CN105753006A - Preparation of silicoaluminophosphate molecular sieve with AEL structure and multi-size holes and molecular sieve - Google Patents
Preparation of silicoaluminophosphate molecular sieve with AEL structure and multi-size holes and molecular sieve Download PDFInfo
- Publication number
- CN105753006A CN105753006A CN201410783716.3A CN201410783716A CN105753006A CN 105753006 A CN105753006 A CN 105753006A CN 201410783716 A CN201410783716 A CN 201410783716A CN 105753006 A CN105753006 A CN 105753006A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- preparation
- uniformly
- molecular sieves
- method described
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a preparation method of a silicoaluminophosphate molecular sieve with an AEL structure and multi-size holes and the molecular sieve. The silicoaluminophosphate molecular sieve with an AEL structure and multi-size holes, wherein the AEL structure is confirmed by the International Zeolite Association, is prepared by taking a low-temperature eutectic mixture as a reaction medium through ionothermal synthesis. The prepared molecular sieve is excellent in stability, has both micropores and mesopores, and has bright application prospects in the field of catalysis. The preparation method is high in economy, is safe and convenient to operate, and is eco-friendly.
Description
Technical field
The present invention relates to the synthetic method of a kind of multi-stage porous silicoaluminophosphamolecular molecular sieves, more precisely about the synthetic method of a kind of multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure.
Background technology
AEL (International Zeolite Association's appointment codes) structure silicoaluminophosphamolecular molecular sieves (AtlasofZeoliteFrameworkTypes, 6thed.,Elsevier,Amsterdam,2007；Http:// www.iza-structure.org/databases/) there are one-dimensional oval 10 ring straight hole roads, aperture size is 0.40nm × 0.65nm.Owing to pore passage structure size and the geometric configuration of this molecular sieve are very beneficial for the formation of single branched paraffin isomer, the Pt-Pd/AEL silicoaluminophosphamolecular molecular sieves of Supported Pt Nanoparticles palladium noble metal shows good catalysis activity and selectivity in the isomerization reaction of linear paraffin.But the micropore itself having is unfavorable for the diffusion of molecule, limit its catalysis activity.For this, researcher adopts various ways 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 the synthesis of surfactant adding costliness when hydro-thermal.Zeolite synthesis under high pressure carries out, and consersion unit investment is big, complex process, operating difficulties；Surfactant is expensive, it is impossible to reclaim, and synthesis cost is high.
Ion thermal synthesis is a kind of novel synthetic method, and it refers to that employing ionic liquid or low-temperature eutectic thing are reaction medium or a kind of synthetic method (Nature, 2004,430,1012-1016) simultaneously as template.Ionic liquid is a kind of fusing point low-temperature molten salt near room temperature, generally by organic cation that specific volume is relatively large (as: imidazol ion, pyridinium ion, quaternary ammonium ion) and volume relatively small inorganic anion (such as halide anion, tetrafluoroborate anion, hexafluoro-phosphate radical anion) constitute.Compared with traditional molecule-type solvent, ionic liquid has the property that ionic liquid vapour pressure is almost nil, is fixedness liquid；Ionic liquid has good electric conductivity；Ion liquid dissolving can regulate, and polar compound and non-polar compound are had very strong solvability；Ionic liquid structure species is complicated, theoretically, has more than ionic liquid trillion kinds possible.Based on the above-mentioned characteristic of ionic liquid, ion thermal synthesis molecular sieve has many advantages, as: Zeolite synthesis reaction can carry out in uncovered non-pressure vessel；Zeolite synthesis need not additionally add other organic formwork agent；There are great potentiality in the molecular sieve of synthesizing new structure and composition.
Although report the preparation of the silicoaluminophosphamolecular molecular sieves with AEL skeleton before, owing to it typically is the crystal of needle-like, single micropore limits its application in catalysis.This patent have employed cheap low temperature fused matter and synthesized AEL type multi-stage porous silicoaluminophosphamolecular molecular sieves, has micropore due to it and mesoporous simultaneously, better will be applied at catalytic field.
Summary of the invention
It is an object of the invention to the preparation method proposing a kind of multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure.
For achieving the above object, the technical solution used in the present invention is:
With low temperature fused matter for solvent, with low temperature fused matter and organic amine for template altogether, phosphorus source, aluminum source and silicon source are synthesized the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure；Comprise the following steps:
1) precursor mixture is prepared: in low temperature fused matter, be added thereto to phosphorus source, aluminum source, silicon successively
Source, stirring adds organic amine after uniformly, continues stirring to being formed uniformly precursor mixture；
2) by prepared precursor mixture heating crystallization, after crystallization terminates, separating solid product, the solid obtained is the multi-stage porous acid Si-Al molecular sieve with AEL structure.
Concretely comprise the following steps:
Organic amine salt hydrochlorate is mixed homogeneously with alcohols, in 40～100 DEG C of thawings；
In above-mentioned solution, uniformly drip phosphorus source, and stir；Aluminum source is joined in low temperature fused matter, stirs；Silicon source is joined in low temperature fused matter, stirs；Organic amine in above-mentioned solution, stirs；By said mixture heating to 80 DEG C～300 DEG C crystallization, it is preferred that crystallization temperature is 100～200 DEG C, and crystallization time was more than or equal to 1 minute, it is preferred that crystallization time is 0.5～480h；
Crystallization separates solid product after terminating, and is cooled to room temperature by reactant mixture, adds deionized water, filters, with deionized water, sample is washed, and room temperature～120 DEG C dry, and the solid sample obtained is the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure；
Organic formwork agent is removed in roasting (300～600 DEG C of air atmosphere roastings were more than or equal to 2 hours) afterwards, obtains the multi-stage porous silicoaluminophosphamolecular molecular sieves of duct dredging, and the dredging of described duct represents in molecular sieve pore passage without organic formwork agent.
Above-mentioned steps 1) Al in precursor mixture2O3: SiO2: P2O5: middle low-temperature eutectic thing: the molar ratio of organic amine is (phosphorus source, silicon source, aluminum source mole all calculate according to its oxide form) 1:0.01～1:0.1～10:0.01～1000:0.01～50, optimization mol ratio is 1:0.1～0.8:0.5～10::5～100:0.1～20；
Phosphorus source is one or two or more kinds in phosphoric acid, ammonium phosphate, monoammonium phosphate and ammonium dihydrogen phosphate, described phosphoric acid quality concentration 50-85%；Aluminum source is one or two or more kinds in aluminum isopropylate., aluminum chloride, boehmite, aluminum sulfate；Silicon was one or two or more kinds in Ludox, waterglass, white carbon, tetraethyl orthosilicate originally；Organic amine is imidazoles.
The low temperature fused matter that above-mentioned synthesis adopts is made up of organic amine salt hydrochlorate and alcohols, and wherein organic amine salt hydrochlorate is: one or two or more kinds in dimethylamine hydrochloride, di-n-propylamine hydrochlorate, diisopropylamine hydrochlorate, tetraethylammonium chloride, diethylamine hydrochloride；Alcohols is: one or two or more kinds in ethanol, ethylene glycol, glycerol, tetramethylolmethane；The mol ratio of organic amine salt hydrochlorate and alcohols is 1:1～8；It is preferably diethylamine hydrochloride and the low temperature fused matter of ethylene glycol composition.
Can containing certain proportion water in above-mentioned synthetic method step in precursor mixture, its water content can be 0～10wt% of precursor mixture gross weight.
Adopt X-ray powder diffraction, X-ray fluorescence spectra is analyzed and this molecular sieve structure and composition are analyzed by scanning electron microscope (SEM), determining that its structure is have International Molecular to sieve the AEL structure that association confirms by comparing with XRD powder diffraction data storehouse card, X-ray fluorescence spectra constituent content analysis result determines Al in this molecular sieve2O3: P2O5: SiO2Molar ratio, is characterized by SEM and determines its pattern.The molecular sieve finally given has International Molecular and sieves the AEL structure that association confirms, Al in this molecular sieve simultaneously2O3:SiO2: P2O5Molar ratio is 1:0.1～0.4:0.8～1.2.Its X-ray diffraction spectrogram at least has diffraction maximum set forth below,
2 θ values expression diffraction maximum positions, 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 feature of this synthetic method is to carry out the synthesis of silicoaluminophosphamolecular molecular sieves in low temperature fused matter system, overcomes the spontaneous high pressure of system in conventional hydrothermal synthesis of molecular sieve process.Synthesized material is the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure.The inventive method has an environmental friendliness, and advantage easy and simple to handle is cheap.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure synthesized by the embodiment of the present invention 1.
Fig. 2 is the nitrogen physisorption curve of the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure synthesized by the embodiment of the present invention 1.
Fig. 3 is the SEM electromicroscopic photograph of the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure synthesized by the embodiment of the present invention 1.
Detailed description of the invention
Embodiment 1
5.12 grams of diethylamine hydrochlorides and 15 grams of ethylene glycol are added in 50 ml beakers, it is warming up to 80 DEG C, magnetic agitation is also uniformly added into 2.00g aluminum isopropylate., uniformly 0.20 gram of tetraethyl orthosilicate of dropping, stir 1 hour to uniformly, dripping 3.00 gram mass concentration wherein is the phosphoric acid of 85%, is then uniformly added into 1.20 grams of imidazoles, continues stirring 30 minutes.Mixture is transferred in the stainless steel cauldron with polytetrafluoro internal memory, is warming up to 180 DEG C, keep 5 days, then reactant mixture is cooled to room temperature, and with deionized water wash 3 times.Being placed in by final white powder in 120 DEG C of baking ovens dry, test through XRD, SEM, this white powder is the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure.Products therefrom through 550 DEG C, roasting 24h under air atmosphere, obtain duct dredging multi-stage porous silicoaluminophosphamolecular molecular sieves.
Embodiment 2
5.80 grams of diethylamine hydrochlorides and 15 grams of ethylene glycol are added in 50 ml beakers, it is warming up to 100 DEG C, magnetic agitation is also uniformly added into 1.80g aluminum isopropylate., uniformly 0.40 gram of tetraethyl orthosilicate of dropping, stir 1 hour to uniformly, dripping 1.98 gram mass concentration wherein is the phosphoric acid of 85%, is then uniformly added into 1.32 grams of imidazoles, continues stirring 30 minutes.Mixture is transferred in the stainless steel cauldron with polytetrafluoro internal memory, is warming up to 200 DEG C, keep 5 days, then reactant mixture is cooled to room temperature, and with deionized water wash 3 times.Being placed in by final white powder in 120 DEG C of baking ovens dry, test through XRD, SEM, this white powder is the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure.
Embodiment 3
6.21 grams of diethylamine hydrochlorides and 15 grams of ethylene glycol are added in 50 ml beakers, it is warming up to 80 DEG C, magnetic agitation is also uniformly added into 2.00 grams of aluminum isopropylate., uniformly 0.60 gram of matter tetraethyl orthosilicate of dropping, stir 1 hour to uniformly, dripping 1.98 gram mass concentration wherein is the phosphoric acid of 85%, is then uniformly added into 1.32 grams of imidazoles, continues stirring 30 minutes.Mixture is transferred in the stainless steel cauldron with polytetrafluoro internal memory, is warming up to 210 DEG C, keep 1 day, then reactant mixture is cooled to room temperature, and with deionized water wash 3 times.Being placed in by final white powder in 120 DEG C of baking ovens dry, test through XRD, SEM, this white powder is the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure.
Embodiment 4
6.20 grams of diethylamine hydrochlorides and 13 grams of glycerol are added in 50 ml beakers, it is warming up to 100 DEG C, magnetic agitation is also uniformly added into 1.80g aluminum isopropylate., uniformly dropping 0.30 tetraethyl orthosilicate, stir 1 hour to uniformly, dripping 3.26 gram mass concentration wherein is the phosphoric acid of 85%, is then uniformly added into 1.32 grams of imidazoles, continues stirring 30 minutes.Mixture is transferred in the stainless steel cauldron with polytetrafluoro internal memory, is warming up to 160 DEG C, keep 15 days, then reactant mixture is cooled to room temperature, and with deionized water wash 3 times.Being placed in by final white powder in 120 DEG C of baking ovens dry, test through XRD, SEM, this white powder is the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure.
Embodiment 5
8.20 grams of di-n-propylamine hydrochlorates and 12 grams of ethylene glycol are added in 50 ml beakers, it is warming up to 80 DEG C, magnetic agitation is also uniformly added into 1.60g aluminum isopropylate., uniformly 0.50 gram of tetraethyl orthosilicate of dropping, stir 1 hour to uniformly, dripping 2.76 gram mass concentration wherein is the phosphoric acid of 85%, is then uniformly added into 1.32 grams of imidazoles, continues stirring 30 minutes.Mixture is transferred in the stainless steel cauldron with polytetrafluoro internal memory, is warming up to 180 DEG C, keep 10 days, then reactant mixture is cooled to room temperature, and with deionized water wash 3 times.Being placed in by final white powder in 120 DEG C of baking ovens dry, test through XRD, SEM, this white powder is the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure.
Embodiment 6
7.20 grams of diisopropylamine hydrochlorates and 10 grams of ethylene glycol are added in 50 ml beakers, it is warming up to 70 DEG C, magnetic agitation is also uniformly added into 1.80g aluminum isopropylate., uniformly 0.30 gram of tetraethyl orthosilicate of dropping, stir 1 hour to uniformly, dripping 2.86 gram mass concentration wherein is the phosphoric acid of 85%, is then uniformly added into 1.32 grams of imidazoles, continues stirring 30 minutes.Mixture is transferred in microwave reactor, is warming up to 160 DEG C, keep 7 days, then reactant mixture is cooled to room temperature, and with deionized water wash 3 times.Being placed in by final white powder in 120 DEG C of baking ovens dry, test through XRD, SEM, this white powder is the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure.
Embodiment 7
6.50 grams of diisopropylamine hydrochlorates and 15 grams of ethylene glycol are added in 50 ml beakers, it is warming up to 90 DEG C, magnetic agitation is also uniformly added into 1.60g aluminum isopropylate., uniformly 0.40 gram of tetraethyl orthosilicate of dropping, stir 2 hours to uniformly, dripping 2.38 gram mass concentration wherein is the phosphoric acid of 85%, is then uniformly added into 1.32 grams of imidazoles, continues stirring 30 minutes.Mixture is transferred in microwave reactor, is warming up to 180 DEG C, keep 3 days, then reactant mixture is cooled to room temperature, and with deionized water wash 3 times.Being placed in by final white powder in 120 DEG C of baking ovens dry, test through XRD, SEM, this white powder is the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure.
Embodiment 8
7.30 grams of diisopropylamine hydrochlorates and 15 grams of ethylene glycol are added in 50 ml beakers, it is warming up to 80 DEG C, magnetic agitation is also uniformly added into 1.80g aluminum isopropylate., uniformly 0.40 gram of tetraethyl orthosilicate of dropping, stir 1 hour to uniformly, dripping 2.80 gram mass concentration wherein is the phosphoric acid of 85%, is then uniformly added into 1.20 grams of imidazoles, continues stirring 30 minutes.Mixture is transferred in microwave reactor, is warming up to 180 DEG C, keep 4 days, then reactant mixture is cooled to room temperature, and with deionized water wash 3 times.Being placed in by final white powder in 120 DEG C of baking ovens dry, test through XRD, SEM, this white powder is the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure.
Embodiment 9
8.20 grams of diisopropylamine hydrochlorates and 12 grams of ethylene glycol are added in 50 ml beakers, it is warming up to 100 DEG C, magnetic agitation is also uniformly added into 1.60g aluminum isopropylate., uniformly 0.50 gram of tetraethyl orthosilicate of dropping, stir 1 hour to uniformly, dripping 2.50 gram mass concentration wherein is the phosphoric acid of 85%, is then uniformly added into 1.60 grams of imidazoles, continues stirring 30 minutes.Mixture is transferred in microwave reactor, is warming up to 160 DEG C, keep 5 days, then reactant mixture is cooled to room temperature, and with deionized water wash 3 times.Being placed in by final white powder in 120 DEG C of baking ovens dry, test through XRD, SEM, this white powder is the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure.
Embodiment 10
6.80 grams of diisopropylamine hydrochlorates and 15 grams of ethylene glycol are added in 50 ml beakers, it is warming up to 90 DEG C, magnetic agitation is also uniformly added into 1.60g aluminum isopropylate., uniformly 0.40 gram of tetraethyl orthosilicate of dropping, stir 1 hour to uniformly, dripping 2.90 gram mass concentration wherein is the phosphoric acid of 85%, is then uniformly added into 2.0 grams of imidazoles, continues stirring 30 minutes.Mixture is transferred in microwave reactor, is warming up to 160 DEG C, keep 6 days, then reactant mixture is cooled to room temperature, and with deionized water wash 3 times.Being placed in by final white powder in 120 DEG C of baking ovens dry, test through XRD, SEM, this white powder is the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure.
Embodiment 11
10.0 grams of di-iso-butylmanice hydrochlorates and 15 grams of ethylene glycol are added in 50 ml beakers, it is warming up to 80 DEG C, magnetic agitation is also uniformly added into 2.30g aluminum isopropylate., uniformly 0.40 gram of tetraethyl orthosilicate of dropping, stir 1 hour to uniformly, dripping 2.38 gram mass concentration wherein is the phosphoric acid of 85%, is then uniformly added into 1.86 grams of imidazoles, continues stirring 30 minutes.Mixture is transferred in microwave reactor, is warming up to 160 DEG C, keep 5 days, then reactant mixture is cooled to room temperature, and with deionized water wash 3 times.Being placed in by final white powder in 120 DEG C of baking ovens dry, test through XRD, SEM, this white powder is the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure.
Embodiment 12
8.0 grams of tetraethylammonium chloride hydrochlorates and 15 grams of ethylene glycol are added in 50 ml beakers, it is warming up to 80 DEG C, magnetic agitation is also uniformly added into 2.00g aluminum isopropylate., uniformly 0.30 gram of tetraethyl orthosilicate of dropping, stir 1 hour to uniformly, dripping 3.00 gram mass concentration wherein is the phosphoric acid of 85%, is then uniformly added into 2.0 grams of imidazoles, continues stirring 30 minutes.Mixture is transferred in microwave reactor, is warming up to 160 DEG C, keep 7 days, then reactant mixture is cooled to room temperature, and with deionized water wash 3 times.Being placed in by final white powder in 120 DEG C of baking ovens dry, test through XRD, SEM, this white powder is the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure.
Embodiment 13
6.80 diethylamine hydrochlorides and 10 grams of ethylene glycol are added in 50 ml beakers, it is warming up to 80 DEG C, magnetic agitation is also uniformly added into 2.00g aluminum isopropylate., uniformly 0.50 gram of tetraethyl orthosilicate of dropping, stir 1 hour to uniformly, dripping 2.76 gram mass concentration wherein is the phosphoric acid of 85%, is then uniformly added into 1.80 grams of imidazoles, continues stirring 30 minutes.Mixture is transferred in microwave reactor, is warming up to 180 DEG C, keep 2 days, then reactant mixture is cooled to room temperature, and with deionized water wash 3 times.Being placed in by final white powder in 120 DEG C of baking ovens dry, test through XRD, SEM, this white powder is the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure.
Claims (9)
1. the synthetic method of an AEL structure multi-stage porous silicoaluminophosphamolecular molecular sieves, it is characterized in that: with low temperature fused matter for solvent, with low temperature fused matter and organic amine for template altogether, phosphorus source, aluminum source and silicon source are synthesized the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure；Comprise the following steps:
1) precursor mixture is prepared: being added thereto to successively in low temperature fused matter containing phosphorus source, aluminum source and silicon source, stirring adds organic amine after uniformly, continues stirring to being formed uniformly precursor mixture；
2) by prepared precursor mixture heating crystallization, after crystallization terminates, separating solid product, the solid obtained is the multi-stage porous silicoaluminophosphamolecular molecular sieves with AEL structure.
2. the synthetic method described in claim 1, it is characterised in that: step 1) Al in precursor mixture2O3: SiO2: P2O5: low-temperature eutectic thing: the molar ratio of organic amine is 1:0.01～1:0.1～10:0.01～1000:0.01～50 (aluminum source, silicon source, phosphorus source mole all calculate according to its oxide form), and optimization mol ratio is 1:0.1～0.8:0.5～10::5～100:0.1～20；Step 2) crystallization temperature is 80 DEG C～300 DEG C, it is preferred that and crystallization temperature is 100～200 DEG C；Crystallization time was more than or equal to 1 minute, it is preferred that crystallization time is 0.5～480h.
3. the preparation method described in claim 1, it is characterised in that: phosphorus source is one or two or more kinds in phosphoric acid, ammonium phosphate, monoammonium phosphate and ammonium dihydrogen phosphate, and described phosphoric acid quality concentration is 50-85%；Aluminum source is one or two or more kinds in aluminum isopropylate., aluminum chloride, boehmite, aluminum sulfate；Silicon was one or two or more kinds in Ludox, waterglass, white carbon, tetraethyl orthosilicate originally；Organic amine is imidazoles.
4. the preparation method described in claim 1, it is characterized in that: described low temperature fused matter is made in 40～100 DEG C of thawings after being mixed with alcohols by organic amine salt hydrochlorate, wherein organic amine salt hydrochlorate is one or two or more kinds in dimethylamine hydrochloride, di-n-propylamine hydrochlorate, diisopropylamine hydrochlorate, tetraethylammonium chloride, diethylamine hydrochloride；Alcohols is: one or two or more kinds in ethanol, ethylene glycol, glycerol, tetramethylolmethane, it is preferred to the low temperature fused matter of diethylamine hydrochloride and ethylene glycol composition.
5. the synthetic method described in claim 4, it is characterised in that: mol ratio 1:1～8 of organic amine salt hydrochlorate and alcohols.
6. the preparation method described in claim 1, it is characterised in that: in described precursor mixture, water content accounts for precursor mixture percentage by weight is 0～10wt%, and the water in precursor mixture can be brought into by raw material, it is possible to additionally adds.
7. the preparation method described in claim 1, it is characterized in that: after the fired removal organic formwork agent of prepared molecular sieve, can obtaining the multi-stage porous silicoaluminophosphamolecular molecular sieves of duct dredging, the dredging of described duct represents in molecular sieve pore passage without organic formwork agent.
8. the preparation method described in claim 7, it is characterised in that: sintering temperature is 300～600 DEG C, and roasting time was more than or equal to 2 hours.
9. use molecular sieve prepared by arbitrary preparation method described in claim 1～8, it is characterised in that: multi-stage porous silicoaluminophosphamolecular molecular sieves has International Molecular and sieves the AEL structure that association confirms, Al in this molecular sieve simultaneously2O3:SiO2: P2O5Molar ratio is 1:0.1～0.4:0.8～1.2；Its X-ray diffraction spectrogram at least has diffraction maximum set forth below,
2 θ values expression diffraction maximum positions, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410783716.3A CN105753006B (en) | 2014-12-17 | 2014-12-17 | A kind of preparation of AEL structure multi-stage porous silicoaluminophosphamolecular molecular sieves and molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410783716.3A CN105753006B (en) | 2014-12-17 | 2014-12-17 | A kind of preparation of AEL structure multi-stage porous silicoaluminophosphamolecular molecular sieves and molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105753006A true CN105753006A (en) | 2016-07-13 |
| CN105753006B CN105753006B (en) | 2018-09-25 |
Family
ID=56339460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410783716.3A Active CN105753006B (en) | 2014-12-17 | 2014-12-17 | A kind of preparation of AEL structure multi-stage porous silicoaluminophosphamolecular molecular sieves and molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105753006B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108298550A (en) * | 2018-04-12 | 2018-07-20 | 正大能源材料(大连)有限公司 | A method of it is mixed using tetrahydrofuran as template with organic amine and prepares multi-stage porous SAPO-34 molecular sieves |
| CN109422277A (en) * | 2017-08-31 | 2019-03-05 | 中国科学院大连化学物理研究所 | A method of synthesis has AEL structure aluminium phosphate molecular sieve |
| CN109422278A (en) * | 2017-08-31 | 2019-03-05 | 中国科学院大连化学物理研究所 | A method of synthesis has AEL structure hetero atom Metal-aluminophosphate Molecular Siever |
| CN114835138A (en) * | 2022-03-17 | 2022-08-02 | 中山大学 | Aluminum phosphate molecular sieve membrane and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913623A (en) * | 2010-08-25 | 2010-12-15 | 中国石油大学(北京) | Multilevel pore channel SAPO-11 molecular sieve and synthetic method of hydrocarbon isomerization catalyst |
| CN102786063A (en) * | 2012-08-10 | 2012-11-21 | 中国海洋石油总公司 | Method for synthesizing silicoaluminophosphate molecular sieve SAPO-11 at normal pressure |
-
2014
- 2014-12-17 CN CN201410783716.3A patent/CN105753006B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913623A (en) * | 2010-08-25 | 2010-12-15 | 中国石油大学(北京) | Multilevel pore channel SAPO-11 molecular sieve and synthetic method of hydrocarbon isomerization catalyst |
| CN102786063A (en) * | 2012-08-10 | 2012-11-21 | 中国海洋石油总公司 | Method for synthesizing silicoaluminophosphate molecular sieve SAPO-11 at normal pressure |
Non-Patent Citations (2)
| Title |
|---|
| LIN GUO ET AL: "Two-stage surfactant-assisted crystallization for enhancing SAPO-11 acidity to improve n-octane di-branched isomerization", 《JOURNAL OF CATALYSIS》 * |
| YAN LIU ET AL: "Catalytically active and hierarchically porous SAPO-11 zeolite synthesised in the presence of polyhexamethylene biguanidine", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109422277A (en) * | 2017-08-31 | 2019-03-05 | 中国科学院大连化学物理研究所 | A method of synthesis has AEL structure aluminium phosphate molecular sieve |
| CN109422278A (en) * | 2017-08-31 | 2019-03-05 | 中国科学院大连化学物理研究所 | A method of synthesis has AEL structure hetero atom Metal-aluminophosphate Molecular Siever |
| CN109422277B (en) * | 2017-08-31 | 2022-08-02 | 中国科学院大连化学物理研究所 | Method for synthesizing aluminum phosphate molecular sieve with AEL structure |
| CN108298550A (en) * | 2018-04-12 | 2018-07-20 | 正大能源材料(大连)有限公司 | A method of it is mixed using tetrahydrofuran as template with organic amine and prepares multi-stage porous SAPO-34 molecular sieves |
| CN114835138A (en) * | 2022-03-17 | 2022-08-02 | 中山大学 | Aluminum phosphate molecular sieve membrane and preparation method and application thereof |
| CN114835138B (en) * | 2022-03-17 | 2024-04-19 | 中山大学 | Aluminum phosphate molecular sieve membrane and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105753006B (en) | 2018-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6280640B2 (en) | Hierarchical porous zeolite | |
| JP5075636B2 (en) | Catalyst material and production method | |
| WO2018113566A1 (en) | Process for the production of a zeolitic material via solvent-free interzeolitic conversion | |
| TWI544961B (en) | Hierarchically porous zeolites | |
| RU2640072C9 (en) | Small crystal ferrierite and method of making the same | |
| KR102172784B1 (en) | Emm-25 molecular sieve material, its synthesis and use | |
| JP6383100B2 (en) | Method for producing high silica alumina ratio Y-type molecular sieve | |
| JP2008525187A5 (en) | ||
| US7267812B2 (en) | Crystalline inorganic porous material and production process therefor | |
| JP6318990B2 (en) | Method for producing AEI zeolite | |
| WO2011091678A1 (en) | Aluminophosphate molecular sieve with -clo structure and preparation method thereof | |
| CN105753006A (en) | Preparation of silicoaluminophosphate molecular sieve with AEL structure and multi-size holes and molecular sieve | |
| US20210188651A1 (en) | Method for synthesizing an afx-structure zeolite of very high purity in the presence of an organic nitrogen-containing structuring agent | |
| Yasong et al. | Research progress in ionothermal synthesis of molecular sieves | |
| Shamzhy et al. | Direct incorporation of B, Al, and Ga into medium-pore ITH zeolite: Synthesis, acidic, and catalytic properties | |
| US20190126258A1 (en) | Nanometer-size zeolitic particles and method for the production thereof | |
| Barrett et al. | Synthesis in fluoride and hydroxide media and structure of the extra-large pore pure silica zeolite CIT-5 | |
| RU2722028C2 (en) | Zeolite materials with pronounced macroporosity of monocrystals and method of their production | |
| CN103466654B (en) | Preparation method of ZSM-5 mesoporous and microporous composite molecular sieve | |
| JP2012116723A (en) | Lev type zeolite having core-shell structure and synthesis method thereof | |
| CN105753014A (en) | AFO structure multistage pore silicoaluminophosphate zeolite and preparation thereof | |
| JPWO2014013969A1 (en) | Method for producing MAZ type zeolite | |
| CN106276964B (en) | A kind of transgranular phosphorous ZSM-5 molecular sieve and preparation method thereof | |
| CN105753013B (en) | The preparation of one kind-CLO structure nano aluminium phosphate molecular sieves and molecular sieve | |
| RU2393992C1 (en) | Micro-mesoporous crystalline material and method of making said material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |