CN102219237A - Method for preparing SAPO (Silico-Aluminophosphate) molecular sieve material with multi-level-hole structure - Google Patents
Method for preparing SAPO (Silico-Aluminophosphate) molecular sieve material with multi-level-hole structure Download PDFInfo
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Abstract
The invention relates to a method for preparing SAPO (SIlico-Aluminophosphate) molecular sieve material with a multi-level-hole structure, mainly solving the problem that the whole SAPO molecular sieve material with the multi-level-hole structure is difficult to obtain in the prior art. The method adopts the following technical scheme for better solving the problem: adopting and hydrolyzing a mixture of phase-separation inducer R1, a gel accelerator R2, an organic solvent R3, water, a phosphorus source, a silicon source and an aluminum source to obtain a precursor I of silicon-phosphorus-aluminum oxide material; carrying out gel aging on the precursor I, thus obtaining a precursor II of the silicon-phosphorus-aluminum oxide material; drying and roasting the precursor II of the silicon-phosphorus-aluminum oxide material, thus obtaining silicon-phosphorus-aluminum oxide material III with a double-continuous-large-hole structure; dipping the silicon-phosphorus-aluminum oxide material III into solution containing a template agent, drying the silicon-phosphorus-aluminum oxide material III, then arranging the silicon-phosphorus-aluminum oxide material III at the upper part of a reaction kettle, adding organic amine solution at the bottom of the reaction kettle, and then crystallizing; and after the crystallization, washing, drying and roasting a sample, thus obtaining the whole SAPO molecular sieve material with the multi-level-hole structure. The method can be used for industrial production of the molecular sieve with multi-level-hole structure.
Description
Technical field
The present invention relates to a kind of preparation method of hierarchical porous structure SAPO molecular sieve integral material.
Background technology
Silicon aluminium phosphate (SAPO) molecular sieve is because it has suitable acid site distribution and special characteristics such as pore structure, in hydrocarbon reactions such as cracking, alkylation, isomerization, polymerization, reformation, hydrogenation, dehydrogenation, hydration reaction, especially in the reaction of catalysis methanol system alkene, shown excellent catalytic performance, but because the problem of aspects such as pore structure, pattern and preparation method makes the application of SAPO molecular sieve be restricted.At first be the pore structure aspect, because traditional SAPO molecular sieve only has microvoid structure, this has greatly limited mass transfer and the diffusion of macromole such as heavy oil component in catalyzer, thereby has suppressed reactive behavior, selectivity and the life-span of catalyzer.Next is the pattern aspect, traditional molecular sieve is a powder, have only through complicated forming step just can be applied in the industrial production, yet the affiliation that adds of a large amount of binding agents causes the obstruction in duct and the embedding of active sites in the moulding process, thereby cause the reduction of catalytic activity.Be the preparation method at last, traditional method for preparing the SAPO molecular sieve is a hydrothermal synthesis method, this method prepares molecular sieve process more complicated, need to use in a large number the organic amine template that can pollute environment, and needs at last just can obtain molecular sieve through numerous and diverse sepn process.
For solving this above problem, Recent study personnel have proposed to be equipped with gas phase crystallization legal system the idea of composite hole zeolite integral material, promptly prepare a kind of catalyzer by gas phase crystallization method, make it have integrated pattern and have two simultaneously and overlap different pore canal system (Holland B T, Abrams L, Stein A.J.Am.Chem.Soc.1999,121,4308-4309).Wherein micro-pore zeolite provides active active centre for reaction, and macroporous/mesoporous duct provides enough diffusion admittances for material.This composite holes integral material has had high diffusion of macroporous/mesoporous material and the highly active advantage of zeolitic material simultaneously, has avoided complicated moulding process again.In addition, compare with traditional hydrothermal synthesis method, the molecular sieve and the mother liquor of gas phase crystallization method gained are directly isolating, can save numerous and diverse sepn process, thereby reduce the consumption of organic formwork agent, and reclaim and reuse organic formwork agent easily.In addition, gas phase crystallization method can not produce a large amount of waste liquids, and is environmentally friendly, is a kind of easy, economic method, and has been successfully applied to the preparation of multiple molecular sieve.People such as Zhao Tianbo are flooded the back by the silicone monolith with original position carbon distribution in silicone monolith or the hole and are assisted rotating crystal method to obtain micropore/macropore Si-Al molecular sieve (Yangchuan Tong by water vapour in containing the molecular sieve precursor solution in aluminium source, Tianbo Zhao, Fengyan Li, Yue Wang.Chem.Mater.2006,18,4218-4220; Qian Lei, Tianbo Zhao, Fengyan Li, Lingling Zhang, Yue Wang.Chem.Commun., 2006,1769-1771).
Although the various countries researchist develops the synthetic method of numerous hierarchical porous structure molecular sieves, the preparation of hierarchical porous structure SAPO molecular sieve integral material at present is still one of difficult point in the synthetic field.This shows that it is simple to develop a kind of preparation process, environmentally friendly and preparation method that have a hierarchical porous structure aluminium silicophosphate molecular sieve integral material of better mass-transfer performance realizes and enlarges its actual key in application place.
Summary of the invention
Technical problem to be solved by this invention is the problem that is difficult to obtain have the SAPO molecular sieve integral material of hierarchical porous structure in the prior preparation method, and a kind of preparation method of the new SAPO molecular sieve integral material that contains mesoporous or macropore is provided.The SAPO molecular sieve integral material of this method preparation has hierarchical porous structure.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of hierarchical porous structure SAPO molecular sieve integral material may further comprise the steps:
A) will be separated mixture hydrolysis under-20 ℃～40 ℃ conditions in inductor R1, gel promotor R2, organic solvent R3, water, phosphorus source, silicon source and aluminium source obtains silicon phosphorus aluminum oxide material presoma I, and wherein, the phosphorus source is by the theoretical P that generates
2O
5Amount meter, aluminium source are by the theoretical Al that generates
2O
3Amount meter, silicon source are by the theoretical SiO that generates
2The amount meter, the mixture weight ratio consists of: R1/Al
2O
3=0.01～1.0; R2/Al
2O
3=1.11～6.66; R3/Al
2O
3=0～11.1; H
2O/Al
2O
3=5.56～22.22; SiO
2/ Al
2O
3=0.04～0.89; P
2O
5/ Al
2O
3=0.06～2.79;
B) above-mentioned silicon phosphorus aluminum oxide material presoma I is put into the mould gel and wear out, obtain silicon phosphorus aluminum oxide material presoma II;
C) make the silicon phosphorus aluminum oxide material III of composite pore structural after silicon phosphorus aluminum oxide material presoma II drying, the roasting;
D) silicon phosphorus aluminum oxide material III is placed the top of reactor, the reactor bottom added a kind of in water or the organic amine solution, 150～220 ℃ of following crystallization 0.5～12 day; Reaction finishes the afterreaction still cools off in state of nature, at last to sample wash, drying and roasting obtain hierarchical porous structure SAPO molecular sieve integral material;
The inductor R1 that wherein is separated be selected from polyoxyethylene glycol, polyoxyethylene or polyethylene oxide at least a, its molecular-weight average is 1000～12000000;
Gel promotor R2 is selected from least a in propylene oxide, propylene oxide derivative, the Racemic glycidol ether compound;
Organic solvent R3 is selected from least a in short chain alcohol (carbochain is less than 7), acetone or the tetrahydrofuran (THF).
In the technique scheme, silicon source preferred version is to be selected from least a in positive quanmethyl silicate, positive tetraethyl orthosilicate, positive silicic acid orthocarbonate, positive silicic acid four butyl esters or the silicon sol.Aluminium source preferred version is at least a for being selected from aluminum nitrate, aluminum chloride or the Tai-Ace S 150.Phosphorus source preferred version is at least a in phosphoric acid, ammonium phosphate, Secondary ammonium phosphate, ammonium hydrogen phosphate, potassiumphosphate, dipotassium hydrogen phosphate, potassium hydrogen phosphate, sodium phosphate, Sodium phosphate dibasic or the sodium hydrogen phosphate.Gel promotor R2 preferred version is at least a in propylene oxide or the propylene oxide derivative.Organic solvent R3 preferred version is at least a in short chain alcohol (carbochain is less than 7) or the acetone.Mixture weight than forming preferable range is in the step a): R1/Al
2O
3=0.04～0.81; R2/Al
2O
3=2.22～5.55; R3/Al
2O
3=1.11～8.88; H
2O/Al
2O
3=8.88～17.77; SiO
2/ Al
2O
3=0.12～0.70; P
2O
5/ Al
2O
3=1.08～2.04.Regulating pH value preferable range with alkali in the step a) is 4～8.5.The alkali preferred version of regulating the pH value in the step a) is at least a in ammoniacal liquor, diethylamine, triethylamine, sodium hydroxide or the potassium hydroxide.Gel aging temperature preferable range is 30～90 ℃ in the step b), and the digestion time preferable range is 2～96 hours.In the step c), the drying temperature preferable range is 10～110 ℃, and time of drying, preferable range was 0.5～7 day; The maturing temperature preferable range is 500～800 ℃, and the roasting time preferable range is 2～10 hours.Organic amine template preferred version is at least a in tetraethyl-oxyammonia, tetraethylammonium bromide, triethylamine or the quadrol in the step d).The crystallization temperature preferable range is 160～200 ℃ in the step d), and the crystallization time preferable range is 1～10 day.
In the inventive method, I puts in the mould of arbitrary shape with silicon phosphorus aluminum oxide material presoma, just can obtain the hierarchical porous structure molecular sieve integral material of respective shapes.
At present, the molecular sieve integral material of hierarchical porous structure mainly concentrates on the sieve and silica-sesquioxide, reports less for the preparation method of the silicon phosphorus aluminum oxide molecular sieve integral material of hierarchical porous structure.The present invention at first makes the amorphous silicon phosphorus aluminum oxide integral material with co-continuous macroporous structure by sol-gel method, to utilize water vapour assist in transmutation method or gas phase crystallization method to make amorphous hole wall zeolitization after its dipping template then, obtain forming certain hierarchical porous structure aluminium silicophosphate molecular sieve integral material, and by regulating the humidity of crystallization process, crystallization time and temperature can obtain the molecular sieve integral material of different crystallization degrees.This method preparation process is simple, control easily, and the degree of crystallinity height has been obtained better technical effect.
Description of drawings
Scanning electron microscope (SEM) photo of the hierarchical porous structure SAPO molecular sieve integral material that Fig. 1 obtains for [embodiment 1].
The X-diffraction spectrogram (XRD) of the hierarchical porous structure SAPO molecular sieve integral material that Fig. 2 obtains for [embodiment 1].
Scanning electron microscope (SEM) photo of the hierarchical porous structure SAPO molecular sieve integral material that Fig. 3 obtains for [embodiment 2].
Scanning electron microscope (SEM) photo of the hierarchical porous structure SAPO molecular sieve integral material that Fig. 4 obtains for [embodiment 3].
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
With 6.63 gram Aluminium chloride hexahydrates, 0.82 gram methyl silicate, 1.5 gram polyoxyethylene glycol (molecular weight 10000, be called for short PEG) and 3.36 gram dipotassium hydrogen phosphates join the mixing solutions that 4.35 gram ethanol and 15.99 restrain water, stirring and dissolving under the room temperature, in mixing solutions, add 5.00 gram propylene oxide (PO), stir.Mixed solution poured in the mould seal, put into 60 ℃ of baking ovens and left standstill aging 24 hours.Take out the back demoulding, 60 ℃ of dryings obtained the only stone material of silicon phosphorus aluminum oxide in 8 hours 550 ℃ of roastings at last.The only stone of amorphous silicon phosphorus aluminum oxide of gained was flooded 24 hours in tetraethyl-oxyammonia solution, and drying at room temperature 24 hours was placed on the top that is placed on gas phase reaction kettle then, and reactor bottom adds water, 200 ℃ of following crystallization 3 days; Reaction finishes the afterreaction still cools off in state of nature, at last to sample washs, drying and roasting obtain containing macropore SAPO molecular sieve integral material (SEM sees Fig. 1, and XRD sees Fig. 2).The weight ratio of each component is: R1/Al
2O
3=0.07, R2/Al
2O
3=5.55, R3/Al
2O
3=4.83, H
2O/Al
2O
3=17.77, SiO
2/ Al
2O
3=0.36, P
2O
5/ Al
2O
3=0.8.
[embodiment 2]
With 6.63 gram Aluminium chloride hexahydrates, 0.82 gram methyl silicate, 1.5 gram polyoxyethylene glycol (molecular weight 10000, abbreviation PEG), 7.83 gram Sodium phosphate dibasics join the mixing solutions of 4.35 gram ethanol and 15.99 gram water, stirring and dissolving under the room temperature, with alkali the pH value is adjusted to 8 then, in mixing solutions, add 5.00 gram propylene oxide (PO), stir.Mixed solution poured in the mould seal, put into 60 ℃ of baking ovens and left standstill aging 24 hours.Take out the back demoulding, 60 ℃ of dryings obtained the only stone material of silicon phosphorus aluminum oxide in 8 hours 550 ℃ of roastings at last.The only stone of amorphous silicon phosphorus aluminum oxide of gained is placed the top of gas phase reaction kettle, and the reactor bottom added tetraethyl ammonium hydroxide solution, 200 ℃ of following crystallization 3 days; Reaction finishes the afterreaction still cools off in state of nature, at last to sample washs, drying and roasting obtain containing macropore SAPO molecular sieve integral material (SEM sees Fig. 3).The weight ratio of each component is: R1/Al
2O
3=0.07, R2/Al
2O
3=5.55, R3/Al
2O
3=4.83, H
2O/Al
2O
3=17.77, SiO
2/ Al
2O
3=0.36, P
2O
5/ Al
2O
3=1.10.
[embodiment 3]
With 6.63 gram Aluminium chloride hexahydrates, 0.82 gram methyl silicate, 1.5 gram polyoxyethylene glycol (molecular weight 10000, abbreviation PEG), 5.83 gram dipotassium hydrogen phosphates join the mixing solutions of 4.35 gram ethanol and 15.99 gram water, stirring and dissolving under the room temperature, with alkali the pH value is adjusted to 8 then, in mixing solutions, add 5.00 gram propylene oxide (PO), stirred 1 minute.Mixed solution poured in the mould seal, put into 60 ℃ of baking ovens and left standstill aging 24 hours.Take out the back demoulding, 60 ℃ of dryings obtained the only stone material of silicon phosphorus aluminum oxide in 8 hours 550 ℃ of roastings at last.The only stone of amorphous silicon phosphorus aluminum oxide of gained was flooded 24 hours in tetraethyl-oxyammonia solution, and drying at room temperature 24 hours was placed on the top that is placed on gas phase reaction kettle then, and reactor bottom adds water, 200 ℃ of following crystallization 1 day; Reaction finishes the afterreaction still cools off in state of nature, at last to sample washs, drying and roasting obtain containing macropore SAPO molecular sieve integral material (SEM sees Fig. 4).The weight ratio of each component is: R1/Al
2O
3=0.07, R2/Al
2O
3=5.55, R3/Al
2O
3=4.83, H
2O/Al
2O
3=17.77, SiO
2/ Al
2O
3=0.36, P
2O
5/ Al
2O
3=1.39.
[embodiment 4]
With 6.63 gram Aluminium chloride hexahydrates, 0.82 gram methyl silicate, 1.5 gram polyoxyethylene glycol (molecular weight 10000, abbreviation PEG), 11.7 gram dipotassium hydrogen phosphates join the mixing solutions of 20 gram water, stirring and dissolving under the room temperature adds 5.00 gram propylene oxide (PO) in mixing solutions, stirred 1 minute.Mixed solution poured in the mould seal, put into 60 ℃ of baking ovens and left standstill aging 24 hours.Take out the back demoulding, 60 ℃ of dryings obtained the only stone material of silicon phosphorus aluminum oxide in 8 hours 550 ℃ of roastings at last.The only stone of amorphous silicon phosphorus aluminum oxide of gained was flooded 24 hours in tetraethyl-oxyammonia solution, and drying at room temperature 24 hours was placed on the top that is placed on gas phase reaction kettle then, and reactor bottom adds water, 200 ℃ of following crystallization 1 day; Reaction finishes the afterreaction still cools off in state of nature, at last to sample washs, drying and roasting obtain containing macropore SAPO molecular sieve integral material.The weight ratio of each component is: R1/Al
2O
3=0.07, R2/Al
2O
3=5.55, R3/Al
2O
3=0, H
2O/Al
2O
3=22.22, SiO
2/ Al
2O
3=0.36, P
2O
5/ Al
2O
3=2.79.
[embodiment 5～31]
According to each Step By Condition of [embodiment 1], make hierarchical porous structure molecular sieve monolith material, just change parameters such as raw material (table 1) proportioning, gel aging temperature, crystallization temperature, crystallization time, specifically list in table 2.The synthetic product has and [embodiment 1], [embodiment 2] or the similar crystalline structure of [embodiment 3] product through characterizing its result of explanation, and its concrete reaction conditions sees Table 2.
[embodiment 32]
Adopt fixed-bed catalytic reactor, reactor is a stainless steel tube, catalyzer to embodiment 3 preparations carries out the evaluation of methanol-to-olefins reaction reactive behavior, investigating used processing condition is: loaded catalyst 0.5g, temperature of reaction is 450 ℃, reaction pressure is 0.1MPa, and water/raw material weight ratio is 0.25, and weight space velocity is 1h
-1Full product on-line analysis.Appraisal result is as shown in table 3.
Table 3
[comparative example 1]
SAPO-34 molecular sieve with the binding agent moulding
According to processing condition used among the patent 200410024734.X: the catalyzer loading capacity is 1.46 grams, and temperature of reaction is 450 ℃, and reaction pressure is a normal pressure, and the weight space velocity of first alcohol and water is respectively 1.25 and 3.75h
-1, the flow of nitrogen is 50 ml/min.Catalyzer (A) to embodiment 3 preparation carries out the evaluation of methanol-to-olefins reaction reactive behavior, and with above-mentioned patent in the reactive behavior of catalyzer CS-02 compare.Appraisal result is as shown in table 4.
Table 4
[comparative example 2]
Do not contain mesoporous and SAPO-34 molecular sieve integral material macropore
6.63 gram Aluminium chloride hexahydrates, 0.82 gram methyl silicate, 5.83 gram dipotassium hydrogen phosphates are joined the mixing solutions of 4.35 gram ethanol and 15.99 gram water, stirring and dissolving under the room temperature, with alkali the pH value is adjusted to 8 then, in mixing solutions, adds 5.00 gram propylene oxide (PO), stirred 1 minute.Mixed solution poured in the mould seal, put into 60 ℃ of baking ovens and left standstill aging 24 hours.Take out the back demoulding, 60 ℃ of dryings obtained the only stone material of silicon phosphorus aluminum oxide in 8 hours 550 ℃ of roastings at last.The only stone of amorphous silicon phosphorus aluminum oxide of gained was flooded 24 hours in tetraethyl-oxyammonia solution, and drying at room temperature 24 hours was placed on the top that is placed on gas phase reaction kettle then, and reactor bottom adds water, 200 ℃ of following crystallization 1 day; Reaction finishes the afterreaction still cools off in state of nature, at last to sample washs, drying and roasting are not contained mesoporous and macropore SAPO-34 molecular sieve integral material.The weight ratio of each component is: R1/Al
2O
3=0.07, R2/Al
2O
3=5.55, H
2O/Al
2O
3=17.77, SiO
2/ Al
2O
3=0.36, P
2O
5/ Al
2O
3=1.39.
According to the processing condition that [embodiment 32] are used the catalyzer (A) of embodiment 3 preparations and the catalyzer (B) of comparative example 2 preparations are carried out the evaluation of methanol-to-olefins reaction reactive behavior.Appraisal result is as shown in table 5.
Table 5
Claims (8)
1. the preparation method of a hierarchical porous structure SAPO molecular sieve integral material may further comprise the steps:
A) will be separated the mixture in inductor R1, gel promotor R2, organic solvent R3, water, phosphorus source, silicon source and aluminium source under-20 ℃～40 ℃ conditions, hydrolysis obtains silicon phosphorus aluminum oxide material presoma I, and wherein, the phosphorus source is by the theoretical P that generates
2O
5Amount meter, aluminium source are by the theoretical Al that generates
2O
3Amount meter, silicon source are by the theoretical SiO that generates
2The amount meter, the mixture weight ratio consists of: R1/Al
2O
3=0.01～1.0; R2/Al
2O
3=1.11～6.66; R3/Al
2O
3=0～11.1; H
2O/Al
2O
3=5.56～22.22; SiO
2/ Al
2O
3=0.04～0.89; P
2O
5/ Al
2O
3=0.06～2.79;
B) above-mentioned silicon phosphorus aluminum oxide material presoma I is put into the mould gel and wear out, obtain silicon phosphorus aluminum oxide material presoma II;
C) after silicon phosphorus aluminum oxide material presoma II drying, the roasting, make the silicon phosphorus aluminum oxide material III of composite pore structural;
D) silicon phosphorus aluminum oxide material III is placed the top of reactor, the reactor bottom added organic amine solution, 150～220 ℃ of following crystallization 0.5～12 day; Reaction finishes the afterreaction still cools off in state of nature, at last to sample wash, drying and roasting obtain hierarchical porous structure SAPO molecular sieve;
The inductor R1 that wherein is separated be selected from polyoxyethylene glycol, polyoxyethylene or polyethylene oxide at least a, its molecular-weight average is 1000～12000000;
Gel promotor R2 is selected from least a in propylene oxide, propylene oxide derivative, the Racemic glycidol ether compound;
Organic solvent R3 is selected from least a less than in 7 short chain alcohol, acetone, the tetrahydrofuran (THF) of carbochain.
2. according to the preparation method of the described hierarchical porous structure SAPO of claim 1 molecular sieve integral material, it is characterized in that the silicon source is selected from least a in positive quanmethyl silicate, positive tetraethyl orthosilicate, positive silicic acid orthocarbonate, positive silicic acid four butyl esters or the silicon sol; The aluminium source is selected from least a in aluminum nitrate, aluminum chloride or the Tai-Ace S 150; The phosphorus source is selected from least a in phosphoric acid, ammonium phosphate, Secondary ammonium phosphate, ammonium hydrogen phosphate, potassiumphosphate, dipotassium hydrogen phosphate, potassium hydrogen phosphate, sodium phosphate, Sodium phosphate dibasic or the sodium hydrogen phosphate.
3. according to the preparation method of the described hierarchical porous structure SAPO of claim 1 molecular sieve integral material, it is characterized in that mixture weight is selected from than forming in the step a): R1/Al
2O
3=0.04～0.81; R2/Al
2O
3=2.22～5.55; R3/Al
2O
3=1.11～8.88; H
2O/Al
2O
3=8.88～17.77; SiO
2/ Al
2O
3=0.12～0.70; P
2O
5/ Al
2O
3Between=1.08～2.04.
4. according to the preparation method of the described hierarchical porous structure SAPO of claim 1 molecular sieve integral material, it is characterized in that regulating pH with alkali in the step a) is 4～8.5.
5. according to the preparation method of the described hierarchical porous structure SAPO of claim 1 molecular sieve integral material, it is characterized in that the gel aging temperature is 30～90 ℃ in the step b), digestion time is 2～96 hours.
6. according to the preparation method of the described hierarchical porous structure SAPO of claim 1 molecular sieve integral material, it is characterized in that in the step c) that drying temperature is 10～110 ℃, be 0.5～7 day time of drying; Maturing temperature is 500～800 ℃, and roasting time is 2～10 hours.
7. according to the preparation method of the described hierarchical porous structure SAPO of claim 1 molecular sieve integral material, it is characterized in that organic amine template in the step d) is selected from least a in tetraethyl-oxyammonia, tetraethylammonium bromide, triethylamine or the quadrol.
8. according to the preparation method of the described hierarchical porous structure SAPO of claim 1 molecular sieve integral material, it is characterized in that crystallization temperature is 160～200 ℃ in the step d), crystallization time is 1～10 day.
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| CN103539144A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | SAPO (Si, Al, P, O)-44 molecular sieve as well as preparation method thereof |
| CN104973608A (en) * | 2015-06-16 | 2015-10-14 | 吉林大学 | SAPO-34 molecular sieve of larger specific surface area and hollow alumina-rich hierarchical pore structures and application thereof |
| CN105460944A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | SAPO molecular sieve material with a layered structure and preparation method thereof |
| CN105460945A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | SAPO molecular sieve material in hierarchical pore structure and preparation method for SAPO molecular sieve material |
| CN105948073A (en) * | 2016-04-25 | 2016-09-21 | 中国科学院上海高等研究院 | Preparation method of SAPO-34 molecular sieve |
| CN106430229A (en) * | 2016-09-12 | 2017-02-22 | 中国华能集团公司 | Method for preparing multi-level-structured molecular sieve by taking mesoporous material as indirect template agent |
| CN106608634A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Preparation method of cocrystallization molecular sieve integral material |
| CN107952477A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | Application of the multi-stage porous SAPO molecular sieve in methanol to olefins reaction |
| CN108557838A (en) * | 2018-06-25 | 2018-09-21 | 陕西延长石油（集团）有限责任公司 | A kind of preparation method of aluminium silicophosphate molecular sieve |
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| CN103539144B (en) * | 2012-07-12 | 2016-05-18 | 中国石油化工股份有限公司 | SAPO-44 molecular sieve and preparation method thereof |
| CN103539144A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | SAPO (Si, Al, P, O)-44 molecular sieve as well as preparation method thereof |
| CN105460944A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | SAPO molecular sieve material with a layered structure and preparation method thereof |
| CN105460945A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | SAPO molecular sieve material in hierarchical pore structure and preparation method for SAPO molecular sieve material |
| CN104973608A (en) * | 2015-06-16 | 2015-10-14 | 吉林大学 | SAPO-34 molecular sieve of larger specific surface area and hollow alumina-rich hierarchical pore structures and application thereof |
| CN106608634B (en) * | 2015-10-22 | 2018-07-17 | 中国石油化工股份有限公司 | The preparation method of cocrystallization molecular sieve integral material |
| CN106608634A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Preparation method of cocrystallization molecular sieve integral material |
| CN105948073A (en) * | 2016-04-25 | 2016-09-21 | 中国科学院上海高等研究院 | Preparation method of SAPO-34 molecular sieve |
| CN106430229A (en) * | 2016-09-12 | 2017-02-22 | 中国华能集团公司 | Method for preparing multi-level-structured molecular sieve by taking mesoporous material as indirect template agent |
| CN106430229B (en) * | 2016-09-12 | 2018-06-26 | 中国华能集团公司 | The method that multilevel hierarchy molecular sieve is prepared using mesoporous material as indirect template agent |
| CN107952477A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | Application of the multi-stage porous SAPO molecular sieve in methanol to olefins reaction |
| CN107952477B (en) * | 2016-10-14 | 2020-09-04 | 中国石油化工股份有限公司 | Application of hierarchical pore SAPO molecular sieve in methanol-to-olefin reaction |
| CN108557838A (en) * | 2018-06-25 | 2018-09-21 | 陕西延长石油（集团）有限责任公司 | A kind of preparation method of aluminium silicophosphate molecular sieve |
| CN108557838B (en) * | 2018-06-25 | 2021-05-07 | 陕西延长石油（集团）有限责任公司 | Preparation method of silicon-phosphorus-aluminum molecular sieve |
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