CN109384246B - Molecular sieve with AEI structure and preparation method and application thereof - Google Patents
Molecular sieve with AEI structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of inorganic porous material synthesis, in particular to an AEI structure molecular sieve and a preparation method and application thereof. The invention provides a preparation method of an AEI structure molecular sieve, which comprises the following steps: (1) reacting raw materials containing an organic template agent, an FAU type silicon-aluminum molecular sieve, alkali liquor and water under a hydrothermal crystallization condition, wherein the FAU type silicon-aluminum molecular sieve provides a silicon source and an aluminum source; (2) and (2) filtering the product obtained in the step (1), performing electrodialysis electrolysis on the filtrate, and recovering organic template and silicon species as the synthesis raw materials of the next batch of AEI molecular sieve. The method for recycling the filtrate effectively avoids mixing amorphous substances and degraded substances into the next batch of feed, reduces the feed error of the AEI molecular sieve, ensures that the obtained AEI molecular sieve has good dispersity and relatively high crystallinity, and improves the total yield of the synthesis of the AEI molecular sieve.
Description
Technical Field
The invention relates to the field of inorganic porous material synthesis, in particular to an AEI structure molecular sieve and a preparation method and application thereof.
Background
The AEI structure molecular sieve has a three-dimensional channel system with large cages, and can form a three-dimensional channel structure through 8-membered rings, and the pore size is large
The cage structure is similar to the CHA molecular sieve, and the cage size can reach the diameter
A sphere. The difference is that adjacent double six-membered rings of the CHA structure in two adjacent double six-membered ring structures connected by a four-membered ring are in a parallel structure in space, and two adjacent double six-membered rings in the AEI structure are in mirror symmetry distribution. The structural difference leads the eight-membered ring channel in the AEI structure to have smaller pore diameter, higher catalytic activity and better carbon deposition resistance. The structures of the AEI silicon-aluminum molecular sieve and the silicon-aluminum-phosphorus molecular sieve are respectively specificRepresented by SSZ-39 and SAPO-18. 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).
Nitrogen oxides (NOx) cause a series of environmental problems such as photochemical smog, acid rain and greenhouse effect, have seriously harmed human health, and as the number of automobiles increases and the industry rapidly develops, the amount of NOx emission increases, which inevitably causes serious deterioration of ecology and environment. Thus, the problem of eliminating NOx pollution is not very mild. Currently, the dominant NOx control technology is selective catalytic reduction (NH) of NH33SCR), which is the key to select a catalyst with excellent performance, and which will determine the success or failure of the whole catalytic reaction system.
Generally, the SCR catalyst is a molecular sieve with a crystal structure, which is prepared by using zeolite as a carrier and loading SCR active components; zeolites are aluminosilicate crystalline materials having relatively regular pore sizes, such as zeolite beta, zeolite Y, zeolite X, zeolite faujasite, mordenite, erionite, ZSM-5, ZSM-8, ZSM-11, ZSM-12, and the like, which may be exchanged with metals such as Cu, Fe, Mn, Ag, V, Ti, Co, or which themselves contain some metals such as Cu, Fe. However, the above known metal-modified zeolite catalysts can purify nitrogen oxides only in a narrow temperature range during the selective catalytic reduction of nitrogen oxides with ammonia, and do not have high NOx purification performance at 200 ℃ or lower, and have poor hydrothermal stability and low activity under low temperature conditions.
Synthetic AEI molecular sieves are produced using Organic Structure Directing Agents (OSDA), which are also referred to as "templates" or "templating agents. Typically, the OSDA acts as a mold around which molecular sieve crystals are formed. After crystal formation, the OSDA is removed from the crystal internal structure, leaving behind a porous molecular sieve cage for the molecules.
In conventional synthesis methods, solid molecular sieve crystals are precipitated from a reaction mixture, which is a reaction precursor mixture of a silicon source, an aluminum source, an alkali source, and an organic templating agent. Synthesis typically requires a longer time to achieve the desired crystallization of the molecular sieve. When the molecular sieve crystallization is complete, the molecular sieve solid product is typically recovered by filtration and the excess filtrate is discharged. The discharged filtrate contains unused organic templating agent (OSDA), which often degrades due to harsh reaction conditions.
Patent CN104591204A increases the yield of silica and/or OSDA by recycling the mother liquor after AEI molecular sieve synthesis, but the direct recycling of the mother liquor cannot effectively solve the problems of high cost and environmental pollution caused by low yield because a small amount of degradation products and amorphous products which are not crystallized in the mother liquor cannot be removed and the product quality is easily unstable.
Disclosure of Invention
To this end, the present invention provides a method for preparing an AEI structure molecular sieve, comprising the steps of:
(1) reacting raw materials containing an organic template agent, an FAU type silicon-aluminum molecular sieve, alkali liquor and water under a hydrothermal crystallization condition, wherein the FAU type silicon-aluminum molecular sieve provides a silicon source and an aluminum source;
(2) and (2) filtering the product obtained in the step (1), performing electrodialysis electrolysis on the filtrate, and recovering organic template and silicon species as the synthesis raw materials of the next batch of AEI molecular sieve.
The invention provides an AEI structure molecular sieve which is prepared by a method comprising the following steps:
(1) reacting raw materials containing an organic template agent, an FAU type silicon-aluminum molecular sieve, alkali liquor and water under a hydrothermal crystallization condition, wherein the FAU type silicon-aluminum molecular sieve provides a silicon source and an aluminum source;
(2) and (2) filtering the product obtained in the step (1), performing electrodialysis electrolysis on the filtrate, and recovering organic template and silicon species as the synthesis raw materials of the next batch of AEI molecular sieve.
The present invention provides a NOXA selective catalytic reduction catalyst is obtained by ion-exchanging an AEI structure molecular sieve with a metal salt solution.
The invention also provides NOXThe preparation method of the selective catalytic reduction catalyst comprises the step of adding the AEI structure molecular sieve into a metal salt solution to obtain NOXA selective catalytic reduction catalyst.
Specifically, the present invention proposes the following technical solutions.
The invention provides a preparation method of an AEI structure molecular sieve, which comprises the following steps:
(1) reacting raw materials containing an organic template agent, an FAU type silicon-aluminum molecular sieve, alkali liquor and water under a hydrothermal crystallization condition, wherein the FAU type silicon-aluminum molecular sieve provides a silicon source and an aluminum source;
(2) and (2) filtering the product obtained in the step (1), performing electrodialysis electrolysis on the filtrate, and recovering organic template and silicon species as the synthesis raw materials of the next batch of AEI molecular sieve.
Preferably, in the preparation process, in the step (1), the organic template is a monocyclic or polycyclic piperidinium compound selected from the group consisting of N, N-dimethyl-3, 5-dimethylpiperidinium, N-dimethyl-2, 6-dimethylpiperidinium, 1,2,2,6, 6-hexamethylpiperidinium, 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, 1-hydroxy-1, 1,2,2, 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, 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.
Preferably, for the preparation method, wherein, in the step (1), the FAU-type silicoaluminophosphate molecular sieve is selected from one of Y zeolite and X zeolite; preferably, the Y zeolite is selected from one of HY zeolite, USY zeolite and NaY zeolite, and the X zeolite is selected from one of NaX zeolite, KX zeolite and HX zeolite.
Preferably, in the preparation method, in the step (1), the hydrothermal crystallization is divided into two stages: (1) the crystallization temperature of the first section is 120-150 ℃, and preferably 130-150 ℃; (2) the second stage crystallization temperature is 150-200 ℃, preferably 160-190 ℃.
Preferably, in the preparation method, in the step (1), the hydrothermal crystallization is divided into two stages: (1) the first crystallization time is 0.5 to 3.0 days, preferably 0.5 to 2.0 days; (2) the second stage crystallization time is 0.5 to 6.0 days, preferably 1.0 to 5.0 days.
Preferably, in the preparation method, in step (1), an additional silicon source is added as a raw material, wherein the additional silicon source 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 and diatomite.
Preferably, in the preparation method, in step (1), the alkali solution is selected from NaOH and Na2O、Na2O2And KOH, or two or more thereof.
Preferably, in the preparation method, in the step (1), the molar ratio of the silicon source, the aluminum source, the alkali solution, the template agent and the water is 1.0: 0.00833-0.1667: 0.1-0.5: 0.05-0.5: 10-50, preferably 1.0: 0.0121-0.0417: 0.22-0.36: 0.08-0.20: 15 to 25.
Preferably, in the production method, in the step (2), the electrodialysis is one selected from four-compartment three-membrane, three-compartment two-membrane, or two-compartment one-membrane.
Preferably, for the preparation method, in step (2), the bipolar membrane is obtained by compounding a cation exchange layer, an interfacial hydrophilic layer and an anion exchange layer.
The invention provides an AEI structure molecular sieve which is prepared by any one of the methods.
Preferably, the molecular sieve with the AEI structure has a molecular molar ratio of silica to alumina of 5-100, preferably 10-80.
The present invention provides a NOXThe selective catalytic reduction catalyst is obtained by carrying out ion exchange on an AEI structure molecular sieve and a metal salt solution.
Preferably, for said NOXThe selective catalytic reduction catalyst is characterized in that the metal salt is one or more than two 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, for said NOXA selective catalytic reduction catalyst, wherein the metal salt is selected from copper or iron salts, preferably copper salts.
Preferably, for said NOXThe selective catalytic reduction catalyst comprises copper salt, copper chloride, copper acetate and copper sulfate, wherein the copper salt is one or more than two of copper nitrate, copper chloride, copper acetate and copper sulfate, and the concentration of copper ions in the copper salt is 0.1-1.5 mol/L.
The invention provides a preparation method of a selective catalytic reduction catalyst, which is characterized in that AEI structure molecular sieve is added into a metal salt solution to obtain NOXA selective catalytic reduction catalyst.
Preferably, the preparation method further comprises the following steps: the obtained NOXThe selective catalytic reduction catalyst is attached to the porous structured material using a binder.
Preferably, in the preparation method, the binder is one or more selected from silica sol, water glass, pseudo-boehmite, and alumina sol.
Preferably, for the preparation method, wherein the porous structured material is selected from one of a honeycomb shape, a plate shape and a corrugated shape.
Preferably, for the production method, the porous structured material is selected from one of cordierite, α -alumina, silicon carbide, aluminum titanate, silicon nitride, zirconia, mullite, spodumene, alumina-silica-magnesia, zirconium silicate or metal flake, preferably cordierite.
A selective catalytic reduction catalyst for its use in the purification of exhaust gas streams, preferably in the purification of automotive exhaust gas streams.
Preferably, for the application, wherein the exhaust gas stream is an automotive exhaust gas stream, preferably an exhaust gas stream of a lean burn engine, more preferably a diesel exhaust gas stream.
The invention provides a purification treatment method of waste gas flow, which is to mix a selective catalytic reduction catalyst with NOXBy contact with the exhaust stream of a vehicle of reducing agent to make NOXSelectively reduced to N2And H2O。
Preferably, for the purification treatment method, the exhaust gas stream is treated with NO before being contacted with the selective catalytic reduction catalystXThe NO2 content is 80 wt% or less, preferably 5 to 70 wt%, more preferably 10to 60 wt%, more preferably 15 to 55 wt%, and still more preferably 20 to 50 wt%, measured as 100 wt%.
The selective catalytic reduction catalyst provided by the invention is a nitrogen oxide selective catalytic reducing agent or a denitration catalyst.
The beneficial effects obtained by the invention are as follows: the method for separating and recovering the organic template agent and the silicon species in the reaction filtrate effectively avoids mixing amorphous substances and degraded substances into the next batch of feed, reduces the feed error of the AEI molecular sieve, and ensures that the obtained AEI molecular sieve has good dispersity and relatively high crystallinity. Compared with 100% crystallinity of the AEI molecular sieve obtained by directly adopting the original organic template and FAU silicon-aluminum molecular sieve raw materials for hydrothermal crystallization, the relative crystallinity of the AEI molecular sieve prepared by separating the organic template from silicon species from the filtrate after reaction is in the range of 95-105%, while the relative crystallinity of the molecular sieve obtained by directly using the filtrate after reaction as a supplementary synthesis raw material for reaction in the prior art is in the range of 56-89%.
Drawings
FIG. 1 a: the schematic diagram of the filtrate after the synthesis of the AEI molecular sieve is electrolyzed by a bipolar membrane;
FIG. 1 b: the filtrate after the synthesis of the AEI molecular sieve is processed by a conventional electrodialysis schematic diagram;
FIG. 2: the XRD pattern of the AEI molecular sieve raw powder obtained in example 1;
FIG. 3: the XRD pattern of the AEI molecular sieve raw powder obtained in example 5;
FIG. 4: XRD pattern of the AEI molecular sieve raw powder obtained in comparative example 1;
FIG. 5: XRD pattern of the AEI molecular sieve raw powder obtained in comparative example 3;
FIG. 6: XRD pattern of the AEI molecular sieve raw powder obtained in comparative example 5;
FIG. 7: SEM image of AEI molecular sieve raw powder obtained in example 1;
FIG. 8: SEM image of AEI molecular sieve raw powder obtained in example 5;
FIG. 9: SEM image of AEI molecular sieve raw powder obtained in comparative example 1;
FIG. 10: SEM image of AEI molecular sieve raw powder obtained in comparative example 3;
FIG. 11: SEM image of the AEI molecular sieve raw powder obtained in comparative example 5.
Detailed Description
The term "AEI" refers to an AEI-type framework recognized by the International Zeolite Association (IZA) structure committee.
As described above, the present invention provides a method for preparing an AEI structure molecular sieve, comprising the steps of:
(1) reacting raw materials containing an organic template agent, an FAU type silicon-aluminum molecular sieve, alkali liquor and water under a hydrothermal crystallization condition, wherein the FAU type silicon-aluminum molecular sieve provides a silicon source and an aluminum source;
(2) and (2) filtering the product obtained in the step (1), performing electrodialysis electrolysis on the filtrate, and recovering organic template and silicon species as the synthesis raw materials of the next batch of AEI molecular sieve.
In a preferred embodiment of the present invention, the silicon source, the aluminum source, the alkali source, the template and the water are mixed in a molar ratio of 1.0: 0.00833-0.1667: 0.1-0.5: 0.05-0.5: 10-50, and reacting under the condition of hydrothermal crystallization, wherein the hydrothermal crystallization is divided into two sections: (1) the crystallization temperature of the first section is 120-150 ℃, and the crystallization time is 0.5-3.0 days; (2) and the second stage crystallization temperature is 150-200 ℃, the crystallization time is 0.5-6.0 days, then the product obtained by the reaction is filtered, the filtrate is subjected to electrodialysis electrolysis, and the organic template and the silicon source which is not completely reacted are recovered, so that raw materials are provided for the next step of synthesizing the AEI molecular sieve. Wherein the electrodialysis is selected from bipolar membrane electrodialysis or electrodialysis well known to those skilled in the art.
The filtrate is recovered by adopting a bipolar membrane, the bipolar membrane is a novel ion exchange composite membrane, and the bipolar membrane is usually formed by compounding a cation exchange layer (N-type membrane), an interface hydrophilic layer (catalyst layer) and an anion exchange layer (P-type membrane), and is a reaction membrane in the true sense. Under the action of a direct current electric field, the bipolar membrane can dissociate water to obtain hydrogen ions and hydroxyl ions on two sides of the membrane respectively. By utilizing the characteristic, the bipolar membrane electrodialysis system combining the bipolar membrane and other anion-cation exchange membranes can convert the salt in the aqueous solution into corresponding acid and alkali without introducing new components, and the method is called as bipolar membrane electrodialysis method.
The invention selects ABS plastic to make a solution tank, after a plurality of equal parts are arranged in the tank, DSA anode electrodes and graphite cathode electrodes are respectively arranged in the electrolytic tank. Between the anode and the cathode of the electrolytic cell, an anion exchange membrane, a cation exchange membrane and a bipolar membrane which are prepared for standby in advance are arranged.
In a preferred embodiment of the present invention, the silicon source is SiO2The aluminum source is calculated as Al2O3Measured by Na, the alkali liquor is measured by2And O, the organic template is calculated as OSDA.
In one embodiment of the present invention, the present invention provides a NOXThe selective catalytic reduction catalyst is obtained by carrying out ion exchange on an AEI structure molecular sieve and a metal salt solution.
In a preferred embodiment of the invention, the AEI molecular sieve is obtained by ion exchange between an AEI molecular sieve and a soluble metal salt solution, wherein the metal salt solution is preferably a copper salt or an iron salt, more preferably a copper salt, the copper salt is selected from one or more of copper nitrate, copper chloride, copper acetate and copper sulfate, and the concentration of copper ions in the copper salt is 0.1 to 1.5 mol/L.
In a more preferred embodiment of the present invention, after ion-exchanging the AEI structure molecular sieve with a copper salt, a copper-modified AEI structure molecular sieve is obtained, and then the copper-modified AEI structure molecular sieve is attached to a porous structured material using a binder, and the porous structured material with a catalyst is disposed in an exhaust gas treatment device to form an automotive exhaust gas treatment device for treating an exhaust gas stream.
The binder is selected from one or more than two of silica sol, water glass, pseudo-boehmite and aluminum sol.
The porous regular material is selected from honeycomb-shaped, plate-shaped or corrugated materials, and the materials are selected from cordierite, alpha-alumina, silicon carbide, aluminum titanate, silicon nitride, zirconia, mullite, spodumene, alumina-silica-magnesia, zirconium silicate or metal sheets; preferably, the cordierite porous honeycomb flow-through type monolith carrier has the carrying capacity of 170-270 g/L.
In one embodiment, the present invention provides a method for the purification treatment of an exhaust gas stream that will contain NOXAnd a reducing agent, contacting said NO with an SCR catalyst compositionXAt least a portion of which is selectively reduced to N2And H2O。
The nitrogenous reductant is selected from ammonia, hydrazine or any suitable ammonia precursor selected from one or more of urea, ammonium carbonate, ammonium carbamate, ammonium bicarbonate or ammonium formate.
In a preferred embodiment of the invention, the catalyst shown in the present invention shows that NO can be obtained in a much wider temperature windowXAnd (4) conversion rate. The temperature range for increasing the conversion is about 150 to 650 ℃, preferably 200 to 650 ℃, and more preferably 200 to 550 ℃, and in these temperature ranges, after exposure to the reducing atmosphere, even after exposure to the reducing atmosphereAnd high temperatures (e.g., up to 850 ℃) can be greater than 55% to 100%, more preferably greater than 90%, and even more preferably greater than 95%.
"relative yield" in the context of the present invention means the ratio of the amount of reactant (or derivative thereof) incorporated into the desired product to the total amount of reactant introduced in the chemical process, and the relative yield of the reactants can be calculated using the following equation: (relative yield)R＝(RP)/(RT) Wherein R is a reactant, RPIs the total weight of the reactants R (or derivatives thereof) incorporated into the desired product, RTIs the total weight of reactant R introduced in the chemical process. The term "total relative yield" refers to the overall relative yield for a chemical process. "Total relative yield on silica" means the total amount of silica incorporated into the total amount of one or more sequential batches of zeolite relative to the total amount of silica introduced into the process as a whole. "Total relative yield on a templating agent" means the amount of organic templating agent used directly in one or more sequential batches of constituent zeolite framework relative to the amount of silica introduced into the process as a whole.
The manufacturers of the raw materials and equipment used in the present example, and the equipment and analysis method used in the product analysis are described below, wherein the chemical substances are not indicated as being chemically pure grades of conventional reagents. The information on the raw materials used in the examples and the information on the experimental facilities are shown in tables 1 and 2.
TABLE 1 information on the raw materials used in the present invention
| Name (R) | Purity of | Manufacturer of the product |
| HY zeolite | 100％ | SHANDONG DUOYOU TECHNOLOGY Co.,Ltd. |
| NaOH pellets | 96％ | Chemical reagent plant of continental Tianjin City |
| USY zeolite | 100％ | BASF Corp. |
| X zeolite | 100％ | TIANJIN NANHUA CATALYST Co.,Ltd. |
| NaY zeolite | 100％ | SHANDONG DUOYOU TECHNOLOGY Co.,Ltd. |
TABLE 2 information on the experimental equipment used in the present invention
| Device | Model number | Manufacturer of the product |
| Scanning electron microscope | TM3030 | Hitachi |
| ICP analyzer | ICPE-9000 | Shimadzu of Japan |
| X-ray diffractometer | X’PertPRO | Parnaceae, Holland |
Example 1 preparation of an AEI-type zeolitic molecular sieve
(1) Adding a certain amount of 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 aqueous 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 moles is as follows:
Na2O：SiO2：Al2O3：OSDA：H2o ═ 0.22: 1.0: 0.03484: 0.20: 25.0; 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;
(2) after crystallization is completed, quickly cooling a product, performing suction filtration separation and washing to obtain filtrate and solid matters, separating the recovered filtrate from organic template and silicate by a bipolar membrane electrodialysis method (shown as figure 1 a), and taking an organic template alkaline solution (marked as SDK-1) and a silicic acid solution (marked as SAA-1) as raw materials to participate in the synthesis of the next batch of AEI molecular sieves;
drying the solid matter at 120 ℃ for 12 hours and roasting the solid matter at 540 ℃ for 4 hours, and confirming the solid matter as an AEI type molecular sieve through XRD, namely AEI molecular sieve raw powder; the AEI molecular sieve showed its SAR of 11.2, marked as A, and the ratio of the molecular sieve synthesis precursor sol, the synthesis conditions, the relative crystallinity and the yield parameters are shown in tables 3 and 4.
Example 2 preparation of an AEI-type zeolitic molecular sieve
(1) Quantitative HY zeolite (Si/Al ratio SAR of 5.3) and water glass (Na)2O：7.44wt％，SiO2: 27.40 wt%) and the SAA-1 solution obtained in example 1 were mixed, and to the mixture, the SDK-1 solution obtained in example 1 and a quantitative N, N-dimethyl-3, 5-dimethylpiperidinium aqueous solution (concentration: 20 wt%), deionized water and NaOH pellets (purity: 96 wt.%), the reaction mixture was then stirred continuously at 200rpm in a sealed vessel at room temperature for 2 hours until all the starting materials were mixed uniformly, with a mixed sol molar ratio of the following molar composition:
Na2O：SiO2：Al2O3：OSDA：H2o ═ 0.24: 1.0: 0.03226: 0.15: 25.0; transferring the obtained solid mixture into a 2000ml hydrothermal crystallization kettle, stirring at the speed of 60rpm, heating to 135 ℃ for crystallization for 36 hours, and then continuously heating to 180 ℃ for crystallization for 48 hours;
(2) after crystallization is completed, the product is rapidly cooled, filtrate and solid substances are obtained through suction filtration separation and washing, the filtrate of the product is collected, and an organic template agent alkaline solution (marked as SDK-2) and an orthosilicic acid solution (SAA-2) are separated in a bipolar membrane electrodialysis mode (shown in figure 1 a) to be used as raw materials for synthesis of the next batch of AEI molecular sieves.
Drying the solid matter at 120 ℃ for 12 hours and roasting the solid matter at 540 ℃ for 4 hours, and confirming the solid matter as an AEI type molecular sieve through XRD, namely AEI molecular sieve raw powder; the AEI molecular sieve showed its SAR of 15.6, denoted as B, and the ratio of molecular sieve synthesis precursor sol, synthesis conditions, relative crystallinity and yield parameters are shown in tables 3 and 4.
Example 3 preparation of an AEI-type zeolitic molecular sieve
(1) The amount of dealuminated USY zeolite having a silica-alumina molar ratio (SAR) of 20.6 and water glass (Na)2O：7.44wt％，SiO2: 27.40 wt%) was mixed with the SAA-2 solution obtained in example 2. To this mixture, the SDK-2 solution obtained in example 2, a quantitative N, N-dimethyl-3, 5-dimethylpiperidinium aqueous solution (concentration: 20 wt%), deionized water and NaOH particles (purity: 96 wt%) were added in this order, and the reaction mixture was then stirred at 200rpm in a closed vessel at room temperature until all the raw materials were uniformly mixed, having a mixed sol molar ratio of the following molar composition:
Na2O：SiO2：Al2O3：OSDA：H2o ═ 0.26: 1.0: 0.02475: 0.15: 25.0; transferring the obtained solid mixture into a 2000ml hydrothermal crystallization kettle, stirring at the speed of 60rpm, heating to 130 ℃ for crystallization for 48 hours, and then continuously heating to 185 ℃ for crystallization for 60 hours;
(2) after crystallization is completed, the product is rapidly cooled, filtrate and solid substances are obtained through suction filtration separation and washing, the filtrate of the product is collected, and an organic template agent alkaline solution (marked as SDK-3) and an orthosilicic acid solution (SAA-3) are separated in a bipolar membrane electrodialysis mode (shown as figure 1 a) to be used as raw materials for the synthesis of the next batch of AEI molecular sieves;
drying the solid matter at 120 ℃ for 12 hours and roasting the solid matter at 540 ℃ for 4 hours, and confirming the solid matter as an AEI type molecular sieve through XRD, namely AEI molecular sieve raw powder; the AEI molecular sieve showed its SAR of 29.7, marked as C, and the ratio of the molecular sieve synthesis precursor sol, the synthesis conditions, the relative crystallinity and the yield parameters are shown in tables 3 and 4.
Example 4 preparation of an AEI-type zeolitic molecular sieve
(1) Quantitative zeolite X with a silica-alumina molar ratio (SAR) of 2.74 and water glass (Na)2O：7.44wt％，SiO2: 27.40 wt%) and the SAA-3 solution obtained in example 3 were mixed, and to the mixture, the SDK-3 solution obtained in example 3 and a quantitative N, N-dimethyl-3, 5-dimethylpiperidinium aqueous solution (concentration: 20 wt%), deionized water and NaOH pellets (purity: 96 wt.%), the reaction mixture was then stirred at 200rpm in a closed vessel at room temperature until all the starting materials were uniformly mixed and had the following molar compositionThe molar ratio of the mixed sol is as follows:
Na2O：SiO2：Al2O3：OSDA：H2o ═ 0.28: 1.0: 0.02045: 0.15: 25.0; transferring the obtained solid mixture into a 2000ml hydrothermal crystallization kettle, stirring at the speed of 60rpm, heating to 150 ℃, crystallizing for 12 hours, and then continuously heating to 170 ℃, crystallizing for 72 hours;
(2) after crystallization is completed, the product is rapidly cooled, filtrate and solid substances are obtained through suction filtration separation and washing, the filtrate of the product is collected, and an organic template agent alkaline solution (marked as SDK-4) and an orthosilicic acid solution (SAA-4) are separated in a bipolar membrane electrodialysis mode (shown as figure 1 a) to be used as raw materials for the synthesis of the next batch of AEI molecular sieves;
drying the solid matter at 120 ℃ for 12 hours and roasting the solid matter at 540 ℃ for 4 hours, and confirming the solid matter as an AEI type molecular sieve through XRD, namely AEI molecular sieve raw powder; the AEI molecular sieve showed its SAR of 39.6, marked as D, and the ratio of the molecular sieve synthesis precursor sol, the synthesis conditions, the relative crystallinity and the yield parameters are shown in tables 3 and 4.
Example 5 preparation of an AEI-type zeolitic molecular sieve
(1) The amount of dealuminated USY zeolite having a silica-alumina molar silica-alumina ratio (SAR) of 28.7 and water glass (Na)2O：7.44wt％，SiO2: 27.40 wt%) and the SAA-4 solution obtained in example 4 were mixed, and to the mixture, the SDK-4 solution obtained in example 4 and a quantitative N, N-dimethyl-3, 5-dimethylpiperidinium aqueous solution (concentration: 20 wt%), deionized water and NaOH pellets (purity: 96 wt%) and the reaction mixture was then stirred at 200rpm in a closed vessel at room temperature until all the raw materials were mixed uniformly, with a mixed sol having the following molar composition in molar ratios:
Na2O：SiO2：Al2O3：OSDA：H2o ═ 0.36: 1.0: 0.01214: 0.08: 25.0; 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;
(2) after crystallization is completed, the product is rapidly cooled, filtrate and solid substances are obtained through suction filtration separation and washing, the filtrate of the product is collected, and an organic template agent alkaline solution (marked as SDK-5) and an orthosilicic acid solution (SAA-5) are separated in a bipolar membrane electrodialysis mode (shown as figure 1 a) to be used as raw materials for the synthesis of the next batch of AEI molecular sieves;
drying the solid matter at 120 ℃ for 12 hours and roasting the solid matter at 540 ℃ for 4 hours, and confirming the solid matter as an AEI type molecular sieve through XRD, namely AEI molecular sieve raw powder; the AEI molecular sieve shows that its SAR is 79.1, marked as E, and the proportion, synthesis conditions and yield parameters of the molecular sieve synthesis precursor sol are shown in tables 3 and 4.
Example 6 preparation of AEI-type zeolitic molecular sieves
(1) Quantitative dealuminated USY zeolite having a silica-alumina molar silica-alumina ratio (SAR) of 28.7, silica Sol (SiO)2: 30.0 wt%) was added to an aqueous solution of organic template 1-ethyl-1-methyl-2, 2,6, 6-hexamethylpiperidinium (concentration: 20 wt%), stirred well, and then added with NaOH pellets (purity: 96 wt%), adding deionized water, stirring thoroughly, and continuously stirring the obtained mixed slurry in a sealed container for 2 hours at room temperature until all the raw materials are uniformly mixed, wherein the molar ratio of the mixed sol is as follows:
Na2O：SiO2：Al2O3：OSDA：H2o ═ 0.29: 1.0: 0.01451: 0.12: 15.0 parts of; transferring the obtained solid mixture into a 2000ml hydrothermal crystallization kettle, stirring at the speed of 60rpm, heating to 135 ℃ for crystallization for 24 hours, and then continuously heating to 180 ℃ for crystallization for 48 hours;
(2) after crystallization is completed, quickly cooling a product, performing suction filtration separation and washing to obtain filtrate and solid matters, and separating the recovered filtrate from the silicon amorphous matters by an electrodialysis method to obtain an organic template alkaline solution (marked as SDL-1) and a silicic acid solution (SAB-1);
drying the solid substance at 110 ℃ for 24 hours and roasting the solid substance at 540 ℃ for 4 hours, and confirming the solid substance as an AEI type molecular sieve, namely AEI molecular sieve raw powder by XRD; the AEI molecular sieve showed its SAR of 31.2, denoted as F, and the ratio of molecular sieve synthesis precursor sol, synthesis conditions, relative crystallinity and yield parameters are shown in tables 3 and 4.
Example 7 preparation of an AEI-type zeolitic molecular sieve
(1) Quantitative dealuminated USY zeolite having a silica-alumina molar silica-alumina ratio (SAR) of 13.3, silica Sol (SiO)2: 30.0 wt%) and the SAB-1 solution obtained in example 6 were mixed, and to the mixture, the SDL-1 solution obtained in example 6 and a quantitative 1-ethyl-1-methyl-2, 2,6, 6-hexamethylpiperidinium aqueous solution (concentration: 20 wt%), deionized water and NaOH pellets (purity: 96 wt%) and the reaction mixture was then stirred at 200rpm in a closed vessel at room temperature until all the raw materials were mixed uniformly, with a mixed sol having the following molar composition in molar ratios:
Na2O：SiO2：Al2O3：OSDA：H2o ═ 0.35: 1.0: 0.0126: 0.08: 15.0 parts of; transferring the obtained solid mixture into a 2000ml hydrothermal crystallization kettle, stirring at the speed of 60rpm, heating to 135 ℃ for crystallization for 48 hours, and then continuously heating to 190 ℃ for crystallization for 36 hours;
(2) after crystallization is completed, the product is rapidly cooled, filtrate and solid substances are obtained through suction filtration separation and washing, the filtrate of the product is collected, and an organic template agent alkaline solution (marked as SDL-2) and an orthosilicic acid solution (SAB-2) are separated in a conventional electrodialysis mode (shown as figure 1 b) and are used as raw materials to participate in the synthesis of the next batch of AEI molecular sieves;
drying the solid substance at 110 ℃ for 24 hours and roasting the solid substance at 540 ℃ for 4 hours, and confirming the solid substance as an AEI type molecular sieve, namely AEI molecular sieve raw powder by XRD; the AEI molecular sieve showed its SAR of 41.8, marked as G, and the ratio of the molecular sieve synthesis precursor sol, the synthesis conditions, the relative crystallinity and the yield parameters are shown in tables 3 and 4.
Example 8 preparation of an AEI-type zeolitic molecular sieve
(1) Quantitative determination of NaY zeolite and silica Sol (SiO) with molar silica-alumina ratio (SAR) of 5.32: 30.0 wt%) and the SAB-2 solution obtained in example 7 were mixed, and the mixture was addedTo this reaction mixture were added the SDL-2 solution obtained in example 7, a quantitative 1-ethyl-1-methyl-2, 2,6, 6-hexamethylpiperidinium aqueous solution (concentration: 20 wt%), deionized water and NaOH particles (purity: 96 wt%) in this order, and the reaction mixture was then stirred at 200rpm in a closed vessel at room temperature until all the raw materials were mixed uniformly, with a mixed sol having the following molar composition:
Na2O：SiO2：Al2O3：OSDA：H2o ═ 0.34: 1.0: 0.01244: 0.10: 15.0 parts of; transferring the obtained solid mixture into a 2000ml hydrothermal crystallization kettle, stirring at the speed of 60rpm, heating to 135 ℃ for crystallization for 24 hours, and then continuously heating to 160 ℃ for crystallization for 120 hours;
(2) after crystallization is completed, the product is rapidly cooled, filtrate and solid substances are obtained through suction filtration separation and washing, the filtrate of the product is collected, and an organic template agent alkaline solution (marked as SDL-3) and a solution of orthosilicic acid (SAB-3) are generated in a conventional electrodialysis mode (shown as figure 1 b) and are used as raw materials to participate in the synthesis of the next batch of AEI molecular sieves;
drying the solid substance at 110 ℃ for 24 hours and roasting the solid substance at 540 ℃ for 4 hours, and confirming the solid substance as an AEI type molecular sieve, namely AEI molecular sieve raw powder by XRD; the AEI molecular sieve showed its SAR of 45.3, recorded as H, and the ratio of the molecular sieve synthesis precursor sol, the synthesis conditions, the relative crystallinity and the yield parameters are shown in tables 3 and 4.
Example 9 preparation of AEI-type zeolitic molecular sieves
(1) Quantitative HY zeolite (silicon-aluminum ratio of 5.3, aluminum source and partial silicon source), silica Sol (SiO)2: 30.0 wt%) and the SAB-3 solution obtained in example 8 were mixed, and to the mixture, the SDL-3 solution obtained in example 8 and a quantitative 1-ethyl-1-methyl-2, 2,6, 6-hexamethylpiperidinium aqueous solution (concentration: 20 wt%), deionized water and NaOH pellets (purity: 96 wt%) and the reaction mixture was then stirred at 200rpm in a closed vessel at room temperature until all the raw materials were mixed uniformly, with a mixed sol having the following molar composition in molar ratios:
Na2O：SiO2：Al2O3：OSDA：H2O＝0.28：1.0：0.02227：0.12：15.0；
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 180 ℃, crystallizing for 72 hours;
(2) after crystallization is completed, the product is rapidly cooled, filtrate and solid substances are obtained through suction filtration separation and washing, the filtrate of the product is collected, and an organic template agent alkaline solution (marked as SDL-4) and an orthosilicic acid solution (SAB-4) are separated in a conventional electrodialysis way (shown in figure 1 b) and used as raw materials to participate in the synthesis of the next batch of AEI molecular sieves;
drying the solid substance at 110 ℃ for 24 hours and roasting the solid substance at 540 ℃ for 4 hours, and confirming the solid substance as an AEI type molecular sieve, namely AEI molecular sieve raw powder by XRD; the AEI molecular sieve showed its SAR of 36.6, marked as I, and the ratio of the molecular sieve synthesis precursor sol, the synthesis conditions, the relative crystallinity and the yield parameters are shown in tables 3 and 4.
Example 10 preparation of an AEI-type zeolitic molecular sieve
(1) A defined amount of dealuminated USY zeolite having a silica to alumina molar silica to alumina ratio (SAR) of 28.7 and the SAB-4 solution obtained in example 9 were mixed, to this mixture was added sequentially the SDL-4 solution obtained in example 9, a defined amount of 1-ethyl-1-methyl-2, 2,6, 6-hexamethylpiperidinium aqueous solution (concentration: 20 wt%), deionized water and NaOH particles (purity: 96 wt%), and the reaction mixture was stirred at 200rpm in a closed vessel at room temperature until all the starting materials were mixed uniformly, the molar ratio of the mixed sol having the following molar composition:
Na2O：SiO2：Al2O3：OSDA：H2o ═ 0.26: 1.0: 0.02778: 0.15: 15.0 parts of; transferring the obtained solid mixture into a 2000ml hydrothermal crystallization kettle, stirring at the speed of 60rpm, heating to 135 ℃ for crystallization for 24 hours, and then continuously heating to 170 ℃ for crystallization for 96 hours;
(2) after crystallization is completed, the product is rapidly cooled, filtrate and solid substances are obtained through suction filtration separation and washing, the filtrate of the product is collected, and an organic template agent alkaline solution (marked as SDL-5) and an orthosilicic acid solution (SAB-5) are separated in a conventional electrodialysis way (shown in figure 1 b) and used as raw materials to participate in the synthesis of the next batch of AEI molecular sieves;
drying the solid substance at 110 ℃ for 24 hours and roasting the solid substance at 540 ℃ for 4 hours, and confirming the solid substance as an AEI type molecular sieve, namely AEI molecular sieve raw powder by XRD; the AEI molecular sieve showed its SAR of 33.8, denoted J, and the ratio of molecular sieve synthesis precursor sol, synthesis conditions, relative crystallinity and yield parameters are shown in tables 3 and 4.
TABLE 3 compounding ratio, synthesis conditions and Si/Al ratio of the synthesized precursor sols in examples 1-10
Comparative examples 1-5 preparation of AEI-type zeolite molecular sieves
AEI zeolites were synthesized in recycled mother liquor using N, N-dimethyl-3, 5-dimethylpiperidinium as an organic template according to the procedure in the example of patent CN104591204A
36g of USY zeolite having a silica to alumina molar silica to alumina ratio SAR of 10.7 were mixed with 1093g of water. For this mixture, 195g of N, N-dimethyl-3, 5-dimethylpiperidinium templating agent and 427g of sodium silicate solution (28.8% by weight of SiO) were mixed with stirring2) Pour slowly into the above mixture. The resulting mixture was sealed in a reactor and heated to 145 ℃ with stirring at 200rpm, and the resulting crystallized mixture was transferred to a separatory funnel after 2 days of crystallization reaction. Under static conditions, the solid sediment and the top clear liquid layer were separated within a few hours. The bulk of the clear mother liquor, referred to as the first pass mother liquor (noted: ML-P1), was collected and the solids in the bottom slurry were recovered and confirmed by XRD as AEI, noted VS 1.
38g of dealuminated USY zeolite with SAR 30 and 21g of USY zeolite with SAR 10.7 were mixed with 1582g of ML-Pl. To the mixture, 45g of N, N-dimethyl-3, 5-dimethylpiperidinium template and 31g of water were added in this order. 34g of sodium silicate liquid (28.8% by weight of SiO) are stirred2) Slowly pour intoIn the above mixture. The reaction mixture was then heated to about 145 ℃ in a stainless steel reactor with stirring at 200 rpm. After 20-35 hours of crystallization reaction, the solid formed was removed and confirmed by XRD to be AEI zeolite designated as VS 2. This mother liquor was collected and referred to as the second pass mother liquor (noted: ML-P2).
ML-P2 in a similar manner produces ML-P3, the AEI zeolite produced is designated VS3, and ML-P4 is produced using ML-P3 in sequence, the AEI zeolite produced is designated VS4, and ML-P5 is produced using ML-P4, the AEI zeolite produced is designated VS 5. The recovered liquid, relative crystallinity and yield parameters used in the synthesis of the molecular sieves are shown in table 4.
TABLE 4 recovered liquids and yields for the molecular sieves of examples 1-10 and comparative examples 1-5
The results in the table show that N, N-dimethyl-3, 5-dimethylpiperidinium template and 1-ethyl-1-methyl-2, 2,6, 6-hexamethylpiperidinium template can be recycled by multiple times of recovery and extraction of organic template lye by means of electrodialysis hydrolysis, and in addition, silicate solution in filtrate can be separated and recovered by means of electrodialysis to be used as AEI molecular sieve synthesis raw material, so that the total relative yield calculated by silica and the total relative yield calculated by template can be improved. The composition of the crystallized precursor gel and process parameters can be varied to obtain AEI molecular sieve crystals with different properties, such as different silicon to aluminum ratio (SAR) values.
With the AEI molecular sieve crystallinity obtained in example 1 defined as 100%, that is, the AEI molecular sieve crystallinity obtained by hydrothermal crystallization directly using the original organic template and the FAU silicoaluminophosphate raw material is 100% (without recovering the organic template and the silicon species), the relative crystallinity of the AEI molecular sieves obtained in examples 2 to 10 of the present invention and comparative examples 1 to 5 was calculated with respect to the AEI molecular sieve crystallinity of 100%, and the AEI molecular sieves prepared in examples of the present invention were calculated to be in the range of 95% to 105%, and the relative crystallinity of the samples in comparative examples 1 to 5 was calculated to be in the range of 56% to 89%, it is obvious that the relative crystallinity of the samples obtained in examples 1 to 10 is significantly higher than that of the samples in comparative examples 1 to 5. In addition, the total relative yield of the molecular sieve obtained in the examples 1 to 10 of the invention calculated by the template agent is in the range of 30 to 95 percent, while the total relative yield of the molecular sieve obtained in the comparative examples 1 to 5 calculated by the template agent is 20 to 75 percent, namely the highest relative yield can reach 95 percent and is far higher than that of the comparative examples; the total relative yield of the molecular sieve obtained in the examples 1-10 of the invention calculated by silicon dioxide is in the range of 39-97%, while the total relative yield of the molecular sieve obtained in the comparative examples 1-5 calculated by template is 32-87%, that is, the highest relative yield can reach 97% which is far higher than that of the comparative example; in addition, as can be seen from fig. 3 and 6, the molecular sieve sample obtained in comparative example 5 has a heterocrystal peak, which indicates that the feeding stability is poor by the method of recycling the mother liquor in the comparative example, and high-purity AEI molecular sieve grains are difficult to obtain. According to the SEM image of the scanning electron microscope in the attached drawing, the AEI molecular sieve sample obtained in the embodiment has good dispersibility and more regular molecular sieve crystal morphology, and the AEI molecular sieve sample obtained in the comparative example has obvious agglomeration of crystal grains and poor grain dispersibility.
Examples 11 to 23
10.0g of the AEI molecular sieve raw powder synthesized in examples 1 to 8 and comparative examples 1 to 5 was added to 100.0g of Cu (NO) having a concentration of 0.3mol/L3)2·3H2Stirring the O aqueous solution uniformly for 1 hour, putting the O aqueous solution into a heat-resistant container, and putting the O aqueous solution and the heat-resistant container together 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; the copper (II) ions in the catalyst prepared according to the ICP analysis results of the resulting copper modified AEI molecular sieve based catalyst are shown in table 5.
Testing of the SCR catalyst:
10-20 mesh A1-H1 prepared from the AEI molecular sieve synthesized in example 1-8, and 10 intent-to-E prepared from the AEI molecular sieve synthesized in comparative example 1-5Catalyst particles of 20 meshes VS 1-VS 5, which are arranged in a reactor
In (1), contains 500ppm NO and 500ppm NH 310% by volume of O2A mixed gas stream of 160mL/min, 5 vol% steam and Ar as the balance gas was passed through a preheater (set at 100 ℃ C.) and then into the 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 NOx, NH at the outlet were measured under steady state conditions by using a Bruker EQUINOX 55 type FT-IR spectrometer3And N2The concentration of O.
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 5. TABLE 5 evaluation of copper content and performance of selective catalytic reduction for copper modified AEI molecular sieves of examples 11-23
As can be seen from the above table, Cu obtained in examples 11 to 18the-AEI molecular sieve catalyst has better low-temperature ignition property and high-temperature activity. In the range of 150-650 ℃, NO when the SCR is in the fresh state in the embodiments 11-18XThe conversion rate of (A) is in the range of 41.8-99.6%, SCR is in an aging state, and NO is inXThe conversion of (a) is in the range of 36.2% to 98.8%, indicating that the activity of the SCR is significantly better than that of the catalyst samples of catalysts VS1 to VS5 obtained from comparative examples 1 to 5, whether the SCR is in a "fresh" state or an "aged" state. Thus, the results obtained from examples 11-18 clearly show that the Cu-AEI molecular sieve catalyst material of the present invention and the catalysts obtained therewith have improved SCR catalytic activity, especially at low conversion temperatures characteristic of cold start conditions when treating NOx in, for example, diesel locomotive applications. For other SCR applications, the Cu-AEI molecular sieve catalyst material of the present invention allows for higher conversion at lower temperatures, thus allowing for higher efficiency and thus, at comparable conversion, for high energy efficiency treatment of NOx-containing exhaust gases, such as exhaust gases from industrial processes.
The foregoing is considered as illustrative and not restrictive in character, and that various modifications, equivalents, and improvements made within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (30)
1. A method for preparing an AEI structured molecular sieve, comprising the steps of:
(1) reacting raw materials containing an organic template agent, an FAU type silicon-aluminum molecular sieve, an alkali source and water under a hydrothermal crystallization condition, wherein the FAU type silicon-aluminum molecular sieve provides a silicon source and an aluminum source;
(2) filtering the product obtained in the step (1), performing electrodialysis electrolysis on the filtrate, and recovering organic template and silicon species as the synthesis raw materials of the next batch of AEI molecular sieve;
wherein, in the step (1), the alkali source is selected from NaOH and Na2O、Na2O2And KOH;
in the step (1), the molar ratio of the silicon source, the aluminum source, the alkali source, the template agent and the water is 1.0: 0.0121-0.0417: 0.22-0.36: 0.08-0.20: 15-25;
in the step (1), the hydrothermal crystallization is divided into two sections: (1) the crystallization temperature of the first section is 120-150 ℃; (2) the second-stage crystallization temperature is 150-200 ℃;
in the step (1), the hydrothermal crystallization is divided into two sections: (1) the first section of crystallization time is 0.5-3.0 days; (2) the second stage crystallization time is 0.5-6.0 days;
wherein, in the step (1), the organic template agent is 1-ethyl-1-methyl-2, 2,6, 6-hexamethyl piperidinium; the FAU-type silicon-aluminum molecular sieve is selected from one of HY zeolite, USY zeolite and NaY zeolite; in the step (1), an additional silicon source is added as a raw material, wherein the additional silicon source is selected from silica sol and/or water glass;
in the step (2), the electrodialysis is one of four-chamber three-membrane, three-chamber two-membrane or two-chamber one-membrane;
the electrodialysis is bipolar membrane electrodialysis, and the bipolar membrane is obtained by compounding a cation exchange layer, an interface hydrophilic layer and an anion exchange layer.
2. The preparation method according to claim 1, wherein, in the step (1), the hydrothermal crystallization is divided into two stages: (1) the crystallization temperature of the first section is 130-150 ℃; (2) the second stage crystallization temperature is 160-190 ℃.
3. The preparation method according to claim 2, wherein, in the step (1), the hydrothermal crystallization is divided into two stages: (1) the first crystallization time is 0.5-2.0 days; (2) the second stage crystallization time is 1.0-5.0 days.
4. An AEI structured molecular sieve produced by the method of any one of claims 1-3.
5. The AEI structured molecular sieve of claim 4, wherein the molecular mole ratio of silica to alumina in the AEI structured molecular sieve is from 5 to 100.
6. The AEI structured molecular sieve of claim 4, wherein the molecular mole ratio of silica to alumina in the AEI structured molecular sieve is from 10to 80.
7. NO (nitric oxide)XA selective catalytic reduction catalyst obtained by ion-exchanging the AEI structure molecular sieve produced by the process of any one of claims 1 to 3 or the AEI structure molecular sieve of claim 4 or 5 with a metal salt solution.
8. NO according to claim 7XThe selective catalytic reduction catalyst is characterized in that the metal salt is one or more than two 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.
9. NO according to claim 8XA selective catalytic reduction catalyst, wherein the metal salt is selected from copper or iron salts.
10. NO according to claim 8XThe selective catalytic reduction catalyst, wherein the metal salt is a copper salt.
11. NO according to claim 9XThe selective catalytic reduction catalyst comprises copper salt, copper chloride, copper acetate and copper sulfate, wherein the copper salt is one or more than two of copper nitrate, copper chloride, copper acetate and copper sulfate, and the concentration of copper ions in the copper salt is 0.1-1.5 mol/L.
12. An NO according to any one of claims 7 to 11XA method for producing a selective catalytic reduction catalyst, which comprises adding the AEI structured molecular sieve produced by the method according to any one of claims 1 to 3 or the AEI structured molecular sieve according to any one of claims 4 to 6 to a metal salt solution to obtainNOXA selective catalytic reduction catalyst.
13. The method of claim 12, further comprising the steps of: the obtained NOXThe selective catalytic reduction catalyst is attached to the porous structured material using a binder.
14. The method according to claim 13, wherein the binder is one or more selected from the group consisting of silica sol, water glass, pseudoboehmite, and alumina sol.
15. The production method according to claim 13 or 14, wherein the porous structured material is selected from one of a honeycomb shape, a plate shape, and a corrugated shape.
16. The production method according to claim 13 or 14, wherein the porous structured material is selected from one of cordierite, α -alumina, silicon carbide, aluminum titanate, silicon nitride, zirconia, mullite, spodumene, alumina-silica-magnesia, zirconium silicate or metal flakes.
17. The production method according to claim 13 or 14, wherein the porous structured material is cordierite.
18. The production method according to claim 15, wherein the porous structured material is selected from one of cordierite, α -alumina, silicon carbide, aluminum titanate, silicon nitride, zirconia, mullite, spodumene, alumina-silica-magnesia, zirconium silicate or metal flakes.
19. The production method according to claim 15, wherein the porous structured material is cordierite.
20. An NO according to any one of claims 7 to 11XA selective catalytic reduction catalyst or a catalyst as claimed in any one of claims 12 to 19NO produced by the methodXUse of a selective catalytic reduction catalyst, characterized in that it is said NOXUse of a selective catalytic reduction catalyst for the purification of an exhaust gas stream.
21. An NO according to any one of claims 7 to 11XA selective catalytic reduction catalyst or NO prepared by the method of any of claims 12 to 19XUse of a selective catalytic reduction catalyst, characterized in that it is said NOXUse of a selective catalytic reduction catalyst for purifying an automotive exhaust gas stream.
22. Use according to claim 20, the exhaust gas stream being an exhaust gas stream emitted by a motor vehicle.
23. Use according to claim 20, the exhaust gas stream being an exhaust gas stream of a lean burn engine.
24. The use according to claim 20, the exhaust gas stream being a diesel exhaust gas stream.
25. A method for the purification treatment of an exhaust gas stream using NO according to any of claims 7 to 11XA selective catalytic reduction catalyst or NO prepared by the method of any of claims 12 to 19XSelective catalytic reduction catalyst and catalyst comprising NOXWith exhaust gas flow of reducing agent to make NOXSelectively reduced to N2And H2O。
26. The purification treatment method of claim 25, wherein said exhaust gas stream is in contact with NOXWith NO before contact with the selective catalytic reduction catalystXMeasured as 100% by weight of NO2The content is less than or equal to 80 weight percent.
27. The purification treatment method of claim 25, wherein said exhaust gas stream is in contact with NOXSelective catalytic reductionBefore contacting the procatalyst with NOXMeasured as 100% by weight of NO2The content is 5 to 70 wt%.
28. The purification treatment method of claim 25, wherein said exhaust gas stream is in contact with NOXWith NO before contact with the selective catalytic reduction catalystXMeasured as 100% by weight of NO2The content is 10to 60 wt%.
29. The purification treatment method of claim 25, wherein said exhaust gas stream is in contact with NOXWith NO before contact with the selective catalytic reduction catalystXMeasured as 100% by weight of NO2The content is 15 to 55 wt%.
30. The purification treatment method of claim 25, wherein said exhaust gas stream is in contact with NOXWith NO before contact with the selective catalytic reduction catalystXMeasured as 100% by weight of NO2The content is 20 to 50 wt%.
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| JP2020529787A JP7090158B2 (en) | 2017-08-10 | 2017-10-13 | Manufacturing method of AEI structural molecular sieve |
| PCT/CN2017/106026 WO2019028999A1 (en) | 2017-08-10 | 2017-10-13 | Aei structure molecular sieve as well as preparation method therefor and application thereof |
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| CN110592610B (en) * | 2019-09-29 | 2021-02-05 | 肯特催化材料股份有限公司 | Preparation method and application of quaternary ammonium salt template agent |
| CN111250152B (en) * | 2020-03-31 | 2021-05-28 | 中国科学院过程工程研究所 | Packaging method of Ni @ ZSM-5 bifunctional catalyst |
| CN112010322B (en) * | 2020-08-20 | 2022-02-15 | 华中科技大学 | Preparation method and application of molecular sieve and utilization method of wastewater |
| CN112221463B (en) * | 2020-09-30 | 2022-04-26 | 中触媒新材料股份有限公司 | Efficient continuous molecular sieve adsorbent post-treatment device and use method |
| CN114477209B (en) * | 2020-10-23 | 2023-10-13 | 中国石油化工股份有限公司 | Silicon-aluminum molecular sieve and preparation method and application thereof |
| CN112517050B (en) * | 2021-01-06 | 2021-11-30 | 南京大学 | Hollow bubble type mesoporous molecular sieve catalyst coated with active bimetallic oxide and preparation method and application thereof |
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| CN116443889A (en) * | 2021-12-30 | 2023-07-18 | 中国石油化工股份有限公司 | Method for recovering template agent in molecular sieve synthesis waste liquid and preparation method of molecular sieve |
| CN114573003B (en) * | 2022-04-25 | 2023-03-31 | 淮安六元环新材料有限公司 | Method for synthesizing SSZ-39 molecular sieve by using seed crystal method |
| CN115710717B (en) * | 2022-11-25 | 2024-06-14 | 华北电力大学 | Method for synthesizing Na-A zeolite molecular sieve by microplasma |
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| WO2019028999A1 (en) | 2019-02-14 |
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