CN106809861A - The preparation method and its molecular sieve of a kind of bigger serface SAPO-11 molecular sieves - Google Patents

Abstract

The invention discloses the preparation method and its molecular sieve of a kind of bigger serface SAPO-11 molecular sieves.It uses dry gel method, with mesoporous SAPO gel as presoma, by impregnating organosilan, synthesis obtains a kind of SAPO-11 molecular sieves that the AEL structure that association (International Zeolite Association) confirms is sieved with International Molecular.SAPO-11 molecular sieves of the invention have big specific surface area, good hydrothermal stability, will be with a wide range of applications in catalytic field particularly lube base oil hydroisomerizing field, and preparation method economy of the present invention is strong, easy-to-operate, it is environment-friendly.

Description

The preparation method and its molecular sieve of a kind of bigger serface SAPO-11 molecular sieves

Technical field

The present invention relates to a kind of synthetic method of bigger serface silicoaluminophosphamolecular molecular sieves, more precisely It is on a kind of synthetic method of bigger serface SAPO-11 molecular sieves.

Background technology

SAPO-11 is the silicoaluminophosphamolecular molecular sieves with AEL (International Zeolite Association's appointment codes) structure (Atlas of Zeolite Framework Types,6^thed.,Elsevier,Amsterdam,2007；http:// Www.iza-structure.org/databases/) it has one-dimensional oval 10 yuan of rings straight hole road, aperture size It is 0.40nm × 0.65nm.Because the pore passage structure size of this molecular sieve is highly beneficial with geometric configuration In the formation of single branched paraffin isomers, the Pt-Pd/AEL silicoaluminophosphamolecular molecular sieves of Supported Pt Nanoparticles palladium noble metal Good catalysis activity and selectivity is shown in the isomerization reaction of linear paraffin.But itself The micropore being had is unfavorable for the diffusion of molecule, limits its catalysis activity.Therefore, researcher is using each Method is planted to attempt to introduce mesoporous or macropore.(J.Catal.2012,294,161-170；J.Catal.2013,301, 162-173).The common feature of these methods is that the surfactant that costliness is added under conditions of hydro-thermal is closed Into.Zeolite synthesis yield is low, complex process, operating difficulties；Surfactant is expensive, no Can reclaim, synthesize high cost.

Xerogel synthesis includes vapor auxiliary law and Vapor-phase transport method, and the method is by China scientist Xu Wen Yang teach method that proposed in nineteen ninety a kind of new prepare molecular sieve (J.Chem.Soc., Chem.Commun.1990,(10),755).The method is typically unformed raw material and water, You Jimo Unformed gel is prepared into after plate agent is well mixed, precursor mixture is obtained after drying.Precursor is mixed During thing is as special container, a small amount of water is added in a kettle., to provide the moisture required for reaction, Then crystallization under steam ambient again.Compared to traditional Hydrothermal Synthesiss, xerogel synthesis has high income, It is low in the pollution of the environment, the features such as raw material availability is high.

Although report prepare the SAPO-11 molecules with AEL skeletons using vapor auxiliary law before The preparation of sieve, its application in terms of catalysis is limited because its specific surface area is smaller.This patent is used The sol-gal process that epoxide is participated in is prepared with bigger serface, big pore volume it is mesoporous SAPO gel precursors mixture, the precursor mixture synthesizes under conditions of vapor auxiliary AEL type multi-stage porous SAPO-11 molecular sieves, because it has big specific surface area, will be in catalytic field Especially lube base oil hydroisomerizing field is preferably applied.

The content of the invention

It is an object of the invention to propose a kind of preparation method of bigger serface SAPO-11 molecular sieves.

To achieve the above object, the technical solution adopted by the present invention is：

With mesoporous SAPO gel as presoma, by impregnating organosilan, there is bar in organic amine Under part, SAPO-11 molecular sieve of the synthesis with bigger serface is aided in by vapor；Including following Step：

1) preparation of precursor mixture：Phosphorus source, silicon source, silicon source are added in solvent, is added after stirring Enter organosilan, epoxide is added after being stirred until homogeneous, aging at a certain temperature and dry Precursor mixture；

2) precursor mixture is placed in container, and is placed in inner liner of reaction kettle, in reactor The bottom of lining adds water and organic amine；

3) heating crystallization, after crystallization terminates, separates solid product, and the solid for obtaining is bigger serface SAPO-11 molecular sieves.

Concretely comprise the following steps：

During phosphorus source added into solvent, and stir；Silicon source is added, is stirred；Silicon source is added To in mixture, stir；Organosilan is added, is stirred, to above-mentioned solution in ethylene Compound, stirs；Said mixture is aging in 0~200 DEG C, the aging temperature of optimization for 10~ 60℃；Mixture after will be aging is dried, and drying temperature is 40~200 DEG C, and the drying temperature of optimization is 60~120 DEG C, precursor mixture is obtained after drying.By precursor mixture in the presence of organic amine, water steams Gas auxiliary crystallization, crystallization temperature be 100~200 DEG C, crystallization time be more than or equal to 1 minute, preferably Crystallization time be 0.5~480h；

Crystallization separates solid product after terminating, will reactant mixture be cooled to room temperature, plus deionized water, Filtering, is washed, room temperature~120 DEG C drying with deionized water to sample, and the solid sample for obtaining is With multi-stage porous SAPO-11 molecular sieves in high yield；

Roasting (300~600 DEG C of air atmosphere roastings are more than or equal to 1 hour) removes organic formwork afterwards Agent, obtains the multi-stage porous silicoaluminophosphamolecular molecular sieves of duct dredging, and the duct dredging is molecular sieve pore passage In be free of organic formwork agent.

Step 1) silicon source in precursor mixture：Silicon source：Phosphorus source：Organosilan：Epoxide：It is molten Al is pressed in agent₂O₃：SiO₂：P₂O₅：Organosilan：Epoxide：Solvent meter, molar ratio is 1:0.01~ 1：0.1~5:0.01~10：0.01~50：5~200, aging temperature is 0~200 DEG C, dries temperature Spend is 40~200 DEG C；Step 2) precursor mixture：Water：The molar ratio of organic amine is 1:0.01~ 1000:0.1~50, wherein the mole of precursor mixture is with the molar amount of phosphorus source；Step 3) crystallization Temperature is 80 DEG C~300 DEG C, and crystallization time is more than or equal to 1 minute.

Step 1) in silicon source in precursor mixture：Silicon source：Phosphorus source：Organosilan：Epoxide： Solvent presses Al₂O₃：SiO₂：P₂O₅：Organosilan：Epoxide：Solvent meter, mol ratio is 1:0.1~ 0.8：0.5~3：0.05~2:0.5~20：10~50, aging temperature is 10~60 DEG C, dries temperature Spend is 60~120 DEG C；Step 2) in) precursor mixture：Water：The mol ratio of organic amine is 1:0.1~ 100:0.5~30, wherein the mole of precursor mixture is with the molar amount of phosphorus source；Step 3) crystalline substance It is 120~240 DEG C to change temperature, and crystallization time is 1~240h.

The solvent be water, ethanol, propyl alcohol, isopropanol and ethylene glycol in one or more； Phosphorus source is one or two or more kinds in phosphoric acid, ammonium phosphate, monoammonium phosphate and ammonium dihydrogen phosphate, institute Phosphoric acid quality concentration is stated for 50-85%；Silicon source be aluminium isopropoxide, crystal aluminum chloride, boehmite, One or two or more kinds in aluminum sulfate；Silicon was Ludox, waterglass, white carbon, positive silicic acid second originally One or two or more kinds in ester；Organosilan is dimethyl tetradecyl base [3- (trimethoxy silicon substrate) third Base] ammonium chloride, dimethyl hexadecyl base [3- (trimethoxy silicon substrate) propyl group] ammonium chloride and dimethyl 18 One or more in alkyl [3- (trimethoxy silicon substrate) propyl group] ammonium chloride；Epoxide is One or two in oxirane and expoxy propane；Organic amine is dimethylamine, diethylamine, two positive third One or two or more kinds in amine, diisopropylamine, n-butylamine.

Organosilan is added during gel is prepared, or the method impregnated after passing through is added.

Product has bigger serface, and specific surface area is 180~450m²g^-1。

After the fired removal organic formwork agent of prepared molecular sieve, the phosphoric acid of duct dredging can be obtained Si-Al molecular sieve, the duct is dredged to be free of organic formwork agent in molecular sieve pore passage.Sintering temperature is 300~600 DEG C, roasting time is more than or equal to 1 hour.

SAPO-11 molecular sieves prepared by the method provided by the present invention use X-ray powder diffraction, X Fluorescent x ray spectroscopy x and SEM (SEM) are divided the molecular sieve structure and composition Analysis, determines that its structure is to sieve to assist with International Molecular by comparing with XRD powder diffraction datas storehouse card The AEL structure that can be confirmed, X-ray fluorescence spectra constituent content analysis result is determined in the molecular sieve Al₂O₃：P₂O₅：SiO₂Molar ratio, is characterized by SEM and determines its pattern.The molecular sieve for finally giving With the AEL structure that International Molecular sieve association confirms, while silicon source in the molecular sieve：Silicon source：Phosphorus source By Al₂O₃:SiO₂：P₂O₅Meter molar ratio is 1:0.1~0.6：0.8~1.2.Its X-ray diffraction Spectrogram at least has diffraction maximum set forth below,

2 θ values expression diffraction maximum position, 2 θ/°：8.10±0.2,9.51±0.2,13.18± 0.2,13.65±0.2,15.71±0.2,16.23±0.2,19.03±0.2,20.38±0.2,21.08 ±0.2,22.12±0.2,22.79±0.2,23.17±0.2,24.77±0.2,26.33± 0.2,28.70±0.2,29.50±0.2。

The beneficial effect of this synthetic method：

The characteristics of this synthetic method is the bigger serface SAPO-11 molecules under conditions of vapor auxiliary The synthesis of sieve, overcomes the characteristics of conventional hydrothermal synthetic product yield is low, and waste discharge is serious.Closed Into material be the bigger serface SAPO-11 molecular sieves with AEL structure.The inventive method has It is environment-friendly, easy to operate, the advantage of high income,.

Brief description of the drawings

Fig. 1 is the XRD of the bigger serface SAPO-11 molecular sieves synthesized by the embodiment of the present invention 1 Spectrogram.

Fig. 2 is the nitrogen thing of the bigger serface SAPO-11 molecular sieves synthesized by the embodiment of the present invention 1 Reason adsorption curve.

Fig. 3 is the SEM electricity of the bigger serface SAPO-11 molecular sieves synthesized by the embodiment of the present invention 1 Mirror photo.

Specific embodiment

Embodiment 1

To 10 grams of water are added in 50 milliliters of beakers, 2.0g crystal aluminum chlorides are added under magnetic agitation, It is even that the phosphoric acid that 1.5 gram mass concentration are 85% is added dropwise, 0.3 gram of tetraethyl orthosilicate is added dropwise after stirring, Stirring 30 minutes, adds 0.10g dimethyl hexadecyls base [3- (trimethoxy silicon substrate) propyl group] ammonium chloride, 2 milliliters of expoxy propane are dropwise added dropwise after stirring, continue to stir 5 minutes.By mixture in 40 DEG C Under aging 24 hours, then in drying to obtain precursor mixture under 100 degree.Take above-mentioned precursor mixture 1 In gram being placed in standoff tetrafluoro pallet, and by pallet as stainless steel cauldron in, in reactor Bottom add 1 gram of water, 0.5 gram of positive di-n-propylamine to be warming up to 200 DEG C after sealing, holding 2 days, so Reactant mixture is cooled to room temperature afterwards, and is washed with deionized 3 times.Final white powder is put Dried in 120 DEG C of baking ovens, tested through XRD, SEM, the white powder is with many of AEL structure Level hole silicoaluminophosphamolecular molecular sieves.Products therefrom is calcined 24h through 570 DEG C under air atmosphere, compared greatly Surface area SAPO-11 molecular sieves.

Embodiment 2

To 5 grams of water, 5 grams of ethanol are added in 50 milliliters of beakers, 2.0g crystallization chlorinations are added under magnetic agitation Aluminium, it is uniform that the phosphoric acid that 1.5 gram mass concentration are 85% is added dropwise, 0.5 gram of positive silicic acid is added dropwise after stirring Ethyl ester, stirs 30 minutes, adds 0.30g dimethyl hexadecyls base [3- (trimethoxy silicon substrate) propyl group] Ammonium chloride, is then dropwise added dropwise 2 milliliters of expoxy propane, continues to stir 5 minutes.By mixture in 40 DEG C Under aging 24 hours, then in drying to obtain precursor mixture under 100 degree.Take above-mentioned precursor mixture 1 In gram being placed in standoff tetrafluoro pallet, and by pallet as stainless steel cauldron in, in reactor Bottom add 1 gram of water, 1 gram of positive di-n-propylamine to be warming up to 200 DEG C after sealing, holding 2 days, then Reactant mixture is cooled to room temperature, and is washed with deionized 3 times.Final white powder is placed in Dried in 120 DEG C of baking ovens, tested through XRD, SEM, the white powder is the multistage with AEL structure Hole silicoaluminophosphamolecular molecular sieves.Products therefrom is calcined 24h through 570 DEG C under air atmosphere, table is compared greatly Area SAPO-11 molecular sieves.

Embodiment 3

To 10 ethanol are added in 50 milliliters of beakers, 2.0g crystal aluminum chlorides are added under magnetic agitation, It is even that the phosphoric acid that 1.5 gram mass concentration are 85% is added dropwise, 0.4 gram of tetraethyl orthosilicate is added dropwise after stirring, Stirring 30 minutes, adds 0.30g dimethyl tetradecyls base [3- (trimethoxy silicon substrate) propyl group] ammonium chloride, Then 3 milliliters of expoxy propane are dropwise added dropwise, continue to stir 5 minutes.By mixture in aging at 40 DEG C 24 hours, then in drying to obtain precursor mixture under 100 degree.1 gram of above-mentioned precursor mixture is taken to be placed in In with standoff tetrafluoro pallet, and by pallet as stainless steel cauldron in, in the bottom of reactor Add 1 gram of water, 0.5 gram of positive di-n-propylamine that 200 DEG C are warming up to after sealing, kept for 2 days, then will be anti- Answer mixture to be cooled to room temperature, and be washed with deionized 3 times.Final white powder is placed in 120 DEG C Dried in baking oven, tested through XRD, SEM, the white powder is the multi-stage porous phosphorus with AEL structure Sour Si-Al molecular sieve.Products therefrom is calcined 24h through 570 DEG C under air atmosphere, obtains bigger serface SAPO-11 molecular sieves.

Embodiment 4

To 8 grams of water are added in 50 milliliters of beakers, 1.5g crystal aluminum chlorides are added under magnetic agitation, uniformly The phosphoric acid that 2.0 gram mass concentration are 85% is added dropwise, 0.3 gram of tetraethyl orthosilicate is added dropwise after stirring, stir Mix 30 minutes, add 0.50g dimethyl stearyl [3- (trimethoxy silicon substrate) propyl group] ammonium chloride, Then 4 milliliters of expoxy propane are dropwise added dropwise, continue to stir 5 minutes.By mixture in aging at 40 DEG C 12 hours, then in drying to obtain precursor mixture under 100 degree.1 gram of above-mentioned precursor mixture is taken to be placed in In with standoff tetrafluoro pallet, and by pallet as stainless steel cauldron in, in the bottom of reactor Add 1 gram of water, 0.5 gram of positive di-n-propylamine that 200 DEG C are warming up to after sealing, kept for 2 days, then will be anti- Answer mixture to be cooled to room temperature, and be washed with deionized 3 times.Final white powder is placed in 120 DEG C Dried in baking oven, tested through XRD, SEM, the white powder is the multi-stage porous phosphorus with AEL structure Sour Si-Al molecular sieve.Products therefrom is calcined 24h through 570 DEG C under air atmosphere, obtains bigger serface SAPO-11 molecular sieves.

Embodiment 5

To 10 grams of water are added in 50 milliliters of beakers, 2.00g crystal aluminum chlorides are added under magnetic agitation, It is even that the phosphoric acid that 1.5 gram mass concentration are 85% is added dropwise, 0.6 gram of tetraethyl orthosilicate is added dropwise after stirring, Stirring 30 minutes, adds 0., 250g dimethyl hexadecyls base [3- (trimethoxy silicon substrate) propyl group] chlorination Ammonium, is then dropwise added dropwise 4 milliliters of expoxy propane, continues to stir 5 minutes.By mixture at 40 DEG C Aging 24 hours, then in drying to obtain precursor mixture under 100 degree.Take 1 gram of above-mentioned precursor mixture In being placed in standoff tetrafluoro pallet, and by pallet as stainless steel cauldron in, in reactor Bottom adds 1 gram of water, 0.5 gram of positive di-n-propylamine to be warming up to 200 DEG C after sealing, holding 2 days, then Reactant mixture is cooled to room temperature, and is washed with deionized 3 times.Final white powder is placed in Dried in 120 DEG C of baking ovens, tested through XRD, SEM, the white powder is the multistage with AEL structure Hole silicoaluminophosphamolecular molecular sieves.Products therefrom is calcined 24h through 570 DEG C under air atmosphere, table is compared greatly Area SAPO-11 molecular sieves.

Embodiment 6

To 10 grams of ethanol are added in 50 milliliters of beakers, 2.00g crystal aluminum chlorides are added under magnetic agitation, It is uniform that the phosphoric acid that 1.2 gram mass concentration are 85% is added dropwise, 0.4 gram of tetraethyl orthosilicate is added dropwise after stirring, Stirring 30 minutes, adds 0.40g dimethyl stearyl [3- (trimethoxy silicon substrate) propyl group] ammonium chloride, Then 2 milliliters of expoxy propane are dropwise added dropwise, continue to stir 5 minutes.By mixture in aging at 40 DEG C 24 hours, then in drying to obtain precursor mixture under 120 degree.1 gram of above-mentioned precursor mixture is taken to be placed in In with standoff tetrafluoro pallet, and by pallet as stainless steel cauldron in, in the bottom of reactor Add 1 gram of water, 0.5 gram of positive di-n-propylamine that 200 DEG C are warming up to after sealing, kept for 1 day, then will be anti- Answer mixture to be cooled to room temperature, and be washed with deionized 3 times.Final white powder is placed in 120 DEG C Dried in baking oven, tested through XRD, SEM, the white powder is the multi-stage porous phosphorus with AEL structure Sour Si-Al molecular sieve.Products therefrom is calcined 24h through 570 DEG C under air atmosphere, obtains bigger serface SAPO-11 molecular sieves.

Embodiment 7

To 12 grams of water are added in 50 milliliters of beakers, 1.50g crystal aluminum chlorides are added under magnetic agitation, uniformly The phosphoric acid that 1.8 gram mass concentration are 85% is added dropwise, 0.3 gram of tetraethyl orthosilicate is added dropwise after stirring, stir Mix 30 minutes, add 0.30g dimethyl hexadecyls base [3- (trimethoxy silicon substrate) propyl group] ammonium chloride, Then 4 milliliters of expoxy propane are dropwise added dropwise, continue to stir 5 minutes.By mixture in aging at 40 DEG C 24 hours, then in drying to obtain precursor mixture under 120 degree.1 gram of above-mentioned precursor mixture is taken to be placed in In with standoff tetrafluoro pallet, and by pallet as stainless steel cauldron in, in the bottom of reactor Add 1 gram of water, 0.5 gram of positive di-n-propylamine that 200 DEG C are warming up to after sealing, kept for 1 day, then will be anti- Answer mixture to be cooled to room temperature, and be washed with deionized 3 times.Final white powder is placed in 120 DEG C Dried in baking oven, tested through XRD, SEM, the white powder is the multi-stage porous phosphorus with AEL structure Sour Si-Al molecular sieve.Products therefrom is calcined 24h through 570 DEG C under air atmosphere, obtains bigger serface SAPO-11 molecular sieves.

Embodiment 8

To 10 grams of water are added in 50 milliliters of beakers, 2.00g crystal aluminum chlorides are added under magnetic agitation, It is even that the phosphoric acid that 1.5 gram mass concentration are 85% is added dropwise, 0.3 gram of tetraethyl orthosilicate is added dropwise after stirring, Stirring 30 minutes, adds 0.20g dimethyl hexadecyls base [3- (trimethoxy silicon substrate) propyl group] ammonium chloride, Then 2 milliliters of expoxy propane are dropwise added dropwise, continue to stir 5 minutes.By mixture in aging at 40 DEG C 24 hours, then in drying to obtain precursor mixture under 100 degree.1 gram of above-mentioned precursor mixture is taken to be placed in In with standoff tetrafluoro pallet, and by pallet as stainless steel cauldron in, in the bottom of reactor Add 0.5 gram of water, 0.8 gram of positive di-n-propylamine that 180 DEG C are warming up to after sealing, kept for 2 days, then will Reactant mixture is cooled to room temperature, and is washed with deionized 3 times.Final white powder is placed in 120 DEG C Dried in baking oven, tested through XRD, SEM, the white powder is the multi-stage porous phosphorus with AEL structure Sour Si-Al molecular sieve.Products therefrom is calcined 24h through 570 DEG C under air atmosphere, obtains bigger serface SAPO-11 molecular sieves.

Embodiment 9

To 10 grams of water are added in 50 milliliters of beakers, 2.00g crystal aluminum chlorides are added under magnetic agitation, uniformly The phosphoric acid that 1.2 gram mass concentration are 85% is added dropwise, 0.2 gram of tetraethyl orthosilicate is added dropwise after stirring, stir Mix 30 minutes, add 0., 500g dimethyl hexadecyls base [3- (trimethoxy silicon substrate) propyl group] ammonium chloride, Then 5 milliliters of expoxy propane are dropwise added dropwise, continue to stir 5 minutes.By mixture in aging at 40 DEG C 24 hours, then in drying to obtain precursor mixture under 100 degree.1 gram of above-mentioned precursor mixture is taken to be placed in In with standoff tetrafluoro pallet, and by pallet as stainless steel cauldron in, in the bottom of reactor Add 1.5 grams of water, 0.7 gram of positive di-n-propylamine that 200 DEG C are warming up to after sealing, kept for 3 days, then will Reactant mixture is cooled to room temperature, and is washed with deionized 3 times.Final white powder is placed in 120 DEG C Dried in baking oven, tested through XRD, SEM, the white powder is the multi-stage porous phosphorus with AEL structure Sour Si-Al molecular sieve.Products therefrom is calcined 24h through 570 DEG C under air atmosphere, obtains bigger serface SAPO-11 molecular sieves.

Claims (9)

1. a kind of preparation method of bigger serface SAPO-11 molecular sieves, it is characterised in that：With mesoporous SAPO gel is presoma, by impregnating organosilan, under organic amine existence condition, is passed through Vapor auxiliary SAPO-11 molecular sieve of the synthesis with bigger serface；Comprise the following steps：

1) preparation of precursor mixture：Phosphorus source, silicon source, silicon source are added in solvent, is added after stirring Enter organosilan, epoxide is added after being stirred until homogeneous, aging at a certain temperature and dry Precursor mixture；

2) precursor mixture is placed in container, and is placed in inner liner of reaction kettle, in reactor The bottom of lining adds water and organic amine；

3) heating crystallization, after crystallization terminates, separates solid product, and the solid for obtaining is bigger serface SAPO-11 molecular sieves.

2. according to the preparation method described in claim 1, it is characterised in that：Step 1) precursor mixing Silicon source in thing：Silicon source：Phosphorus source：Organosilan：Epoxide：Solvent presses Al₂O₃：SiO₂：P₂O₅： Organosilan：Epoxide：Solvent meter, molar ratio is 1:0.01~1：0.1~5:0.01~ 10：0.01~50：5~200, aging temperature is 0~200 DEG C, and drying temperature is 40~200 DEG C； Step 2) precursor mixture：Water：The molar ratio of organic amine is 1:0.01~1000:0.1~50, its The mole of middle precursor mixture is with the molar amount of phosphorus source；Step 3) crystallization temperature be 80 DEG C~ 300 DEG C, crystallization time is more than or equal to 1 minute.

3. according to the preparation method described in claim 1 or 2, it is characterised in that：Step 1) in precursor Silicon source in mixture：Silicon source：Phosphorus source：Organosilan：Epoxide：Solvent presses Al₂O₃：SiO₂： P₂O₅：Organosilan：Epoxide：Solvent meter, mol ratio is 1:0.1~0.8：0.5~3：0.05~ 2:0.5~20：10~50, aging temperature is 10~60 DEG C, and drying temperature is 60~120 DEG C；Step It is rapid 2) in) precursor mixture：Water：The mol ratio of organic amine is 1:0.1~100:0.5~30, its The mole of middle precursor mixture is with the molar amount of phosphorus source；Step 3) crystallization temperature for 120~ 240 DEG C, crystallization time is 1~240h.

4. according to the preparation method described in claim 1, it is characterised in that：The solvent is water, second One or more in alcohol, propyl alcohol, isopropanol and ethylene glycol；Phosphorus source be phosphoric acid, ammonium phosphate, One or two or more kinds in monoammonium phosphate and ammonium dihydrogen phosphate, the phosphoric acid quality concentration is 50-85%；Silicon source be aluminium isopropoxide, crystal aluminum chloride, boehmite, aluminum sulfate in one kind or More than two kinds；Silicon was one kind or two kinds in Ludox, waterglass, white carbon, tetraethyl orthosilicate originally More than；Organosilan is dimethyl tetradecyl base [3- (trimethoxy silicon substrate) propyl group] ammonium chloride, diformazan Base cetyl [3- (trimethoxy silicon substrate) propyl group] ammonium chloride and dimethyl stearyl [3- (trimethoxies Base silicon substrate) propyl group] one or more in ammonium chloride；Epoxide is oxirane and epoxy One or two in propane；Organic amine be dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, One or two or more kinds in n-butylamine.

5., according to the preparation method described in claim 1, organosilan adds during gel is prepared Enter, or the method impregnated after passing through is added.

6. according to the preparation method described in claim 1, it is characterised in that：Product has Large ratio surface Product, specific surface area is 180~450m²g^-1。

7. according to the preparation method described in claim 1, it is characterised in that：Prepared molecular sieve warp After roasting removal organic formwork agent, the silicoaluminophosphamolecular molecular sieves of duct dredging can be obtained, the duct is dredged Lead to be free of organic formwork agent in molecular sieve pore passage.

8. according to the preparation method described in claim 7, it is characterised in that：Sintering temperature be 300~ 600 DEG C, roasting time is more than or equal to 1 hour.

9. the molecular sieve that prepared by any preparation method described in usage right requirement 1~7, it is characterised in that： There is SAPO-11 molecular sieves International Molecular to sieve the AEL structure that association confirms, while silicon source in the molecular sieve： Silicon source：Phosphorus source presses Al₂O₃:SiO₂：P₂O₅Meter molar ratio is 1:0.1~0.6：0.8~1.2；Its X-ray diffraction spectrogram at least has diffraction maximum set forth below,

2 θ values expression diffraction maximum position, 2 θ/°：8.10±0.2,9.51±0.2,13.18± 0.2,13.65±0.2,15.71±0.2,16.23±0.2,19.03±0.2,20.38±0.2,21.08 ±0.2,22.12±0.2,22.79±0.2,23.17±0.2,24.77±0.2,26.33± 0.2,28.70±0.2,29.50±0.2。