CN109384246A - A kind of AEI structure molecular screen and its preparation method and application - Google Patents

A kind of AEI structure molecular screen and its preparation method and application Download PDF

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CN109384246A
CN109384246A CN201710681346.6A CN201710681346A CN109384246A CN 109384246 A CN109384246 A CN 109384246A CN 201710681346 A CN201710681346 A CN 201710681346A CN 109384246 A CN109384246 A CN 109384246A
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aei
preparation
molecular sieve
zeolite
catalytic reduction
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CN109384246B (en
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李进
王志光
王炳春
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Dalian Heterogeneous Catalyst Co Ltd
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Dalian Heterogeneous Catalyst Co Ltd
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Priority to PCT/CN2017/106026 priority patent/WO2019028999A1/en
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Abstract

The present invention relates to inorganic porous materials to synthesize field, and in particular to a kind of AEI structure molecular screen and its preparation method and application.The present invention provides a kind of preparation methods of AEI structure molecular screen, it includes following step: (1) reacting the raw material containing organic formwork agent, FAU type Si-Al molecular sieve, lye and water under the conditions of hydrothermal crystallizing, wherein, FAU type Si-Al molecular sieve provides silicon source and silicon source；(2) product for obtaining step (1) filters, and filtrate carries out Wastewater treatment, recycles synthesis material of the species of organic formwork agent and silicon as next group AEI molecular sieve.The method that filtrate provided by the invention recycles, amorphous substance, degradation material is effectively avoided to be mixed into during next group feeds intake, reduce AEI molecular sieve to feed intake error, the AEI molecular sieve made has good dispersibility and relatively high crystallinity, improves the overall yield of AEI Zeolite synthesis.

Description

A kind of AEI structure molecular screen and its preparation method and application
Technical field
The present invention relates to inorganic porous materials to synthesize field, and in particular to a kind of AEI structure molecular screen and preparation method thereof And application.
Background technique
AEI structure molecular screen has the 3 D pore canal system of big cage, can constitute three-dimensional open-framework, hole by 8 member rings Diameter sizeSeemingly, cage size can reach comprising diameter for its basket structure and CHA molecular sieveSphere.Difference Adjacent double hexatomic rings of CHA structure are spatially in parallel junction in the two neighboring double six-membered ring structures connected with four-membered ring Structure, and two adjacent double hexatomic rings are symmetrical in mirror surface in AEI structure.Such structure difference leads to eight yuan in AEI structure Annular distance road has lesser aperture, and catalytic activity is higher, and anti-carbon performance is more excellent.AEI Si-Al molecular sieve and sial phosphorus molecule Sieve structure is respectively specifically using SSZ-39 and SAPO-18 as representative.The AEI molecular sieve of ion exchange or carried metal active component is urged Agent shows unique selective reduction (SCR) activity, has good reduction treatment performance to nitrogen oxides (NOx), Caused extensive concern.
Nitrogen oxides (NOx) can cause a series of environmental problems such as photochemical fog, acid rain and greenhouse effects, seriously endanger The health of victimization class, and the rapid development of increase and the industry with vehicles number, NOx discharge is increasing, will Cause the severe exacerbation of ecology and environment.Thus, it is very urgent to eliminate NOx pollution problem.Currently, the leading control technology of NOx is NH3 selective catalytic reduction (NH3- SCR), key is the catalyst that selection is had excellent performance, this will determine entire catalysis reaction The success or failure of system.
Usual SCR catalyst is usually to have crystal structure using zeolite as what carrier, load SCR activity component were prepared Molecular sieve；Zeolite is the silicon aluminate crystal material with quite regular pore size, such as β zeolite, Y zeolite, X boiling Stone, faujasite, modenite, erionite, ZSM-5, ZSM-8, ZSM-11, ZSM-12 zeolite etc., these zeolites can with Cu, The metal exchanges or zeolite itself such as Fe, Mn, Ag, V, Ti, Co contain the metals such as some Cu, Fe.But it is above-mentioned known Metal-modified zeolite catalyst can only be in relatively narrow temperature region model during ammine selectivity catalytic reduction nitrous oxides The interior purification for carrying out nitrogen oxides is enclosed, does not all have the NOx purifying property of high activity at 200 DEG C or less, hydrothermal stability is poor, low Activity is lower under the conditions of temperature.
Synthesis AEI molecular sieve is produced using Organic structure directing agent (OSDA), also referred to as " template " or " template Agent ".In general, OSDA acts as mold, molecular sieve crystal is formed around it.After Crystallization, by OSDA out of this crystal It is removed in portion's structure, leaves the porous molecular screen cage of molecule.
In conventional synthesis process, solid molecular sieves crystal is precipitated out from reaction mixture, and the reaction precursor is mixed Close object silicon source, silicon source, alkali source and organic formwork agent.Synthesis usually requires the long period to realize desired crystallization of molecular sieves.When After the completion of crystallization of molecular sieves, molecular sieve solid product usually is recycled with filter method, and discharge extra filtrate.The filter of the discharge It include not used organic formwork agent (OSDA) often to be degraded due to harsh reaction condition in liquid.
Patent CN104591204A increases silica and/or OSDA by the Recycling Mother Solution after AEI Zeolite synthesis The yield of meter, but mother liquor direct circulation can not remove due to degradation product a small amount of in mother liquor and uncrystallized unformed product, hold Easily cause unstable product quality, thus not can effectively solve due to yield it is low caused by high cost and environmental pollution the problem of.
Summary of the invention
For this purpose, it includes following step the present invention provides a kind of preparation method of AEI structure molecular screen:
(1) raw material containing organic formwork agent, FAU type Si-Al molecular sieve, lye and water is anti-under the conditions of hydrothermal crystallizing It answers, wherein FAU type Si-Al molecular sieve provides silicon source and silicon source；
(2) product for obtaining step (1) filters, and filtrate carries out Wastewater treatment, recycles the object of organic formwork agent and silicon Synthesis material of the kind as next group AEI molecular sieve.
The present invention provides a kind of AEI structure molecular screens, are made by the inclusion of the method for following step:
(1) raw material containing organic formwork agent, FAU type Si-Al molecular sieve, lye and water is anti-under the conditions of hydrothermal crystallizing It answers, wherein FAU type Si-Al molecular sieve provides silicon source and silicon source；
(2) product for obtaining step (1) filters, and filtrate carries out Wastewater treatment, recycles the object of organic formwork agent and silicon Synthesis material of the kind as next group AEI molecular sieve.
The present invention provides a kind of NOXSelective catalytic reduction catalysts are that AEI structure molecular screen and metal salt is molten Liquid ion exchange and obtain.
The present invention also provides a kind of NOXThe preparation method of selective catalytic reduction catalysts is by AEI structural molecule Sieve is added in metal salt solution, obtains NOXSelective catalytic reduction catalysts.
Specifically, the invention proposes following technical solutions.
One aspect of the present invention provides a kind of preparation method of AEI structure molecular screen, and it includes following step:
(1) raw material containing organic formwork agent, FAU type Si-Al molecular sieve, lye and water is anti-under the conditions of hydrothermal crystallizing It answers, wherein FAU type Si-Al molecular sieve provides silicon source and silicon source；
(2) product for obtaining step (1) filters, and filtrate carries out Wastewater treatment, recycles the object of organic formwork agent and silicon Synthesis material of the kind as next group AEI molecular sieve.
Preferably, for the preparation method, wherein in step (1), the organic formwork agent is monocycle or polycyclic Piperidines, the piperidine compounds are selected from N, N- dimethyl -3,5- lupetidine, N, N- dimethyl - Lupetidine, 1,1,2,2,6,6- pregnancy phenylpiperidines, 1,1,2,2,6,6- hexamethyl -4- oxo-piperidine, 1, 1,3,5- tetramethyl -4- oxo-piperidine, 1- hydroxyl -1,1,2,2,6,6- pregnancy phenylpiperidines, 1,1- dimethyl -4,4- dipropyl Oxygroup piperidines, 3,5- dimethoxy -1,1- lupetidine, 3,5- dihydroxy -1,1- lupetidine, 4- ethyl - 1,1- dimethyl -3,5- dioxopiperidine, 1- ethyl -1- methyl -2,2,6,6- pregnancy phenylpiperidines, 1- glycidyl -1- Methyl -2,2,6,6- pregnancy phenylpiperidines, N, N- dimethyl -2- (2- ethoxy) piperidines and N, N- dimethyl -2- ethyl piperazine It is one or more kinds of in pyridine.
Preferably, for the preparation method, wherein in step (1), the FAU type Si-Al molecular sieve is selected from Y One of zeolite and X zeolite；Preferably, the Y zeolite is selected from one of HY zeolite, USY zeolite and NaY zeolite, institute X zeolite is stated selected from one of NaX zeolite, KX zeolite and HX zeolite.
Preferably, for the preparation method, wherein in step (1), the hydrothermal crystallizing is divided into two sections: (1) One section of crystallization temperature is 120~150 DEG C, preferably 130~150 DEG C；(2) second segment crystallization temperature is 150~200 DEG C, preferably It is 160~190 DEG C.
Preferably, for the preparation method, wherein in step (1), the hydrothermal crystallizing is divided into two sections: (1) One section of crystallization time is 0.5~3.0 day, preferably 0.5~2.0 day；(2) second segment crystallization time is 0.5~6.0 day, preferably It is 1.0~5.0 days.
Preferably, for the preparation method, wherein in step (1), it is raw material, the volume that additional silicon source, which is added, Outer silicon source selected from white carbon black, macro porous silica gel, silochrom, Kiselgel A, tlc silica gel, Type B silica gel, sodium metasilicate, It is one or more kinds of in silica solution, waterglass, alkyl silicate and diatomite.
Preferably, for the preparation method, wherein in step (1), the lye is selected from NaOH, Na2O、 Na2O2One or more of with KOH.
Preferably, for the preparation method, wherein in step (1), the silicon source, silicon source, lye, template Molar ratio with water is 1.0:0.00833~0.1667:0.1~0.5:0.05~0.5:10~50, preferably 1.0:0.0121 ~0.0417:0.22~0.36:0.08~0.20:15~25.
Preferably, for the preparation method, wherein in step (2), the electrodialysis selected from four Room, three film, One of one film of three Room, two film or two Room.
Preferably, for the preparation method, wherein in step (2), the Bipolar Membrane is exchanged by cation Layer, interface hydrophilic layer and anion exchange layer is compound obtains.
It the present invention provides a kind of AEI structure molecular screen, is prepared by method described in any of the above embodiments.
Preferably, for the AEI structure molecular screen, wherein silica and oxygen in the AEI structure molecular screen The molecule molar ratio for changing aluminium is 5~100, preferably 10~80.
The present invention provides a kind of NOXSelective catalytic reduction catalysts are that AEI structure molecular screen and metal salt is molten Liquid carries out ion exchange and obtains.
Preferably, for the NOXSelective catalytic reduction catalysts, wherein the metal salt selected from copper, iron, Cobalt, tungsten, nickel, zinc, molybdenum, vanadium, tin, titanium, zirconium, manganese, chromium, niobium, bismuth, antimony, ruthenium, germanium, palladium, indium, platinum, gold or silver soluble-salt in one Kind is two or more.
Preferably, for the NOXSelective catalytic reduction catalysts, wherein the metal salt selected from mantoquita or Molysite, preferably mantoquita.
Preferably, for the NOXSelective catalytic reduction catalysts, wherein the mantoquita is selected from copper nitrate, chlorine Change one or more in copper, copper acetate and copper sulphate, the concentration of copper ion is 0.1~1.5mol/L in the mantoquita.
It is to add AEI structure molecular screen the present invention provides a kind of preparation method of selective catalytic reduction catalysts Enter into metal salt solution, obtains NOXSelective catalytic reduction catalysts.
It preferably, also include following step: by obtained NO for the preparation methodXSelective catalytic reduction Catalyst is attached on porous regular material using binder.
Preferably, for the preparation method, wherein the binder is selected from silica solution, waterglass, intends thin water aluminium It is one or more kinds of in stone and Aluminum sol.
Preferably, for the preparation method, wherein the porous regular material selected from honeycombed, board-like shape and It is one of corrugated.
Preferably, for the preparation method, wherein the porous regular material is selected from cordierite, alph-alumine, carbon SiClx, aluminium titanates, silicon nitride, zirconium oxide, mullite, spodumene, alumina-silica magnesia, zirconium silicate or metal foil One of piece, preferably cordierite.
A kind of selective catalytic reduction catalysts, in its application in purification waste gas stream, preferably in purification automobile waste Application in air-flow.
Preferably, for the application, wherein the waste gas stream is the waste gas stream of vehicular emission, preferably lean-burn The waste gas stream of engine, more preferably diesel exhaust stream.
The present invention provides a kind of purifying treatment method of waste gas stream, be by selective catalytic reduction catalysts with comprising NOXIt is in contact with the automobile waste air-flow of reducing agent, makes NOXSelectively it is reduced into N2And H2O。
Preferably, for the purifying treatment method, wherein the waste gas stream with selective catalytic reduction catalysts Before contact, with NOXMeasuring is 100 weight %, the NO2 content≤80 weight %, preferably 5~70 weight %, more preferably For 10~60 weight %, more preferably 15~55 weight %, more preferably 20~50 weight %.
Selective catalytic reduction catalysts provided by the present invention are that nitrous oxides selectivity catalytic reducer or denitration are urged Agent.
Beneficial effect obtained by the present invention is: the organic formwork agent and silicon species provided by the invention in reaction filtrate The method of separation and recovery effectively avoids amorphous substance, degradation material from being mixed into during next group feeds intake, reduces the throwing of AEI molecular sieve Expect error, the AEI molecular sieve made has good dispersibility and relatively high crystallinity.Original have compared to directlying adopt Machine template and FAU Si-Al molecular sieve raw material carry out the crystallinity for the AEI molecular sieve 100% that hydrothermal crystallizing obtains, the present invention couple Filtrate after reaction has separated the AEI molecular sieve that organic formwork agent and silicon species are prepared, and relative crystallinity is in 95% In~105% range, and obtained by the filtrate after reaction directly is used to react by the prior art directly as supplement synthesis material Its relative crystallinity of molecular sieve be in the range of 56%~89%, it is clear that AEI molecular sieve that the present invention obtains is opposite to be crystallized Degree is all apparently higher than the relative crystallinity for the AEI molecular sieve that the prior art obtains, and the present invention improves AEI Zeolite synthesis Overall efficiency, and greatly improve yield, total relative productivity of the present invention based on silica reaches as high as 97%, much Higher than total relative productivity in the prior art.
Detailed description of the invention
Filtrate after Fig. 1 a:AEI Zeolite synthesis is electrolysed schematic diagram by Bipolar Membrane；
Filtrate after Fig. 1 b:AEI Zeolite synthesis passes through conventional electrodialysis schematic diagram；
Fig. 2: the XRD diagram of AEI molecular screen primary powder obtained in embodiment 1；
Fig. 3: the XRD diagram of AEI molecular screen primary powder obtained in embodiment 5；
Fig. 4: the XRD diagram of AEI molecular screen primary powder obtained in comparative example 1；
Fig. 5: the XRD diagram of AEI molecular screen primary powder obtained in comparative example 3；
Fig. 6: the XRD diagram of AEI molecular screen primary powder obtained in comparative example 5；
Fig. 7: the SEM figure of AEI molecular screen primary powder obtained in embodiment 1；
Fig. 8: the SEM figure of AEI molecular screen primary powder obtained in embodiment 5；
Fig. 9: the SEM figure of AEI molecular screen primary powder obtained in comparative example 1；
Figure 10: the SEM figure of AEI molecular screen primary powder obtained in comparative example 3；
Figure 11: the SEM figure of AEI molecular screen primary powder obtained in comparative example 5.
Specific embodiment
Term " AEI " refers to the AEI type skeleton approved by (IZA) the structure committee, International Zeolite Association.
As described above, it includes following step the present invention provides a kind of preparation method of AEI structure molecular screen:
(1) raw material containing organic formwork agent, FAU type Si-Al molecular sieve, lye and water is anti-under the conditions of hydrothermal crystallizing It answers, wherein FAU type Si-Al molecular sieve provides silicon source and silicon source；
(2) product for obtaining step (1) filters, and filtrate carries out Wastewater treatment, recycles the object of organic formwork agent and silicon Synthesis material of the kind as next group AEI molecular sieve.
In a kind of preferred embodiment of the present invention, be by silicon source, silicon source, alkali source, template and water by mole Than being mixed for 1.0:0.00833~0.1667:0.1~0.5:0.05~0.5:10~50, under the conditions of hydrothermal crystallizing into Row reaction, the hydrothermal crystallizing are divided into two sections: (1) first segment crystallization temperature is 120~150 DEG C, and crystallization time is 0.5~3.0 It；(2) second segment crystallization temperature is 150~200 DEG C, and crystallization time is 0.5~6.0 day, then will react obtained product It is filtered, filtrate carries out Wastewater treatment, the silicon source for recycling organic formwork agent and not reacting completely, for synthesis AEI in next step Molecular sieve provides raw material.Wherein, the electrodialysis is selected from bipolar membrane electrodialysis or well known to a person skilled in the art electrodialysis.
Wherein, the filtrate is recycled using Bipolar Membrane, and Bipolar Membrane is a kind of novel ion-exchange composite membranes, it is logical It is often combined by cation exchange layer (N-type film), interface hydrophilic layer (Catalytic Layer) and anion exchange layer (p-type film), is true Reaction film in positive meaning.Under DC electric field effect, hydrolytic dissociation can be respectively obtained hydrogen ion and hydrogen in film two sides by Bipolar Membrane Oxygen radical ion.Using this feature, the bipolar membrane electrodialysis system that Bipolar Membrane and other anion and cation exchange membranes are combined into, energy Enough to convert corresponding bronsted lowry acids and bases bronsted lowry for the salt in aqueous solution in the case where not being introduced into new component, this method is known as Bipolar Membrane electricity Dialysis.
The present invention chooses ABS plastic and solution slot is made, and in slot after several equal parts, installs DSA anode electricity respectively in electrolytic cell Pole, graphite cathode electrode.Between anode electrolytic cell and cathode, be provided with previously prepared spare anion-exchange membrane, sun from Proton exchange and Bipolar Membrane.
In a kind of currently preferred specific embodiment, the silicon source is with SiO2Meter, source of aluminium is with Al2O3Meter, The lye is with Na2O meter, the organic formwork agent is in terms of OSDA.
In one embodiment of the invention, the present invention provides a kind of NOXSelective catalytic reduction catalysts are AEI structure molecular screen is subjected to ion exchange with metal salt solution and is obtained.
It is that AEI structure molecular screen and soluble metallic salt is molten in a kind of preferred embodiment of the present invention Liquid carries out ion exchange and obtains, and the metal salt solution is preferably mantoquita or molysite, more preferably mantoquita, described in the mantoquita Mantoquita is one or more kinds of in copper nitrate, copper chloride, copper acetate and copper sulphate, the concentration of copper ion in the mantoquita For 0.1~1.5mol/L.
In a kind of preferred embodiment of the present invention, after AEI structure molecular screen and mantoquita are carried out ion exchange, The modified AEI structure molecular screen of copper is obtained, is then attached to the modified AEI structure molecular screen of copper using binder porous regular On material, the porous regular material with catalyst, which is placed in exhaust gas treating device, forms motor-driven vehicle treatment apparatus progress exhaust gas The processing of stream.
The binder is one or more kinds of in silica solution, waterglass, boehmite and Aluminum sol.
The porous regular material is selected from honeycombed, board-like shape or corrugated material, and the material is selected from cordierite, α- Alumina, silicon carbide, aluminium titanates, silicon nitride, zirconium oxide, mullite, spodumene, alumina-silica magnesia, zirconium silicate Or sheet metal；It is preferred that the honeycomb of porous cordierite flows through type monolith carrier, bearing capacity is 170~270g/L.
It is that will wrap the present invention provides a kind of purifying treatment method of waste gas stream in a kind of specific embodiment Containing NOXIt is in contact with the waste gas stream of reducing agent with SCR catalyst composition, by the NOXAt least part is selectively reduced into N2And H2O。
The nitrogenous reducing agent is selected from ammonia, hydrazine or any suitable ammonia precursor, and any suitable ammonia precursor is selected from In one or more of urea, ammonium carbonate, aminoquinoxaline, ammonium hydrogen carbonate or ammonium formate.
In a kind of preferred embodiment of the present invention, catalyst shown in the present invention is shown in much broader temperature NO is obtained in windowXConversion ratio.About 150~650 DEG C of temperature range for improving conversion ratio, preferably 200~650 DEG C, more preferable 200 It~550 DEG C, in these temperature ranges, is exposed to after reducing atmosphere, or even is exposed to reducing atmosphere and high temperature and (such as is up to 850 DEG C) after transformation efficiency may be greater than 55% to 100%, more preferably greater than 90% transformation efficiency, even more preferably Transformation efficiency greater than 95%.
Reactant that " relative productivity " of the invention indicates to be mixed into desired product (or derivatives thereof) amount account for The relative productivity of the ratio of the reaction-ure mixture introduced in the chemical method, reactant can be calculated with following formula: (opposite Yield)R=(RP)/(RT), wherein R is reactant, RPBe be mixed into desired product reactant R (or derivatives thereof) Total weight, RTIt is the total weight of the reactant R introduced in the chemical method.Term " total relative productivity " is indicated for chemistry The whole relative productivity of method.It is raw that " total relative productivity based on silica " expression is mixed into one or more sequential batch Total amount of the total amount of silica in the zeolite total amount of production relative to the silica being generally introduced into this method." press mould The organic formwork agent directly used in the composition zeolite skeleton of the one or more sequential batch of total relative productivity of plate agent meter " expression Amount of the amount relative to the silica being generally introduced into this method.
The equipment and analysis that manufacturer to raw material used in the present embodiment and equipment and product analysis below uses Method is described as follows, wherein the chemical substance do not indicate be conventional reagent the pure rank of chemistry.Wherein, real The information of the information and experimental facilities of applying raw material used in example is as shown in Table 1 and Table 2.
The information of raw material used in 1 present invention of table
Title Purity Manufacturer
HY zeolite 100% Shandong Duo You Science and Technology Ltd.
NaOH particle 96% Tianjin continent chemical reagent factory
USY zeolite 100% BASF AG
X zeolite 100% Tianjin Nan Hua catalyst Co., Ltd
NaY zeolite 100% Shandong Duo You Science and Technology Ltd.
The information of experimental facilities used in 2 present invention of table
Equipment Model Producer
Scanning electron microscope TM3030 Hitachi
Icp analysis instrument ICPE-9000 Japanese Shimadzu
X-ray diffractometer X’PertPRO Dutch Panaco company
The preparation of 1 AEI type zeolite molecular sieve of embodiment
(1) USY zeolite for the de-aluminate for being 28.7 by mole silica alumina ratio (SAR) of quantitative silica and aluminium oxide It is added to organic formwork agent N, in N- dimethyl -3,5- lupetidine aqueous solution (concentration: 20wt%), is sufficiently stirred, then It is added NaOH particle (purity: 96wt%), supplement is added deionized water and is sufficiently stirred, and gained mixed serum is at room temperature in sealing It is continuously stirred in container 2 hours, until all raw materials are uniformly mixed, the mixed sols molar ratio formed by following mole are as follows:
Na2O:SiO2: Al2O3: OSDA:H2O=0.22:1.0:0.03484:0.20:25.0；Obtained solid mixture is moved It is stirred into 2000ml hydrothermal crystallizing kettle, and under 60rpm speed, is warming up to 140 DEG C of crystallization 24 hours, then proceed to be warming up to 170 DEG C crystallization 60 hours；
(2) after crystallization is complete, product is cooled down rapidly, and by filtering separation, washing obtains filtrate and solid matter, will be returned The filtrate of receipts separates organic formwork agent and silicate by the method (as shown in Figure 1a) of bipolar membrane electrodialysis, obtains organic mould Plate agent alkaline solution (being denoted as SDK-1) and silicate solution (being denoted as SAA-1) participate in the conjunction of next group AEI molecular sieve as raw material At；
4 hours are roasted at drying 12 hours and 540 DEG C at 120 DEG C of solid matter, and AEI type is confirmed as by XRD Molecular sieve, i.e. AEI molecular screen primary powder；The AEI molecular sieve shows that its SAR is 11.2, is denoted as A, and Zeolite synthesis predecessor is molten The proportion of glue, synthesis condition, relative crystallinity and yield parameter are as shown in Tables 3 and 4.
The preparation of 2 AEI type zeolite molecular sieve of embodiment
(1) by quantitative HY zeolite (silica alumina ratio SAR is 5.3), waterglass (Na2O:7.44wt%, SiO2: 27.40wt%) It is mixed with SAA-1 solution obtained in embodiment 1, into the mixture, SDK-1 solution obtained in sequence addition embodiment 1, Quantitative N, N- dimethyl -3,5- lupetidine aqueous solution (concentration: 20wt%), deionized water and NaOH particle (purity: 96wt%), then which continuously stirs 2 hours in 200rpm speed in sealing container at room temperature, until all Raw material is uniformly mixed, the mixed sols molar ratio formed by following mole are as follows:
Na2O:SiO2: Al2O3: OSDA:H2O=0.24:1.0:0.03226:0.15:25.0；Obtained solid mixture is moved It is stirred into 2000ml hydrothermal crystallizing kettle, and under 60rpm speed, is warming up to 135 DEG C of crystallization 36 hours, then proceed to be warming up to 180 DEG C crystallization 48 hours；
(2) after crystallization is complete, product is cooled down rapidly, and by filtering separation, washing obtains filtrate and solid matter, is collected The filtrate of the product, separation organic formwork agent alkaline solution (as shown in Figure 1a) (is denoted as equally in a manner of bipolar membrane electrodialysis SDK-2) and the solution of orthosilicic acid (SAA-2), the synthesis of next group AEI molecular sieve is participated in as raw material.
4 hours are roasted at drying 12 hours and 540 DEG C at 120 DEG C of solid matter, and AEI type is confirmed as by XRD Molecular sieve, i.e. AEI molecular screen primary powder；The AEI molecular sieve shows that its SAR is 15.6, is denoted as B, and Zeolite synthesis predecessor is molten The proportion of glue, synthesis condition, relative crystallinity and yield parameter are as shown in Tables 3 and 4.
The preparation of 3 AEI type zeolite molecular sieve of embodiment
(1) USY for the de-aluminate for being 20.6 by mole silica alumina ratio (SAR) of quantitative silica and aluminium oxide boils Stone, waterglass (Na2O:7.44wt%, SiO2: 27.40wt%) and embodiment 2 obtained in SAA-2 solution mixing.To the mixing In object, sequence adds SDK-2 solution obtained in embodiment 2, quantitative N, N- dimethyl -3,5- lupetidine aqueous solution (concentration: 20wt%), deionized water and NaOH particle (purity: 96wt%), the reaction mixture and then at room temperature closed appearance It is stirred under 200rpm speed in device, until all raw materials are uniformly mixed, the mixed sols molar ratio formed by following mole are as follows:
Na2O:SiO2: Al2O3: OSDA:H2O=0.26:1.0:0.02475:0.15:25.0；Obtained solid mixture is moved It is stirred into 2000ml hydrothermal crystallizing kettle, and under 60rpm speed, is warming up to 130 DEG C of crystallization 48 hours, then proceed to be warming up to 185 DEG C crystallization 60 hours；
(2) after crystallization is complete, product is cooled down rapidly, and by filtering separation, washing obtains filtrate and solid matter, is collected The filtrate of the product, separation organic formwork agent alkaline solution (as shown in Figure 1a) (is denoted as equally in a manner of bipolar membrane electrodialysis SDK-3) and the solution of orthosilicic acid (SAA-3), the synthesis of next group AEI molecular sieve is participated in as raw material；
4 hours are roasted at drying 12 hours and 540 DEG C at 120 DEG C of solid matter, and AEI type is confirmed as by XRD Molecular sieve, i.e. AEI molecular screen primary powder；The AEI molecular sieve shows that its SAR is 29.7, is denoted as C, and Zeolite synthesis predecessor is molten The proportion of glue, synthesis condition, relative crystallinity and yield parameter are as shown in Tables 3 and 4.
The preparation of 4 AEI type zeolite molecular sieve of embodiment
(1) the X zeolite by mole silica alumina ratio (SAR) of quantitative silica and aluminium oxide for 2.74, waterglass (Na2O:7.44wt%, SiO2: 27.40wt%) and embodiment 3 obtained in SAA-3 solution mixing, into the mixture, sequence SDK-3 solution obtained in addition embodiment 3, quantitative N, N- dimethyl -3,5- lupetidine aqueous solution (concentration: 20wt%), deionized water and NaOH particle (purity: 96wt%), the reaction mixture is then at room temperature in closed container It is stirred under 200rpm speed, until all raw materials are uniformly mixed, the mixed sols molar ratio formed by following mole are as follows:
Na2O:SiO2: Al2O3: OSDA:H2O=0.28:1.0:0.02045:0.15:25.0；Obtained solid mixture moves to It in 2000ml hydrothermal crystallizing kettle, and is stirred under 60rpm speed, is warming up to 150 DEG C of crystallization 12 hours, then proceed to be warming up to 170 DEG C crystallization 72 hours；
(2) after crystallization is complete, product is cooled down rapidly, and by filtering separation, washing obtains filtrate and solid matter, is collected The filtrate of the product, separation organic formwork agent alkaline solution (as shown in Figure 1a) (is denoted as equally in a manner of bipolar membrane electrodialysis SDK-4) and the solution of orthosilicic acid (SAA-4), the synthesis of next group AEI molecular sieve is participated in as raw material；
4 hours are roasted at drying 12 hours and 540 DEG C at 120 DEG C of solid matter, and AEI type is confirmed as by XRD Molecular sieve, i.e. AEI molecular screen primary powder；The AEI molecular sieve shows that its SAR is 39.6, is denoted as D, and Zeolite synthesis predecessor is molten The proportion of glue, synthesis condition, relative crystallinity and yield parameter are as shown in Tables 3 and 4.
The preparation of 5 AEI type zeolite molecular sieve of embodiment
(1) USY for the de-aluminate for being 28.7 by mole silica alumina ratio (SAR) of quantitative silica and aluminium oxide boils Stone, waterglass (Na2O:7.44wt%, SiO2: 27.40wt%) and embodiment 4 obtained in SAA-4 solution mixing, to the mixing In object, sequence adds SDK-4 solution obtained in embodiment 4, quantitative N, N- dimethyl -3,5- lupetidine aqueous solution (concentration: 20wt%), deionized water and NaOH particle (purity: 96wt%), the reaction mixture and then at room temperature closed appearance It is stirred under 200rpm speed in device, until all raw materials are uniformly mixed, the mixed sols molar ratio formed by following mole are as follows:
Na2O:SiO2: Al2O3: OSDA:H2O=0.36:1.0:0.01214:0.08:25.0；Obtained solid mixture is moved It is stirred into 2000ml hydrothermal crystallizing kettle, and under 60rpm speed, is warming up to 140 DEG C of crystallization 24 hours, then proceed to be warming up to 170 DEG C crystallization 60 hours；
(2) after crystallization is complete, product is cooled down rapidly, and by filtering separation, washing obtains filtrate and solid matter, is collected The filtrate of the product, separation organic formwork agent alkaline solution (as shown in Figure 1a) (is denoted as equally in a manner of bipolar membrane electrodialysis SDK-5) and the solution of orthosilicic acid (SAA-5), the synthesis of next group AEI molecular sieve is participated in as raw material；
4 hours are roasted at drying 12 hours and 540 DEG C at 120 DEG C of solid matter, and AEI type is confirmed as by XRD Molecular sieve, i.e. AEI molecular screen primary powder；The AEI molecular sieve shows that its SAR is 79.1, is denoted as E, and Zeolite synthesis predecessor is molten The proportion of glue, synthesis condition and yield parameter are as shown in Tables 3 and 4.
The preparation of 6 AEI type zeolite molecular sieve of embodiment
(1) USY for the de-aluminate for being 28.7 by mole silica alumina ratio (SAR) of quantitative silica and aluminium oxide boils Stone, silica solution (SiO2: 30.0wt%) it is added to organic formwork agent 1- ethyl -1- methyl -2,2,6,6- pregnancy phenylpiperidines water It in solution (concentration: 20wt%), is sufficiently stirred, adds NaOH particle (purity: 96wt%), it is abundant that deionized water is added in supplement Stirring, gained mixed serum in sealing container at room temperature in continuously stirring 2 hours, until all raw materials are uniformly mixed, have with The mixed sols molar ratio of lower mole of composition are as follows:
Na2O:SiO2: Al2O3: OSDA:H2O=0.29:1.0:0.01451:0.12:15.0；Obtained solid mixture is moved It is stirred into 2000ml hydrothermal crystallizing kettle, and under 60rpm speed, is warming up to 135 DEG C of crystallization 24 hours, then proceed to be warming up to 180 DEG C crystallization 48 hours；
(2) after crystallization is complete, product is cooled down rapidly, and by filtering separation, washing obtains filtrate and solid matter, will be returned The filtrate of receipts separates organic formwork agent and silicon amorphous substance by electrodialytic method, obtains organic formwork agent alkaline solution (being denoted as SDL-1) and silicate solution (SAB-1)；
4 hours are roasted at drying 24 hours and 540 DEG C at 110 DEG C of solid matter, and AEI type is confirmed as by XRD Molecular sieve, i.e. AEI molecular screen primary powder；The AEI molecular sieve shows that its SAR is 31.2, is denoted as F, and Zeolite synthesis predecessor is molten The proportion of glue, synthesis condition, relative crystallinity and yield parameter are as shown in Tables 3 and 4.
The preparation of 7 AEI type zeolite molecular sieve of embodiment
(1) USY for the de-aluminate for being 13.3 by mole silica alumina ratio (SAR) of quantitative silica and aluminium oxide boils Stone, silica solution (SiO2: 30.0wt%) and embodiment 6 obtained in SAB-1 solution mixing, into the mixture, sequence add SDL-1 solution obtained in embodiment 6, quantitatively 1- ethyl -1- methyl -2,2,6,6- hexamethyl aqueous piperidine solution (concentration: 20wt%), deionized water and NaOH particle (purity: 96wt%), the reaction mixture is then at room temperature in closed container It is stirred under 200rpm speed, until all raw materials are uniformly mixed, the mixed sols molar ratio formed by following mole are as follows:
Na2O:SiO2: Al2O3: OSDA:H2O=0.35:1.0:0.0126:0.08:15.0；Obtained solid mixture is moved It is stirred into 2000ml hydrothermal crystallizing kettle, and under 60rpm speed, is warming up to 135 DEG C of crystallization 48 hours, then proceed to be warming up to 190 DEG C crystallization 36 hours；
(2) after crystallization is complete, product is cooled down rapidly, and by filtering separation, washing obtains filtrate and solid matter, is collected The filtrate of the product, conventional electrodialytic mode separation organic formwork agent alkaline solution (being denoted as SDL-2) (as shown in Figure 1 b) and The solution (SAB-2) of orthosilicic acid participates in the synthesis of next group AEI molecular sieve as raw material；
4 hours are roasted at drying 24 hours and 540 DEG C at 110 DEG C of solid matter, and AEI type is confirmed as by XRD Molecular sieve, i.e. AEI molecular screen primary powder；The AEI molecular sieve shows that its SAR is 41.8, is denoted as G, and Zeolite synthesis predecessor is molten The proportion of glue, synthesis condition, relative crystallinity and yield parameter are as shown in Tables 3 and 4.
The preparation of 8 AEI type zeolite molecular sieve of embodiment
(1) NaY zeolite by mole silica alumina ratio (SAR) of quantitative silica and aluminium oxide for 5.3, silica solution (SiO2: 30.0wt%) and embodiment 7 obtained in SAB-2 solution mixing, into the mixture, sequence add embodiment 7 in Obtained SDL-2 solution, is gone quantitative 1- ethyl -1- methyl -2,2,6,6- hexamethyl aqueous piperidine solution (concentration: 20wt%) Ionized water and NaOH particle (purity: 96wt%), the reaction mixture is then at room temperature in closed container under 200rpm speed Stirring, until all raw materials are uniformly mixed, the mixed sols molar ratio formed by following mole are as follows:
Na2O:SiO2: Al2O3: OSDA:H2O=0.34:1.0:0.01244:0.10:15.0；Obtained solid mixture is moved It is stirred into 2000ml hydrothermal crystallizing kettle, and under 60rpm speed, is warming up to 135 DEG C of crystallization 24 hours, then proceed to be warming up to 160 DEG C crystallization 120 hours；
(2) after crystallization is complete, product is cooled down rapidly, and by filtering separation, washing obtains filtrate and solid matter, is collected The filtrate of the product, (as shown in Figure 1 b) (is denoted as SDL- to generate organic formwork agent alkaline solution in such a way that routine is electrodialytic 3) with the solution of orthosilicic acid (SAB-3), the synthesis of next group AEI molecular sieve is participated in as raw material；
4 hours are roasted at drying 24 hours and 540 DEG C at 110 DEG C of solid matter, and AEI type is confirmed as by XRD Molecular sieve, i.e. AEI molecular screen primary powder；The AEI molecular sieve shows that its SAR is 45.3, is denoted as H, and Zeolite synthesis predecessor is molten The proportion of glue, synthesis condition, relative crystallinity and yield parameter are as shown in Tables 3 and 4.
The preparation of 9 AEI type zeolite molecular sieve of embodiment
(1) by quantitative HY zeolite (silica alumina ratio 5.3 provides silicon source and part silicon source), silica solution (SiO2: 30.0wt%) sequentially added obtained in embodiment 8 with the mixing of SAB-3 solution obtained in embodiment 8 into the mixture SDL-3 solution, quantitative 1- ethyl -1- methyl -2,2,6,6- hexamethyl aqueous piperidine solution (concentration: 20wt%), deionized water With NaOH particle (purity: 96wt%), then which stirs in closed container under 200rpm speed at room temperature, directly It is uniformly mixed to all raw materials, the mixed sols molar ratio formed by following mole are as follows:
Na2O:SiO2: Al2O3: OSDA:H2O=0.28:1.0:0.02227:0.12:15.0；
Obtained solid mixture is moved in 2000ml hydrothermal crystallizing kettle, and is stirred under 60rpm speed, is warming up to 140 It DEG C crystallization 24 hours, then proceedes to be warming up to 180 DEG C of crystallization 72 hours；
(2) after crystallization is complete, product is cooled down rapidly, and by filtering separation, washing obtains filtrate and solid matter, is collected The filtrate of the product, the separation organic formwork agent alkaline solution (being denoted as SDL-4) (as shown in Figure 1 b) in such a way that routine is electrodialytic With the solution (SAB-4) of orthosilicic acid, the synthesis of next group AEI molecular sieve is participated in as raw material；
4 hours are roasted at drying 24 hours and 540 DEG C at 110 DEG C of solid matter, and AEI type is confirmed as by XRD Molecular sieve, i.e. AEI molecular screen primary powder；The AEI molecular sieve shows that its SAR is 36.6, is denoted as I, and Zeolite synthesis predecessor is molten The proportion of glue, synthesis condition, relative crystallinity and yield parameter are as shown in Tables 3 and 4.
The preparation of 10 AEI type zeolite molecular sieve of embodiment
(1) USY zeolite for the de-aluminate for being 28.7 by mole silica alumina ratio (SAR) of quantitative silica and aluminium oxide It is mixed with SAB-4 solution obtained in embodiment 9, into the mixture, SDL-4 solution obtained in sequence addition embodiment 9, Quantitative 1- ethyl -1- methyl -2,2,6,6- hexamethyl aqueous piperidine solution (concentration: 20wt%), deionized water and NaOH particle (purity: 96wt%), then which stirs in closed container under 200rpm speed at room temperature, until all raw materials It is uniformly mixed, the mixed sols molar ratio formed by following mole are as follows:
Na2O:SiO2: Al2O3: OSDA:H2O=0.26:1.0:0.02778:0.15:15.0；Obtained solid mixture is moved It is stirred into 2000ml hydrothermal crystallizing kettle, and under 60rpm speed, is warming up to 135 DEG C of crystallization 24 hours, then proceed to be warming up to 170 DEG C crystallization 96 hours；
(2) after crystallization is complete, product is cooled down rapidly, and by filtering separation, washing obtains filtrate and solid matter, is collected The filtrate of the product, the separation organic formwork agent alkaline solution (being denoted as SDL-5) (as shown in Figure 1 b) in such a way that routine is electrodialytic With the solution (SAB-5) of orthosilicic acid, the synthesis of next group AEI molecular sieve is participated in as raw material；
4 hours are roasted at drying 24 hours and 540 DEG C at 110 DEG C of solid matter, and AEI type is confirmed as by XRD Molecular sieve, i.e. AEI molecular screen primary powder；The AEI molecular sieve shows that its SAR is 33.8, is denoted as J, and Zeolite synthesis predecessor is molten The proportion of glue, synthesis condition, relative crystallinity and yield parameter are as shown in Tables 3 and 4.
Proportion, synthesis condition and the product silica alumina ratio of predecessor colloidal sol are synthesized in 3 embodiment 1-10 of table
The preparation of comparative example 1-5AEI type zeolite molecular sieve
N is used according to method in patent CN104591204A embodiment, N- dimethyl -3,5- lupetidine is organic Template synthesizes AEI zeolite in recycling mother liquor
36g silica is mixed with the aluminium dioxide mole silica alumina ratio SAR USY zeolite for being 10.7 with the water of 1093g.It is right In the mixture, under stiring by the N of 195g, the sodium metasilicate of N- dimethyl -3,5- lupetidine template and 427g are molten Liquid (the SiO of 28.8wt%2) slowly pour into said mixture.It is formed by mixture sealing reactor, 200rpm is stirred It mixes down and is heated to 145 DEG C, crystalline mixture will be formed by after crystallization 2 days and be transferred to separatory funnel.In a static condition, The transparency liquid layer at solid sediment and top is separated within several hours.Collect most transparent mother liquor, referred to as first Road mother liquor (is denoted as: ML-P1), is recycled the solid in the slurry of bottom, and be confirmed as AEI by XRD, is denoted as VS1.
The USY zeolite and 1582g that SAR by the USY zeolite of the SAR of the 38g de-aluminate for being 30 and 21g is 10.7 ML-Pl mixing.Into the mixture, sequence adds the N of 45g, N- dimethyl -3,5- lupetidine template and 31g's Water.Under stiring, by the sodium silicate liquid of the 34g (SiO of 28.8wt%2) slowly pour into said mixture.The reaction is mixed It closes object and is then heated to about 145 DEG C under 200rpm stirring in stainless steel reactor.After crystallization 20~35 hours, remove It is formed by solid and turns out to be AEI zeolite with XRD, be denoted as VS2.Collect the mother liquor, and referred to as second mother liquor (be denoted as: ML-P2)。
ML-P2 generates ML-P3 in a similar way, and generated AEI zeolite is denoted as VS3, and in turn uses ML- P3 generates ML-P4, and generated AEI zeolite is denoted as VS4, and ML-P5 is generated using ML-P4, generated AEI zeolite note For VS5.Withdrawal liquid, relative crystallinity used in Zeolite synthesis and yield parameter are as shown in table 4.
Withdrawal liquid and yield used in 4 embodiment 1-10 of table and comparative example 1-5 molecular sieve
Upper table is the results show that N, N- dimethyl -3,5- lupetidine template and 1- ethyl -1- methyl -2,2, and 6, The agent of 6- hexamethyl piperidine template can repeatedly recycle extraction organic formwork agent lye by the method that electrodialysis hydrolyzes and obtain weight It is multiple to utilize, it is closed in addition, the silicate solutions in filtrate can also use electrodialytic method to be separated and recovered as AEI molecular sieve It is used at raw material, to improve total relative productivity based on silica and total relative productivity based on template.It can change crystalline substance Change predecessor gel composition and technological parameter to obtain the AEI molecular sieve with for example different silica alumina ratio (SAR) values of different performance Crystal.
It is defined as 100% with AEI molecular sieve crystallinity obtained in embodiment 1, that is, directlys adopt original organic formwork agent The AEI molecular sieve crystallinity that hydrothermal crystallizing obtains, which is carried out, with FAU Si-Al molecular sieve raw material (does not recycle organic formwork for 100% Agent and silicon species), relative to the crystallinity of above-mentioned AEI molecular sieve 100%, calculate the embodiment of the present invention 2~10 and comparative example 1 ~5 obtained AEI molecular sieve relative crystallinities obtain the opposite knot of the AEI molecular sieve prepared in the embodiment of the present invention after calculating Brilliant degree is in 95%~105% range, and the relative crystallinity of sample is in the range of 56%~89% in comparative example 1~5, Obviously, Examples 1 to 10 obtains the relative crystallinity that sample relative crystallinity is all apparently higher than sample in comparative example 1~5.Separately Outside, total relative productivity in the molecular sieve reaction that the embodiment of the present invention 1~10 obtains based on template is in 30%~95% model In enclosing, and total relative productivity of the molecular sieve that comparative example 1~5 obtains based on template is 20%~75%, that is to say, that highest It can achieve the 95% total relative productivity for being significantly larger than comparative example；In the reaction of molecular sieve that the embodiment of the present invention 1~10 obtains by Total relative productivity of silica meter is in 39%~97% range, and the molecular sieve that comparative example 1~5 obtains is based on template Total relative productivity be 32%~87%, that is to say, that highest can achieve 97% significantly larger than comparative example total relative productivity； In addition, this explanation uses comparative example as can be seen that the sieve sample that comparative example 5 obtains will appear stray crystal peak from Fig. 3 and Fig. 6 The method of the middle mother liquor reuse stability that feeds intake is poor, it is difficult to obtain high-purity AEI zeolite crystal.The scanning electron microscope sem from attached drawing Figure can analyze out, and the AEI sieve sample that embodiment obtains has good dispersed and more regular molecular sieve crystal Pattern, and the reunion of AEI sieve sample crystal grain obtained in comparative example is obvious, grain dispersion is poor.
Embodiment 11-23
The embodiment 1-8 and comparative example 1-5 10.0g AEI molecular screen primary powder synthesized, which is added to 100.0g concentration, is Cu (the NO of 0.3mol/L3)2·3H2In O aqueous solution, it is placed in heatproof container after stirring evenly 1 hour, and be put into togerther and have In the drier of pressure reducing valve；After the pressure in drier is extracted into 10Torr or less with vacuum pump, room temperature carries out degassing in 1 hour Processing, it is 12 hours dry to be then warming up to 90 DEG C of conditions, by the sample after drying under normal atmosphere pressure 500 DEG C of temperature calcinations 4 hours；The modified AEI molecular sieve of the copper is obtained, according in the catalyst of icp analysis result preparation, copper (II) ion is accounted for point Sub- sieve catalyst total weight it is as shown in table 5.
SCR catalyst test:
The AEI molecular sieve of standby 10~20 mesh A1~H1, comparative example the 1-5 synthesis of the AEI system with molecular sieve for preparing of embodiment 1-8 synthesis 10~20 mesh VS1~VS5 catalyst granules are prepared, reactor is mounted inIn, it include 500ppmNO, 500ppm NH3, 10 volume %O2, mixed airflow 160mL/min that 5 volume % steam and Ar are Balance Air, first pass through preheater and (be set as 100 DEG C), subsequently into SCR reactor.In 150~650 DEG C of reaction temperatures and it is based on 48000h-1It is right under volume gas hourly space velocity Sample is tested.The temperature is by being located at the interior thermocouple monitoring at sample position.
Fresh SCR catalyst each in used above-described embodiment and comparative example is carried out the durable processing of hydro-thermal to be aged SCR catalyst, hydro-thermal it is durable processing test condition are as follows:
Space velocity SV:30000/h, temperature: 800 DEG C, the time: 16 hours, moisture concentration: 10%, oxygen concentration: 10%, Nitrogen concentration: balance.
After carrying out hydro-thermal ripening according to above-mentioned parameter, continue to comment as SCR catalyst for NOx catalytic reduction reaction Valence test:
NO conversion ratio or " de- NOx " activity are under steady state conditions, a reactor by using 55 type FT-IR spectrum of Bruker EQUINOX NOx, the NH in instrument measurement exit3And N2O concentration and determine.
Using above-mentioned SCR catalyst activity laboratory evaluation device, the loaded Cu that embodiment and comparative example is prepared SCR catalyst carry out NOx selective catalytic reduction performance evaluation, the results are shown in Table 5.Copper changes in 5 embodiment 11-23 of table Property AEI molecular sieve copper content and carry out selective catalytic reduction performance evaluation
As can be seen from the above table, the Cu-AEI molecular sieve catalyst that embodiment 11~18 obtains has preferable low temperature ignition Property and high temperature active.In the range of 150~650 DEG C, SCR is in the case of fresh dose in embodiment 11~18, NOXConversion Rate is in the range of 41.8%~99.6%, and SCR is under ageing state, NOXConversion ratio be in 36.2%~98.8% In range, no matter illustrating that SCR is in " fresh " state or " ageing " state, activity is substantially better than to be obtained by comparative example 1~5 To the catalyst samples of catalyst VS1~VS5.Therefore, the present invention is clearly shown by the result that embodiment 11~18 obtains Cu-AEI molecular sieve catalytic agent material and with its obtain catalyst have improved SCR catalytic activity, especially for example Under low conversion temperature specific to cold start when handling NOx in diesel locomotive application.For other SCR application, this The Cu-AEI molecular sieve catalytic agent material of invention allows to have higher conversion ratio at lower temperatures, therefore allows higher effect Rate and therefore under comparable conversion ratio, handles the exhaust gas containing NOx with allowing energy-efficient, such as from industrial Exhaust gas.
The above is only the preferred embodiment that the present invention is implemented, and not does limitation in any form to the present invention, all The modifications, equivalent substitutions and improvements etc. done within the spirit and principles in the present invention are required to be included in protection of the invention Within the scope of.

Claims (26)

1. a kind of preparation method of AEI structure molecular screen, it includes following step:
(1) raw material containing organic formwork agent, FAU type Si-Al molecular sieve, lye and water is reacted under the conditions of hydrothermal crystallizing, In, FAU type Si-Al molecular sieve provides silicon source and silicon source；
(2) product for obtaining step (1) filters, and filtrate carries out Wastewater treatment, and the species for recycling organic formwork agent and silicon are made For the synthesis material of next group AEI molecular sieve.
2. preparation method according to claim 1, wherein in step (1), the organic formwork agent is monocycle or polycyclic Piperidines, the piperidine compounds are selected from N, N- dimethyl -3,5- lupetidine, N, N- dimethyl - Lupetidine, 1,1,2,2,6,6- pregnancy phenylpiperidines, 1,1,2,2,6,6- hexamethyl -4- oxo-piperidine, 1, 1,3,5- tetramethyl -4- oxo-piperidine, 1- hydroxyl -1,1,2,2,6,6- pregnancy phenylpiperidines, 1,1- dimethyl -4,4- dipropyl Oxygroup piperidines, 3,5- dimethoxy -1,1- lupetidine, 3,5- dihydroxy -1,1- lupetidine, 4- ethyl - 1,1- dimethyl -3,5- dioxopiperidine, 1- ethyl -1- methyl -2,2,6,6- pregnancy phenylpiperidines, 1- glycidyl -1- Methyl -2,2,6,6- pregnancy phenylpiperidines, N, N- dimethyl -2- (2- ethoxy) piperidines and N, N- dimethyl -2- ethyl piperazine It is one or more kinds of in pyridine.
3. preparation method according to claim 1 or 2, wherein in step (1), the FAU type silicoaluminophosphate molecular screened from In one of Y zeolite and X zeolite；It is preferred that the Y zeolite is selected from one of HY zeolite, USY zeolite and NaY zeolite, institute X zeolite is stated selected from one of NaX zeolite, KX zeolite and HX zeolite.
4. preparation method according to claim 1-3, wherein in step (1), the hydrothermal crystallizing is divided into two Section: (1) first segment crystallization temperature is 120~150 DEG C, preferably 130~150 DEG C；(2) second segment crystallization temperature is 150~200 DEG C, preferably 160~190 DEG C.
5. the preparation method according to claim 4, wherein in step (1), the hydrothermal crystallizing is divided into two sections: (1) One section of crystallization time is 0.5~3.0 day, preferably 0.5~2.0 day；(2) second segment crystallization time is 0.5~6.0 day, preferably It is 1.0~5.0 days.
6. preparation method according to claim 1-5, wherein in step (1), additional silicon source is added as original Material, the additional silicon source selected from white carbon black, macro porous silica gel, silochrom, Kiselgel A, tlc silica gel, Type B silica gel, It is one or more kinds of in sodium metasilicate, silica solution, waterglass, alkyl silicate and diatomite.
7. preparation method according to claim 1-6, wherein in step (1), the lye is selected from NaOH、Na2O、Na2O2One or more of with KOH.
8. preparation method according to claim 1-7, wherein in step (1), the silicon source, silicon source, alkali The molar ratio of liquid, template and water is 1.0:0.00833~0.1667:0.1~0.5:0.05~0.5:10~50, preferably 1.0:0.0121~0.0417:0.22~0.36:0.08~0.20:15~25.
9. preparation method according to claim 1-8, wherein in step (2), the electrodialysis is selected from four One of one film of three film of room, three Room, two film or two Room.
10. -9 described in any item preparation methods according to claim 1, wherein in step (2), the Bipolar Membrane is to pass through Cation exchange layer, interface hydrophilic layer and anion exchange layer is compound obtains.
11. a kind of AEI structure molecular screen is prepared by any one of claim 1-10 the method.
12. AEI structure molecular screen according to claim 11, wherein silica in the AEI structure molecular screen and The molecule molar ratio of aluminium oxide is 5~100, preferably 10~80.
13. a kind of NOXSelective catalytic reduction catalysts are that the described in any item methods of claim 1-10 are prepared AEI structure molecular screen or claim 11 or 12 described in AEI structure molecular screen and metal salt solution carry out ion exchange and It obtains.
14. selective catalytic reduction catalysts according to claim 13, wherein the metal salt selected from copper, iron, Cobalt, tungsten, nickel, zinc, molybdenum, vanadium, tin, titanium, zirconium, manganese, chromium, niobium, bismuth, antimony, ruthenium, germanium, palladium, indium, platinum, gold or silver soluble-salt in one Kind is two or more.
15. selective catalytic reduction catalysts according to claim 14, wherein the metal salt is selected from mantoquita or iron Salt, preferably mantoquita.
16. selective catalytic reduction catalysts according to claim 15, wherein the mantoquita is selected from copper nitrate, chlorine Change one or more in copper, copper acetate and copper sulphate, the concentration of copper ion is 0.1~1.5mol/L in the mantoquita.
17. a kind of preparation method of the described in any item selective catalytic reduction catalysts of claim 13-16, is by right It is required that AEI structure described in AEI structure molecular screen or claim 11 or 12 that the described in any item methods of 1-10 are prepared Molecular sieve is added in metal salt solution, obtains NOXSelective catalytic reduction catalysts.
18. preparation method according to claim 17 also includes following step: by obtained NOXSelective catalytic reduction Catalyst is attached on porous regular material using binder.
19. preparation method according to claim 18, wherein the binder is selected from silica solution, waterglass, intends thin water It is one or more kinds of in aluminium stone and Aluminum sol.
20. preparation method described in 8 or 19 according to claim 1, wherein the porous regular material is selected from honeycombed, plate Formula shape and one of corrugated.
21. the described in any item preparation methods of 8-20 according to claim 1, wherein the porous regular material is green selected from violet Stone, alph-alumine, silicon carbide, aluminium titanates, silicon nitride, zirconium oxide, mullite, spodumene, alumina-silica magnesia, silicon One of sour zirconium or sheet metal, preferably cordierite.
22. any one of a kind of described in any item selective catalytic reduction catalysts of claim 13-16 or claim 17-21 The selective catalytic reduction catalysts that the method is prepared, the application in purification waste gas stream, preferably in purification vapour Application in vehicle waste gas stream.
23. application according to claim 22, the waste gas stream is the waste gas stream of vehicular emission, and preferably lean-burn starts The waste gas stream of machine, more preferably diesel exhaust stream.
24. a kind of purifying treatment method of waste gas stream, the described in any item selective catalytic reduction of claim 13-16 are urged Selective catalytic reduction catalysts that agent or the described in any item methods of claim 17-21 are prepared with comprising NOXWith The automobile waste air-flow of reducing agent is in contact, and makes NOXSelectively it is reduced into N2And H2O。
25. purifying treatment method according to claim 24, wherein the waste gas stream is catalyzed with selective catalytic reduction Before agent contact, with NOXMetering is 100 weight %, and the NO2 content≤80 weight %, preferably 5~70 weight % are more excellent It is selected as 10~60 weight %, more preferably 15~55 weight %, more preferably 20~50 weight %.
26. described in the described in any item selective catalytic reduction catalysts of claim 13-16 or claim any one of 17-21 The selective catalytic reduction catalysts that are prepared of method, the selective catalytic reduction catalysts are nitrous oxides selectivity Catalytic reducer or denitrating catalyst.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110592610A (en) * 2019-09-29 2019-12-20 肯特催化材料股份有限公司 Preparation method and application of quaternary ammonium salt template agent
CN111250152A (en) * 2020-03-31 2020-06-09 中国科学院过程工程研究所 Packaging method of Ni @ ZSM-5 bifunctional catalyst
CN112010322A (en) * 2020-08-20 2020-12-01 华中科技大学 Preparation method and application of molecular sieve and utilization method of wastewater
CN112239214A (en) * 2019-07-17 2021-01-19 中国石油化工股份有限公司 Silicon germanic acid salts and preparation method thereof
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

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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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
KR102484715B1 (en) 2021-04-06 2023-01-03 손원일 Portable hot-water boiler
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104030499A (en) * 2014-05-22 2014-09-10 浙江工业大学 Comprehensive treatment method of special-type molecular sieve synthesis mother solution
CN104591204A (en) * 2013-10-31 2015-05-06 庄信万丰股份有限公司 Aei zeolite synthesis
KR101560091B1 (en) * 2014-05-16 2015-10-13 이원근 Manufacturing method of a H-type zeolite using electro-dialysis system
CN105540743A (en) * 2015-10-30 2016-05-04 中国石油化工股份有限公司 Wastewater treatment method, molecular sieve preparation method and molecular sieve preparation system

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100525208B1 (en) * 2003-08-18 2005-11-04 한국화학연구원 The preparation method of nanoporous VSB-5 molecular sieve
CN100503042C (en) 2004-04-05 2009-06-24 埃克森美孚化学专利公司 Crystal symbiotic material and its synthetic and application in conversion of oxygen-containing compound to olefin
US7807122B2 (en) 2005-11-02 2010-10-05 Exxonmobil Chemical Patents Inc. Metalloaluminophosphate molecular sieves, their synthesis and use
CN103771436B (en) * 2012-10-25 2015-07-29 中国石油化工股份有限公司 A kind of molecular sieve ion-exchange techniques and application thereof
CN103771434B (en) * 2012-10-25 2015-10-28 中国石油化工股份有限公司 A kind of molecular sieve ion-exchange techniques
CN110540215B (en) * 2014-11-21 2024-02-06 三菱化学株式会社 AEI-type aluminosilicate zeolite, catalyst and exhaust gas treatment process
ES2586775B1 (en) * 2015-04-16 2017-08-14 Consejo Superior De Investigaciones Científicas (Csic) METHOD OF PREPARATION OF THE AEI ZEOLITHIC STRUCTURE IN ITS SILICOALUMINATE FORM WITH GREAT PERFORMANCES, AND ITS APPLICATION IN CATALYSIS
BR112018009465B1 (en) * 2015-11-11 2022-08-16 Johnson Matthey Public Limited Company METHOD FOR PREPARING A ZEOLITE HAVING AN AEI MAIN CHAIN
CN106745057B (en) * 2017-03-10 2018-11-13 中触媒新材料股份有限公司 The AEI/MFI eutectics Si-Al molecular sieve and synthetic method of a kind of binder free and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104591204A (en) * 2013-10-31 2015-05-06 庄信万丰股份有限公司 Aei zeolite synthesis
KR101560091B1 (en) * 2014-05-16 2015-10-13 이원근 Manufacturing method of a H-type zeolite using electro-dialysis system
CN104030499A (en) * 2014-05-22 2014-09-10 浙江工业大学 Comprehensive treatment method of special-type molecular sieve synthesis mother solution
CN105540743A (en) * 2015-10-30 2016-05-04 中国石油化工股份有限公司 Wastewater treatment method, molecular sieve preparation method and molecular sieve preparation system

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112239214A (en) * 2019-07-17 2021-01-19 中国石油化工股份有限公司 Silicon germanic acid salts and preparation method thereof
CN110592610A (en) * 2019-09-29 2019-12-20 肯特催化材料股份有限公司 Preparation method and application of quaternary ammonium salt template agent
CN111250152A (en) * 2020-03-31 2020-06-09 中国科学院过程工程研究所 Packaging method of Ni @ ZSM-5 bifunctional catalyst
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
CN112010322A (en) * 2020-08-20 2020-12-01 华中科技大学 Preparation method and application of molecular sieve and utilization method of wastewater
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
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

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