WO2019028999A1 - 一种aei结构分子筛及其制备方法和应用 - Google Patents

一种aei结构分子筛及其制备方法和应用 Download PDF

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WO2019028999A1
WO2019028999A1 PCT/CN2017/106026 CN2017106026W WO2019028999A1 WO 2019028999 A1 WO2019028999 A1 WO 2019028999A1 CN 2017106026 W CN2017106026 W CN 2017106026W WO 2019028999 A1 WO2019028999 A1 WO 2019028999A1
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molecular sieve
aei
catalytic reduction
selective catalytic
zeolite
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French (fr)
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李进
王志光
王炳春
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中触媒新材料股份有限公司
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Priority to JP2020529787A priority Critical patent/JP7090158B2/ja
Priority to KR1020207006726A priority patent/KR102370849B1/ko
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

Definitions

  • the invention relates to the field of synthesis of inorganic porous materials, in particular to an AEI molecular sieve and a preparation method and application thereof.
  • AEI structural molecular sieve has a three-dimensional pore system of large cage, which can form a three-dimensional pore structure through an 8-membered ring, and the pore size Its cage structure is similar to that of CHA molecular sieves, and the cage size can contain diameters up to Sphere.
  • the adjacent double six-membered ring of the CHA structure in the adjacent two double six-membered ring structures connected by a four-membered ring is spatially parallel, and the two adjacent double six-membered rings in the AEI structure are mirror-symmetrically distributed. Such a structural difference results in an eight-membered ring channel in the AEI structure having a smaller pore size, higher catalytic activity, and better carbon deposition resistance.
  • the AEI silica-alumina molecular sieve and the silicoaluminophosphate molecular sieve structure are represented by SSZ-39 and SAPO-18, respectively.
  • the ion-exchanged or metal-supported AEI molecular sieve catalyst exhibits a unique selective reduction reaction (SCR) activity and has excellent reduction treatment properties for nitrogen oxides (NOx), which has attracted extensive attention.
  • NOx Nitrogen oxides
  • NH 3 -SCR NH3 selective catalytic reduction
  • the SCR catalyst is usually a molecular sieve prepared by loading a SCR active component with zeolite as a carrier;
  • the zeolite is a crystalline material of aluminosilicate having a fairly regular pore size, such as zeolite beta, zeolite Y, zeolite X. , faujasite, mordenite, erionite, ZSM-5, ZSM-8, ZSM-11, ZSM-12 zeolite, etc.
  • these zeolites can be exchanged with metals such as Cu, Fe, Mn, Ag, V, Ti, Co, etc.
  • the zeolite itself contains a part of a metal such as Cu or Fe.
  • the above-mentioned known metal-modified zeolite catalyst can only be used in the process of selective catalytic reduction of nitrogen oxides by ammonia.
  • the purification of nitrogen oxides in a narrow temperature range does not have high activity NOx purification performance below 200 ° C, poor hydrothermal stability, and low activity under low temperature conditions.
  • Synthetic AEI molecular sieves are produced using an organic structure directing agent (OSDA), which is also referred to as a “template” or “templating agent.”
  • OSDA organic structure directing agent
  • template organic structure directing agent
  • templating agent acts as a mold to form molecular sieve crystals around it. After crystal formation, the OSDA is removed from the internal structure of the crystal, leaving a porous molecular sieve cage of the molecule.
  • solid molecular sieve crystals are precipitated from a reaction mixture comprising a silicon source, an aluminum source, an alkali source, and an organic templating agent.
  • the synthesis usually takes a long time to achieve the desired molecular sieve crystallization.
  • the molecular sieve is crystallized, the molecular sieve solid product is usually 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.
  • OSDA organic templating agent
  • Patent CN104591204A increases the yield of silica and/or OSDA by the mother liquor circulation after synthesis of AEI molecular sieve, but the direct circulation of mother liquor can not be removed due to the small amount of degradant and uncrystallized amorphous product in the mother liquor, which is easy to cause product quality. It is stable, so it cannot effectively solve the problems of high cost and environmental pollution caused by low yield.
  • the present invention provides a method for preparing an AEI structural molecular sieve comprising the following steps:
  • step (2) The product obtained in the step (1) is filtered, and the filtrate is subjected to electrodialysis electrolysis to recover the organic template and the silicon species as synthetic raw materials for the next batch of AEI molecular sieves.
  • the present invention provides an AEI structural molecular sieve which is obtained by a process comprising the following steps:
  • step (2) The product obtained in the step (1) is filtered, and the filtrate is subjected to electrodialysis electrolysis to recover the organic template and the silicon species as synthetic raw materials for the next batch of AEI molecular sieves.
  • the present invention provides an NO X selective catalytic reduction catalyst, which is the AEI molecular sieve structure with a metal salt solution obtained by ion exchange.
  • the present invention further provides a method of preparing NO X selective catalytic reduction catalyst, which is added to the zeolite structure of the AEI metal salt solution to obtain a NO X selective catalytic reduction catalyst.
  • the present invention proposes the following technical solutions.
  • the invention provides a method for preparing an AEI molecular sieve, which comprises the following steps:
  • step (2) The product obtained in the step (1) is filtered, and the filtrate is subjected to electrodialysis electrolysis to recover the organic template and the silicon species as synthetic raw materials for the next batch of AEI molecular sieves.
  • the organic templating agent is a monocyclic or polycyclic piperidinium compound
  • the piperidinium compound is selected from N, N-di Methyl-3,5-dimethylpiperidinium, N,N-dimethyl-2,6-dimethylpiperidinium, 1,1,2,2,6,6-hexamethylpiperidine ⁇ , 1,1,2,2,6,6-hexamethyl-4-oxopiperidinium, 1,1,3,5-tetramethyl-4-oxopiperidinium, 1-hydroxy- 1,1,2,2,6,6-hexamethylpiperidinium, 1,1-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-hex
  • the FAU-type silica-alumina molecule is selected from one of Y zeolite and X zeolite; preferably, the Y zeolite is selected from HY One of zeolite, USY zeolite and NaY zeolite selected from one of NaX zeolite, KX zeolite and HX zeolite.
  • the hydrothermal crystallization is divided into two segments: (1) the first segment has a crystallization temperature of 120 to 150 ° C, preferably 130 to 150. °C; (2) The second stage crystallization temperature is 150 to 200 ° C, preferably 160 to 190 ° C.
  • the hydrothermal crystallization is divided into two segments: (1) the first crystallization time is 0.5 to 3.0 days, preferably 0.5 to 2.0. (2) The second stage crystallization time is 0.5 to 6.0 days, preferably 1.0 to 5.0 days.
  • an additional silicon source is selected as a raw material, and the additional silicon source is selected from the group consisting of white carbon black, macroporous silica gel, coarse pore silica gel, and fine pore silica gel.
  • the additional silicon source is selected from the group consisting of white carbon black, macroporous silica gel, coarse pore silica gel, and fine pore silica gel.
  • Thin layer One or more of silica gel, B-type silica gel, sodium metasilicate, silica sol, water glass, alkyl silicate and diatomaceous earth are analyzed.
  • the alkali liquid is selected from one or more selected from the group consisting of NaOH, Na 2 O, Na 2 O 2 and KOH.
  • the molar ratio of the silicon source, the aluminum source, the alkali solution, the templating agent and the water is 1.0:0.00833 to 0.1667:0.1 to 0.5:0.05.
  • 0.5:10 to 50 preferably 1.0:0.0121 to 0.0417: 0.22 to 0.36: 0.08 to 0.20: 15 to 25.
  • the electrodialysis is selected from one of a four-chamber three-film, a three-chamber two-film or a two-chamber one membrane.
  • the bipolar membrane is obtained by compounding a cation exchange layer, an interface hydrophilic layer and an anion exchange layer.
  • the present invention provides an AEI structural molecular sieve which is prepared by the method described in any of the above.
  • the molecular weight ratio of silica to alumina in the AEI structure molecular sieve is 5 to 100, preferably 10 to 80.
  • the present invention provides an NO X selective catalytic reduction catalyst, which is the AEI molecular sieve structure with a metal salt solution obtained by ion exchange.
  • the metal salt is selected from copper, iron, cobalt, tungsten, nickel, zinc, molybdenum, vanadium, tin, titanium, zirconium, manganese, chromium, One or more of soluble salts of ruthenium, osmium, iridium, osmium, iridium, palladium, indium, platinum, gold or silver.
  • the metal salt is selected from copper or iron, preferably copper.
  • the copper salt is selected from copper nitrate, copper chloride, copper acetate and copper sulfate of one or two or more
  • the copper salt of copper The concentration of ions is from 0.1 to 1.5 mol/L.
  • the present invention provides a method for preparing a selective catalytic reduction catalyst, which is added to the zeolite structure of the AEI metal salt solution to obtain a NO X selective catalytic reduction catalyst.
  • the NO X selective catalytic reduction catalyst is obtained using an adhesive material deposited on a porous structured.
  • the binder is one or more selected from the group consisting of silica sol, water glass, pseudoboehmite, and aluminum sol.
  • the porous structured material is selected from the group consisting of a honeycomb shape, a plate shape and a corrugated shape.
  • the porous structured material is selected from the group consisting of cordierite, ⁇ -alumina, silicon carbide, aluminum titanate, silicon nitride, zirconia, mullite, spodumene, One of alumina-silica-magnesia, zirconium silicate or metal flakes, preferably cordierite.
  • a selective catalytic reduction catalyst which is used in the purification of exhaust gas streams, preferably in the purification of automotive exhaust streams.
  • the exhaust gas stream is an exhaust gas stream emitted by a motor vehicle, preferably an exhaust gas stream of a lean-burn engine, more preferably a diesel exhaust gas stream.
  • the present invention provides a method for purifying an exhaust gas stream, which is a selective catalytic reduction catalyst will be contacted with an automobile exhaust gas stream containing NO X and the reducing agent, so that selective reduction of NO X to N 2 and H 2 O.
  • the method for purification wherein the waste gas stream prior to contact with the selective catalytic reduction catalyst, NO in the measurement X 100% by weight, of the NO2 content of ⁇ 80 wt.%, Preferably 5 to 70
  • the weight % is more preferably 10 to 60% by weight, still more preferably 15 to 55% by weight, still more preferably 20 to 50% by weight.
  • the selective catalytic reduction catalyst provided by the present invention is a nitrogen oxide selective catalytic reduction 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 provided by the invention effectively avoids mixing of the amorphous substance and the degradation substance into the next batch of materials, thereby reducing the feeding error of the AEI molecular sieve.
  • the resulting AEI molecular sieve has good dispersibility and relatively high crystallinity.
  • the present invention separates the organic templating agent and the AEI molecular sieve prepared by the silicon species from the filtrate after the reaction.
  • the relative crystallinity is in the range of 95% to 105%, and the molecular sieve obtained by directly reacting the filtrate after the reaction as a supplementary synthetic raw material for the reaction has a relative crystallinity ranging from 56% to 89%.
  • the relative crystallinity of the AEI molecular sieve obtained by the invention is significantly higher than the relative crystallinity of the AEI molecular sieve obtained by the prior art, and The invention improves the overall efficiency of the synthesis of AEI molecular sieves and greatly improves the yield.
  • the total relative yield of the invention according to the silica is up to 97%, which is much higher than the total relative yield in the prior art. .
  • Figure 1a Schematic diagram of the filtrate after synthesis of AEI molecular sieve through bipolar membrane electrolysis
  • Figure 1b Schematic diagram of the filtrate after synthesis of AEI molecular sieve by conventional electrodialysis
  • Figure 2 XRD pattern of the AEI molecular sieve raw powder obtained in Example 1;
  • Figure 3 XRD pattern of the original AEI molecular sieve powder obtained in Example 5;
  • Figure 7 SEM image of the original AEI molecular sieve powder obtained in Example 1;
  • Figure 8 SEM image of the original AEI molecular sieve powder obtained in Example 5;
  • Figure 11 SEM image of the AEI molecular sieve raw powder obtained in Comparative Example 5.
  • AEI refers to an AEI type skeleton approved by the International Zeolite Association (IZA) Structural Committee.
  • the present invention provides a method for preparing an AEI structural molecular sieve comprising the following steps:
  • step (2) The product obtained in the step (1) is filtered, and the filtrate is subjected to electrodialysis electrolysis to recover the organic template and the silicon species as synthetic raw materials for the next batch of AEI molecular sieves.
  • the silicon source, the aluminum source, the alkali source, the templating agent and the water molar ratio are 1.0:0.00833 to 0.1667:0.1 to 0.5:0.05 to 0.5:10 to 50.
  • the reaction is carried out under hydrothermal crystallization conditions, and the hydrothermal crystallization is divided into two segments: (1) the first crystallization temperature is 120 to 150 ° C, crystallization time is 0.5 to 3.0 days; (2) second stage crystallization temperature is 150 to 200 ° C, crystallization time is 0.5 to 6.0 days, then the product obtained by the reaction is filtered, the filtrate is carried out Electrodialysis electrolysis, recovery of organic templating agent and incompletely reacted silicon source to provide raw materials for the next synthesis of AEI molecular sieves.
  • the electrodialysis is selected from the group consisting of bipolar membrane electrodialysis or electrodialysis well known to those skilled in the art.
  • the filtrate is recovered by a bipolar membrane, which is a novel ion exchange composite membrane, which is usually composed of a cation exchange layer (N type membrane), an interface hydrophilic layer (catalytic layer) and an anion exchange layer (The P-type film is compounded and is a true reaction film.
  • the bipolar membrane dissociates the water and obtains hydrogen ions and hydroxide ions on both sides of the membrane.
  • a bipolar membrane electrodialysis system combining a bipolar membrane with other anion-cation exchange membranes can convert a salt in an aqueous solution into a corresponding acid and base without introducing a new component.
  • the method is called bipolar membrane electrodialysis.
  • the invention selects ABS plastic to make the unsinking, and after aliquoting in the tank, the DSA anode electrode and the graphite cathode electrode are respectively installed in the electrolytic tank. Between the anode and the cathode of the electrolytic cell, a spare anion exchange membrane, a cation exchange membrane, and a bipolar membrane are prepared in advance.
  • the silicon source is based on SiO 2
  • the aluminum source is based on Al 2 O 3
  • the alkali solution is based on Na 2 O
  • the organic template is in OSDA. meter.
  • the present invention provides an NO X selective catalytic reduction catalyst, which is the AEI molecular sieve structure with a metal salt solution obtained by ion exchange.
  • the AEI structure molecular sieve is obtained by ion exchange with a soluble metal salt solution, and 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 copper ion has a copper ion concentration of 0.1 to 1.5 mol/L.
  • a copper-modified AEI molecular sieve is obtained, and then the copper-modified AEI molecular sieve is attached to the porous regularity using a binder.
  • a porous structured material with a catalyst is disposed in the exhaust gas processor to form a vehicle exhaust processor for processing the exhaust stream.
  • the binder is selected from one or more of silica sol, water glass, pseudoboehmite, and aluminum sol.
  • the porous structured material is selected from the group consisting of a honeycomb, a plate or a corrugated material, and the material is selected from the group consisting of Cordierite, ⁇ -alumina, silicon carbide, aluminum titanate, silicon nitride, zirconia, mullite, spodumene, alumina-silica-magnesia, zirconium silicate or metal flakes; preferably cordierite
  • the porous honeycomb flow-through type monolith carrier has a carrying capacity of 170 to 270 g/L.
  • the present invention provides a method for purifying an exhaust gas stream, which is comprising a NO X and the reducing agent in contact with the exhaust gas stream of the SCR catalyst composition, at least a portion of the NO X selected Reductively reduced to N 2 and H 2 O.
  • the nitrogen-containing reducing agent is selected from the group consisting of ammonia, hydrazine or any suitable ammonia precursor, and any suitable ammonia precursor is selected from the group consisting of urea, ammonium carbonate, ammonium carbamate, ammonium hydrogencarbonate or ammonium formate. Or two or more.
  • the catalyst of the present invention is shown in a display obtained in the NO X conversion rate in a much wider temperature window.
  • the temperature range for increasing the conversion is about 150 to 650 ° C, preferably 200 to 650 ° C, more preferably 200 to 550 ° C, in these temperature ranges, after exposure to a reducing atmosphere, even to a reducing atmosphere and high temperature (for example, up to 850 ° C)
  • the subsequent conversion efficiency may be greater than 55% to 100%, more preferably greater than 90% conversion efficiency, even more preferably greater than 95% conversion efficiency.
  • the “relative yield” of the present invention means the ratio of the amount of the reactant (or its derivative) mixed into the desired product to the total amount of the reactant introduced in the chemical method, and the relative yield of the reactant can be used.
  • Formula to calculate: (relative yield) R (R P ) / (R T ), where R is the reactant and R P is the total weight of the reactant R (or its derivative) incorporated into the desired product.
  • R T is the total weight of the reactant R introduced in the chemical process.
  • total relative yield means the relative yield of the whole for a chemical process.
  • Total relative yield by silica means the total amount of silica mixed into the total amount of one or more sequentially mass produced zeolites relative to the total amount of silica introduced into the process as a whole.
  • Total relative yield by templating agent means the amount of organic templating agent used directly in the constituent zeolite framework in one or more sequential batches relative to the amount of silica typically introduced into the process.
  • the solid matter was dried at 120 ° C for 12 hours and at 540 ° C for 4 hours, and confirmed by XRD as an AEI type molecular sieve, that is, AEI molecular sieve raw powder; the AEI molecular sieve showed that its SAR was 11.2, which was recorded as A, and the molecular sieve synthesis precursor
  • the formulation ratio, synthesis conditions, relative crystallinity and yield parameters of the sol were as shown in Tables 3 and 4.
  • the solid matter was dried at 120 ° C for 12 hours and at 540 ° C for 4 hours, and confirmed by XRD as an AEI type molecular sieve, that is, AEI molecular sieve raw powder; the AEI molecular sieve showed that its SAR was 15.6, which was recorded as B, and the precursor of molecular sieve synthesis
  • the formulation ratio, synthesis conditions, relative crystallinity and yield parameters of the sol were as shown in Tables 3 and 4.
  • the SAA-2 solution obtained in Example 2 was mixed.
  • the SDK-2 solution obtained in Example 2 the quantitative N,N-dimethyl-3,5-dimethylpiperidinium aqueous solution (concentration: 20% by weight), deionized water and NaOH were sequentially added.
  • the solid matter was dried at 120 ° C for 12 hours and at 540 ° C for 4 hours, and confirmed by XRD as an AEI type molecular sieve, that is, AEI molecular sieve raw powder; the AEI molecular sieve showed that its SAR was 29.7, which was recorded as C, and the molecular sieve synthesis precursor
  • the formulation ratio, synthesis conditions, relative crystallinity and yield parameters of the sol were as shown in Tables 3 and 4.
  • Example 3 (1) X zeolite, water glass (Na 2 O: 7.44 wt%, SiO 2 : 27.40 wt%) having a molar ratio of silica to alumina of a silica and alumina of 2.74 and obtained in Example 3
  • the SAA-3 solution was mixed, and the SDK-3 solution obtained in Example 3 was added to the mixture in this order, and the aqueous solution of N,N-dimethyl-3,5-dimethylpiperidinium was quantitatively determined (concentration: 20% by weight).
  • the solid matter was dried at 120 ° C for 12 hours and at 540 ° C for 4 hours, and confirmed by XRD as an AEI type molecular sieve, that is, AEI molecular sieve raw powder; the AEI molecular sieve showed that its SAR was 39.6, which was recorded as D, and the molecular sieve synthesis precursor
  • the formulation ratio, synthesis conditions, relative crystallinity and yield parameters of the sol were as shown in Tables 3 and 4.
  • Example 4 (1) a USZ zeolite, water glass (Na 2 O: 7.44% by weight, SiO 2 : 27.40% by weight) of a decalcified alumina having a molar ratio of silica to alumina of a silica and alumina of 28.7 and a water glass (Na 2 O: 7.44% by weight, and SiO 2 : 27.40% by weight)
  • the SAA-4 solution obtained in Example 4 was mixed, and the SDK-4 solution obtained in Example 4 was added to the mixture in this order, and the aqueous solution of N,N-dimethyl-3,5-dimethylpiperidinium was quantitatively quantified.
  • the solid matter was dried at 120 ° C for 12 hours and at 540 ° C for 4 hours, and confirmed by XRD as an AEI type molecular sieve, that is, AEI molecular sieve raw powder; the AEI molecular sieve showed that its SAR was 79.1, which was recorded as E, and the molecular sieve synthesis precursor
  • the formulation ratio, synthesis conditions and yield parameters of the sol were as shown in Tables 3 and 4.
  • the solid matter was dried at 110 ° C for 24 hours and at 540 ° C for 4 hours, and confirmed by XRD as an AEI type molecular sieve, that is, AEI molecular sieve raw powder; the AEI molecular sieve showed that its SAR was 31.2, which was denoted as F, and the molecular sieve synthesis precursor
  • the formulation ratio, synthesis conditions, relative crystallinity and yield parameters of the sol were as shown in Tables 3 and 4.
  • Example 6 A decalcified USY zeolite, a silica sol (SiO 2 : 30.0 wt%) having a molar ratio of silica to alumina of a silica and alumina of 13.3, and SAB obtained in Example 6 1
  • the solution was mixed, and the SDL-1 solution obtained in Example 6 was added to the mixture in this order, and the aqueous solution of 1-ethyl-1-methyl-2,2,6,6-hexamethylpiperidinium was quantified (concentration).
  • the solid matter was dried at 110 ° C for 24 hours and at 540 ° C for 4 hours, and confirmed by XRD as an AEI type molecular sieve, that is, AEI molecular sieve raw powder; the AEI molecular sieve showed that its SAR was 41.8, which was recorded as G, molecular sieve synthesis precursor
  • the formulation ratio, synthesis conditions, relative crystallinity and yield parameters of the sol were as shown in Tables 3 and 4.
  • the solid matter was dried at 110 ° C for 24 hours and at 540 ° C for 4 hours, and confirmed by XRD as an AEI type molecular sieve, that is, AEI molecular sieve raw powder; the AEI molecular sieve showed that its SAR was 45.3, which was recorded as H, molecular sieve synthesis precursor
  • the formulation ratio, synthesis conditions, relative crystallinity and yield parameters of the sol were as shown in Tables 3 and 4.
  • a quantitative HY zeolite having a silicon-to-aluminum ratio of 5.3, providing an aluminum source and a partial silicon source
  • a silica sol SiO 2 : 30.0 wt%
  • a SAB-3 solution obtained in Example 8 were mixed to the mixture.
  • the SDL-3 solution obtained in Example 8 was added in order, and the aqueous solution of 1-ethyl-1-methyl-2,2,6,6-hexamethylpiperidinium was quantitatively determined (concentration: 20% by weight), deionized.
  • the obtained solid mixture was transferred to a 2000 ml hydrothermal crystallization vessel, and stirred at a speed of 60 rpm, heated to 140 ° C for 24 hours, and then further heated to 180 ° C for 72 hours;
  • the solid matter was dried at 110 ° C for 24 hours and at 540 ° C for 4 hours, and confirmed by XRD as an AEI type molecular sieve, that is, AEI molecular sieve raw powder; the AEI molecular sieve showed that its SAR was 36.6, which was denoted as I, molecular sieve synthesis precursor
  • the formulation ratio, synthesis conditions, relative crystallinity and yield parameters of the sol were as shown in Tables 3 and 4.
  • a quantitative amount of a desalic acid-containing USY zeolite having a silica-alumina ratio (SAR) of 28.7 and a SAB-4 solution obtained in Example 9 was added to the mixture, and sequentially added to the mixture.
  • SDL-4 solution obtained in Example 9 quantitative 1-ethyl-1-methyl-2,2,6,6-hexamethylpiperidinium aqueous solution (concentration: 20% by weight), deionized water and NaOH particles (Purity: 96 wt%), the reaction mixture was then stirred at a speed of 200 rpm in a closed vessel at room temperature until all the raw materials were uniformly mixed, and the molar ratio of the mixed sol having the following molar composition was:
  • the solid matter was dried at 110 ° C for 24 hours and at 540 ° C for 4 hours, and confirmed by XRD as an AEI type molecular sieve, that is, AEI molecular sieve raw powder; the AEI molecular sieve showed that its SAR was 33.8, which was denoted as J, a molecular sieve synthesis precursor.
  • the formulation ratio, synthesis conditions, relative crystallinity and yield parameters of the sol were as shown in Tables 3 and 4.
  • ML-P2 produced ML-P3 in a similar manner, the AEI zeolite produced was recorded as VS3, and ML-P3 was sequentially used to produce ML-P4, the produced AEI zeolite was recorded as VS4, and ML-P4 was used.
  • ML-P5 was produced and the resulting AEI zeolite was designated VS5.
  • Table 4 The recovered liquid, relative crystallinity and yield parameters used in molecular sieve synthesis are shown in Table 4.
  • the results in the above table show that N,N-dimethyl-3,5-dimethylpiperidinium templating agent and 1-ethyl-1-methyl-2,2,6,6-hexamethylpiperidinium
  • the templating agent can be repeatedly recovered by electrodialysis hydrolysis to extract and reuse the organic template lye, and the silicate solution in the filtrate can also be separated and recovered by electrodialysis as a raw material for AEI molecular sieve to improve The total relative yield by silica and the total relative yield by templating agent.
  • the crystallized precursor gel composition and process parameters can be varied to obtain AEI molecular sieve crystals having different properties such as different silicon to aluminum (SAR) values.
  • the crystallinity of the AEI molecular sieve obtained in Example 1 was defined as 100%, that is, the crystallinity of the AEI molecular sieve obtained by hydrothermal crystallization directly using the original organic templating agent and the FAU silica-alumina molecular material was 100% (no organic template was recovered and Silicon species), relative to 100% of the above AEI molecular sieves Crystallinity, the relative crystallinity of the AEI molecular sieve obtained in Examples 2 to 10 and Comparative Examples 1 to 5 of the present invention was calculated, and the relative crystallinity of the AEI molecular sieve prepared in the examples of the present invention was calculated to be in the range of 95% to 105%.
  • the relative crystallinity of the samples in Comparative Examples 1 to 5 was in the range of 56% to 89%. Obviously, the relative crystallinity of the samples obtained in Examples 1 to 10 was significantly higher than that in the samples in Comparative Examples 1 to 5.
  • the total relative yield in the molecular sieve reaction obtained in Examples 1 to 10 of the present invention in the range of 30% to 95% by the templating agent, and the total relative yield of the molecular sieve obtained in Comparative Examples 1 to 5 according to the templating agent.
  • the total relative yield in terms of silica in the molecular sieve reaction obtained in Examples 1 to 10 of the present invention is In the range of 39% to 97%, the total relative yield of the molecular sieves obtained in Comparative Examples 1 to 5 according to the template is 32% to 87%, that is, the highest can reach 97%, which is much higher than the total relative ratio of the comparative examples. Yield; in addition, it can be seen from Fig. 3 and Fig.
  • the dried sample was calcined at a normal atmospheric pressure of 500 ° C for 4 hours; the copper modified AEI molecular sieve was obtained, and the copper (II) ion accounted for the total weight of the molecular sieve catalyst in the catalyst prepared according to the ICP analysis result. As shown in Table 5.
  • Examples 1-8 Synthesized AEI molecular sieves prepared 10-20 mesh A1-H1, Comparative Examples 1-5 synthesized AEI molecular sieves to prepare 10-20 mesh VS1 ⁇ VS5 catalyst particles, installed in the reactor
  • the mixed gas stream containing 500 ppm NO, 500 ppm NH 3 , 10 vol% O 2 , 5 vol% steam, and Ar as a balance gas was passed through a preheater (set at 100 ° C) and then into the SCR reactor.
  • the samples were tested at a reaction temperature of 150 to 650 ° C and at a space hourly space velocity of 48,000 h -1 .
  • the temperature is monitored by an internal thermocouple located at the sample location.
  • the used fresh SCR catalysts in the above examples and comparative examples were subjected to hydrothermal durability treatment to obtain an aged SCR catalyst, and the conditions of the hydrothermal durability treatment test were as follows:
  • Space velocity SV 30000/h, temperature: 800 ° C, time: 16 hours, water concentration: 10%, oxygen concentration: 10%, nitrogen concentration: equilibrium.
  • the Cu-AEI molecular sieve catalysts obtained in Examples 11 to 18 have good low-temperature light-off property and high-temperature activity.
  • the conversion rate of NO X in the range of 41.8% ⁇ 99.6%, and SCR in the aging state the conversion of NO X is in In the range of 36.2% to 98.8%, it is indicated that the SCR is significantly better than the catalyst samples obtained from the catalysts VS1 to VS5 in the comparative examples 1 to 5 regardless of whether it is in a "fresh" state or an "aging" state.
  • the results obtained from Examples 11 to 18 clearly show that the Cu-AEI molecular sieve catalyst material of the present invention and the catalyst obtained therefrom have improved SCR catalytic activity, especially in the treatment of NOx in, for example, diesel locomotive applications. Under the low conversion temperature peculiar to the start-up conditions. For other SCR applications, the Cu-AEI molecular sieve catalyst material of the present invention allows for higher conversions at lower temperatures, thus allowing for higher efficiencies and thus allowing for high energy efficiency processing at comparable conversion rates. NOx-containing exhaust gas, such as exhaust gas from industrial production.

Abstract

一种AEI结构分子筛及其制备方法和应用。其制备方法包含下述步骤：(1)将含有有机模板剂、FAU型硅铝分子筛、碱液和水的原料在水热晶化条件下反应，其中，FAU型硅铝分子筛提供硅源和铝源；(2)将步骤(1)得到的产物过滤，滤液进行电渗析电解，回收有机模板剂和硅的物种作为下一批AEI分子筛的合成原料。这种滤液回收利用的方法，有效避免无定形物质、降解物质混入下一批投料中，减少了AEI分子筛投料误差，使得到的AEI分子筛具有良好的分散性和相对高的结晶度，提高了AEI分子筛合成的总体收率。

Description

一种AEI结构分子筛及其制备方法和应用 技术领域
本发明涉及无机多孔材料合成领域，具体涉及一种AEI结构分子筛及其制备方法和应用。
背景技术
AEI结构分子筛具有大笼的三维孔道体系，可以通过8元环构成三维孔道结构，孔径尺寸
Figure PCTCN2017106026-appb-000001
其笼结构与CHA分子筛类似，笼尺寸能够包含直径达到
Figure PCTCN2017106026-appb-000002
球体。区别在以四元环连接的相邻两个双六元环结构中CHA结构的相邻双六元环在空间上呈平行结构，而AEI结构中两相邻双六元环呈镜面对称分布。这样的结构区别导致AEI结构中的八元环孔道具有较小的孔径，其催化活性更高，抗积碳性能更优。AEI硅铝分子筛和硅铝磷分子筛结构分别具体以SSZ-39和SAPO-18为代表。离子交换或负载金属活性组分的AEI分子筛催化剂，展现出独特的选择还原反应(SCR)活性，对氮氧化物(NOx)有很好的还原处理性能，已经引起了广泛的关注。
氮氧化物(NOx)会引起光化学烟雾、酸雨和温室效应等一系列环境问题，已严重危害人类的健康，并且随着机动车数量的增加和工业的迅速发展，NOx排放量日益增多，必将引起生态和环境的严重恶化。因而，消除NOx污染问题刻不容缓。目前，NOx主导控制技术是NH3选择性催化还原(NH3-SCR)，其关键是选择性能优异的催化剂，这将决定整个催化反应体系的成败。
通常SCR催化剂通常是以沸石为载体、负载SCR活性组分制备而成的具有晶体结构的分子筛；沸石是具有相当规整的孔径大小的硅铝酸盐晶体材料，比如β沸石、Y沸石、X沸石、八面沸石、丝光沸石、毛沸石、ZSM-5、ZSM-8、ZSM-11、ZSM-12沸石等，这些沸石可以与Cu、Fe、Mn、Ag、V、Ti、Co等金属交换，或者沸石本身含有一部分Cu、Fe等金属。但是，上述已知的金属改性的沸石催化剂在氨选择性催化还原氮氧化物的过程中只能在 较窄的温度区域范围内进行氮氧化物的净化，在200℃以下都不具有高活性的NOx净化性能，水热稳定性差，低温条件下活性较低。
合成AEI分子筛使用有机结构导向剂(OSDA)来生产，其也被称作“模板”或者“模板剂”。通常，OSDA充当了模具，在其周围形成分子筛晶体。在晶体形成后，将OSDA从该晶体内部结构中除去，留下分子的多孔分子筛笼。
在常规合成方法中，固体分子筛晶体从反应混合物中沉淀出来，所述反应前驱混合物硅源、铝源、碱源和有机模板剂。合成通常需要较长时间来实现期望的分子筛结晶。当分子筛结晶完成后，通常用过滤方法回收分子筛固体产物，并排放多余的滤液。该排放的滤液中包含未使用的有机模板剂(OSDA)，其经常由于苛刻的反应条件而降解。
专利CN104591204A通过AEI分子筛合成后的母液循环来增加二氧化硅和/或OSDA计的收率，但母液直接循环由于母液中少量的降解物及未结晶的无定型产物无法去掉，容易引起产品质量不稳定，所以不能有效解决由于收率低引起的成本高和环境污染的问题。
发明内容
为此，本发明提供了一种AEI结构分子筛的制备方法，其包含下述步骤：
(1)将含有有机模板剂、FAU型硅铝分子筛、碱液和水的原料在水热晶化条件下反应，其中，FAU型硅铝分子筛提供硅源和铝源；
(2)将步骤(1)得到的产物过滤，滤液进行电渗析电解，回收有机模板剂和硅的物种作为下一批AEI分子筛的合成原料。
本发明提供了一种AEI结构分子筛，其通过包含下述步骤的方法制得：
(1)将含有有机模板剂、FAU型硅铝分子筛、碱液和水的原料在水热晶化条件下反应，其中，FAU型硅铝分子筛提供硅源和铝源；
(2)将步骤(1)得到的产物过滤，滤液进行电渗析电解，回收有机模板剂和硅的物种作为下一批AEI分子筛的合成原料。
本发明提供了一种NOX选择性催化还原催化剂，其是将AEI结构分子筛与金属盐溶液离子交换而得到。
本发明还提供了一种NOX选择性催化还原催化剂的制备方法，其是将AEI结构分子筛加入到金属盐溶液中，得到NOX选择性催化还原催化剂。
具体来说，本发明提出了如下技术方案。
本发明一方面提供了一种AEI结构分子筛的制备方法，其包含下述步骤：
(1)将含有有机模板剂、FAU型硅铝分子筛、碱液和水的原料在水热晶化条件下反应，其中，FAU型硅铝分子筛提供硅源和铝源；
(2)将步骤(1)得到的产物过滤，滤液进行电渗析电解，回收有机模板剂和硅的物种作为下一批AEI分子筛的合成原料。
优选的，对于所述的制备方法，其中，在步骤(1)中，所述有机模板剂为单环或多环哌啶鎓类化合物，所述哌啶鎓化合物选自于N,N-二甲基-3,5-二甲基哌啶鎓、N,N-二甲基-2,6-二甲基哌啶鎓、1,1,2,2,6,6-六甲基哌啶鎓、1,1,2,2,6,6-六甲基-4-氧代哌啶鎓、1,1,3,5-四甲基-4-氧代哌啶鎓、1-羟基-1,1,2,2,6,6-六甲基哌啶鎓、1,1-二甲基-4,4-二丙氧基哌啶鎓、3,5-二甲氧基-1,1-二甲基哌啶鎓、3,5-二羟基-1,1-二甲基哌啶鎓、4-乙基-1,1-二甲基-3,5-二氧代哌啶鎓、1-乙基-1-甲基-2,2,6,6-六甲基哌啶鎓、1-环氧丙基-1-甲基-2,2,6,6-六甲基哌啶鎓、N,N-二甲基-2-(2-羟乙基)哌啶鎓和N,N-二甲基-2-乙基哌啶鎓中一种或两种以上。
优选的，对于所述的制备方法，其中，在步骤(1)中，所述FAU型硅铝分子筛选自于Y沸石和X沸石中的一种；优选的，所述Y沸石选自于HY沸石、USY沸石和NaY沸石中的一种，所述X沸石选自于NaX沸石、KX沸石和HX沸石中的一种。
优选的，对于所述的制备方法，其中，在步骤(1)中，所述水热晶化分为两段：(1)第一段晶化温度为120～150℃，优选为130～150℃；(2)第二段晶化温度为150～200℃，优选为160～190℃。
优选的，对于所述的制备方法，其中，在步骤(1)中，所述水热晶化分为两段：(1)第一段晶化时间为0.5～3.0天，优选为0.5～2.0天；(2)第二段晶化时间为0.5～6.0天，优选为1.0～5.0天。
优选的，对于所述的制备方法，其中，在步骤(1)中，加入额外硅源为原料，所述额外硅源选自于白炭黑、大孔硅胶、粗孔硅胶、细孔硅胶、薄层层 析硅胶、B型硅胶、偏硅酸钠、硅溶胶、水玻璃、烷基硅酸酯和硅藻土中一种或两种以上。
优选的，对于所述的制备方法，其中，在步骤(1)中，所述碱液选自于NaOH、Na2O、Na2O2和KOH中的一种或两种以上。
优选的，对于所述的制备方法，其中，在步骤(1)中，所述硅源、铝源、碱液、模板剂和水的摩尔比为1.0:0.00833～0.1667:0.1～0.5：0.05～0.5：10～50，优选为1.0:0.0121～0.0417：0.22～0.36:0.08～0.20：15～25。
优选的，对于所述的制备方法，其中，在步骤(2)中，所述电渗析选自于四室三膜、三室两膜或两室一膜中的一种。
优选的，对于所述的制备方法，其中，在步骤(2)中，所述双极膜是通过阳离子交换层、界面亲水层和阴离子交换层复合得到。
本发明提供了一种AEI结构分子筛，其是通过上述任一项所述的方法制备得到。
优选的，对于所述的AEI结构分子筛，其中，所述AEI结构分子筛中的二氧化硅和氧化铝的分子摩尔比为5～100，优选为10～80。
本发明提供了一种NOX选择性催化还原催化剂，其是将AEI结构分子筛与金属盐溶液进行离子交换而得到。
优选的，对于所述的NOX选择性催化还原催化剂，其中，所述金属盐选自于铜、铁、钴、钨、镍、锌、钼、钒、锡、钛、锆、锰、铬、铌、铋、锑、钌、锗、钯、铟、铂、金或银的可溶性盐中一种或两种以上。
优选的，对于所述的NOX选择性催化还原催化剂，其中，所述金属盐选自于铜盐或铁盐，优选为铜盐。
优选的，对于所述的NOX选择性催化还原催化剂，其中，所述铜盐选自于硝酸铜、氯化铜、醋酸铜和硫酸铜中一种或两种以上，所述铜盐中铜离子的浓度为0.1～1.5mol/L。
本发明提供了一种选择性催化还原催化剂的制备方法，其是将AEI结构分子筛加入到金属盐溶液中，得到NOX选择性催化还原催化剂。
优选的，对于所述的制备方法，还包含下述步骤：将所得到的NOX选择性催化还原催化剂使用粘结剂附着在多孔规整材料上。
优选的，对于所述的制备方法，其中，所述粘结剂选自于硅溶胶、水玻璃、拟薄水铝石和铝溶胶中一种或两种以上。
优选的，对于所述的制备方法，其中，所述多孔规整材料选自于蜂窝形、板式形和波纹形中的一种。
优选的，对于所述的制备方法，其中，所述多孔规整材料选自于堇青石、α-矾土、碳化硅、钛酸铝、氮化硅、氧化锆、莫来石、锂辉石、氧化铝-二氧化硅-氧化镁、硅酸锆或金属薄片中的一种，优选为堇青石。
一种选择性催化还原催化剂，其在其在净化废气流中的应用，优选在净化汽车废气流中的应用。
优选的，对于所述的应用，其中，所述废气流为机动车排放的废气流，优选为稀燃发动机的废气流，更优选为柴油机废气流。
本发明提供了一种废气流的净化处理方法，其是将选择性催化还原催化剂与包含NOX和还原剂的汽车废气流相接触，使NOX选择性地还原成N2和H2O。
优选的，对于所述的净化处理方法，其中，所述废气流在与选择性催化还原催化剂接触之前，以NOX计量为100重量％，所述NO2含量≤80重量％，优选为5～70重量％，更优选为10～60重量％，更优选为15～55重量％，更优选为20～50重量％。
本发明所提供的选择性催化还原催化剂为氮氧化物选择性催化还原剂或脱硝催化剂。
本发明所取得的有益效果是：本发明提供的对反应滤液中的有机模板剂和硅物种分离回收的方法，有效避免无定形物质、降解物质混入下一批投料中，减少了AEI分子筛投料误差，使得到的AEI分子筛具有良好的分散性和相对高的结晶度。相比于直接采用原始有机模板剂和FAU硅铝分子筛原料进行水热晶化得到的AEI分子筛100％的结晶度，本发明对反应后的滤液分离了有机模板剂和硅物种制备得到的AEI分子筛，其相对结晶度处于95％～105％范围内，而现有技术直接将反应后的滤液直接作为补充合成原料用于反应所得到的分子筛其相对结晶度处于56％～89％的范围内，显然，本发明得到的AEI分子筛相对结晶度都明显高于现有技术得到的AEI分子筛的相对结晶度，并且本 发明提高了AEI分子筛合成的总体效率，并极大的提高了收率，本发明按二氧化硅计的总相对产率最高可达97％，远远高于现有技术中的总相对产率。
附图说明
图1a：AEI分子筛合成后的滤液通过双极膜电解示意图；
图1b：AEI分子筛合成后的滤液通过常规电渗析示意图；
图2：实施例1中得到的AEI分子筛原粉的XRD图；
图3：实施例5中得到的AEI分子筛原粉的XRD图；
图4：对比例1中得到的AEI分子筛原粉的XRD图；
图5：对比例3中得到的AEI分子筛原粉的XRD图；
图6：对比例5中得到的AEI分子筛原粉的XRD图；
图7：实施例1中得到的AEI分子筛原粉的SEM图；
图8：实施例5中得到的AEI分子筛原粉的SEM图；
图9：对比例1中得到的AEI分子筛原粉的SEM图；
图10：对比例3中得到的AEI分子筛原粉的SEM图；
图11：对比例5中得到的AEI分子筛原粉的SEM图。
具体实施方式
术语“AEI”指的是由国际沸石协会(IZA)结构委员会认可的AEI型骨架。
如上所述，本发明提供了一种AEI结构分子筛的制备方法，其包含下述步骤：
(1)将含有有机模板剂、FAU型硅铝分子筛、碱液和水的原料在水热晶化条件下反应，其中，FAU型硅铝分子筛提供硅源和铝源；
(2)将步骤(1)得到的产物过滤，滤液进行电渗析电解，回收有机模板剂和硅的物种作为下一批AEI分子筛的合成原料。
在本发明一种优选的具体实施方式中，是将硅源、铝源、碱源、模板剂和水按摩尔比为1.0:0.00833～0.1667:0.1～0.5：0.05～0.5：10～50进行混合，在水热晶化条件下进行反应，所述水热晶化分为两段：(1)第一段晶化温度为 120～150℃，晶化时间为0.5～3.0天；(2)第二段晶化温度为150～200℃，晶化时间为0.5～6.0天，然后将反应所得到的产物进行过滤，滤液进行电渗析电解，回收有机模板剂和未完全反应的硅源，为下一步合成AEI分子筛提供原料。其中，所述电渗析选自于双极膜电渗析或本领域技术人员公知的电渗析。
其中，所述滤液采用双极膜进行回收，双极膜是一种新型的离子交换复合膜，它通常由阳离子交换层(N型膜)、界面亲水层(催化层)和阴离子交换层(P型膜)复合而成，是真正意义上的反应膜。在直流电场作用下，双极膜可将水离解，在膜两侧分别得到氢离子和氢氧根离子。利用这一特点，将双极膜与其它阴阳离子交换膜组合成的双极膜电渗析系统，能够在不引入新组分的情况下将水溶液中的盐转化为对应的酸和碱，这种方法称为双极膜电渗析法。
本发明选取ABS塑料制成解槽，槽内若干等分后，在电解槽内分别安装DSA阳极电极，石墨阴极电极。在电解槽阳极和阴极之间，设置有预先制备备用的阴离子交换膜、阳离子交换膜和双极膜。
在本发明优选的一种具体实施方式中，所述硅源是以SiO2计，所述铝源以Al2O3计，所述碱液以Na2O计，所述有机模板剂以OSDA计。
在本发明的一种实施方式中，本发明提供了一种NOX选择性催化还原催化剂，其是将AEI结构分子筛与金属盐溶液进行离子交换而得到。
在本发明一种优选的具体实施方式中，其是将AEI结构分子筛与可溶性金属盐溶液进行离子交换而得到，所述金属盐溶液优选为铜盐或铁盐，更优选为铜盐，所述铜盐所述铜盐选自于硝酸铜、氯化铜、醋酸铜和硫酸铜中一种或两种以上，所述铜盐中铜离子的浓度为0.1～1.5mol/L。
在本发明一种更优选的实施方式中，将AEI结构分子筛与铜盐进行离子交换之后，得到铜改性的AEI结构分子筛，然后使用粘结剂将铜改性的AEI结构分子筛附着在多孔规整材料上，带有催化剂的多孔规整材料安置在尾气处理器中形成机动车尾气处理器进行废气流的处理。
所述粘结剂选自于硅溶胶、水玻璃、拟薄水铝石和铝溶胶中一种或两种以上。
所述多孔规整材料选自于蜂窝形、板式形或波纹形材料，所述材质选自 堇青石、α-矾土、碳化硅、钛酸铝、氮化硅、氧化锆、莫来石、锂辉石、氧化铝-二氧化硅-氧化镁、硅酸锆或金属薄片；优选堇青石多孔的蜂窝状流过型整料载体，其承载量为170～270g/L。
在一种具体的实施方式中，本发明提供了一种废气流的净化处理方法，其是将包含NOX和还原剂的废气流与SCR催化剂组合物相接触，将所述NOX至少一部分选择性地还原成N2和H2O。
所述含氮还原剂选自于氨、肼或任何合适的氨前体，所述任何合适的氨前体选自于尿素、碳酸铵、氨基甲酸铵、碳酸氢铵或甲酸铵中的一种或两种以上。
在本发明一种优选的具体实施方式中，本发明所示的催化剂显示在宽得多的温度窗口中获得NOX转化率。提高转化率的温度范围约150～650℃，优选200～650℃，更优选200～550℃，在这些温度范围内，暴露于还原气氛之后，甚至暴露于还原气氛和高温(例如高达850℃)之后的转化效率可以是大于55％至100％，更优选大于90％的转化效率，甚至更优选大于95％的转化效率。
本发明的“相对产率”表示混入到期望的产物中的反应物(或其衍生物)的量占在该化学方法中引入的反应物总量的比例，反应物的相对产率可以用下述公式来计算：(相对产率)R＝(RP)/(RT)，其中R是反应物，RP是混入到期望的产物中的反应物R(或其衍生物)的总重量，RT是在该化学方法中引入的反应物R的总重量。术语“总的相对产率”表示用于化学方法的整体的相对产率。“按二氧化硅计的总相对产率”表示混入到一个或多个顺序批量生产的沸石总量中的二氧化硅的总量相对于总体上引入该方法中的二氧化硅的总量。“按模板剂计的总相对产率”表示一个或多个顺序批量的构成沸石骨架中直接使用的有机模板剂的量相对于总体上引入该方法中的二氧化硅的量。
下面对本实施例所用的原料及设备的生产厂家，以及产品分析使用的设备和分析方法进行说明如下，其中所述的化学物质没有标明的均为常规试剂的化学纯级别。其中，实施例所用到的原料的信息及实验设备的信息如表1和表2所示。
表1本发明所用到的原料的信息
名称 纯度 生产厂家
HY沸石 100％ 山东多友科技有限公司
NaOH颗粒 96％ 天津市大陆化学试剂厂
USY沸石 100％ 巴斯夫公司
X沸石 100％ 天津南化催化剂有限公司
NaY沸石 100％ 山东多友科技有限公司
表2本发明所用的实验设备的信息
设备 型号 厂家
扫描电镜 TM3030 Hitachi
ICP分析仪 ICPE-9000 日本岛津
X射线衍射仪 X’PertPRO 荷兰帕纳科公司
实施例1 AEI型沸石分子筛的制备
(1)将定量的二氧化硅和氧化铝的摩尔硅铝比(SAR)为28.7的脱铝酸盐的USY沸石加入到有机模板剂N,N-二甲基-3,5-二甲基哌啶鎓水溶液(浓度：20wt％)中，充分搅拌，再加入NaOH颗粒(纯度：96wt％)，补充加入去离子水充分搅拌，所得混合浆液在室温下于密封容器内连续搅拌2小时，直至所有原料混合均匀，有以下摩尔组成的混合溶胶摩尔比为：
Na2O：SiO2：Al2O3：OSDA：H2O＝0.22：1.0：0.03484：0.20：25.0；将所得固体混合物移至2000ml水热晶化釜中，并在60rpm速度下搅拌，升温到140℃晶化24小时，然后继续升温到170℃晶化60小时；
(2)待晶化完全后，产物迅速冷却，经过抽滤分离、洗涤得到滤液和固体物质，将回收的滤液经过双极膜电渗析的方法(如图1a所示)将有机模板剂和硅酸盐分离，得到有机模板剂碱性溶液(记为SDK-1)以及硅酸溶液(记为SAA-1)作为原料参与下一批AEI分子筛的合成；
固体物质120℃下烘干12小时和540℃下焙烧4个小时，并且通过XRD确认为AEI型分子筛，即AEI分子筛原粉；该AEI分子筛显示它的SAR是11.2，记为A，分子筛合成前驱物溶胶的配比、合成条件、相对结晶度和收率参数如表3和4所示。
实施例2 AEI型沸石分子筛的制备
(1)将定量的HY沸石(硅铝比SAR为5.3)、水玻璃(Na2O：7.44wt％，SiO2：27.40wt％)和实施例1中得到的SAA-1溶液混合，向该混合物中，顺序添加实施例1中得到的SDK-1溶液、定量N,N-二甲基-3,5-二甲基哌啶鎓水溶液(浓度：20wt％)、去离子水和NaOH颗粒(纯度：96wt％)，该反应混合物然后在室温下于密封容器内200rpm速度连续搅拌2小时，直至所有原料混合均匀，有以下摩尔组成的混合溶胶摩尔比为：
Na2O：SiO2：Al2O3：OSDA：H2O＝0.24：1.0：0.03226：0.15：25.0；将所得固体混合物移至2000ml水热晶化釜中，并在60rpm速度下搅拌，升温到135℃晶化36小时，然后继续升温到180℃晶化48小时；
(2)待晶化完全后，产物迅速冷却，经过抽滤分离、洗涤得到滤液和固体物质，收集该产物的滤液，同样以双极膜电渗析的方式(如图1a所示)分离有机模板剂碱性溶液(记为SDK-2)和原硅酸的溶液(SAA-2)，作为原料参与下一批AEI分子筛的合成。
固体物质120℃下烘干12小时和540℃下焙烧4个小时，并且通过XRD确认为AEI型分子筛，即AEI分子筛原粉；该AEI分子筛显示它的SAR是15.6，记为B，分子筛合成前驱物溶胶的配比、合成条件、相对结晶度和收率参数如表3和4所示。
实施例3 AEI型沸石分子筛的制备
(1)将定量的二氧化硅和氧化铝的摩尔硅铝比(SAR)为20.6的脱铝酸盐的USY沸石、水玻璃(Na2O：7.44wt％，SiO2：27.40wt％)和实施例2中得到的SAA-2溶液混合。向该混合物中，顺序添加实施例2中得到的SDK-2溶液、定量N,N-二甲基-3,5-二甲基哌啶鎓水溶液(浓度：20wt％)、去离子水和NaOH颗粒(纯度：96wt％)，该反应混合物然后在室温下密闭容器中200rpm速度下搅拌，直至所有原料混合均匀，有以下摩尔组成的混合溶胶摩尔比为：
Na2O：SiO2：Al2O3：OSDA：H2O＝0.26：1.0：0.02475：0.15：25.0；将 所得固体混合物移至2000ml水热晶化釜中，并在60rpm速度下搅拌，升温到130℃晶化48小时，然后继续升温到185℃晶化60小时；
(2)待晶化完全后，产物迅速冷却，经过抽滤分离、洗涤得到滤液和固体物质，收集该产物的滤液，同样以双极膜电渗析的方式(如图1a所示)分离有机模板剂碱性溶液(记为SDK-3)和原硅酸的溶液(SAA-3)，作为原料参与下一批AEI分子筛的合成；
固体物质120℃下烘干12小时和540℃下焙烧4个小时，并且通过XRD确认为AEI型分子筛，即AEI分子筛原粉；该AEI分子筛显示它的SAR是29.7，记为C，分子筛合成前驱物溶胶的配比、合成条件、相对结晶度和收率参数如表3和4所示。
实施例4 AEI型沸石分子筛的制备
(1)将定量的二氧化硅和氧化铝的摩尔硅铝比(SAR)为2.74的X沸石、水玻璃(Na2O：7.44wt％，SiO2：27.40wt％)和实施例3中得到的SAA-3溶液混合，向该混合物中，顺序添加实施例3中得到的SDK-3溶液、定量N,N-二甲基-3,5-二甲基哌啶鎓水溶液(浓度：20wt％)、去离子水和NaOH颗粒(纯度：96wt％)，该反应混合物然后在室温下密闭容器中200rpm速度下搅拌，直至所有原料混合均匀，有以下摩尔组成的混合溶胶摩尔比为：
Na2O：SiO2：Al2O3：OSDA：H2O＝0.28：1.0：0.02045：0.15：25.0；所得固体混合物移至2000ml水热晶化釜中，并在60rpm速度下搅拌，升温到150℃晶化12小时，然后继续升温到170℃晶化72小时；
(2)待晶化完全后，产物迅速冷却，经过抽滤分离、洗涤得到滤液和固体物质，收集该产物的滤液，同样以双极膜电渗析的方式(如图1a所示)分离有机模板剂碱性溶液(记为SDK-4)和原硅酸的溶液(SAA-4)，作为原料参与下一批AEI分子筛的合成；
固体物质120℃下烘干12小时和540℃下焙烧4个小时，并且通过XRD确认为AEI型分子筛，即AEI分子筛原粉；该AEI分子筛显示它的SAR是39.6，记为D，分子筛合成前驱物溶胶的配比、合成条件、相对结晶度和收率参数如表3和4所示。
实施例5 AEI型沸石分子筛的制备
(1)将定量的二氧化硅和氧化铝的摩尔硅铝比(SAR)为28.7的脱铝酸盐的USY沸石、水玻璃(Na2O：7.44wt％，SiO2：27.40wt％)和实施例4中得到的SAA-4溶液混合，向该混合物中，顺序添加实施例4中得到的SDK-4溶液、定量N,N-二甲基-3,5-二甲基哌啶鎓水溶液(浓度：20wt％)、去离子水和NaOH颗粒(纯度：96wt％)，该反应混合物然后在室温下密闭容器中200rpm速度下搅拌，直至所有原料混合均匀，有以下摩尔组成的混合溶胶摩尔比为：
Na2O：SiO2：Al2O3：OSDA：H2O＝0.36：1.0：0.01214：0.08：25.0；将所得固体混合物移至2000ml水热晶化釜中，并在60rpm速度下搅拌，升温到140℃晶化24小时，然后继续升温到170℃晶化60小时；
(2)待晶化完全后，产物迅速冷却，经过抽滤分离、洗涤得到滤液和固体物质，收集该产物的滤液，同样以双极膜电渗析的方式(如图1a所示)分离有机模板剂碱性溶液(记为SDK-5)和原硅酸的溶液(SAA-5)，作为原料参与下一批AEI分子筛的合成；
固体物质120℃下烘干12小时和540℃下焙烧4个小时，并且通过XRD确认为AEI型分子筛，即AEI分子筛原粉；该AEI分子筛显示它的SAR是79.1，记为E，分子筛合成前驱物溶胶的配比、合成条件和收率参数如表3和4所示。
实施例6 AEI型沸石分子筛的制备
(1)将定量的二氧化硅和氧化铝的摩尔硅铝比(SAR)为28.7的脱铝酸盐的USY沸石、硅溶胶(SiO2：30.0wt％)加入到有机模板剂1-乙基-1-甲基-2,2,6,6-六甲基哌啶鎓水溶液(浓度：20wt％)中，充分搅拌，再加入NaOH颗粒(纯度：96wt％)，补充加入去离子水充分搅拌，所得混合浆液在室温下于密封容器内连续搅拌2小时，直至所有原料混合均匀，有以下摩尔组成的混合溶胶摩尔比为：
Na2O：SiO2：Al2O3：OSDA：H2O＝0.29：1.0：0.01451：0.12：15.0；将 所得固体混合物移至2000ml水热晶化釜中，并在60rpm速度下搅拌，升温到135℃晶化24小时，然后继续升温到180℃晶化48小时；
(2)待晶化完全后，产物迅速冷却，经过抽滤分离、洗涤得到滤液和固体物质，将回收的滤液经过电渗析的方法将有机模板剂和硅无定形物质分离，得到有机模板剂碱性溶液(记为SDL-1)以及硅酸溶液(SAB-1)；
固体物质110℃下烘干24小时和540℃下焙烧4个小时，并且通过XRD确认为AEI型分子筛，即AEI分子筛原粉；该AEI分子筛显示它的SAR是31.2，记为F，分子筛合成前驱物溶胶的配比、合成条件、相对结晶度和收率参数如表3和4所示。
实施例7 AEI型沸石分子筛的制备
(1)将定量的二氧化硅和氧化铝的摩尔硅铝比(SAR)为13.3的脱铝酸盐的USY沸石、硅溶胶(SiO2：30.0wt％)和实施例6中得到的SAB-1溶液混合，向该混合物中，顺序添加实施例6中得到的SDL-1溶液、定量1-乙基-1-甲基-2,2,6,6-六甲基哌啶鎓水溶液(浓度：20wt％)、去离子水和NaOH颗粒(纯度：96wt％)，该反应混合物然后在室温下密闭容器中200rpm速度下搅拌，直至所有原料混合均匀，有以下摩尔组成的混合溶胶摩尔比为：
Na2O：SiO2：Al2O3：OSDA：H2O＝0.35：1.0：0.0126：0.08：15.0；将所得固体混合物移至2000ml水热晶化釜中，并在60rpm速度下搅拌，升温到135℃晶化48小时，然后继续升温到190℃晶化36小时；
(2)待晶化完全后，产物迅速冷却，经过抽滤分离、洗涤得到滤液和固体物质，收集该产物的滤液，常规电渗析的方式(如图1b所示)分离有机模板剂碱性溶液(记为SDL-2)和原硅酸的溶液(SAB-2)，作为原料参与下一批AEI分子筛的合成；
固体物质110℃下烘干24小时和540℃下焙烧4个小时，并且通过XRD确认为AEI型分子筛，即AEI分子筛原粉；该AEI分子筛显示它的SAR是41.8，记为G，分子筛合成前驱物溶胶的配比、合成条件、相对结晶度和收率参数如表3和4所示。
实施例8 AEI型沸石分子筛的制备
(1)将定量的二氧化硅和氧化铝的摩尔硅铝比(SAR)为5.3的NaY沸石、硅溶胶(SiO2：30.0wt％)和实施例7中得到的SAB-2溶液混合，向该混合物中，顺序添加实施例7中得到的SDL-2溶液、定量1-乙基-1-甲基-2,2,6,6-六甲基哌啶鎓水溶液(浓度：20wt％)、去离子水和NaOH颗粒(纯度：96wt％)，该反应混合物然后在室温下密闭容器中200rpm速度下搅拌，直至所有原料混合均匀，有以下摩尔组成的混合溶胶摩尔比为：
Na2O：SiO2：Al2O3：OSDA：H2O＝0.34：1.0：0.01244：0.10：15.0；将所得固体混合物移至2000ml水热晶化釜中，并在60rpm速度下搅拌，升温到135℃晶化24小时，然后继续升温到160℃晶化120小时；
(2)待晶化完全后，产物迅速冷却，经过抽滤分离、洗涤得到滤液和固体物质，收集该产物的滤液，以常规电渗析的方式(如图1b所示)来产生有机模板剂碱性溶液(记为SDL-3)和原硅酸的溶液(SAB-3)，作为原料参与下一批AEI分子筛的合成；
固体物质110℃下烘干24小时和540℃下焙烧4个小时，并且通过XRD确认为AEI型分子筛，即AEI分子筛原粉；该AEI分子筛显示它的SAR是45.3，记为H，分子筛合成前驱物溶胶的配比、合成条件、相对结晶度和收率参数如表3和4所示。
实施例9 AEI型沸石分子筛的制备
(1)将定量的HY沸石(硅铝比为5.3，提供铝源和部分硅源)、硅溶胶(SiO2：30.0wt％)和实施例8中得到的SAB-3溶液混合，向该混合物中，顺序添加实施例8中得到的SDL-3溶液、定量1-乙基-1-甲基-2,2,6,6-六甲基哌啶鎓水溶液(浓度：20wt％)、去离子水和NaOH颗粒(纯度：96wt％)，该反应混合物然后在室温下密闭容器中200rpm速度下搅拌，直至所有原料混合均匀，有以下摩尔组成的混合溶胶摩尔比为：
Na2O：SiO2：Al2O3：OSDA：H2O＝0.28：1.0：0.02227：0.12：15.0；
将所得固体混合物移至2000ml水热晶化釜中，并在60rpm速度下搅拌，升温到140℃晶化24小时，然后继续升温到180℃晶化72小时；
(2)待晶化完全后，产物迅速冷却，经过抽滤分离、洗涤得到滤液和固体物质，收集该产物的滤液，以常规电渗析的方式(如图1b所示)分离有机模板剂碱性溶液(记为SDL-4)和原硅酸的溶液(SAB-4)，作为原料参与下一批AEI分子筛的合成；
固体物质110℃下烘干24小时和540℃下焙烧4个小时，并且通过XRD确认为AEI型分子筛，即AEI分子筛原粉；该AEI分子筛显示它的SAR是36.6，记为I，分子筛合成前驱物溶胶的配比、合成条件、相对结晶度和收率参数如表3和4所示。
实施例10 AEI型沸石分子筛的制备
(1)将定量的二氧化硅和氧化铝的摩尔硅铝比(SAR)为28.7的脱铝酸盐的USY沸石和实施例9中得到的SAB-4溶液混合，向该混合物中，顺序添加实施例9中得到的SDL-4溶液、定量1-乙基-1-甲基-2,2,6,6-六甲基哌啶鎓水溶液(浓度：20wt％)、去离子水和NaOH颗粒(纯度：96wt％)，该反应混合物然后在室温下密闭容器中200rpm速度下搅拌，直至所有原料混合均匀，有以下摩尔组成的混合溶胶摩尔比为：
Na2O：SiO2：Al2O3：OSDA：H2O＝0.26：1.0：0.02778：0.15：15.0；将所得固体混合物移至2000ml水热晶化釜中，并在60rpm速度下搅拌，升温到135℃晶化24小时，然后继续升温到170℃晶化96小时；
(2)待晶化完全后，产物迅速冷却，经过抽滤分离、洗涤得到滤液和固体物质，收集该产物的滤液，以常规电渗析的方式(如图1b所示)分离有机模板剂碱性溶液(记为SDL-5)和原硅酸的溶液(SAB-5)，作为原料参与下一批AEI分子筛的合成；
固体物质110℃下烘干24小时和540℃下焙烧4个小时，并且通过XRD确认为AEI型分子筛，即AEI分子筛原粉；该AEI分子筛显示它的SAR是33.8，记为J，分子筛合成前驱物溶胶的配比、合成条件、相对结晶度和收率参数如表3和4所示。
表3实施例1-10中合成前驱物溶胶的配比、合成条件及产品硅铝比
Figure PCTCN2017106026-appb-000003
对比例1-5 AEI型沸石分子筛的制备
按照专利CN104591204A实施例中方法使用N,N-二甲基-3,5-二甲基哌啶鎓为有机模板剂在再循环母液中合成AEI沸石
将36g二氧化硅与二氧化铝摩尔硅铝比SAR为10.7的USY沸石与1093g的水混合。对于该混合物，在搅拌下将195g的N,N-二甲基-3,5-二甲基哌啶鎓模板剂和427g的硅酸钠溶液(28.8wt％的SiO2)缓慢倾倒入上述混合物中。所形成的混合物密封反应器中，200rpm搅拌下加热到145℃，晶化反应2天后将所形成的结晶混合物转移到分液漏斗。在静态条件下，将固体沉降物和顶部的透明液体层在几个小时内分离。收集大部分的透明母液，称作第一道母液(记为：ML-P1)，回收底部浆料中的固体，并且通过XRD确认为AEI，记为VS1。
将38g的SAR为30的脱铝酸盐的USY沸石和21g的SAR为10.7的USY沸石与1582g的ML-Pl混合。向该混合物中，顺序添加45g的N,N-二甲基-3,5-二甲基哌啶鎓模板剂和31g的水。在搅拌下，将34g的硅酸钠液体(28.8wt％的SiO2)缓慢倾倒入上述混合物中。该反应混合物然后在不锈钢反应器中在200rpm搅拌下加热到约145℃。晶化反应20～35小时后，除去所形成的固体和用XRD证实为AEI沸石，记为VS2。收集该母液，并且称作 第二道母液(记为：ML-P2)。
ML-P2以类似的方式来产生ML-P3，所产生的AEI沸石记为VS3，并且依次地使用ML-P3来产生ML-P4，所产生的AEI沸石记为VS4，和使用ML-P4来产生ML-P5，所产生的AEI沸石记为VS5。分子筛合成所用回收液体、相对结晶度和收率参数如表4所示。
表4实施例1-10及对比例1-5分子筛所用回收液体和收率
Figure PCTCN2017106026-appb-000004
上表结果显示，N,N-二甲基-3,5-二甲基哌啶鎓模板剂和1-乙基-1-甲基-2,2,6,6-六甲基哌啶鎓模板剂可以通过电渗析水解的方法多次回收提取有机模板剂碱液得到重复利用，另外，滤液中的硅酸盐溶液也可以用电渗析的方法进行分离回收作为AEI分子筛合成原料使用，来提高按二氧化硅计的总相对产率和按模板剂计的总相对产率。可以改变晶化前驱物凝胶组成和工艺参数来获得具有不同性能例如不同硅铝比(SAR)值的AEI分子筛晶体。
以实施例1中得到的AEI分子筛结晶度定义为100％，即直接采用原始有机模板剂和FAU硅铝分子筛原料进行水热晶化得到的AEI分子筛结晶度为100％(没有回收有机模板剂和硅物种)，相对于上述AEI分子筛100％的 结晶度，计算本发明的实施例2～10和对比例1～5得到的AEI分子筛相对结晶度，计算后得到本发明的实施例中制备的AEI分子筛相对结晶度处于95％～105％范围内，对比例1～5中样品的相对结晶度处于56％～89％的范围内，显然，实施例1～10得到样品相对结晶度都明显高于对比例1～5中样品的相对结晶度。另外，本发明实施例1～10得到的分子筛反应中按模板剂计的总相对产率处于30％～95％范围内，而对比例1～5得到的分子筛按模板剂计的总相对产率为20％～75％，也就是说最高可以达到95％远远高于对比例的总相对产率；本发明实施例1～10得到的分子筛反应中按二氧化硅计的总相对产率处于39％～97％范围内，而对比例1～5得到的分子筛按模板剂计的总相对产率为32％～87％，也就是说最高可以达到97％远远高于对比例的总相对产率；此外，从图3和图6中可以看出，对比例5得到的分子筛样品会出现杂晶峰，这说明用对比例中母液回用的方法投料稳定性差，难以得到高纯的AEI分子筛晶粒。从附图中扫描电镜SEM图可以分析出，实施例得到的AEI分子筛样品具有良好的分散性和较为规整的分子筛晶体形貌，而对比例中得到的AEI分子筛样品晶粒团聚比较明显，晶粒分散性较差。
实施例11-23
将实施例1-8和对比例1-5合成的10.0g AEI分子筛原粉加入到100.0g浓度为0.3mol/L的Cu(NO3)2·3H2O水溶液中，搅拌均匀1小时后置入耐热容器中，并一起放入带有减压阀的干燥器内；用真空泵将干燥器内的压强抽到10Torr以下后，室温进行1小时的脱气处理，然后升温到90℃条件干燥12小时，将干燥后的样品在正常大气压强下500℃温度焙烧4小时；得到所述的铜改性AEI分子筛，根据ICP分析结果制备的催化剂中，铜(II)离子占分子筛催化剂总重量的如表5所示。
SCR催化剂测试：
实施例1-8合成的AEI分子筛制备的10～20目A1～H1、对比例1-5合成的AEI分子筛制备10～20目VS1～VS5催化剂颗粒，装在反应器
Figure PCTCN2017106026-appb-000005
中，包含500ppmNO、500ppm NH3、10体积％O2、5体积％蒸汽和Ar为平衡气的混合 气流160mL/min，先通过预热器(设定为100℃)，然后进入SCR反应器。在150～650℃的反应温度和基于48000h-1体积气时空速下对试样进行测试。所述温度通过位于试样位置处的内热电偶监测。
将使用过的上述实施例和对比例中各新鲜SCR催化剂进行水热耐久处理得到陈化的SCR催化剂，水热耐久处理试验的条件为：
空间速度SV：30000/h，温度：800℃，时间：16小时，水分浓度：10％，氧浓度：10％，氮浓度：平衡。
按照上述参数进行水热陈化处理后，继续作为SCR催化剂用于NOx催化还原反应评价测试：
NO转化率或“脱NOx”活性在稳态条件下通过使用Bruker EQUINOX 55型FT-IR光谱仪测量出口处的NOx、NH3和N2O浓度而确定。
Figure PCTCN2017106026-appb-000006
采用上述SCR催化剂活性实验室评价装置，对实施例和对比例制备得到的负载Cu的SCR催化剂进行NOx的选择性催化还原性能评价，结果如表5所示。
表5实施例11-23中铜改性的AEI分子筛的含铜量及进行选择性催化还原性能评价
Figure PCTCN2017106026-appb-000007
从上表可以看出，实施例11～18得到的Cu-AEI分子筛催化剂具有较好的低温起燃性和高温活性。在150～650℃的范围内，实施例11～18中SCR处于新鲜剂情况下，NOX的转化率处于41.8％～99.6％的范围内，SCR处于陈化状态下，NOX的转化率处于36.2％～98.8％范围内，说明SCR不论处于“新鲜”状态还是“陈化”状态，其活性明显优于由对比例中1～5得到催化剂VS1～VS5的催化剂试样。因此，由实施例11～18获得的结果清楚地显示出本发明的Cu-AEI分子筛催化剂材料和用其获得的催化剂具有改善的SCR催化活性，尤其是在例如柴油机车应用中处理NOx时的冷启动条件所特有的低转化温度下。就其他SCR应用而言，本发明的Cu-AEI分子筛催化剂材料允许在更低温度下具有更高的转化率，因此允许更高的效率以及因此在相当的转化率下，允许高能量效率地处理含NOx的废气，例如来自工业生产的废气。
以上所述，仅是本发明实施的较佳实施例，并非对本发明做任何形式上的限制，凡在本发明的精神和原则之内所做的修改、等同替换和改进等，均需要包含在本发明的保护范围之内。

Claims (26)

  1. 一种AEI结构分子筛的制备方法，其包含下述步骤：
    (1)将含有有机模板剂、FAU型硅铝分子筛、碱液和水的原料在水热晶化条件下反应，其中，FAU型硅铝分子筛提供硅源和铝源；
    (2)将步骤(1)得到的产物过滤，滤液进行电渗析电解，回收有机模板剂和硅的物种作为下一批AEI分子筛的合成原料。
  2. 根据权利要求1所述的制备方法，其中，在步骤(1)中，所述有机模板剂为单环或多环哌啶鎓类化合物，所述哌啶鎓化合物选自于N,N-二甲基-3,5-二甲基哌啶鎓、N,N-二甲基-2,6-二甲基哌啶鎓、1,1,2,2,6,6-六甲基哌啶鎓、1,1,2,2,6,6-六甲基-4-氧代哌啶鎓、1,1,3,5-四甲基-4-氧代哌啶鎓、1-羟基-1,1,2,2,6,6-六甲基哌啶鎓、1,1-二甲基-4,4-二丙氧基哌啶鎓、3,5-二甲氧基-1,1-二甲基哌啶鎓、3,5-二羟基-1,1-二甲基哌啶鎓、4-乙基-1,1-二甲基-3,5-二氧代哌啶鎓、1-乙基-1-甲基-2,2,6,6-六甲基哌啶鎓、1-环氧丙基-1-甲基-2,2,6,6-六甲基哌啶鎓、N,N-二甲基-2-(2-羟乙基)哌啶鎓和N,N-二甲基-2-乙基哌啶鎓中一种或两种以上。
  3. 根据权利要求1或2所述的制备方法，其中，在步骤(1)中，所述FAU型硅铝分子筛选自于Y沸石和X沸石中的一种；优选所述Y沸石选自于HY沸石、USY沸石和NaY沸石中的一种,所述X沸石选自于NaX沸石、KX沸石和HX沸石中的一种。
  4. 根据权利要求1-3任一项所述的制备方法，其中，在步骤(1)中，所述水热晶化分为两段：(1)第一段晶化温度为120～150℃，优选为130～150℃；(2)第二段晶化温度为150～200℃，优选为160～190℃。
  5. 根据权利要求4所述的制备方法，其中，在步骤(1)中，所述水热晶化分为两段：(1)第一段晶化时间为0.5～3.0天，优选为0.5～2.0天；(2)第二段晶化时间为0.5～6.0天，优选为1.0～5.0天。
  6. 根据权利要求1-5任一项所述的制备方法，其中，在步骤(1)中，加入额外硅源为原料，所述额外硅源选自于白炭黑、大孔硅胶、粗孔硅胶、细孔硅胶、薄层层析硅胶、B型硅胶、偏硅酸钠、硅溶胶、水玻璃、烷基硅酸酯和硅藻土中一种或两种以上。
  7. 根据权利要求1-6任一项所述的制备方法，其中，在步骤(1)中，所述碱液选自于NaOH、Na2O、Na2O2和KOH中的一种或两种以上。
  8. 根据权利要求1-7任一项所述的制备方法，其中，在步骤(1)中，所述硅源、铝源、碱液、模板剂和水的摩尔比为1.0:0.00833～0.1667:0.1～0.5：0.05～0.5：10～50，优选为1.0:0.0121～0.0417：0.22～0.36:0.08～0.20：15～25。
  9. 根据权利要求1-8任一项所述的制备方法，其中，在步骤(2)中，所述电渗析选自于四室三膜、三室两膜或两室一膜中的一种。
  10. 根据权利要求1-9任一项所述的制备方法，其中，在步骤(2)中，所述双极膜是通过阳离子交换层、界面亲水层和阴离子交换层复合得到。
  11. 一种AEI结构分子筛，其通过权利要求1-10任一项所述方法制备得到。
  12. 根据权利要求11所述的AEI结构分子筛，其中，所述AEI结构分子筛中的二氧化硅和氧化铝的分子摩尔比为5～100，优选为10～80。
  13. 一种NOX选择性催化还原催化剂，其是将权利要求1-10任一项所述的方法制备得到的AEI结构分子筛或权利要求11或12所述的AEI结构分子筛与金属盐溶液进行离子交换而得到。
  14. 根据权利要求13所述的选择性催化还原催化剂，其中，所述金属盐选自于铜、铁、钴、钨、镍、锌、钼、钒、锡、钛、锆、锰、铬、铌、铋、锑、钌、锗、钯、铟、铂、金或银的可溶性盐中一种或两种以上。
  15. 根据权利要求14所述的选择性催化还原催化剂，其中，所述金属盐选自于铜盐或铁盐，优选为铜盐。
  16. 根据权利要求15所述的选择性催化还原催化剂，其中，所述铜盐选自于硝酸铜、氯化铜、醋酸铜和硫酸铜中一种或两种以上，所述铜盐中铜离子的浓度为0.1～1.5mol/L。
  17. 一种权利要求13-16任一项所述的选择性催化还原催化剂的制备方法，其是将权利要求1-10任一项所述的方法制备得到的AEI结构分子筛或权利要求11或12所述的AEI结构分子筛加入到金属盐溶液中，得到NOX选择性催化还原催化剂。
  18. 根据权利要求17所述的制备方法，还包含下述步骤：将所得到的 NOX选择性催化还原催化剂使用粘结剂附着在多孔规整材料上。
  19. 根据权利要求18所述的制备方法，其中，所述粘结剂选自于硅溶胶、水玻璃、拟薄水铝石和铝溶胶中一种或两种以上。
  20. 根据权利要求18或19所述的制备方法，其中，所述多孔规整材料选自于蜂窝形、板式形和波纹形中的一种。
  21. 根据权利要求18-20任一项所述的制备方法，其中，所述多孔规整材料选自于堇青石、α-矾土、碳化硅、钛酸铝、氮化硅、氧化锆、莫来石、锂辉石、氧化铝-二氧化硅-氧化镁、硅酸锆或金属薄片中的一种，优选为堇青石。
  22. 一种权利要求13-16任一项所述的选择性催化还原催化剂或权利要求17-21任一项所述的方法制备得到的选择性催化还原催化剂，其在净化废气流中的应用，优选在净化汽车废气流中的应用。
  23. 根据权利要求22所述的应用，所述废气流为机动车排放的废气流，优选为稀燃发动机的废气流，更优选为柴油机废气流。
  24. 一种废气流的净化处理方法，其将权利要求13-16任一项所述的选择性催化还原催化剂或权利要求17-21任一项所述的方法制备得到的选择性催化还原催化剂与包含NOX和还原剂的汽车废气流相接触，使NOX选择性地还原成N2和H2O。
  25. 根据权利要求24所述的净化处理方法，其中，所述废气流在与选择性催化还原催化剂接触之前，以NOX计量为100重量％，所述NO2含量≤80重量％，优选为5～70重量％，更优选为10～60重量％，更优选为15～55重量％，更优选为20～50重量％。
  26. 权利要求13-16任一项所述的选择性催化还原催化剂或权利要求17-21任一项所述的方法制备得到的选择性催化还原催化剂，所述选择性催化还原催化剂为氮氧化物选择性催化还原剂或脱硝催化剂。
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