CN103318914B - Preparation of AEL structure aluminophosphate molecular sieve membrane supported by porous alumina carrier - Google Patents
Preparation of AEL structure aluminophosphate molecular sieve membrane supported by porous alumina carrier Download PDFInfo
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- CN103318914B CN103318914B CN201210076747.6A CN201210076747A CN103318914B CN 103318914 B CN103318914 B CN 103318914B CN 201210076747 A CN201210076747 A CN 201210076747A CN 103318914 B CN103318914 B CN 103318914B
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Abstract
The invention specifically relates to a preparation method of an AEL structure aluminophosphate molecular sieve membrane supported by a porous alumina carrier. According to the method, an ionic liquid is taken as a reaction medium, and under the auxiliary effect of a mineralizer, the porous alumina carrier reacts with a phosphorus-containing compound, so that the AEL structure microporous aluminophosphate molecular sieve membrane can be synthesized on the surface of the alumina carrier. The AEL molecular sieve membrane prepared by the method disclosed in the invention has good gas permeation separation performance. The method provided in the invention is characterized by synthesis of the molecular sieve membrane in the ionic liquid, thus overcoming self-generation of high pressure by the system during conventional hydrothermal synthesis of a molecular sieve membrane. The method involved in the invention has the advantages of environmental-friendliness and simple operation.
Description
Technical field
The invention relates to a kind of ion process for thermosynthesizing of microporous aluminophosphates molecular screen membrane, more precisely about a kind of, there is the zeolite structured aluminophosphate molecular sieve membrane of AEL type and its preparation method.
Background technology
Molecular sieve is the inorganic microporous material that a class has regular pore canal structure.In decades, investigator and engineering staff are devoted to the catalyzer of molecular sieve as specified chemical reaction process studying and synthesize different ducts feature always.Along with the continuous progress of science and technology, can by molecular sieve film forming if people recognize gradually, just can binding molecule sieve material and the feature that has of thin-film material, greatly widen its Application Areas: the accurate molecular screening function utilizing microporous molecular sieve duct, simultaneously combination film material is high as efficiency during separating film, energy consumption is low, continuous seepage, handiness are strong and the feature such as environmental protection, realize blending ingredients efficient, be continuously separated.Even to this day, because molecular screen material has diversified skeleton pore passage structure, the adjustable sex change of mould material microtexture in addition, about the research report of molecular screen membrane is increasing, vitality is also shone by continuing in this field.
The separation of long chain alkane isomers is a significant process in industrial gas oil, and mineral membrane isolation technique has unique advantage in this field.AEL type molecular sieve is the one of aluminium phosphate molecular sieve, and containing one dimension ten-ring straight hole structure, duct is oval, and size is 4.0 × 6.5nm.Its aperture is greater than straight-chain paraffin, is less than branched paraffin, has application prospect in the separation of therefore AEL molecular screen membrane long chain alkane isomers in industrial gas oil.Traditional molecular screen membrane is prepared synthetic method and is mainly contained: (1) in situ synthesis, by substrate direct impregnation in synthesis liquid, obtains molecular screen membrane after Crystallizing treatment; (2) secondary growth method is also the most frequently used a kind of masking strategy, substrate is first adhered to the nano-class molecular sieve crystal of one deck pre-synthesis as crystal seed, then continues crystallization in immersion synthesis liquid, forms continuous print molecular screen membrane.There is certain weak point in above-mentioned preparation method: the requirement of in-situ synthesis to substrate and synthesis condition is stricter; Two-step fabrication inevitably wants previously prepared nano-class molecular sieve crystal as crystal seed, is coated with membrane process heavy complexity thereupon; In addition, because these two kinds of methods are all based on Hydrothermal Synthesis technology, the system autogenous pressure produced in its building-up process can cause certain potential safety hazard; In addition a large amount of acid-base waste fluids produced in building-up process, also can cause certain pollution to environment.
2004, the people such as Russel E professor Morris of University of St Andrews of Britain reported the ion thermal synthesis method using ionic liquid as solvent and the synthetic microporous aluminium phosphate molecular sieve of template, i.e. ion thermal synthesis method.Ionic liquid is the low temperature molten salt of a kind of fusing point near room temperature, is generally made up of organic cation and inorganic anion.With traditional molecule-type solvent phase ratio, ionic liquid vapour pressure is almost nil, is non-volatile liquid; Therefore compared with the Hydrothermal Synthesis of routine and solvent process for thermosynthesizing, ion thermal synthesis reaction can be carried out at ambient pressure, so just can eliminate the potential safety hazard because high pressure that solvent in reaction process is spontaneous brings.In addition, in the process of the hot method synthetic inorganic material of ion, ionic liquid not only as solvent, can also participate in building-up reactions as template sometimes, and these features meet Green Chemistry requirement all very much, and building-up process is fool proof, environmental protection.
As can be seen from the above introduction to molecular screen membrane and ion thermal synthesis, if hot for ion method can be applied to the synthesis field of molecular screen membrane, will be expected to develop a kind of simple and easy, environmental protection, fast molecular screen membrane preparation method.
Summary of the invention
The object of the invention is to the preparation method proposing the AEL structure aluminophosphate molecular sieve membrane that a kind of porous alumina carrier supports.
Synthetic method provided by the present invention adopts synthetic method feature to be: be reaction medium with ionic liquid, take porous alumina carrier as supporter, at supporting body surface synthesis AEL type microporous aluminophosphates molecular screen membrane.
Specific operation process is as follows,
1) precursors reaction solution is prepared: mixed with phosphorous raw material, mineralizer by (liquid or solid-state) ionic liquid, form precursors reaction solution after stirring, P in reaction soln
2o
5: F
-: the molar ratio of ionic liquid is 1: 0.1 ~ 2: 40 ~ 400;
For under normal temperature for liquid or through with reactant mix and blend after can be formed directly in the ionic liquid of solution, do not need in precursors reaction solution preparation process to heat; For being still solid-state ionic liquid after mix and blend, precursors reaction liquid (temperature can be 80 ~ 120 DEG C) should be prepared at a temperature above its melting point;
2) porous alumina carrier is inserted above-mentioned precursors reaction solution, at 100 ~ 300 DEG C, carries out crystallization, crystallization time >=1 minute;
3) crystallization terminates, and takes out porous alumina carrier, after removing organic formwork, obtains AEL aluminophosphate molecular sieve membrane.
The AEL aluminophosphate molecular sieve membrane prepared with aforesaid method is by determining with the card comparison of XRD powder diffraction data storehouse the AEL structure that its structure has International Zeolite Association and confirms, the molecular sieve crystal forming this molecular screen membrane has one dimension ten-ring straight hole structure, and its X-ray diffraction spectrogram has at least following listed diffraction peak (2 θ values represent diffraction peak position): 2 θ/°: 8.03 ± 0.2; 9.40 ± 0.2; 13.12 ± 0.2; 15.63 ± 0.2; 16.20 ± 0.2; 18.95 ± 0.2; 20.37 ± 0.2; 20.93 ± 0.2; 22.10 ± 0.2; 22.43 ± 0.2; 22.70 ± 0.2; 23.17 ± 0.2; 24.70 ± 0.2; 26.54 ± 0.2;
Above-mentioned synthetic method intermediate ion liquid is for having following positively charged ion: quaternary ammonium alkyl salt ion [NR
4]
+, alkyl quaternary phosphine ion [PR
4]
+, the imidazol ion [Rim] that alkyl replaces
+, the pyridinium ion [Rpy] that alkyl replaces
+in a kind of ionic liquid, R is the alkyl of C1-C16; The negatively charged ion of ionic liquid can be: Br
-, Cl
-, I
-, BF
4 -, PF
6 -, PO
4 3-, NO
3 -, SO
4 2-in one.
Phosphorous raw material is one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate or primary ammonium phosphate, is preferably the phosphoric acid of 85%.
Mineralizer is one or more in hydrofluoric acid, Neutral ammonium fluoride or Sodium Fluoride, is preferably the hydrofluoric acid of 40%.
Take porous alumina carrier as supporter.Porous alumina carrier is prepared by extrusion process, teeming practice or Method for bonding; Its shape is the various shapes such as round sheet, Polygons sheet or cylindrical; Its material is gama-alumina, δ-aluminum oxide or θ-aluminum oxide.
P in precursors reaction solution in precursors reaction solution in above-mentioned synthetic method
2o
5: F
-: the preferred molar ratio example of ionic liquid is 1: 0.2 ~ 1: 80 ~ 320.
In above-mentioned synthetic method step, preferred crystallization temperature is 120 ~ 280 DEG C, and preferred crystallization time is 0.5 ~ 480h.
After crystallization terminates, X-ray diffraction is carried out to synthesized molecular screen membrane and characterizes to determine its structure.For the molecular screen membrane synthesized on chip carrier, can directly characterize its surface; For the molecular screen membrane that tubular carrier synthesizes, the molecular sieve crystal of carrier surface need be scraped and characterize.
The method removing template in molecular screen membrane duct is: rise to 500 ~ 550 DEG C with the temperature rise rate of 0.2 ~ 1K/min from room temperature in air atmosphere, and keep 4 ~ 8h; Or rise to 500 ~ 550 DEG C with the temperature rise rate of 0.2 ~ 1K/min from room temperature under rare gas element (nitrogen) atmosphere, and keep 4 ~ 8h; Or rise to 150 ~ 250 DEG C with the temperature rise rate of 1 ~ 5K/min from room temperature under ozone atmosphere, and keep 4 ~ 8h;
The AEL molecular screen membrane of single-component gas-permeable experiment to removing template is adopted to carry out penetrating quality analysis, namely under certain temperature and pressure condition, in unit of measure's time, by the ratio of flow and the size of corresponding Knudsen diffusion coefficient, gas with various, by the flow of certain molecular screen membrane, determines whether surveyed molecular screen membrane possesses good gas-permeable separation performance by comparing gas with various respectively.
The separation of long chain alkane isomers is a significant process in industrial gas oil, and mineral membrane isolation technique has unique advantage in this field.AEL type molecular sieve is the one of aluminium phosphate molecular sieve, and containing one dimension ten-ring straight hole structure, duct is oval, and size is 4.0 × 6.5nm.Its aperture is greater than straight-chain paraffin, is less than branched paraffin, has application prospect in the separation of therefore AEL molecular screen membrane long chain alkane isomers in industrial gas oil.
The present invention is that reaction medium prepares the AEL type aluminophosphate molecular sieve membrane not yet can prepared so far under hydrothermal conditions with ionic liquid.Porous alumina carrier participates in building-up reactions directly as supporter and aluminium source simultaneously, and under overcoming ion heat condition, the molecular sieve crystal seed needed for film forming is difficult to the difficulty being attached to carrier surface.Ionic liquid vapour pressure is almost nil, and the present invention does not produce the spontaneous high pressure of system in preparation process.Synthesized molecular screen membrane possesses good gas delivery penetrating quality.The inventive method has environmental friendliness, advantage easy and simple to handle, is particularly advantageous in the large-scale production of molecular screen membrane.
Accompanying drawing explanation
The XRD spectra of the AEL type aluminophosphate molecular sieve membrane of Fig. 1 synthesized by the embodiment of the present invention 1;
The SEM electromicroscopic photograph of the AEL type aluminophosphate molecular sieve membrane of Fig. 2 synthesized by the embodiment of the present invention 1;
The single-component gas-permeable experimental data of the AEL type aluminophosphate molecular sieve membrane of Fig. 3 synthesized by the embodiment of the present invention 1.
Embodiment
Embodiment 1
Added in 100 ml beakers by 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 100 DEG C, evenly dripping 0.5 gram mass concentration is the hydrofluoric acid of 40%, and stir 2 little of evenly, dripping 1.15 gram mass concentration is wherein the phosphoric acid of 85%, P
2o
5: F
-: the molar ratio of ionic liquid is 1: 2: 80, continue stirring 10 minutes, then poured into by reaction solution in the reactor that placed δ-round sheet alumina supporter in advance, notice that carrier need be submerged in reaction solution completely, the amount ratio of supporter and precursors reaction solution is 0.5 (cm
2ml
-1supporting body surface is amassed), reactor is warming up to 150 DEG C, keeps 12 hours, subsequently reactor is down to room temperature, take out carrier, in deionized water supersound washing three times, and use acetone washing by soaking.Carrier after washed is placed in 110 DEG C of baking ovens dry.In air atmosphere, rise to 550 DEG C with the temperature rise rate of 1K/min from room temperature, and keep 6h, the organism in removing molecular screen membrane duct, thus obtain AEL type molecular screen membrane.
As seen from Figure 1, the molecular screen membrane prepared is pure phase, not containing stray crystal; As seen from Figure 2, the molecular screen membrane prepared is fine and close, complete, continuously; Thickness is 15 microns; As seen from Figure 3, prepared molecular screen membrane possesses good gas permeability.
Embodiment 2
Added in 100 ml beakers by 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 120 DEG C, evenly dripping 0.25 gram mass concentration is the hydrofluoric acid of 40%, and stir 2 little of evenly, dripping 0.575 gram mass concentration is wherein the phosphoric acid of 85%, P
2o
5: F
-: the molar ratio of ionic liquid is 1: 2: 160, continue stirring 10 minutes, then poured into by reaction solution in the reactor that placed δ-round sheet alumina supporter in advance, notice that carrier need be submerged in reaction solution completely, the amount ratio of supporter and precursors reaction solution is 0.6 (cm
2ml
-1supporting body surface is amassed), reactor is warming up to 160 DEG C, keeps 24 hours, subsequently reactor is down to room temperature, take out carrier, in deionized water supersound washing three times, and use acetone washing by soaking.Carrier after washed is placed in 110 DEG C of baking ovens dry.In air atmosphere, rise to 550 DEG C with the temperature rise rate of 1K/min, and keep 6h, the organism in removing molecular screen membrane duct, thus obtain AEL type molecular screen membrane.
Embodiment 3
Added in 100 ml beakers by 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 90 DEG C, evenly dripping 0.1 gram mass concentration is the hydrofluoric acid of 40%, and stir 2 little of evenly, dripping 0.23 gram mass concentration is wherein the phosphoric acid of 85%, P
2o
5: F
-: the molar ratio of ionic liquid is 1: 2: 400, continue stirring 10 minutes, then poured into by reaction solution in the reactor that placed θ-square sheet alumina supporter in advance, notice that carrier need be submerged in reaction solution completely, the amount ratio of supporter and precursors reaction solution is 0.4 (cm
2ml
-1supporting body surface is amassed), reactor is warming up to 120 DEG C, keeps 480 hours, subsequently reactor is down to room temperature, take out carrier, in deionized water supersound washing three times, and use acetone washing by soaking.Carrier after washed is placed in 110 DEG C of baking ovens dry.In air atmosphere, rise to 550 DEG C with the temperature rise rate of 1K/min, and keep 6h, the organism in removing molecular screen membrane duct, thus obtain AEL type molecular screen membrane.
Embodiment 4
Added in 100 ml beakers by 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 100 DEG C, evenly dripping 0.05 gram mass concentration is the hydrofluoric acid of 40%, and stir 2 little of evenly, dripping 2.3 gram mass concentration is wherein the phosphoric acid of 85%, P
2o
5: F
-: the molar ratio of ionic liquid is 1: 0.1: 40, continue stirring 10 minutes, then poured into by reaction solution in the reactor that placed γ-cylindrical alumina supporter in advance, notice that carrier need be submerged in reaction solution completely, the amount ratio of supporter and precursors reaction solution is 0.5 (cm
2ml
-1supporting body surface is amassed), reactor is warming up to 280 DEG C, keeps 0.5 hour, subsequently reactor is down to room temperature, take out carrier, in deionized water supersound washing three times, and use acetone washing by soaking.Carrier after washed is placed in 110 DEG C of baking ovens dry.In air atmosphere, rise to 550 DEG C with the temperature rise rate of 1K/min, and keep 6h, the organism in removing molecular screen membrane duct, thus obtain AEL type molecular screen membrane.
Embodiment 5
Added in 100 ml beakers by 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 100 DEG C, evenly dripping 0.25 gram mass concentration is the hydrofluoric acid of 40%, and stirring 2 is little of evenly, adds 0.66 gram of ammonium hydrogen phosphate wherein, P
2o
5: F
-: the molar ratio of ionic liquid is 1: 2: 160, continue stirring 10 minutes, then poured into by reaction solution in the reactor that placed δ-square sheet alumina supporter in advance, notice that carrier need be submerged in reaction solution completely, the amount ratio of supporter and precursors reaction solution is 0.2 (cm
2ml
-1supporting body surface is amassed), reactor is warming up to 150 DEG C, keeps 12 hours, subsequently reactor is down to room temperature, take out carrier, in deionized water supersound washing three times, and use acetone washing by soaking.Carrier after washed is placed in 110 DEG C of baking ovens dry.In nitrogen atmosphere, rise to 550 DEG C with the temperature rise rate of 1K/min, and keep 6h, the organism in removing molecular screen membrane duct, thus obtain AEL type molecular screen membrane.
Embodiment 6
Added in 100 ml beakers by 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 90 DEG C, evenly add 0.21 gram of Sodium Fluoride, stirring 2 is little of evenly, adds 0.575 gram of primary ammonium phosphate wherein, P
2o
5: F
-: the molar ratio of ionic liquid is 1: 2: 160, continue stirring 10 minutes, then poured into by reaction solution in the reactor that placed δ-square sheet alumina supporter in advance, notice that carrier need be submerged in reaction solution completely, the amount ratio of supporter and precursors reaction solution is 0.8 (cm
2ml
-1supporting body surface is amassed), reactor is warming up to 150 DEG C, keeps 12 hours, subsequently reactor is down to room temperature, take out carrier, in deionized water supersound washing three times, and use acetone washing by soaking.Carrier after washed is placed in 110 DEG C of baking ovens dry.In nitrogen atmosphere, rise to 550 DEG C with the temperature rise rate of 1K/min, and keep 6h, the organism in removing molecular screen membrane duct, thus obtain AEL type molecular screen membrane.
Embodiment 7
Added in 100 ml beakers by 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 100 DEG C, evenly add 0.185 gram of Neutral ammonium fluoride, stir 2 little of evenly, dripping 0.575 gram mass concentration is wherein the phosphoric acid of 85%, P
2o
5: F
-: the molar ratio of ionic liquid is 1: 2: 160, continue stirring 10 minutes, then poured into by reaction solution in the reactor that placed δ-round sheet aluminum oxide in advance, notice that carrier need be submerged in reaction solution completely, the amount ratio of supporter and precursors reaction solution is 0.5 (cm
2ml
-1supporting body surface is amassed), reactor is warming up to 150 DEG C, keeps 12 hours, subsequently reactor is down to room temperature, take out carrier, in deionized water supersound washing three times, and use acetone washing by soaking.Carrier after washed is placed in 110 DEG C of baking ovens dry.In containing the air atmosphere of ozone 50mg/L, rise to 140 DEG C with the temperature rise rate of 4K/min, and keep 8h, the organism in removing molecular screen membrane duct, thus obtain AEL type molecular screen membrane.
Embodiment 8
82.0 grams of 1-propyl group-3-methylimidazolium chloride ionic liquids are added in 100 ml beakers, be warming up to 90 DEG C, evenly add 0.0925 gram of Neutral ammonium fluoride and 0.105 gram of Sodium Fluoride, stir 2 little of evenly, add 0.33 gram of ammonium hydrogen phosphate and 0.29 gram of primary ammonium phosphate wherein, P
2o
5: F
-: the molar ratio of ionic liquid is 1: 2: 160, continue stirring 10 minutes, then poured into by reaction solution in the reactor that placed δ-cylindrical tubular aluminum oxide in advance, notice that carrier need be submerged in reaction solution completely, the amount ratio of supporter and precursors reaction solution is 0.5 (cm
2ml
-1supporting body surface is amassed), reactor is warming up to 150 DEG C, keeps 12 hours, subsequently reactor is down to room temperature, take out carrier, in deionized water supersound washing three times, and use acetone washing by soaking.Carrier after washed is placed in 110 DEG C of baking ovens dry.In containing the air atmosphere of ozone 50mg/L, rise to 200 DEG C with the temperature rise rate of 4K/min, and keep 6h, the organism in removing molecular screen membrane duct, thus obtain AEL type molecular screen membrane.
The XRD diffraction peak position of sample and relatively strong and weak in table 1 embodiment of the present invention 1 ~ 8
As seen from the above table, in the Reaction conditions range that present method is stated, all can prepare the AEL type aluminophosphate molecular sieve membrane of pure phase.
Claims (10)
1. the preparation of AEL structure aluminophosphate molecular sieve membrane that supports of porous alumina carrier, is characterized in that: be reaction medium with ionic liquid, take porous alumina carrier as supporter, at supporting body surface synthesis AEL type microporous aluminophosphates molecular screen membrane;
Specific operation process is as follows,
1) prepare precursors reaction solution: mixed with phosphorous raw material, mineralizer by ionic liquid, described mineralizer is for containing F
-compound, form precursors reaction solution after stirring, P in reaction soln
2o
5: F
-: the molar ratio of ionic liquid is 1:0.1 ~ 2:40 ~ 400;
2) porous alumina carrier is inserted above-mentioned precursors reaction solution, at 100 ~ 300 DEG C, carries out crystallization, crystallization time >=1 minute;
3) crystallization terminates, and takes out porous alumina carrier, after removing organic formwork, obtains AEL aluminophosphate molecular sieve membrane.
2. according to preparation according to claim 1, it is characterized in that: the molecular sieve crystal forming this molecular screen membrane has the AEL structure of International Zeolite Association's confirmation, the molecular sieve crystal forming this molecular screen membrane has one dimension ten-ring straight hole structure, and its X-ray diffraction spectrogram has at least following listed diffraction peak:
2 θ values represent diffraction peak position, 2 θ/°: 8.03 ± 0.2; 9.40 ± 0.2; 13.12 ± 0.2; 15.63 ± 0.2; 16.20 ± 0.2; 18.95 ± 0.2; 20.37 ± 0.2; 20.93 ± 0.2; 22.10 ± 0.2; 22.43 ± 0.2; 22.70 ± 0.2; 23.17 ± 0.2; 24.70 ± 0.2; 26.54 ± 0.2.
3. according to preparation according to claim 1, it is characterized in that: F in precursors reaction solution
-be 1:400 ~ 1600 with the mol ratio of ionic liquid.
4. according to preparation according to claim 1, it is characterized in that: reaction medium is ionic liquid, the positively charged ion of this ionic liquid is: quaternary ammonium alkyl salt ion [NR
4]
+, alkyl quaternary phosphine ion [PR
4]
+, the imidazol ion [Rim] that alkyl replaces
+, the pyridinium ion [Rpy] that alkyl replaces
+in one, R is the alkyl of C1-C16; Wherein the negatively charged ion of ionic liquid is: Br
-, Cl
-, I
-, BF
4 -, PF
6 -, PO
4 3-, NO
3 -, SO
4 2-in one.
5. according to preparation according to claim 1, it is characterized in that: phosphorous raw material is one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate or primary ammonium phosphate;
Mineralizer is one or more in hydrofluoric acid, Neutral ammonium fluoride or Sodium Fluoride.
6. according to preparation according to claim 1, it is characterized in that: take porous alumina carrier as supporter, the alumina crystalline phase of porous alumina carrier is the one in gama-alumina, δ-aluminum oxide or θ-aluminum oxide;
The ratio that supporter is amassed by surface-area and the precursors reaction liquid of the supporter contacted with solution with the amount ratio of precursors reaction solution calculates, and is 0.2 ~ 0.8cm that every mL solution is corresponding
2the surface-area of supporter.
7. according to preparation according to claim 1, it is characterized in that: P in precursors reaction solution
2o
5: F
-: the molar ratio of ionic liquid is 1:0.2 ~ 1:80 ~ 320.
8. according to preparation according to claim 1, it is characterized in that: crystallization temperature is 120 ~ 280 DEG C, crystallization time 0.5 ~ 480h.
9. according to preparation according to claim 1, it is characterized in that: in described precursors reaction solution, water content is the 0-10wt% of precursors reaction solution weight.
10. according to preparation according to claim 9, it is characterized in that: the water in described precursors reaction solution is brought into by raw material, or additionally adds.
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| CN201210076747.6A CN103318914B (en) | 2012-03-21 | 2012-03-21 | Preparation of AEL structure aluminophosphate molecular sieve membrane supported by porous alumina carrier |
| PCT/CN2012/082950 WO2013139121A1 (en) | 2012-03-21 | 2012-11-19 | Preparation of aluminum phosphate molecular sieve membrane supported on porous aluminum oxide carrier |
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| CN201210076747.6A CN103318914B (en) | 2012-03-21 | 2012-03-21 | Preparation of AEL structure aluminophosphate molecular sieve membrane supported by porous alumina carrier |
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| CN105776247B (en) * | 2014-12-17 | 2018-05-15 | 中国科学院大连化学物理研究所 | A kind of ion process for thermosynthesizing of AEI types Metal-aluminophosphate Molecular Siever |
| CN114835138B (en) * | 2022-03-17 | 2024-04-19 | 中山大学 | Aluminum phosphate molecular sieve membrane and preparation method and application thereof |
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| CN1765744A (en) * | 2004-10-28 | 2006-05-03 | 中国石油化工股份有限公司 | Synthesis method for AEL structure molecular screen |
| CN101269821A (en) * | 2008-05-07 | 2008-09-24 | 中国科学院过程工程研究所 | Ion thermal method for preparing molecular sieve in alcohol amine ion liquid |
| CN101269822A (en) * | 2008-05-09 | 2008-09-24 | 中国石油天然气股份有限公司 | Process for synthesizing heteroatom substituted AEL cage construction aluminophosphates molecular sieve |
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| US20100119736A1 (en) * | 2008-10-07 | 2010-05-13 | The Regents Of The University Of California | Ambient pressure synthesis of zeolite films and their application as corrosion resistant coatings |
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| CN1765744A (en) * | 2004-10-28 | 2006-05-03 | 中国石油化工股份有限公司 | Synthesis method for AEL structure molecular screen |
| CN101269821A (en) * | 2008-05-07 | 2008-09-24 | 中国科学院过程工程研究所 | Ion thermal method for preparing molecular sieve in alcohol amine ion liquid |
| CN101269822A (en) * | 2008-05-09 | 2008-09-24 | 中国石油天然气股份有限公司 | Process for synthesizing heteroatom substituted AEL cage construction aluminophosphates molecular sieve |
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| "Ionothermal Synthesis of Oriented Zeolite AEL Films and Their Application as Corrosion-Resistant Coatings";Rui Cai et al.;《Angewandte Chemie International Edition》;20071031;第47卷;第525－528页 * |
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