CN104108721A - Preparation for AEL structural aluminium-phosphate molecular-sieve membrane supported by porous alumina carrier - Google Patents

Preparation for AEL structural aluminium-phosphate molecular-sieve membrane supported by porous alumina carrier Download PDF

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CN104108721A
CN104108721A CN201310137863.9A CN201310137863A CN104108721A CN 104108721 A CN104108721 A CN 104108721A CN 201310137863 A CN201310137863 A CN 201310137863A CN 104108721 A CN104108721 A CN 104108721A
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ionic liquid
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mineralizer
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CN104108721B (en
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田志坚
李科达
厉晓蕾
马怀军
徐仁顺
王炳春
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention discloses an ionothermal synthetic method for a micropore aluminium-phosphate molecular-sieve membrane. An imidazolyl ionic liquid is taken as a solvent, on the surface of an aluminium oxide carrier, an ionothermal two-step synthesis method is utilized to synthesize the AlPO4-11 molecular sieve membrane. The method is characterized in that the ionic liquid is employed as the solvent and a template, and a crystallization reaction is performed at normal pressure, so that the safety hidden trouble brought by system authigenic pressure in a routine synthesis process of a molecular sieve membrane is overcome; no acid and alkali waste liquids are discharged, and the method is friendly to environment; and the method is simple in operation, does not need to perform ageing of a synthetic solution, does not need to introduce a crystal seed, and is easy for industrialized enlargement production.

Description

The preparation of the AEL structure aluminium phosphate molecular sieve film that porous alumina carrier supports
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 aluminium phosphate molecular sieve (AlPO of AEL type 4-11) with and synthetic method in ionic liquid.
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 molecular sieve of research and synthetic different ducts feature as the catalyzer of specific chemical reaction process always.Continuous progress along with science and technology, can be by molecular sieve film forming if people recognize gradually, just can binding molecule the feature that has of sieve material and thin-film material, greatly widen its Application Areas: the accurate molecule screening function that utilizes microporous molecular sieve duct, simultaneously efficiency is high during separating film the most, energy consumption is low, continuous production, handiness is strong and the feature such as environmental protection for combination film material, realize blending ingredients efficiently, continuous separate from.Even to this day, because molecular screen material has diversified skeleton pore passage structure, the adjustable sex change of mould material microtexture in addition, the research report of relevant molecular screen membrane is increasing, and vitality also will be continued to shine in this field.
Traditional molecular screen membrane is prepared synthetic method and is mainly contained: (1) in situ synthesis, and by substrate direct impregnation, in synthetic liquid, crystallization obtains molecular screen membrane after processing; (2) diauxic growth method, is also the most frequently used a kind of masking strategy, first adheres to the nano-class molecular sieve crystal of one deck pre-synthesis as crystal seed in substrate, then continues crystallization in the synthetic liquid of immersion, forms continuous molecular screen membrane.There is certain weak point in above-mentioned preparation method: in-situ synthesis is stricter to the requirement of substrate and synthesis condition; Secondary synthesis method 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 producing in its building-up process can cause certain potential safety hazard; In addition a large amount of acid-base waste fluids that produce in building-up process, also can cause certain pollution to environment.
2004, the people such as Russel E professor Morris of Britain University of St Andrews reported and have used ionic liquid as the ion thermal synthesis method of solvent and the synthetic microporous aluminium phosphate molecular sieve of template, i.e. ion thermal synthesis method.Compare with conventional Hydrothermal Synthesis and solvent process for thermosynthesizing, ion thermal synthesis reaction can be carried out under normal pressure, so just can eliminate the potential safety hazard of bringing due to the spontaneous high pressure of solvent in reaction process.In addition, in the process of the hot method synthetic inorganic material of ion, ionic liquid not only can be used as solvent, sometimes can also participate in building-up reactions as template, and these features all meet Green Chemistry requirement very much, and building-up process is fool proof, environmental protection.
From finding out the introduction of molecular screen membrane and ion thermal synthesis above, if the hot method of ion can be applied to the synthetic field of molecular screen membrane, will be expected to develop a kind of simple and easy, environmental protection, molecular screen membrane preparation method fast.
Summary of the invention
The object of the invention is to propose the preparation method of the AEL structure aluminium phosphate molecular sieve film that a kind of porous alumina carrier supports.
The preparation method of the AEL structure aluminium phosphate molecular sieve film that a kind of porous alumina carrier supports, it is characterized in that: take ionic liquid as reaction medium, ionic liquid positively charged ion is template, take porous alumina carrier as supporter, in two steps at the synthetic AEL type microporous aluminophosphates molecular screen membrane of supporting body surface order:
(1) take ionic liquid as reaction medium, make mineralizer ionic liquid solution in mineralizer being added to ionic liquid under certain temperature and violent stirring, its mol ratio is: 1HF:1～800ILs;
(2) take ionic liquid as reaction medium, make phosphorous ionic liquid solution in the precursor compound of phosphorus being added to ionic liquid under certain temperature and strong stirring, its mol ratio is: 1P 2o 5: 2～1600ILs;
(3) building-up process is divided into two steps, the first step reaction is carried out in hydrofluoric acid ionic liquid solution: the alumina substrate after roasting is vertically inserted to the reactor that contains hydrofluoric acid ionic liquid solution, temperature of reaction is 100 ℃～300 ℃, reaction times >=1 minute;
(4) second step reaction is carried out in phosphorous ionic liquid solution: will carry out the reacted alumina substrate of the first step and insert phosphorous ionic liquid solution, temperature of reaction is 100 ℃～300 ℃, reaction times >=1 minute;
(5) after second step reaction finishes, reactor cooling, to room temperature, is taken out to substrate, extremely neutral with acetone and deionized water repetitive scrubbing, dry at 100～120 ℃, obtain AEL molecular screen membrane.
(6) in air atmosphere, the temperature rise rate with 0.5～2K/min is warming up to 500～600 ℃, and keeps 4-16h, to slough the organism in molecular sieve fenestra.
The AEL aluminium phosphate molecular sieve film of preparing with aforesaid method is by comparing and determine that its structure has the AEL structure that International Zeolite Association confirms with XRD powder diffraction data storehouse card, the crystal structure of molecular sieve that forms this molecular screen membrane comprises the chabazite cage being connected by two six-rings, has octatomic ring window and the neighbour Fourth Ring structure being connected; Its X-ray diffraction spectrogram has at least following listed diffraction peak (2 θ value representation diffraction peak position):
2θ/°：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, the alkyl that R is 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 a kind of.
Phosphorous raw material is one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate or primary ammonium phosphate, is preferably 85% phosphoric acid.
Fluorine-containing raw material is one or more in hydrofluoric acid, Neutral ammonium fluoride or Sodium Fluoride, is preferably 40% hydrofluoric acid.
Take porous alumina carrier as supporter.Porous alumina carrier is prepared by extrusion process, teeming practice or Method for bonding; It is shaped as the various shapes such as round sheet, Polygons sheet or cylindrical tubular; Its material is gama-alumina, δ-aluminum oxide or θ-aluminum oxide.
F in preferred mineralizer ionic liquid solution in above-mentioned synthetic method -: the molar ratio of ionic liquid is 1:10～400; P in preferred phosphorous ionic liquid solution 2o 5: the molar ratio of ionic liquid is 1:20～800.
In above-mentioned synthetic method step, to react preferred crystallization temperature be 120～280 ℃ to the first step, and preferred crystallization time is 0.5～480h; It is 120～280 ℃ that second step reacts preferred crystallization temperature, and preferred crystallization time is 0.5～480h; .
After crystallization finishes, the molecular screen membrane of synthesized is carried out to X-ray diffraction sign to determine its structure.For molecular screen membrane synthetic on chip carrier, can directly to its surface, characterize; For molecular screen membrane synthetic on tubular carrier, the molecular sieve crystal of carrier surface need be scraped and characterizes.
The method of removing template in molecular screen membrane duct is: the temperature rise rate with 0.2～1K/min under air atmosphere rises to 500～550 ℃ from room temperature, and keeps 4～8h; Or the temperature rise rate with 0.2～1K/min rises to 500～550 ℃ from room temperature under rare gas element (nitrogen) atmosphere, and keep 4～8h; Or the temperature rise rate with 1～5K/min rises to 150～250 ℃ from room temperature under ozone atmosphere, and keep 4～8h;
Adopt the experiment of single-component gas-permeable to carry out penetrating quality analysis to removing the AEL molecular screen membrane of template, under certain temperature and pressure condition, in unit of measure's time, gas with various, by the flow of certain molecular screen membrane, determines by the ratio of flow and the size of corresponding Knudsen diffusion coefficient 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 a kind of of aluminium phosphate molecular sieve, contains one dimension ten-ring straight hole structure, and duct is oval, and size is 0.4 * 0.65nm.Its aperture is greater than straight-chain paraffin, is less than branched paraffin, so AEL molecular screen membrane has application prospect aspect long chain alkane isomers separated in industrial gas oil.
The present invention be take ionic liquid and is prepared the AEL type aluminium phosphate molecular sieve film that not yet can prepare so far as reaction medium under hydrothermal condition.Porous alumina carrier is participated in building-up reactions directly as supporter and aluminium source simultaneously, has overcome under ion heat condition, and the required molecular sieve crystal seed of film forming is difficult to be attached to the difficulty of 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.The molecular screen membrane of synthesized possesses good gas delivery penetrating quality.The inventive method has environmental friendliness, and advantage easy and simple to handle is particularly advantageous in the large-scale production of molecular screen membrane.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the AEL type aluminium phosphate molecular sieve film of the embodiment of the present invention 1 synthesized; A: the reacted XRD spectra of the first step; B: the reacted XRD spectra of second step.
Fig. 2 is the SEM electromicroscopic photograph of the AEL type aluminium phosphate molecular sieve film of the embodiment of the present invention 1 synthesized;
Fig. 3 is the single-component gas-permeable experimental data of the AEL type aluminium phosphate molecular sieve film of the embodiment of the present invention 1 synthesized.
Embodiment
Embodiment 1
In two 100 ml beakers, add respectively 76.4 grams of 1-ethyl-3-methyl bromination imidazole ion liquids, be warming up to 100 ℃, evenly drip respectively the phosphoric acid that hydrofluoric acid that 0.5 gram mass concentration is 40% and 1.15 gram mass concentration are 85%, stir respectively 2 hours to even, F in gained mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:40; P in phosphorous ionic liquid solution 2o 5: the molar ratio of ionic liquid is 1:80; Then hydrofluoric acid ionic liquid solution is poured in the reactor of having placed in advance alumina supporter, noticed 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 long-pending), reactor is warming up to 210 ℃, keeps 1 hour, subsequently carrier is taken out, put into another reactor, pour wherein phosphate ion liquor into, reactor is warming up to 210 ℃, keep 3 hours, subsequently by reactor cooling to room temperature, take out carrier, deionized water for ultrasonic washing three times, and use acetone washing by soaking.Washing carrier is later placed in to 110 ℃ of baking ovens dries.Temperature rise rate with 0.2K/min in air atmosphere rises to 550 ℃, and keeps 8h, removes the organism in molecular screen membrane duct, thereby obtains AEL type molecular screen membrane.
As seen from Figure 1, the molecular screen membrane of preparing is pure phase, not containing stray crystal; As seen from Figure 2, the molecular screen membrane of preparing is fine and close, complete, continuously; As seen from Figure 3, prepared molecular screen membrane possesses good gas permeability.
Embodiment 2
In two 100 ml beakers, add respectively 76.4 grams of 1-ethyl-3-methyl bromination imidazole ion liquids, be warming up to 100 ℃, evenly drip respectively the phosphoric acid that hydrofluoric acid that 2 gram mass concentration are 40% and 1.15 gram mass concentration are 85%, stir respectively 2 hours to even, F in gained mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:10; P in phosphorous ionic liquid solution 2o 5: the molar ratio of ionic liquid is 1:80; Then hydrofluoric acid ionic liquid solution is poured in the reactor of having placed in advance alumina supporter, noticed 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 long-pending), reactor is warming up to 280 ℃, keeps 0.5 hour, subsequently carrier is taken out, put into another reactor, pour wherein phosphate ion liquor into, reactor is warming up to 280 ℃, keep 0.5 hour, subsequently by reactor cooling to room temperature, take out carrier, deionized water for ultrasonic washing three times, and use acetone washing by soaking.Washing carrier is later placed in to 110 ℃ of baking ovens dries.Temperature rise rate with 1K/min in air atmosphere rises to 500 ℃, and keeps 4h, removes the organism in molecular screen membrane duct, thereby obtains AEL type molecular screen membrane.
Embodiment 3
In two 100 ml beakers, add respectively 76.4 grams of 1-ethyl-3-methyl bromination imidazole ion liquids, be warming up to 100 ℃, evenly drip respectively the phosphoric acid that hydrofluoric acid that 0.5 gram mass concentration is 40% and 4.6 gram mass concentration are 85%, stir respectively 2 hours to even, F in gained mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:40; P in phosphorous ionic liquid solution 2o 5: the molar ratio of ionic liquid is 1:20; Then hydrofluoric acid ionic liquid solution is poured in the reactor of having placed in advance alumina supporter, noticed 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 long-pending), reactor is warming up to 120 ℃, keeps 3 hours, subsequently carrier is taken out, put into another reactor, pour wherein phosphate ion liquor into, reactor is warming up to 120 ℃, keep 3 hours, subsequently by reactor cooling to room temperature, take out carrier, deionized water for ultrasonic washing three times, and use acetone washing by soaking.Washing carrier is later placed in to 110 ℃ of baking ovens dries.Temperature rise rate with 0.2K/min in nitrogen atmosphere rises to 550 ℃, and keeps 8h, removes the organism in molecular screen membrane duct, thereby obtains AEL type molecular screen membrane.
Embodiment 4
In two 100 ml beakers, add respectively 76.4 grams of 1-ethyl-3-methyl bromination imidazole ion liquids, be warming up to 100 ℃, evenly drip respectively the phosphoric acid that hydrofluoric acid that 0.5 gram mass concentration is 40% and 1.15 gram mass concentration are 85%, stir respectively 2 hours to even, F in gained mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:40; P in phosphorous ionic liquid solution 2o 5: the molar ratio of ionic liquid is 1:80; Then hydrofluoric acid ionic liquid solution is poured in the reactor of having placed in advance alumina supporter, noticed 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 long-pending), reactor is warming up to 480 ℃, keeps 3 hours, subsequently carrier is taken out, put into another reactor, pour wherein phosphate ion liquor into, reactor is warming up to 160 ℃, keep 480 hours, subsequently by reactor cooling to room temperature, take out carrier, deionized water for ultrasonic washing three times, and use acetone washing by soaking.Washing carrier is later placed in to 110 ℃ of baking ovens dries.Temperature rise rate with 1K/min in nitrogen atmosphere rises to 500 ℃, and keeps 4h, removes the organism in molecular screen membrane duct, thereby obtains AEL type molecular screen membrane.
Embodiment 5
In two 100 ml beakers, add respectively 76.4 grams of 1-ethyl-3-methyl bromination imidazole ion liquids, be warming up to 100 ℃, evenly drip respectively the phosphoric acid that hydrofluoric acid that 0.05 gram mass concentration is 40% and 0.115 gram mass concentration are 85%, stir respectively 2 hours to even, F in gained mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:400; P in phosphorous ionic liquid solution 2o 5: the molar ratio of ionic liquid is 1:800; Then hydrofluoric acid ionic liquid solution is poured in the reactor of having placed in advance alumina supporter, noticed 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 long-pending), reactor is warming up to 120 ℃, keeps 3 hours, subsequently carrier is taken out, put into another reactor, pour wherein phosphate ion liquor into, reactor is warming up to 120 ℃, keep 3 hours, subsequently by reactor cooling to room temperature, take out carrier, deionized water for ultrasonic washing three times, and use acetone washing by soaking.Washing carrier is later placed in to 110 ℃ of baking ovens dries.Temperature rise rate with 1K/min in air atmosphere rises to 550 ℃, and keeps 6h, removes the organism in molecular screen membrane duct, thereby obtains AEL type molecular screen membrane.
Embodiment 6
In two 100 ml beakers, add respectively 76.4 grams of 1-ethyl-3-methyl bromination imidazole ion liquids, be warming up to 100 ℃, evenly drip respectively hydrofluoric acid and 0.66 gram of ammonium hydrogen phosphate that 0.25 gram mass concentration is 40%, stir respectively 2 hours to even, F in gained mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:80; P in phosphorous ionic liquid solution 2o 5: the molar ratio of ionic liquid is 1:80; Then hydrofluoric acid ionic liquid solution is poured in the reactor of having placed in advance alumina supporter, noticed 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 long-pending), reactor is warming up to 120 ℃, keeps 3 hours, subsequently carrier is taken out, put into another reactor, pour wherein phosphate ion liquor into, reactor is warming up to 120 ℃, keep 3 hours, subsequently by reactor cooling to room temperature, take out carrier, deionized water for ultrasonic washing three times, and use acetone washing by soaking.Washing carrier is later placed in to 110 ℃ of baking ovens dries.Temperature rise rate with 1K/min in air atmosphere rises to 550 ℃, and keeps 6h, removes the organism in molecular screen membrane duct, thereby obtains AEL type molecular screen membrane.
Embodiment 6
In two 100 ml beakers, add respectively 76.4 grams of 1-ethyl-3-methyl bromination imidazole ion liquids, be warming up to 100 ℃, evenly drip respectively 0.21 gram of Sodium Fluoride and 0.575 gram of primary ammonium phosphate, stir respectively 2 hours to even, F in gained mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:80; P in phosphorous ionic liquid solution 2o 5: the molar ratio of ionic liquid is 1:80; Then hydrofluoric acid ionic liquid solution is poured in the reactor of having placed in advance alumina supporter, noticed 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 long-pending), reactor is warming up to 120 ℃, keeps 3 hours, subsequently carrier is taken out, put into another reactor, pour wherein phosphate ion liquor into, reactor is warming up to 120 ℃, keep 3 hours, subsequently by reactor cooling to room temperature, take out carrier, deionized water for ultrasonic washing three times, and use acetone washing by soaking.Washing carrier is later placed in to 110 ℃ of baking ovens dries.Temperature rise rate with 1K/min in air atmosphere rises to 550 ℃, and keeps 6h, removes the organism in molecular screen membrane duct, thereby obtains AEL type molecular screen membrane.
Embodiment 7
In two 100 ml beakers, add respectively 76.4 grams of 1-ethyl-3-methyl bromination imidazole ion liquids, be warming up to 100 ℃, evenly drip respectively the phosphoric acid that 0.185 gram of Neutral ammonium fluoride and 0.575 gram mass concentration are 85%, stir respectively 2 hours to even, F in gained mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:80; P in phosphorous ionic liquid solution 2o 5: the molar ratio of ionic liquid is 1:80; Then hydrofluoric acid ionic liquid solution is poured in the reactor of having placed in advance alumina supporter, noticed 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 long-pending), reactor is warming up to 120 ℃, keeps 3 hours, subsequently carrier is taken out, put into another reactor, pour wherein phosphate ion liquor into, reactor is warming up to 120 ℃, keep 3 hours, subsequently by reactor cooling to room temperature, take out carrier, deionized water for ultrasonic washing three times, and use acetone washing by soaking.Washing carrier is later placed in to 110 ℃ of baking ovens dries.Containing the temperature rise rate with 1K/min in the air atmosphere of ozone 50mg/L, rising to 150 ℃, and keeping 4h, removing the organism in molecular screen membrane duct, thereby obtain AEL type molecular screen membrane.
Embodiment 8
In two 100 ml beakers, add respectively 76.4 grams of 1-ethyl-3-methyl bromination imidazole ion liquids, be warming up to 100 ℃, evenly drip respectively 0.0925 gram of Neutral ammonium fluoride, 0.105 gram of Sodium Fluoride and 0.33 gram of ammonium hydrogen phosphate, 0.29 gram of primary ammonium phosphate, stir respectively 2 hours to even, F in gained mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:80; P in phosphorous ionic liquid solution 2o 5: the molar ratio of ionic liquid is 1:80; Then hydrofluoric acid ionic liquid solution is poured in the reactor of having placed in advance alumina supporter, noticed 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 long-pending), reactor is warming up to 120 ℃, keeps 3 hours, subsequently carrier is taken out, put into another reactor, pour wherein phosphate ion liquor into, reactor is warming up to 120 ℃, keep 3 hours, subsequently by reactor cooling to room temperature, take out carrier, deionized water for ultrasonic washing three times, and use acetone washing by soaking.Washing carrier is later placed in to 110 ℃ of baking ovens dries.Containing the temperature rise rate with 5K/min in the air atmosphere of ozone 50mg/L, rising to 250 ℃, and keeping 8h, removing the organism in molecular screen membrane duct, thereby 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 of stating in present method, all can prepare the AEL type aluminium phosphate molecular sieve film of pure phase.

Claims (10)

1. the preparation of the AEL structure aluminium phosphate molecular sieve film that porous alumina carrier supports, it is characterized in that: take ionic liquid as reaction medium, ionic liquid positively charged ion is template, take porous alumina carrier as supporter, in two steps at the synthetic AEL type microporous aluminophosphates molecular screen membrane of supporting body surface order:
(1) take ionic liquid as reaction medium, under agitation mineralizer is added in ionic liquid (ILs) and make mineralizer ionic liquid solution, mineralizer is with F -meter, the mol ratio of mineralizer and ionic liquid is: 1F -: 1～800ILs;
(2) take ionic liquid as reaction medium, under agitation the precursor compound of phosphorus is added in ionic liquid (ILs) and makes phosphorous ionic liquid solution, the precursor compound of phosphorus is with P 2o 5meter, the precursor compound of phosphorus and the mol ratio of ionic liquid are: 1P 2o 5: 2～1600ILs;
(3) building-up process is divided into two steps, and the first step reaction is carried out in mineralizer ionic liquid solution: the alumina substrate after roasting is inserted to the reactor that contains mineralizer ionic liquid solution, temperature of reaction is 100 ℃～300 ℃, reaction times >=1 minute;
(4) second step reaction is carried out in phosphorous ionic liquid solution: will carry out the reacted alumina substrate of the first step and insert phosphorous ionic liquid solution, temperature of reaction is 100 ℃～300 ℃, reaction times >=1 minute;
(5) after second step reaction finishes, reactor cooling, to room temperature, is taken out to substrate, extremely neutral with acetone and deionized water repetitive scrubbing, dry at 100～120 ℃, obtain AEL molecular screen membrane;
(6) in air atmosphere, the temperature rise rate with 0.5～2K/min is warming up to 500～600 ℃ from room temperature, and keeps 4-16h, to slough the organism in molecular sieve fenestra.
2. according to preparation method claimed in claim 1, it is characterized in that: the molecular sieve crystal that forms this molecular screen membrane has the AEL structure that International Zeolite Association confirms, the molecular sieve crystal that forms 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 value representation diffraction peak positions, 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 method claimed in claim 1, it is characterized in that: the mineralizer adding is for containing F -compound, F in precursors reaction solution -with the mol ratio of ionic liquid be 1:1～1600.
4. according to preparation method claimed in claim 1, it is characterized in that: reaction medium is ionic liquid; This ionic liquid has 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, the alkyl that R is C1-C16; Wherein 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 a kind of.
5. according to preparation method claimed in 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;
Fluorine-containing raw material is one or more in hydrofluoric acid, Neutral ammonium fluoride or Sodium Fluoride.
6. according to preparation method claimed in claim 1, it is characterized in that: take porous alumina carrier as supporter; The aluminum oxide crystalline phase of porous alumina carrier can be a kind of in gama-alumina, δ-aluminum oxide or θ-aluminum oxide;
The amount ratio of supporter and precursors reaction solution is calculated by the long-pending ratio of the surface-area of the supporter contacting with solution and precursors reaction liquid, is 0.2～0.8cm corresponding to every ml solution 2the surface-area of supporter.
7. according to preparation method claimed in claim 1, it is characterized in that:
F in mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:10～400;
P in phosphorous ionic liquid solution 2o 5: the molar ratio of ionic liquid is 1:20～800.
8. according to preparation method claimed in claim 1, it is characterized in that:
Crystallization time 0.5～the 480h of the first step reaction; Preferred temperature of reaction is 120～280 ℃;
Crystallization time 0.5～the 480h of second step reaction; Preferred temperature of reaction is 120～280 ℃.
9. according to preparation method claimed in 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 method claimed in claim 9, it is characterized in that: the water in described precursors reaction solution is brought into by raw material or additionally added.
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