution, dropwise adding dilute nitric acid into the solution to adjust the pH value to 6.5, uniformly stirring, putting into a heat-resistant container, and putting into a dryer with a pressure reducing valve; vacuumizing the pressure in the dryer to be below 10Torr by using a vacuum pump, degassing at room temperature for 1 hour, heating to 90 ℃, drying for 12 hours, and roasting the dried sample at the temperature of 500 ℃ for 4 hours under normal atmospheric pressure; according to the obtained copper modified SSZ-39/SSZ-16 intergrowth composite silicon-aluminum molecular sieve, in the catalyst prepared according to an XRF analysis result, copper (II) ions account for 3.5 percent of the total weight of the molecular sieve catalyst, namely the copper loading is 3.5 weight percent, and the Na ion content is lower than 200 ppm.
4) 40.0g of the copper-modified molecular sieve obtained in 3) above was mixed with 20.0g of silica sol (SiO2 content: 30.0 wt%) and 106.7g of deionized water were uniformly mixed to prepare a catalyst slurry with a solid content of 27.6 wt%, and the catalyst slurry was coated on a cordierite honeycomb porous structured material (#400cpsi, 20mm in diameter and 40mm in length) by an impregnation method, excess slurry droplets were blown off by compressed air, dried at 105 ℃ for 24 hours, coated 2 times under the same conditions, and calcined at 500 ℃ for 2 hours to prepare an SCR catalyst, wherein the loading on the structured material was 192.2g/L (the weight of the weight increased by the structured material after calcination was divided by the volume of the space occupied by the structured material, and the definitions of the subsequent examples and comparative examples with respect to the loading were the same), and in order to obtain an SCR catalyst denoted as a, the preparation parameters and the species were as shown in tables 1,2 and 3.
Example 2
The process for synthesizing the SSZ-39/SSZ-16 intergrowth composite molecular sieve is similar to the example 1, except that the molar ratio of the mixed sol, the type of the organic template agent, the type of the silicon source, the type of the FAU zeolite, the silicon-aluminum ratio, the crystallization temperature, the crystallization time and the like in the step 1) and the step 2) are adopted, 50.0g of H-type SSZ-39/SSZ-16 intergrowth composite silicon-aluminum molecular sieve is taken in the step 3), different types, concentrations, solution volumes and metal loading amounts of soluble metal salts are adopted, and 40.0g of copper modified SSZ-39/SSZ-16 intergrowth composite molecular sieve and 20.0g of silica Sol (SiO) are taken in the step 4)2The content is as follows: 30.0 wt%) and 75.7g of deionized water were mixed uniformly to prepare a catalyst slurry having a solid content of 33.9 wt%, which was coated on a cordierite structured material by an impregnation method. Specific parameters in this example are shown in tables 1,2 and 3.
Example 3
The process method for synthesizing the SSZ-39/SSZ-16 intergrowth composite molecular sieve is similar to the methodExample 1, except that the molar ratio of the mixed sol, the type of the organic template, the type of the silicon source, the type of the FAU zeolite, the silicon-aluminum ratio, the crystallization temperature, the crystallization time and the like in the step 1) and the step 2), 50.0g of H-type SSZ-39/SSZ-16 intergrowth composite silicon-aluminum molecular sieve is taken in the step 3), different soluble metal salt types, different concentrations, different solution volumes and different metal loading amounts are adopted, and 40g of copper modified SSZ-39/SSZ-16 intergrowth composite molecular sieve and 20.0g of silica Sol (SiO) are taken in the step 4)2The content is as follows: 30.0 wt%) and 57.9g of deionized water were mixed uniformly to prepare a catalyst slurry having a solid content of 39.0 wt%, which was coated on a cordierite structured material by an impregnation method. Specific parameters in this example are shown in tables 1,2 and 3.
Example 4
The process for synthesizing the SSZ-39/SSZ-16 intergrowth composite molecular sieve is similar to example 1, except that the molar ratio of the mixed sol, the type of the organic template, the type of the silicon source, the type of the FAU zeolite and the silica-alumina ratio, the crystallization temperature and the crystallization time, etc. in step 1) and step 2), 50.0g of the H-type SSZ-39/SSZ-16 intergrowth composite silica-alumina molecular sieve is taken in step 3), and different types, concentrations, solution volumes and metal loading amounts of soluble metal salts are adopted, and 4) 40g of the copper-modified SSZ-39/SSZ-16 intergrowth composite molecular sieve is taken in step 4), and mixed with 20.0g of silica sol (SiO2 content: 30.0 wt%) and 67.1g of deionized water were mixed uniformly to prepare a catalyst slurry having a solid content of 36.2 wt%, which was coated on a cordierite structured material by an impregnation method. Specific parameters in this example are shown in tables 1,2 and 3.
Example 5
The process for synthesizing the SSZ-39/SSZ-16 intergrowth composite molecular sieve is similar to that of example 1, except that the molar ratio of the mixed sol, the type of the organic template agent, the type of the silicon source, the type of FAU zeolite, the silicon-aluminum ratio, the crystallization temperature, the crystallization time and the like in the step 1) and the step 2) are adopted, 3.33g of solid NaOH (with the purity of 99%) is added, 50.0g of H-type SSZ-39/SSZ-16 intergrowth composite silicon-aluminum molecular sieve is taken in the step 3), different soluble metal salt types, concentrations, solution volumes and metal loading amounts are adopted, and 4) 40g of copper-modified SSZ-39/SSZ-16 intergrowth composite molecular sieve and 30.0g of aluminum sol (Al) are taken in the step 4)2O3The content is as follows: 20.0 wt%) and 53.7g of deionized water were mixed uniformly to prepare a catalyst slurry having a solid content of 39.6 wt%, which was coated on a cordierite structured material by an impregnation method. Specific parameters in this example are shown in tables 1,2 and 3.
Example 6
The process for synthesizing the SSZ-39/SSZ-16 intergrowth composite molecular sieve is similar to that of example 1, except that the molar ratio of the mixed sol, the type of the organic template agent, the type of the silicon source, the type of the FAU zeolite, the silicon-aluminum ratio, the crystallization temperature, the crystallization time and the like in the step 1) and the step 2) are increased by 5.76g of solid NaOH (with the purity of 99 percent); step 3) taking 50.0g of H-type SSZ-39/SSZ-16 symbiotic composite silicon-aluminum molecular sieve, adopting different soluble metal salt types, concentrations, solution volumes and metal loading amounts, and step 4) taking 40g of copper modified SSZ-39/SSZ-16 symbiotic composite molecular sieve and 30.0g of aluminum sol (Al)2O3The content is as follows: 20.0 wt%) and 122.2g of deionized water were mixed uniformly to prepare a catalyst slurry having a solid content of 25.5 wt%, and the catalyst slurry was coated on a cordierite structured material by an impregnation method. Specific parameters in this example are shown in tables 1,2 and 3.
Example 7
The process for synthesizing the SSZ-39/SSZ-16 intergrowth composite molecular sieve is similar to that of example 1, except that the molar ratio of the mixed sol, the type of the organic template, the type of the silicon source, the type of the FAU zeolite, the silicon-aluminum ratio, the crystallization temperature, the crystallization time and the like in the step 1) and the step 2) are increased by 2.94g of solid NaOH (with the purity of 99 percent); step 3) taking 50.0g of H-type SSZ-39/SSZ-16 symbiotic composite silicon-aluminum molecular sieve, adopting different soluble metal salt types, concentrations, solution volumes and metal loading amounts, and step 4) taking 40g of copper modified SSZ-39/SSZ-16 symbiotic composite molecular sieve and 30.0g of aluminum sol (Al)2O3The content is as follows: 20.0 wt%) and 51.3g of deionized water were mixed uniformly to prepare a catalyst slurry having a solid content of 40.4 wt%, which was coated on a cordierite structured material by an impregnation method. Specific parameters in this example are shown in tables 1,2 and 3.
Example 8
The process method for synthesizing the SSZ-39/SSZ-16 intergrowth composite molecular sieve is similar to the methodExample 1, except that the molar ratio of the mixed sol, the kind of the organic template, the kind of the silicon source, the kind of the FAU zeolite and the silicon-aluminum ratio, the crystallization temperature and the crystallization time, etc. in the steps 1) and 2) were increased by 1.79g of solid NaOH (purity 99%); step 3) taking 50.0g of H-type SSZ-39/SSZ-16 symbiotic composite silicon-aluminum molecular sieve, adopting different soluble metal salt types, concentrations, solution volumes and metal loading amounts, and step 4) taking 40g of copper modified SSZ-39/SSZ-16 symbiotic composite molecular sieve and 30.0g of aluminum sol (Al)2O3The content is as follows: 20.0 wt%) and 79.8g of deionized water were mixed uniformly to prepare a catalyst slurry having a solid content of 32.7 wt%, and the catalyst slurry was coated on a cordierite structured material by an impregnation method. Specific parameters in this example are shown in tables 1,2 and 3.
TABLE 1
Figure BDA0002318316390000171
Figure BDA0002318316390000181
TABLE 2
Figure BDA0002318316390000182
TABLE 3
Figure BDA0002318316390000183
Comparative example 1
(1) Adding a quantitative dealuminated USY zeolite with a silica-alumina molar silica-alumina ratio (SAR) of 28.7 into an organic template agent N, N-dimethyl-3, 5-dimethylpiperidinium quaternary ammonium aqueous alkali solution (concentration: 20 wt%), fully stirring, adding NaOH particles (purity: 96 wt%), supplementing deionized water, fully stirring, and continuously stirring the obtained mixed slurry in a sealed container at room temperature for 2 hours until all raw materials are uniformly mixed, wherein the molar ratio of the mixed sol consisting of the following mol:
nNa2O:nSiO2:nAl2O3:nOSDA:nH2O＝0.22:1.0:0.03484:0.20:25；
transferring the obtained solid mixture into a 2000ml hydrothermal crystallization kettle, stirring at the speed of 60rpm, heating to 140 ℃, crystallizing for 24 hours, and then continuously heating to 170 ℃, and crystallizing for 60 hours; after crystallization is completed, the product is rapidly cooled, filtrate and solid substances are obtained through suction filtration separation and washing, the solid substances are dried for 12 hours at the temperature of 120 ℃ and roasted for 4 hours at the temperature of 540 ℃, and the solid substances are confirmed to be AEI type SSZ-39 molecular sieve, namely SSZ-39 molecular sieve raw powder through XRD; the SSZ-39 molecular sieve showed an SAR of 20.4. The molecular sieve raw powder and ammonium nitrate solution with the concentration of 1.0mol/L are subjected to ion exchange for 2 hours at the temperature of 90 ℃ according to the solid-liquid mass ratio of 1:10, and then filter cakes obtained by filtration are subjected to ion exchange twice with fresh ammonium nitrate solution again under the same condition, so that the Na ion content is lower than 500 ppm. The filter cake obtained by subsequent filtration is dried at 110 ℃ overnight to obtain ammonium type molecular sieve NH4And (4) heating to 450 ℃ and roasting for 16 hours to obtain the H-type SSZ-39 molecular sieve.
(2) The SSZ-39 molecular sieve type 10g H was added to 100g of Cu (NO) with a concentration of 0.3mol/L3)2·3H2And (3) dripping dilute nitric acid into the O aqueous solution to adjust the pH value to 5.8, and uniformly stirring. After stirring was stopped for 1 hour, the supernatant was siphoned off when SSZ-39 zeolite settled. The exchange with fresh copper nitrate solution was repeated once and finally the exchanged SSZ-39 zeolite was filtered, washed with deionized water. Drying at 90 ℃ for 12 hours under the low pressure of 10Torr, and then roasting at 500 ℃ for 4 hours under normal atmospheric pressure to obtain the copper modified SSZ-39 molecular sieve powder. According to XRF analysis, copper (II) ions accounted for 2.9% of the total weight of the molecular sieve catalyst.
(3) 15g of the resulting copper-modified SSZ-39 molecular sieve were taken and mixed with 6.00g of silica sol (30 wt% SiO)2) Mixing with 25.00g deionized water uniformly to prepare catalyst slurry with the solid content of 36.52 wt%, coating the catalyst slurry on a honeycomb-shaped porous regular material (400 cpsi, the diameter of 20mm and the length of 40mm) made of cordierite by an impregnation method, blowing off redundant slurry drops by compressed air, drying for 12 hours at 110 ℃,and then coating the slurry again, roasting the slurry at 500 ℃ for 2 hours to prepare an SCR catalyst, and measuring the catalyst loading amount on the structured material to be 221.5g/L and marking the catalyst loading amount as VS-1.
Comparative example 2
An AFX type SSZ-16 molecular sieve was prepared according to the method of the CN107207270A patent example:
1) mixing water glass (Na)2O：7.48wt％，SiO2: 24.61 wt%), 98% sulfuric acid, iron-free aluminum sulfate (Al)2O3：16.28wt％，SO3 2-: 38.35 wt%) and deionized water in a predetermined amount, and the resulting gel is subjected to solid-liquid separation and washed with pure water. To the washed gel, prescribed amounts of water, 1, 3-bis (1-adamantyl) imidazolium bromide (dadlbr) as a template, and a 48% NaOH solution were added and mixed thoroughly. The composition of the resulting mixture (raw material composition) in terms of mole ratios is as follows:
nNa2O:nSiO2:nAl2O3:nDAdIBr:nOH-:nH2O＝0.075:1.0:0.03636:0.05:0.15:40
the obtained mixture was sealed in an autoclave made of stainless steel, and the autoclave was heated at 180 ℃ for 48 hours while being rotated to obtain a product. And filtering and cleaning the product, drying the product at 110 ℃ in the air overnight, roasting the dried product in the air at 600 ℃ for 2 hours, and determining the product by XRD (X-ray diffraction) to be AFX type SSZ-16 molecular sieve raw powder. The molecular sieve raw powder and ammonium nitrate solution with the concentration of 1.0mol/L are subjected to ion exchange for 2 hours at the temperature of 90 ℃ according to the solid-liquid mass ratio of 1:10, and then filter cakes obtained by filtration are subjected to ion exchange twice with fresh ammonium nitrate solution again under the same condition, so that the Na ion content is lower than 500 ppm. The filter cake obtained by subsequent filtration is dried at 110 ℃ overnight to obtain ammonium type molecular sieve NH4Heating to 450 ℃ and roasting for 16 hours to obtain the H-type SSZ-16 molecular sieve.
3) 10g of SSZ-16 molecular sieve type H was added to 100g of Cu (NO) at a concentration of 0.2mol/L3)2·3H2And (3) dripping dilute nitric acid into the O aqueous solution to adjust the pH value to 4.0, and uniformly stirring. After stirring was stopped for 1 hour, the supernatant was siphoned off when the SSZ-16 molecular sieve had settled. Can be repeatedly usedAnd exchanging the fresh copper nitrate solution twice, and finally filtering and washing the exchanged SSZ-16 molecular sieve by deionized water. Drying at 90 ℃ for 12 hours under the low pressure of 10Torr, and then roasting at 500 ℃ for 4 hours under normal atmospheric pressure to obtain the copper modified SSZ-16 molecular sieve powder. According to XRF analysis, copper (II) ions accounted for 3.0% of the total weight of the molecular sieve catalyst.
4) 15g of the resulting copper-modified SSZ-16 molecular sieve were taken and mixed with 7.5g of silica sol (30 wt% SiO)2) And 26.8g of deionized water are uniformly mixed to prepare catalyst slurry with the solid content of 35.0 wt%, the catalyst slurry is coated on a honeycomb-shaped porous regular material (400 cpsi, the diameter of 20mm and the length of 40mm) made of cordierite through an impregnation method, redundant slurry drops are blown off by compressed air, the drying is carried out for 12 hours at the temperature of 110 ℃, then, the slurry is coated again, the SCR catalyst is prepared after the calcination is carried out for 2 hours at the temperature of 500 ℃, and the measured catalyst loading capacity on the regular material is 208.4g/L and is marked as VS-2.
Examples 9 to 16
Testing of the SCR catalyst:
SCR catalysts prepared in examples 1 to 6 and comparative examples 1 to 2 were installed in a reactor
Figure BDA0002318316390000223
160mL/min of a mixed gas stream containing 500ppm of NO, 500ppm of NH3, 10 vol% of O2, 5 vol% of steam and Ar as a balance gas firstly passes through a preheater (set at 250 ℃) and then enters an SCR reactor. At a reaction temperature of 150-650 ℃ for 48000h-1The test specimens were tested at a volumetric gas hourly space velocity. The temperature is monitored by an internal thermocouple located at the sample site.
The used fresh SCR catalysts of the above examples and comparative examples were subjected to a hydrothermal durability treatment under the conditions of the hydrothermal durability treatment test to obtain aged SCR catalysts:
space velocity SV: 30000/h, temperature: 800 ℃, time: 16 hours, water concentration: 10%, oxygen concentration: 10%, nitrogen concentration: and (4) balancing.
After hydrothermal aging treatment is carried out according to the parameters, the catalyst is continuously used as an SCR catalyst for NOx catalytic reduction reaction evaluation test:
NO conversion or "denox" activity was determined under steady state conditions by measuring NOx, NH3, and N2O concentrations at the outlet using a Bruker EQUINOX model 55 FT-IR spectrometer.
Figure BDA0002318316390000221
The SCR catalyst activity laboratory evaluation device described above was used to evaluate the selective catalytic reduction performance of NOx on the Cu-supported SCR catalysts prepared in examples and comparative examples, and the results are shown in table 4.
TABLE 4
Figure BDA0002318316390000222
Figure BDA0002318316390000231
As can be seen from Table 4, the catalysts Cu-SSZ-39/SSZ-16 or Fe-SSZ-39/SSZ-16 prepared in examples 9-14 by using the catalysts of examples 1-6 have better low-temperature ignition performance and high-temperature activity, and the SCR activity is obviously better than that of the catalysts VS-1 and VS-2 prepared in comparative examples 1 and 2 in examples 15-16, no matter the catalysts are in a 'fresh' state or an 'aged' state.
Thus, the results obtained from examples 9-14 clearly show that the Cu-SSZ-39/SSZ-16 or Fe-SSZ-39/SSZ-16 catalyst materials of the present invention and the catalysts obtained therewith have improved SCR catalytic activity, especially at low conversion temperatures typical of cold start conditions when treating NOx in, for example, diesel locomotive applications.
For other SCR applications, the Cu-SSZ-39/SSZ-16 or Fe-SSZ-39/SSZ-16 catalyst materials of the present invention allow for higher conversion at lower temperatures, thus allowing for higher efficiency and thus, at comparable conversion, high energy efficiency in the treatment of NOx-containing exhaust gases, such as exhaust gases obtained from industrial processes.
The above-mentioned embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (10)

1. An AEI/AFX structure intergrowth composite molecular sieve, which is characterized in that: the composite material is formed by intergrowth of AEI and AFX topological structure molecular sieves, wherein the AEI structure molecular sieve accounts for 60-99% of the total weight, and the AFX structure molecular sieve accounts for 1.0-40% of the total weight; the molar ratio of silicon oxide to aluminum oxide in the intergrowth composite molecular sieve is 10-200; the molecular sieve X-ray diffraction phase spectrogram of the intergrowth structure has characteristic peaks at the 2 theta angles of 7.42 +/-0.2, 8.64 +/-0.2, 9.48 +/-0.2, 10.60 +/-0.2, 11.56 +/-0.2, 12.86 +/-0.2, 12.90 +/-0.2, 15.50 +/-0.2, 16.06 +/-0.2, 16.85 +/-0.2, 17.16 +/-0.2, 17.78 +/-0.2, 19.64 +/-0.2, 20.20 +/-0.2, 20.70 +/-0.2, 21.34 +/-0.2, 21.62 +/-0.2, 23.90 +/-0.2, 25.88 +/-0.2, 26.26 +/-0.2, 27.82 +/-0.2, 30.32 +/-0.2 and 31.26 +/-0.2.
2. The intergrowth composite molecular sieve having an AEI/AFX structure of claim 1, wherein: the AEI structure molecular sieve specifically comprises any one or more of SSZ-39, SAPO-18, AlPO-18 and SIZ-8, and is preferably an SSZ-39 silicon-aluminum molecular sieve; the AFX structure molecular sieve specifically comprises any one or more of SAPO-56 and SSZ-16, and preferably is an SSZ-16 silicon-aluminum molecular sieve.
3. The synthesis method of intergrowth composite molecular sieve with AEI/AFX structure according to claim 1 or 2, characterized in that:
1) uniformly stirring NaOH, a composite template agent and deionized water in an ultrasonic manner, and then adding an FAU type molecular sieve and a silicon source into the mixture to be uniformly mixed into gel; FAU type silicon-aluminum molecular sieve provides aluminum source and partial silicon source, and the silicon source is SiO in the mixed slurry2The aluminum source is A12O3The composite template agent is calculated by OSDA, NaOH is calculated by Na2Calculated by O, the molar ratio of the components is nSiO2:nA12O3:nNa2O:nOSDA:nH2O＝1:(0.005～0.1):(0.05～0.5):(0.05～1.0):(10～100)；
2) Stirring the mixture obtained in the step 1), transferring the mixture into a hydrothermal crystallization reaction kettle, performing two-section or multi-section crystallization at the autogenous pressure and the temperature of 120-200 ℃ for 48-168 hours in total, and filtering, washing, drying and roasting the obtained crystallized liquid to obtain raw powder of a symbiotic composite silicon-aluminum molecular sieve;
the composite template agent OSDA in the step 1) comprises organic template agents R1 and R2, wherein the molar ratio of the two organic template agents is nR1, nR2 is 1 (0.05-0.8);
the organic template R1 in the step 1) comprises the following types: n, N-dimethyl-3, 5-dimethylpiperidinium, N-dimethyl-2, 6-dimethylpiperidinium, 1,2,2,6, 6-hexamethylpiperidinium, 1,2,2,6, 6-hexamethyl-4-oxopiperidinium, 1,3, 5-tetramethyl-4-oxopiperidinium, 1-hydroxy-1, 1,2,2,6, 6-hexamethylpiperidinium, 1-dimethyl-4, 4-dipropoxypiperidinium, 3, 5-dimethoxy-1, 1-dimethylpiperidinium, 3, 5-dihydroxy-1, 1-dimethylpiperidinium, 4-ethyl-1, 1-dimethyl-3, one or more of 5-dioxopiperidinium, 1-ethyl-1-methyl-2, 2,6, 6-hexamethylpiperidinium, 1-epoxypropyl-1-methyl-2, 2,6, 6-hexamethylpiperidinium, N-dimethyl-2- (2-hydroxyethyl) piperidinium and N, N-dimethyl-2-ethylpiperidinium;
the organic template R2 in the step 1) is a compound containing a structure of alkane substituted by double six-membered ring or double five-membered heterocyclic group, and comprises the following 11 chemical formulas:
Figure FDA0002318316380000021
Figure FDA0002318316380000031
the molar ratio of silicon to aluminum in the intergrowth composite molecular sieve is 10-200, preferably 10-100, and more preferably 10-50.
4. The method of synthesis according to claim 3, characterized in that: the aluminum source is selected from four-coordinate aluminum in FAU type silicon-aluminum zeolite, wherein the FAU type molecular sieve comprises an X molecular sieve, a Y molecular sieve and a USY molecular sieve.
5. The method of synthesis according to claim 3, characterized in that: the silicon source in the step 1) is selected from one or more of white carbon black, macroporous silica gel, coarse porous silica gel, fine porous silica gel, thin layer chromatography silica gel, B type silica gel, sodium metasilicate, silica sol, water glass, alkyl silicate, diatomite and gas phase method silica gel, and preferably chromatography silica gel, white carbon black, silica sol, water glass and alkyl silicate.
6. A synthesis method according to claim 3, characterized in that: the organic template R2 is of the following types: any one or more of 1, 4-bis ([ 4-aza-1-azoniabicyclo [2.2.2]) butane, 1, 4-bis (quinuclidinium) butane, 1, 4-bis (N-methylpiperidinium) butane, 1, 4-bis (N-methylpiperazinium) butane, 1, 4-bis (N-methylmorpholinium) butane, 1, 4-bis (N-methylpiperidinium) butane, 1, 4-bis (N-methylpyrrolidium) butane, 1, 4-bis (N-methylimidazolium) butane, 1, 4-bis (2, 3-dimethylimidazolium) butane and 1, 4-bis (N-methylimidazolium) butane.
7. A synthesis method according to claim 3, characterized in that: mixing the intergrowth composite molecular sieve raw powder obtained in the step 2) with an ammonium salt solution with the concentration of 0.1-5.0 mol/L according to the solid-liquid mass ratio of 1: (5-50) carrying out ion exchange at 80-120 ℃, wherein each time of exchange is 0.5-6 hours, and repeatedly exchanging the obtained filter cake with a fresh ammonium ion solution for 1-3 times until the Na content in the molecular sieve sample is lower than 500 ppm; then filtering and separating out a solid product, repeatedly washing the solid product with deionized water to be neutral, drying a filter cake at 100-130 ℃ for 12-48 hours, and roasting the filter cake at 400-600 ℃ for 2-8 hours to obtain an H-type symbiotic composite silicon-aluminum molecular sieve;
the ammonium salt is a mixture formed by mixing any one, two or more than two of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium acetate in any proportion.
8. An SCR catalyst for denitration, which is prepared by carrying out ion exchange on the intergrowth composite silicon-aluminum molecular sieve with the AEI/AFX structure and a soluble metal salt solution according to any one of claims 1 or 2, forming slurry with a solid content of 25.0-48.0 wt% with a binder and deionized water, and coating the slurry on a carrier of a porous regular material or an integral filter substrate to form a proper coating to obtain the metal-promoted SCR catalyst with the intergrowth composite molecular sieve with the AEI/LEV topological structure. .
9. The catalyst of claim 7, wherein: the soluble metal salt is selected from one or a combination of more of soluble salts of copper, iron, cobalt, tungsten, nickel, zinc, molybdenum, vanadium, tin, titanium, zirconium, manganese, chromium, niobium, bismuth, antimony, ruthenium, germanium, palladium, indium, platinum, gold or silver, preferably any one or two of copper salt and iron salt, and further preferably copper salt; the copper salt is one or more of copper nitrate, copper chloride, copper acetate or copper sulfate; the concentration of copper ions in the copper salt aqueous solution is 0.1-0.5 mol/L.
10. The SCR catalyst according to claim 7, wherein the binder is selected from the group consisting of silica sol, alumina sol and pseudo-boehmite, or a mixture thereof, and the porous structured material or monolithic filter substrate is made of cordierite, α -alumina, silicon carbide, aluminum titanate, silicon nitride, zirconia, mullite, spodumene, alumina-silica-magnesia or zirconium silicate.
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Application publication date: 20200414