CN105152182A - Pollened core-shell typed SAPO (silicoaluminophosphate)-34 molecular sieve and preparation method and application thereof - Google Patents

Pollened core-shell typed SAPO (silicoaluminophosphate)-34 molecular sieve and preparation method and application thereof Download PDF

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CN105152182A
CN105152182A CN201510547816.0A CN201510547816A CN105152182A CN 105152182 A CN105152182 A CN 105152182A CN 201510547816 A CN201510547816 A CN 201510547816A CN 105152182 A CN105152182 A CN 105152182A
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molecular sieve
sapo
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hud typed
saop
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CN105152182B (en
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任素贞
马少博
郝策
杨莹
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Dalian University of Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

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Abstract

The invention discloses a novel pollened core-shell typed SAPO (silicoaluminophosphate)-34 molecular sieve taking resorcinol formaldehyde resin (RF) as a template. The preparation method includes the steps of 1), synthesizing RF microspheres under the alkaline conditions; 2), respectively taking aluminum isopropoxide, phosphoric acid and 30wt% of silica sol as aluminum source, phosphorus source and silicon source, and synthesizing the SAPO-34 molecular sieve through solvothermal reaction by taking the RF as the template, performing crystallization for 24 hours under the temperature of 180DEG C prior to washing, centrifuging, vacuum drying and calcining to remove the template to obtain the pollened core-shell typed SAPO-34 molecular sieve. The preparation method is simple in operation, organic amines are not taken as synthetic guiding agents of the molecular sieve, the synthesized SAPO-34 small particles which are of cubic structures are evenly wrapped in the outer side of an RF carbon sphere with uniform morphology, the novel core-shell structured molecular sieve unique in appearance has certain absorption and catalytic activity and is applicable to catalytic reaction of methanol to olefin and the like.

Description

Hud typed SAPO-34 molecular sieve of a kind of pollen shape and its preparation method and application
Technical field
The present invention relates to a kind of pollen shape new type structure of hud SAPO-34 Catalysts and its preparation method; And the application of hud typed SAPO-34 molecular sieve catalyst in methanol to olefins reaction.
Background technology
Ethene, propylene etc. are the maximum basic chemical industry products of current global consumption.Short chain olefin is mainly derived from oil, and methyl alcohol wide material sources, by Coal Chemical Industry, petrochemical complex, gas chemical industry's technology can methanol.So methanol-to-olefins (MTO) technology provides an effective way for preparing short chain olefin, significant at current chemical industry.SAPO-34 molecular sieve is because of the CHA hole basket structure of its uniqueness, and suitable surface acidity, good thermostability, shows fabulous catalytic activity in MTO reaction.Conventional SAPO-34 Zeolite synthesis adopts solvent-thermal method, by adding the organic amines such as triethylamine, diethylamine, tetraethyl ammonium hydroxide, morpholine as structure directing agent, add suitable aluminium source, silicon source and phosphorus source, but for the synthesis mechanism of SAPO-34 molecular sieve and the also ununified understanding of silicon doping mechanism.Therefore to probe in the synthesis mechanism of SAPO-34 molecular sieve and alternative building-up process expensive structure directing agent or adopt without directed agents synthesis method, be present stage urgent need deal with problems.This patent, adopts non-structure directing agent method to take RF as the SAPO-34 molecular sieve of the pollen shape nucleocapsid structure of templated synthesis novel structure, new synthesizes thinking without directed agents for such SAPO molecular sieve provides one.This synthetic method also has great potentiality in the synthesis of other molecular sieve analog simultaneously, can probe into and imitate.
Summary of the invention
The present invention synthesizes thinking novelty, do not use conventional organic amine structure directing agent, with RF carbon ball for template, respectively with the silicon sol of 30wt%, aluminum isopropylate, 85% phosphoric acid be silicon source, aluminium source and phosphorus source, adopt solvent-thermal process method to synthesize the SAPO-34 molecular sieve of pollen shape nucleocapsid structure.The present invention will disclose the molecular sieve preparation method of this kind of novel structure.
The invention provides the preparation method of the hud typed SAPO-34 molecular sieve of a kind of pollen shape, comprise the steps:
1) by the presoma of carbon, Resorcinol and formaldehyde, under weak basic condition, adopt solvent-thermal process method synthesis RF microballoon; And by washing, centrifugally obtain RF gel; Or the RF ball obtained after continuation vacuum-drying is as the template of synthesis nucleocapsid mechanism SAPO-34 molecular sieve;
2) using step 1) the RF gel that synthesizes or RF carbon ball be as template, add silicon source, phosphorus source, aluminium source, at 180 DEG C, 24h is reacted by solvent thermal reaction, after being down to room temperature, washing, centrifugal, vacuum-drying, then high-temperature calcination in 550 DEG C of air, prepares the SAPO-34 molecular sieve that pollen shape is hud typed.
Further, in technique scheme, step 1) in the mass ratio of Resorcinol and formaldehyde be 1:0.87.
Further, in technique scheme, step 1) middle ammoniacal liquor is as catalyzer, and the mass ratio of Resorcinol and ammoniacal liquor is 1:0.036.
Further, in technique scheme, step 1) in hydrothermal temperature be 85 DEG C, 24 hours time.
Further, in technique scheme, step 2) in, silicon source is the silicon sol of 30wt%.
Further, in technique scheme, step 2) in, aluminium source is aluminum isopropylate.
Further, in technique scheme, step 2) in, phosphorus source is the phosphoric acid of 85%.
Further, in technique scheme, step 2) in, the mass ratio in RF microballoon or RF gel and silicon source, aluminium source, phosphorus source is 1:8-8.5:20:12.
The hud typed SAOP-34 molecular sieve that the present invention separately provides above-mentioned preparation method to obtain, the little uniform crystal particles of SAPO-34 of synthesis is distributed in RF ball surface.
Further, in technique scheme, the little crystal grain of SAPO-34 of synthesis is 1:16 with RF spherical diameter ratio.
The invention provides the application of above-mentioned molecular sieve in methanol to olefins reaction.
Invention beneficial effect
This preparation method first synthesizes RF micro-nano carbon ball, then with it for template is by solvent thermal reaction, synthesis SAPO-34 molecular sieve.This RF carbon ball, in the process of synthesis, had both served the template action of product nucleus shell structure, also may serve the effect of conventional organic amine to SAPO-34 zeolite crystal structure directing.This synthetic method is simple, and the SAPO-34 micro-nano ball pattern of the pollen shape nucleocapsid structure of synthesis is unique, and size is homogeneous, and stability is high, can as the catalyzer of methanol to olefins reaction and sorbing material.
Accompanying drawing explanation
Fig. 1 is the SEM shape appearance figure of resorcinol formaldehyde resin (RF) micro-nano ball prepared by step 1;
Fig. 2 is the SEM shape appearance figure of pollen shape nucleocapsid structure SAPO-34 sieve particle prepared by embodiment 4;
Fig. 3 is the EDS-mapping figure of pollen shape nucleocapsid structure SAPO-34 sieve particle prepared by embodiment 4;
Fig. 4 is routine prepared by embodiment 2 take TEAOH as the SEM figure that directed agents synthesizes SAPO-34 molecular sieve;
Fig. 5 preparing propylene from methanol reaction path schematic diagram;
Fig. 6 MTO reaction mechanism figure.
Embodiment
Following nonlimiting examples can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.Formaldehyde mass content 37%, density 1.081g/cm in embodiment 3; Strong aqua mass content 25%, density 0.904g/cm 3.
The SAPO-34 molecular sieve of pollen shape nucleocapsid structure, its preparation method is as follows:
1) respectively with Resorcinol and formaldehyde for presoma, under the weak basic condition of ammoniacal liquor, adopt solvent-thermal process method to synthesize RF micro-nano carbon ball.
2) with RF ball for template, respectively with the silicon sol of 30wt%, aluminum isopropylate, 85% phosphoric acid be silicon source, aluminium source and phosphorus source, adopt solvent-thermal process method at 180 DEG C of crystallization 24h, after being down to room temperature, washing, high speed centrifugation, vacuum-drying, then the lower 550 DEG C of high-temperature calcinations of air atmosphere, obtain the hud typed SAPO-34 molecular sieve of pollen shape of this special appearance.
Embodiment 1
The present invention, by the SAPO-34 molecular sieve of synthesizing new, wishes the catalytic activity improving SAPO molecular sieve, and the selectivity of product propylene, and its schematic diagram is as Fig. 5.
Embodiment 2
Get 2.0g aluminum isopropylate, be dissolved in 9g deionized water, and fully stir, then 5.3g tetraethyl ammonium hydroxide (TEAOH) is added, stir 60min, then add the silicon sol of 0.8g30%, continue to stir 30min, slowly add the phosphoric acid of 1.2g85% again, after stirring for some time, mixed solution is gone to reactor, at 180 DEG C of reaction 24h, then use deionized water, washing with alcohol for several times, centrifugal, 60 DEG C of vacuum-dryings.Finally, remove templates in air atmosphere in 550 DEG C of high-temperature calcination 6h, thus to obtain proportioning be 1Al 2o 3: 0.8SiO 2: 1P 2o 5: 2TEAOH:100H 2the SAPO-34 molecular sieve of O.Preparing product pattern is shown in Fig. 4.
Embodiment 3
1) get 1.6g Resorcinol, 3.5ml formaldehyde, in beaker, stirs 10min, then 0.25ml strong aqua is dripped, by 85 DEG C of hydro-thermal reaction 24h in transferred product to reactor, then use water and washing with alcohol repeatedly, centrifugal, vacuum-drying, finally obtain RF micro-nano carbon ball.
2) get 2.0g aluminum isopropylate, be dissolved in 9g deionized water, and fully stir, then add 0.1g step one and synthesize RF micro-nano ball, stir 30min, then add the silicon sol of 0.8g30%, continue to stir 30min, slowly add the phosphoric acid of 1.2g85% again, after stirring for some time, mixed solution is gone to reactor, at 180 DEG C of reaction 24h, then use deionized water, washing with alcohol for several times, centrifugal, 60 DEG C of vacuum-dryings.Finally, remove templates in air atmosphere in 550 DEG C of high-temperature calcination 6h, thus to obtain proportioning be 1Al 2o 3: 0.8SiO 2: 1P 2o 5: 100H 2the SAPO-34 pollen shape core-shell type molecular sieve of O.
Embodiment 4
1) get 1.6g Resorcinol, 3.5ml formaldehyde, in beaker, stirs 10min, then 0.25ml strong aqua is dripped, by 85 DEG C of hydro-thermal reaction 24h in transferred product to reactor, then use water and washing with alcohol repeatedly, centrifugal, vacuum-drying, finally obtain RF micro-nano carbon ball.
2) get 2.0g aluminum isopropylate, be dissolved in 9g deionized water, and fully stir, then add 0.1g step one and synthesize RF micro-nano ball, stir 30min, then add 0.85gTEOS, continue to stir 30min, slowly add the phosphoric acid of 1.2g85% again, after stirring for some time, mixed solution is gone to reactor, at 180 DEG C of reaction 24h, then use deionized water, washing with alcohol for several times, centrifugal, 60 DEG C of vacuum-dryings.Finally, remove templates in air atmosphere in 550 DEG C of high-temperature calcination 6h, thus to obtain proportioning be 1Al 2o 3: 0.8SiO 2: 1P 2o 5: 100H 2the SAPO-34 pollen shape core-shell type molecular sieve of O.
The pollen shape core-shell type molecular sieve obtained is the hud typed SAOP-34 molecular sieve of pollen shape, and the little uniform crystal particles of SAPO-34 of synthesis is distributed in RF ball surface.The little crystal grain of SAPO-34 and RF spherical diameter are than being 1:16.
Embodiment 5
1) get 1.6g Resorcinol, 3.5ml formaldehyde, in beaker, stirs 10min, then 0.25ml strong aqua is dripped, by 85 DEG C of hydro-thermal reaction 24h in transferred product to reactor, then use water and washing with alcohol repeatedly, centrifugal, the template that preparation RF gel synthesizes as lower step.
2) get 2.0g aluminum isopropylate, be dissolved in 9g deionized water, and fully stir, then add 0.1g step one and synthesize RF gel, stir 30min, then add the silicon sol of 0.8g30%, continue to stir 30min, slowly add the phosphoric acid of 1.2g85% again, after stirring for some time, mixed solution is gone to reactor, at 180 DEG C of reaction 24h, then use deionized water, washing with alcohol for several times, centrifugal, 60 DEG C of vacuum-dryings.Finally, remove templates in air atmosphere in 550 DEG C of high-temperature calcination 6h, thus to obtain proportioning be 1Al 2o 3: 0.8SiO 2: 1P 2o 5: 100H 2the SAPO-34 pollen shape core-shell type molecular sieve of O.
Embodiment 6
1) get 1.6g Resorcinol, 3.5ml formaldehyde, in beaker, stirs 10min, then 0.25ml strong aqua is dripped, by 85 DEG C of hydro-thermal reaction 24h in transferred product to reactor, then use water and washing with alcohol repeatedly, centrifugal, the template that preparation RF gel synthesizes as lower step.
2) get 2.0g aluminum isopropylate, be dissolved in 9g deionized water, and fully stir, then add 0.1g step one and synthesize RF gel, stir 30min, then add 0.85gTEOS, continue to stir 30min, slowly add the phosphoric acid of 1.2g85% again, after stirring for some time, mixed solution is gone to reactor, at 180 DEG C of reaction 24h, then use deionized water, washing with alcohol for several times, centrifugal, 60 DEG C of vacuum-dryings.Finally, remove templates in air atmosphere in 550 DEG C of high-temperature calcination 6h, thus to obtain proportioning be 1Al 2o 3: 0.8SiO 2: 1P 2o 5: 100H 2the SAPO-34 pollen shape core-shell type molecular sieve of O.
Embodiment 7
1) get 1.6g Resorcinol, 3.5ml formaldehyde, in beaker, stirs 10min, then 0.25ml strong aqua is dripped, by 85 DEG C of hydro-thermal reaction 24h in transferred product to reactor, then use water and washing with alcohol repeatedly, centrifugal, vacuum-drying, finally obtain RF micro-nano carbon ball.
2) 2.0g aluminum isopropylate is got, be dissolved in 9g deionized water, and fully stir, then add 0.5g step one and synthesize RF micro-nano ball, and then add 2.5g tetraethyl ammonium hydroxide (TEAOH) structure directing agent, stir 30min, then the silicon sol of 0.8g30% is added, continue to stir 30min, more slowly add the phosphoric acid of 1.2g85%, after stirring for some time, mixed solution is gone to reactor, at 180 DEG C of reaction 24h, then use deionized water, washing with alcohol for several times, centrifugal, 60 DEG C of vacuum-dryings.Finally, remove templates in air atmosphere in 550 DEG C of high-temperature calcination 6h, thus to obtain proportioning be 1Al 2o 3: 0.8SiO 2: 1P 2o 5: 100H 2the SAPO-34 pollen shape core-shell type molecular sieve of O.
Embodiment 8
1) get 1.6g Resorcinol, 3.5ml formaldehyde, in beaker, stirs 10min, then 0.25ml strong aqua is dripped, by 85 DEG C of hydro-thermal reaction 24h in transferred product to reactor, then use water and washing with alcohol repeatedly, centrifugal, vacuum-drying, finally obtain RF micro-nano carbon ball.
2) 2.0g aluminum isopropylate is got, be dissolved in 9g deionized water, and fully stir, then add 0.5g step one and synthesize RF micro-nano ball, and then add 2.5g tetraethyl ammonium hydroxide (TEAOH) structure directing agent, stir 30min, then 0.85gTEOS is added, continue to stir 30min, more slowly add the phosphoric acid of 1.2g85%, after stirring for some time, mixed solution is gone to reactor, at 180 DEG C of reaction 24h, then use deionized water, washing with alcohol for several times, centrifugal, 60 DEG C of vacuum-dryings.Finally, remove templates in air atmosphere in 550 DEG C of high-temperature calcination 6h, thus to obtain proportioning be 1Al 2o 3: 0.8SiO 2: 1P 2o 5: 100H 2the SAPO-34 pollen shape core-shell type molecular sieve of O.
Embodiment 9
1) get 1.6g Resorcinol, 3.5ml formaldehyde, in beaker, stirs 10min, then 0.25ml strong aqua is dripped, by 85 DEG C of hydro-thermal reaction 24h in transferred product to reactor, then use water and washing with alcohol repeatedly, centrifugal, the template that preparation RF gel synthesizes as lower step.
2) 2.0g aluminum isopropylate is got, be dissolved in 9g deionized water, and fully stir, then add 0.5g step one and synthesize RF gel, and then add 2.5g tetraethyl ammonium hydroxide (TEAOH) structure directing agent, stir 30min, then the silicon sol of 0.8g30% is added, continue to stir 30min, more slowly add the phosphoric acid of 1.2g85%, after stirring for some time, mixed solution is gone to reactor, at 180 DEG C of reaction 24h, then use deionized water, washing with alcohol for several times, centrifugal, 60 DEG C of vacuum-dryings.Finally, remove templates in air atmosphere in 550 DEG C of high-temperature calcination 6h, thus to obtain proportioning be 1Al 2o 3: 0.8SiO 2: 1P 2o 5: 100H 2the SAPO-34 pollen shape core-shell type molecular sieve of O.
Embodiment 10
1) get 1.6g Resorcinol, 3.5ml formaldehyde, in beaker, stirs 10min, then 0.25ml strong aqua is dripped, by 85 DEG C of hydro-thermal reaction 24h in transferred product to reactor, then use water and washing with alcohol repeatedly, centrifugal, the template that preparation RF gel synthesizes as lower step.
2) get 2.0g aluminum isopropylate, be dissolved in 9g deionized water, and fully stir, then add 0.5g step one and synthesize RF gel, and then add 2.5g tetraethyl ammonium hydroxide (TEAOH) structure directing agent, stir 30min, then 0.85gTEOS is added, continue to stir 30min, more slowly add the phosphoric acid of 1.2g85%, after stirring for some time, mixed solution is gone to reactor, at 180 DEG C of reaction 24h, then use deionized water, washing with alcohol for several times, centrifugal, 60 DEG C of vacuum-dryings.Finally, remove templates in air atmosphere in 550 DEG C of high-temperature calcination 6h, thus to obtain proportioning be 1Al 2o 3: 0.8SiO 2: 1P 2o 5: 100H 2the SAPO-34 pollen shape core-shell type molecular sieve of O.
Embodiment 11
The pollen shape core-shell type molecular sieve of the gained prepared by embodiment 4 is because have Hierarchical porosity structure, in same methanol to olefins reaction as shown in Figure 5, temperature of reaction is 450 DEG C, and reactor is quartz tube reactor, Propylene Selectivity (52.0%).C2 ~ C4 low-carbon alkene transformation efficiency (61.8%).
The pollen shape core-shell type molecular sieve prepared by embodiment 4 is because have Hierarchical porosity structure, (prepared by embodiment 2 for the SAPO-34 molecular sieve standby with conventional template agent legal system, see Fig. 4), pattern and acidity have very big-difference, are expected to the selectivity improving propylene in methanol to olefins reaction.
Embodiment 12
Synthesis step, with embodiment 7 ~ 10 is identical before, uses mechanism's directed agents such as diethylamine, triethylamine, morpholine respectively, with RF gel or RF micro-nano carbon ball for template, obtains the SAPO-34 molecular sieve that different structure directed agents and RF template are mixed into template.
Embodiment 13
Synthesis step, with embodiment 4 is identical before, does not add structure directing agent, and with RF gel or RF micro-nano carbon ball for template, the add-on of adjusting template, obtains the hud typed SAPO-34 molecular sieve of pollen shape of different templates agent content.
Embodiment 14
Synthesis step is identical with implementing 4 examples before, does not add structure directing agent, adds RF template, regulates crystallization temperature at 160-220 DEG C respectively, obtains the SAPO-34 molecular sieve under different crystallization temperature.
Embodiment 15
Synthesis step is identical with enforcement 4 example, does not add structure directing agent, adds RF template, the content 1Al of silicon in Molecular regulator sieve 2o 3: 0.6-1.2SiO 2: 1P 2o 5: 100H 2o, obtains the SAPO-34 molecular sieve of different silicon-containing amount.

Claims (10)

1. a preparation method for the hud typed SAPO-34 molecular sieve of pollen shape, is characterized in that comprising the steps:
1) by the presoma of carbon, Resorcinol and formaldehyde, under weak basic condition, adopt solvent-thermal process method synthesis RF microballoon; And by washing, centrifugally obtain RF gel; Or the RF ball obtained after continuation vacuum-drying is as the template of synthetic kernel shell structure SAPO-34 molecular sieve;
2) using step 1) the RF gel that synthesizes or RF carbon ball be as template, add silicon source, phosphorus source, aluminium source, at 180 DEG C, 24h is reacted by solvent thermal reaction, after being down to room temperature, washing, centrifugal, vacuum-drying, then high-temperature calcination in 550 DEG C of air, prepares the SAPO-34 molecular sieve that pollen shape is hud typed.
2. the preparation method of hud typed SAOP-34 molecular sieve according to claim 1, is characterized in that: step 1) in the mass ratio of Resorcinol and formaldehyde be 1:0.87.
3. the preparation method of hud typed SAOP-34 molecular sieve according to claim 1, is characterized in that: step 1) middle ammoniacal liquor is as catalyzer, and the mass ratio of Resorcinol and ammoniacal liquor is 1:0.036.
4. the preparation method of hud typed SAOP-34 molecular sieve according to claim 1, is characterized in that: step 1) in hydrothermal temperature be 85 DEG C, time 24h.
5. the preparation method of hud typed SAOP-34 molecular sieve according to claim 1, is characterized in that: step 2) in, silicon source is the silicon sol of 30wt%.
6. the preparation method of hud typed SAOP-34 molecular sieve according to claim 1, is characterized in that: step 2) in, aluminium source is aluminum isopropylate.
7. the preparation method of hud typed SAOP-34 molecular sieve according to claim 1, is characterized in that: step 2) in, phosphorus source is the phosphoric acid of 85%.
8. the hud typed SAOP-34 molecular sieve that preparation method obtains as described in claim 1 ~ 7, is characterized in that: the little uniform crystal particles of SAPO-34 of synthesis is distributed in RF ball surface.
9. hud typed SAOP-34 molecular sieve according to claim 8, is characterized in that: the little crystal grain of SAPO-34 of synthesis is 1:16 with RF spherical diameter ratio.
10. the application of molecular sieve in methanol to olefins reaction as described in claim 8 or 9.
CN201510547816.0A 2015-08-31 2015-08-31 A kind of hud typed molecular sieves of SAPO 34 of pollen shape and its preparation method and application Expired - Fee Related CN105152182B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107459048A (en) * 2017-07-03 2017-12-12 华东理工大学 The@Silicalite 1 of core shell structure molecular sieve SAPO 34 preparation method

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Publication number Priority date Publication date Assignee Title
CN101633508A (en) * 2008-07-24 2010-01-27 中国石油化工股份有限公司 SAPO-34 molecular sieve and synthesis method thereof
CN103936027A (en) * 2014-04-04 2014-07-23 南京工业大学 SAPO (silicoaluminophosphate)-34 zeolite material assembled by nanosheets and having controllable flower shape, as well as preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101633508A (en) * 2008-07-24 2010-01-27 中国石油化工股份有限公司 SAPO-34 molecular sieve and synthesis method thereof
CN103936027A (en) * 2014-04-04 2014-07-23 南京工业大学 SAPO (silicoaluminophosphate)-34 zeolite material assembled by nanosheets and having controllable flower shape, as well as preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107459048A (en) * 2017-07-03 2017-12-12 华东理工大学 The@Silicalite 1 of core shell structure molecular sieve SAPO 34 preparation method
CN107459048B (en) * 2017-07-03 2020-03-24 华东理工大学 Preparation method of core-shell structure molecular sieve SAPO-34@ Silicalite-1

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