CN101450806A - AEI/CHA eutectic molecular sieve containing triethylamine and synthetic method thereof - Google Patents
AEI/CHA eutectic molecular sieve containing triethylamine and synthetic method thereof Download PDFInfo
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- CN101450806A CN101450806A CNA2007101787809A CN200710178780A CN101450806A CN 101450806 A CN101450806 A CN 101450806A CN A2007101787809 A CNA2007101787809 A CN A2007101787809A CN 200710178780 A CN200710178780 A CN 200710178780A CN 101450806 A CN101450806 A CN 101450806A
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Abstract
The invention discloses an AEI/CHA eutectic molecule sieve containing triethylamine. An anhydrous chemical composition of the AEI/CHA eutectic molecule sieve is expressed as mR.(Six.Aly.Pz)O2, wherein x, y and z are molar fractions of Si, Al and P respectively; the x is between 0.001 and 0.98; the y is between 0.01 and 0.6; the z is between 0.01 and 0.6, x+y+z is equal to 1; the R is a template agent, and the m is a mole number of the R; and the value of the m is between 0.02 and 0.6. A preparation method for the AEI/CHA eutectic molecule sieve comprises the following steps: a) according to the mol ratio of oxides of various components, stirring and mixing evenly a silicon source, an aluminum resource, a phosphorus source, the template agent, and water are to obtain an initial gel mixture; and b) transferring the initial gel mixture into a stainless steel synthesis kettle to be sealed, then heating the kettle to a crystallization temperature of between 160 and 250 DEG C, and performing crystallization at constant temperature for 1 to 120 hours under the self-generated pressure, and separating a solid product, washing the solid product to be neutral, and drying the solid product to obtain the AEI/CHA eutectic molecule sieve. The molecule sieve can be used as a catalyst for an acid catalytic reaction after the template agent is removed through the baking.
Description
Technical field
The present invention relates to contain the molecular sieve with AEI/CHA eutectic structure of triethylamine.
The invention still further relates to the preparation method of above-mentioned molecular sieve.
The invention still further relates to the application of above-mentioned molecular sieve in acid catalyzed reaction.
Background technology
The SAPO molecular sieve is the silicon aluminium phosphate series SAPO molecular sieve (US 4440871) by U.S. combinating carbide company (UCC) exploitation.This molecular sieve is a class crystalline silicoaluminophosphate salt, and its three-dimensional framework structure is by PO
2 +, AlO
2 -And SiO
2Tetrahedron constitutes.Its anhydrous chemical constitution can be expressed as mR (Si
xAl
yP
z) O
2, wherein x, y, z are the molar fraction of Si, Al, P, and R is the template that is present in the molecular sieve crystal micropore, and m is the mole number of template R.The MeSAPO molecular sieve is to introduce metal heteroatom and the molecular sieve that obtains in SAPO, and its anhydrous chemical constitution can be expressed as mR (Me
wSi
xAl
yP
z) O
2, wherein x, y, z, w are the molar fraction of Si, Al, P, Me, and R is the template that is present in the molecular sieve crystal micropore, and m is the mole number of template R.
SAPO-34 is a kind of crystalline silicoaluminophosphate salt molecular sieve with class chabazite (CHA) structure, and its synthetic method has patent report, and (US 4440871; CN 1088483).SAPO-18 is a kind of crystalline silicoaluminophosphate salt molecular sieve of the AEI of having structure type, and its synthetic method is at document (J.S.Chen, J.M.Thomas, P.A.Wright, R.P.Townsend, " Catalysis Letters ", 28 (1994) 241-248) middle report.
SAPO molecular sieve with AEI/CHA eutectic structure is meant the structural unit that contains AEI and CHA in molecular sieve, and has a class novel molecular sieve of stacking fault.World patent WO98/15496 discloses a kind of composition of microporous crystalline silico-alumino-phosphate, comprises the catalytic material of said composition, and is used for by methanol production alkene.Catalyzer contains the silicoaluminophosphamaterial material with AEI/CHA mixed phase composition.The catalyzer of being invented is compared with the catalyzer of prior art and has been prolonged the life-span.
U.S. Pat 2002/003334 relates to the intergrowth silicoaluminophosphamolecular molecular sieves mutually that comprises at least a AEI of having and CHA framework types molecular sieve, the x-ray diffraction pattern of the roasting sample of wherein said silicoaluminophosphamolecular molecular sieves, the ratio of the AEI/CHA by the described intergrowth phase of DIFFaX assay determination is about 5/95 to 40/60.Also relate to its preparation method and in the application of methyl alcohol to the catalyzed conversion of alkene.
It is the catalyst composition of alkene that U.S. Pat 2005/035288 discloses a kind of being used for oxygenate, comprises the first crystal metal aluminophosphate molecular sieve (first crystalline material) and is different from described first molecular sieve and aluminate or phosphate is arranged or second crystalline material that the dehydration of metallic aluminium phosphoric acid salt hydrate forms.The wherein said first crystal metal aluminophosphate molecular sieve comprises at least a symbiotic form of AEI framework types material and CHA framework types material.
U.S. Pat 2005/0233895 discloses a kind of silicoaluminophosphamolecular molecular sieve, and its composition comprises two kinds of coexisting phases of AEI framework types material and CHA framework types material.By the DIFFaX assay determination, wherein the ratio of the AEI/CHA of the first kind of coexisting phase ratio that is about the AEI/CHA of 5/95 to 40/60, the second kind of coexisting phase is about 30/70 to 55/45, and the sial atomic ratio of described molecular sieve is about 0.13 to 0.24.
The silicoaluminophosphamolecular molecular sieve that more than has AEI and CHA eutectic structure, the template in its molecular sieve crystal micropore are tetraethyl ammonium hydroxide or contain a small amount of dipropyl amine.And contain the SAPO with AEI/CHA eutectic structure of triethylamine and the research of MeSAPO molecular sieve and synthetic method thereof yet there are no report.
Summary of the invention
The object of the present invention is to provide a kind of contain triethylamine have an AEI/CHA eutectic structure molecular sieve.
Another purpose of the present invention is to provide a kind of method for preparing above-mentioned molecular sieve.
For achieving the above object, the AEI/CHA eutectic molecular sieve that contains triethylamine provided by the invention, its anhydrous chemical constitution is expressed as:
mR·(Si
x·Al
y·P
z)O
2
Wherein x, y, z are respectively the molar fraction of Si, Al, P;
X=0.001～0.98; Y=0.01～0.6; Z=0.01～0.6; And x+y+z=1;
R is the template that is present in the molecular sieve crystal micropore; M is the mole number of template R; The value of m is 0.02～0.6; Wherein template R is a triethylamine or based on the organic compounds containing nitrogen group of triethylamine, the amount of triethylamine accounts for more than the 50 weight % of template total amount.
Can also contain metallic compound in the described molecular sieve, the anhydrous chemical constitution of its molecular sieve is expressed as:
mR·(Me
w·Si
x·Al
y·P
z)O
2
Wherein x, y, z, w are respectively the molar fraction of Si, Al, P, Me; Me is a metal; X=0.001～0.98; Y=0.01～0.6; Z=0.01～0.6; W=0～0.6; And x+y+z+w=1;
R is the template that is present in the molecular sieve crystal micropore; M is the mole number of template R; The value of m is 0.02～0.6; Wherein template R is a triethylamine or based on the organic compounds containing nitrogen group of triethylamine.
Described molecular sieve, wherein, organic compounds containing nitrogen is N, N-diisopropyl ethyl amine, tetraethyl ammonium hydroxide, diethylamine, morpholine, hexahydroaniline, Tri N-Propyl Amine, Isopropylamine, di-n-propylamine, Diisopropylamine, tripropyl amine, n-Butyl Amine 99 or isobutylamine.
Described molecular sieve, wherein, x-ray diffraction pattern has a characteristic diffraction peak at least in the scope of 16.7 ° to 17.1 ° or 21.0 ° to 21.4 ° (2 θ).
The method of the above-mentioned molecular sieve of preparation provided by the invention, its step is as follows:
A) by following each component oxide mol ratio, mix, get initial gel mixture with water:
SiO
2/Al
2O
3＝0.001～1.0；
P
2O
5/Al
2O
3＝0.5～2；
H
2O/Al
2O
3＝10～100；
Me/Al
2O
3=0～1, Me is a metal;
R/Al
2O
3=1～5, wherein R is a template;
B) with sealing in the initial gel mixture material immigration stainless steel synthesis reactor, being heated to 160～250 ℃ of crystallization temperatures then, is 180～220 ℃ best, and under autogenous pressure, thermostatic crystallization 1-120 hour is 5～80 hours best; The separate solid product, washing is to neutral, and drying obtains the AEI/CHA eutectic molecular sieve.
Described method, wherein, used phosphorus source is a kind of or any several mixture in ortho-phosphoric acid, phosphoric acid salt, Organophosphorous compounds or the phosphorous oxides.
Described method, wherein, used aluminium source is a kind of or any several mixture in aluminium salt, aluminate, activated alumina, aluminum alkoxide, false boehmite or the pseudo-boehmite.
Described method, wherein, used silicon source is a kind of or any several mixture in silicon sol, water glass, active silica or the positive silicon ester.
Described method, wherein, employed metallic compound is a kind of in the oxide compound, oxychlorination thing of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, magnesium, calcium, strontium, barium and lanthanum or inorganic, the organic acid salt or several mixture arbitrarily.
AEI/CHA eutectic molecular sieve of the present invention after template is removed in roasting in 550～700 ℃ of air, can be used as the catalyzer of acid catalyzed reaction, reacts as converting oxygen-containing compound to low-carbon olefins.
Description of drawings
Fig. 1: the X-ray spectrogram (XRD) of sample and pure AEI and CHA in the embodiment of the invention 1,2,3; Among the figure: A, B, C are respectively the XRD spectra of cocrystallization sieve sample among the embodiment 1,2,3; D is the XRD spectra of pure AEI crystalline phase; E is the XRD spectra of pure CHA crystalline phase.
Fig. 2: the sem photograph of sample (SEM) in the embodiment of the invention 1.
Embodiment
SAPO and MeSAPO molecular sieve with AEI/CHA eutectic structure provided by the invention, its anhydrous chemical constitution can be expressed as:
MR (Si
xAl
yP
z) O
2And mR (Me
wSi
xAl
yP
z) O
2,
Wherein x, y, z, w are the molar fraction of Si, Al, P, Me, and Me is a metal;
X=0.001～0.98; Y=0.01～0.6; Z=0.01～0.6; W=0～0.6; And x+y+z+w=1;
R is the template that is present in the molecular sieve crystal micropore, and m is the mole number of template R, and the value of m is 0.02～0.6;
Wherein template R be triethylamine or based on the organic compounds containing nitrogen group of triethylamine (other organic compounds containing nitrogen is N, N-diisopropyl ethyl amine, tetraethyl ammonium hydroxide, diethylamine, morpholine, hexahydroaniline, Tri N-Propyl Amine, Isopropylamine, di-n-propylamine, Diisopropylamine, tripropyl amine, n-Butyl Amine 99, isobutylamine), wherein the amount of triethylamine accounts for more than the 50 weight % of template total amount.
Described AEI/CHA eutectic molecular sieve, its x-ray diffraction pattern have a characteristic diffraction peak at least in the scope of 16.7 ° to 17.1 ° or 21.0 ° to 21.4 ° (2 θ).
The preparation method of molecular sieve provided by the invention, used phosphorus source can be one or more the mixture in ortho-phosphoric acid, phosphoric acid salt, Organophosphorous compounds or the phosphorous oxides, and wherein the phosphorus source is an ortho-phosphoric acid preferably; The aluminium source is a kind of or any several mixture in aluminium salt, aluminate, activated alumina, aluminum alkoxide, false boehmite or the pseudo-boehmite; The silicon source is a kind of or any several mixture in silicon sol, water glass, active silica or the positive silicon ester; Used metal heteroatom (Me) is from a kind of or any several mixture in titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, magnesium, calcium, strontium, barium and the lanthanum.
Described synthetic method may further comprise the steps:
A) in proportion silicon source material, aluminium source material, phosphorus source material, metallic compound, template and water are under agitation mixed, get initial gel mixture.Each component oxide mole proportioning is in the initial synthesized gel rubber mixture:
SiO
2/Al
2O
3＝0.001～1.0；
P
2O
5/Al
2O
3＝0.5～2；
Me/Al
2O
3=0～1, Me is a metal;
H
2O/Al
2O
3＝10～100；
R/Al
2O
3=1～5, wherein R is a template.
B) with sealing in the initial gel mixture material immigration stainless steel synthesis reactor, be heated to crystallization temperature then, under autogenous pressure, carry out thermostatic crystallization; After treating that crystallization is fully, the separate solid product, washing is to neutral, and drying obtains the AEI/CHA eutectic molecular sieve.
Described synthetic method, crystallization temperature is 160-250 ℃ in its step b), preferable crystallization temperature is 180～220 ℃.
Described synthetic method, the crystallization time in its step b) are 1～120 hour, and preferable crystallization time is 5-80 hour.
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to following examples.
Embodiment 1
The 11.2g pseudo-boehmite (is contained Al
2O
372.6wt%, Fushun No.3 Petroleum Factory's catalyst plant) powder dissolution is in the 66ml deionized water, and adding 18.4g phosphoric acid successively (contains H down in stirring
3PO
485wt%, chemical reagent work of Liaoning Province medicine economy and trade company) and the 5.1g silicon sol (contain SiO
228.1wt%, Shanghai reagent two factories).Add 24.5g triethylamine (analytical pure, Shenyang Xin Xi chemical reagent work) at last, after mixing, will seal in this mixture immigration stainless steel synthesis reactor.Crystallization is 48 hours under 200 ℃ and autogenous pressure, and the solid matter with deionized water washing promptly obtains sample A to neutral at 100 ℃ of air dryings, and its XRD analysis is shown in Figure 1A.With the collection of illustrative plates of gained sample XRD spectra and mimic standard A EI/CHA eutectic molecular sieve (referring to " Collection of Simulated XRDPowder Patterns for Zeolites " by M.M.J.Treacy and J.B.Higgins, 2007, FifthRevised Edition, published on behalf of the Structure Commission of theInternational Zeolite Association, p479) relatively, prove that this molecular sieve is the SAPO molecular sieve of AEI/CHA eutectic.Small amount of sample A after spraying plating, is obtained SEM Electronic Speculum figure shown in Figure 2 on the KYKY-AMRAY-1000B of Scientific Instrument Factory of C.A.S type scanning electronic microscope.As can be seen from the figure product is uniform crystal grain, does not have other stray crystal.Prove that this method synthetic molecular sieve is uniform AEI/CHA eutectic molecular sieve, but not the physical mixture of AEI and CHA.
Embodiment 2
The 11.2g pseudo-boehmite (is contained Al
2O
372.6wt%, Fushun No.3 Petroleum Factory's catalyst plant) powder dissolution is in the 60ml deionized water, and adding 18.4g phosphoric acid successively (contains H down in stirring
3PO
485wt%, chemical reagent work of Liaoning Province medicine economy and trade company) and the 8.5g silicon sol (contain SiO
228.1wt%, Shanghai reagent two factories).Add 22.5g triethylamine (analytical pure, Shenyang Xin Xi chemical reagent work) and 10g tetraethyl ammonium hydroxide (10wt%, the emerging good fortune fine chemistry in Beijing institute) at last, after mixing, will seal in this mixture immigration stainless steel synthesis reactor.Crystallization is 24 hours under 200 ℃ and autogenous pressure, and the solid matter with deionized water washing promptly obtains sample B to neutral at 100 ℃ of air dryings, and its XRD analysis is shown in Figure 1B.The collection of illustrative plates of gained sample XRD spectra and mimic standard A EI/CHA eutectic molecular sieve is compared, prove that this molecular sieve is the SAPO molecular sieve of AEI/CHA eutectic.
Embodiment 3
The 11.2g pseudo-boehmite (is contained Al
2O
372.6%, Fushun No.3 Petroleum Factory's catalyst plant) powder dissolution is in the 62ml deionized water, and adding 18.4g phosphoric acid successively (contains H down in stirring
3PO
485%, Liaoning Province chemical reagent work of medicine economy and trade company), the 5.1g silicon sol (contains SiO
228.1%, Shanghai reagent two factories) and 0.43g magnesium acetate (analytical pure, Shanghai reagent head factory second subsidiary factory).Add 24.5g triethylamine (analytical pure, Shenyang Xin Xi chemical reagent work) and 1g morpholine (analytical pure, Tianjin good fortune chemical reagent in morning factory) at last, after mixing, will seal in this mixture immigration stainless steel synthesis reactor.Crystallization is 24 hours under 200 ℃ and autogenous pressure, and the solid matter with deionized water washing promptly obtains sample C to neutral at 100 ℃ of air dryings, and its XRD analysis is shown in Fig. 1 C.The collection of illustrative plates of gained sample XRD spectra and mimic standard A EI/CHA eutectic molecular sieve is compared, prove that this molecular sieve is the MgSAPO molecular sieve of AEI/CHA eutectic.
Embodiment 4
The 11.2g pseudo-boehmite (is contained Al
2O
372.6%, Fushun No.3 Petroleum Factory's catalyst plant) powder dissolution is in the 62ml deionized water, and adding 18.4g phosphoric acid successively (contains H down in stirring
3PO
485%, Liaoning Province chemical reagent work of medicine economy and trade company), the 5.1g silicon sol (contains SiO
228.1%, Shanghai reagent two factories) and 0.6g nickelous nitrate (analytical pure, Shanghai reagent head factory second subsidiary factory).Add 22.5g triethylamine (analytical pure, Shenyang Xin Xi chemical reagent work) and 2g N at last, N-diisopropyl ethyl amine (analytical pure, new Dehua, Zhejiang worker company limited) after mixing, will seal in this mixture immigration stainless steel synthesis reactor.Crystallization is 24 hours under 210 ℃ and autogenous pressure, and the solid matter with deionized water washing is to neutral, at 100 ℃ of air dryings.The collection of illustrative plates of gained sample XRD spectra and mimic standard A EI/CHA eutectic molecular sieve is compared, prove that this molecular sieve is the NiSAPO molecular sieve of AEI/CHA eutectic.
Embodiment 5
The 11.2g pseudo-boehmite (is contained Al
2O
372.6%, Fushun No.3 Petroleum Factory's catalyst plant) powder dissolution is in the 62ml deionized water, and adding 18.4g phosphoric acid successively (contains H down in stirring
3PO
485%, Liaoning Province chemical reagent work of medicine economy and trade company), the 5.1g silicon sol (contains SiO
228.1%, Shanghai reagent two factories) and 0.5g manganous acetate (analytical pure, Beijing dicyclo chemical reagent factory).Add 22.5g triethylamine (analytical pure, Shenyang Xin Xi chemical reagent work) and 2g diethylamine (analytical pure, Shenyang Xin Xi chemical reagent work) at last, after mixing, will seal in this mixture immigration stainless steel synthesis reactor.Crystallization is 24 hours under 180 ℃ and autogenous pressure, and the solid matter with deionized water washing is to neutral, at 100 ℃ of air dryings.The collection of illustrative plates of gained sample XRD spectra and mimic standard A EI/CHA eutectic molecular sieve is compared, prove that this molecular sieve is the MnSAPO molecular sieve of AEI/CHA eutectic.
Embodiment 6
Synthesizing of the AEI/CHA eutectic molecular sieve (TiSAPO) of containing metal Ti, used titanium source is titanium sulfate (analytical pure, Peng Zhen barracks chemical plant, Nanhui), and the amount of adding is 0.7g, and other synthesis condition is with embodiment 1.
Embodiment 7
Synthesizing of the AEI/CHA eutectic molecular sieve (CrSAPO) of containing metal Cr, used chromium source is chromium nitrate (analytical pure, Beijing dicyclo chemical reagent factory), and the amount of adding is 0.74g, and other synthesis condition is with embodiment 1.
Embodiment 8
Synthesizing of the AEI/CHA eutectic molecular sieve (FeSAPO) of containing metal Fe, used source of iron is iron nitrate (analytical pure, a Tianjin Bo Di chemical reagent work), and the amount of adding is 0.74g, and other synthesis condition is with embodiment 1.
Embodiment 9
Synthesizing of the AEI/CHA eutectic molecular sieve (CoSAPO) of containing metal Co, used cobalt source is cobaltous acetate (analytical pure, Beijing dicyclo chemical reagent factory), and the amount of adding is 1.0g, and other synthesis condition is with embodiment 1.
Synthesizing of the AEI/CHA eutectic molecular sieve (CuSAPO) of containing metal Cu, used copper source is cupric nitrate (analytical pure, a Dongling fine chemistry company), and the amount of adding is 0.98g, and other synthesis condition is with embodiment 1.
Embodiment 11
Synthesizing of the AEI/CHA eutectic molecular sieve (ZnSAPO) of containing metal Zn, used zinc source is zinc nitrate (analytical pure, Shenyang City's reagent five factories), and the amount of adding is 0.5g, and other synthesis condition is with embodiment 1.
Embodiment 12
Synthesizing of the AEI/CHA eutectic molecular sieve (LaSAPO) of containing metal La, used lanthanum source is lanthanum nitrate (analytical pure, a Shanghai chemical reagents corporation of Chinese Medicine group), and the amount of adding is 0.6g, and other synthesis condition is with embodiment 1.
Embodiment 13
Synthesizing of the AEI/CHA eutectic molecular sieve (ZnMgSAPO) of containing metal Zn and Mg, used zinc source is a zinc nitrate (analytical pure, Shenyang City's reagent five factories), the amount that adds is 0.2g, used magnesium source is a magnesium acetate (analytical pure, Shanghai reagent head factory second subsidiary factory), the amount of adding is 0.2g, and other synthesis condition is with embodiment 1.
Embodiment 14
The 5.6g pseudo-boehmite (is contained Al
2O
372.6wt%, Fushun No.3 Petroleum Factory's catalyst plant) and the 8.6g aluminum isopropylate be dissolved in the 68ml deionized water, stir that adding 18.4g phosphoric acid successively (contains H down
3PO
485wt%, Liaoning Province chemical reagent work of medicine economy and trade company), the 5.1g silicon sol (contains SiO
228.1wt%, Shanghai reagent two factories) and 0.5g white carbon black (industrial goods, Shenyang Chemical Co., Ltd.).Add 24.5g triethylamine (analytical pure, Shenyang Xin Xi chemical reagent work) at last, after mixing, will seal in this mixture immigration stainless steel synthesis reactor.Crystallization is 48 hours under 200 ℃ and autogenous pressure, and the solid matter with deionized water washing is to neutral, at 100 ℃ of air dryings.Institute's synthetic molecular sieve is uniform AEI/CHA eutectic SAPO molecular sieve.
Embodiment 15
With resulting sample A among the embodiment 1 in 550 ℃ of following bubbling air roastings 4 hours.Then compressing tablet, be crushed to 20～40 orders.Take by weighing the 1.0g sample fixed-bed reactor of packing into, carry out methanol-to-olefins reaction (MTO) reaction evaluating.Charging is 30wt% methyl alcohol (analytical pure, the federal chemical reagent work in Shenyang) and 70wt% water, the pump charging, and weight space velocity WHSV is 2h
-1, temperature of reaction is 450 ℃, reaction product is analyzed by online gas-chromatography.Guaranteeing that the selectivity of low-carbon alkene in the reaction product (ethene+propylene) is up to 89%, about 350min of life-span under the situation that methyl alcohol 100% transforms.
The reaction result explanation adopts synthetic eutectic molecular sieve of the present invention to have higher selectivity of light olefin and long reaction life-span.
Claims (9)
1, a kind of AEI/CHA eutectic molecular sieve that contains triethylamine, its anhydrous chemical constitution is expressed as:
mR·(Si
x·Al
y·P
z)O
2
Wherein x, y, z are respectively the molar fraction of Si, Al, P;
X=0.001～0.98; Y=0.01～0.6; Z=0.01～0.6; And x+y+z=1;
R is the template that is present in the molecular sieve crystal micropore; M is the mole number of template R; The value of m is 0.02～0.6; Wherein template R is a triethylamine or based on the organic compounds containing nitrogen group of triethylamine, the amount of triethylamine accounts for more than the 50 weight % of template total amount.
2, molecular sieve as claimed in claim 1 wherein, contains metal M e, and the anhydrous chemical constitution of its molecular sieve is expressed as:
mR·(Me
w·Si
x·Al
y·P
z)O
2
W=0～0.6 wherein; And x+y+z+w=1;
Me is a kind of or any several mixture in titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, magnesium, calcium, strontium, barium and the lanthanum.
3, molecular sieve as claimed in claim 1, wherein, organic compounds containing nitrogen is N, N-diisopropyl ethyl amine, tetraethyl ammonium hydroxide, diethylamine, morpholine, hexahydroaniline, Tri N-Propyl Amine, Isopropylamine, di-n-propylamine, Diisopropylamine, tripropyl amine, n-Butyl Amine 99 or isobutylamine.
4, molecular sieve as claimed in claim 1 or 2, wherein, x-ray diffraction pattern has a characteristic diffraction peak at least in the scope of 16.7 ° to 17.1 ° or 21.0 ° to 21.4 ° (2 θ).
5, a kind of method for preparing the described molecular sieve of claim 1, its step is as follows:
A) by following each component oxide mol ratio, mix, get initial gel mixture with water:
SiO
2/Al
2O
3＝0.001～1.0；
P
2O
5/Al
2O
3＝0.5～2；
H
2O/Al
2O
3＝10～100；
Me/Al
2O
3=0～1, Me is a metal;
R/Al
2O
3=1～5, wherein R is a template;
B) with sealing in the initial gel mixture material immigration stainless steel synthesis reactor, be heated to 160～250 ℃ of crystallization temperatures then, under autogenous pressure, thermostatic crystallization 1-120 hour; The separate solid product, washing is to neutral, and drying obtains the AEI/CHA eutectic molecular sieve.
6, method as claimed in claim 5, wherein, used phosphorus source is a kind of or any several mixture in ortho-phosphoric acid, phosphoric acid salt, Organophosphorous compounds or the phosphorous oxides; Used aluminium source is a kind of or any several mixture in aluminium salt, aluminate, activated alumina, aluminum alkoxide, false boehmite or the pseudo-boehmite; Used silicon source is a kind of or any several mixture in silicon sol, water glass, active silica or the positive silicon ester; Used metal is a kind of of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, magnesium, calcium, strontium, barium and lanthanum or any several mixture.
7, method as claimed in claim 5, wherein, crystallization temperature is 180～220 ℃.
8, method as claimed in claim 5, wherein, crystallization time is 5～80 hours.
9, claim 1 or 2 described molecular sieves after the roasting, are used as the catalyzer of acid catalyzed reaction in 550～700 ℃ of air.
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| CN105174286A (en) * | 2015-08-17 | 2015-12-23 | 久泰能源科技有限公司 | Preparation method for high-proportion AEI/CHA eutectic molecular sieve |
| CN107032364A (en) * | 2016-02-04 | 2017-08-11 | 中国科学院大连化学物理研究所 | A kind of silicoaluminophosphamolecular molecular sieves, its preparation method and application |
| CN107032363A (en) * | 2016-02-04 | 2017-08-11 | 中国科学院大连化学物理研究所 | The new SAPO molecular sieve of one class and its synthetic method |
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