CN103318915B - The preparation of the AFO structure aluminium phosphate molecular sieve film that porous alumina carrier supports - Google Patents
The preparation of the AFO structure aluminium phosphate molecular sieve film that porous alumina carrier supports Download PDFInfo
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- CN103318915B CN103318915B CN201210076754.6A CN201210076754A CN103318915B CN 103318915 B CN103318915 B CN 103318915B CN 201210076754 A CN201210076754 A CN 201210076754A CN 103318915 B CN103318915 B CN 103318915B
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Abstract
The present invention is specifically related to a kind of preparation method of AFO structure aluminium phosphate molecular sieve film of porous alumina carrier support. Institute's inventive method is taking ionic liquid as reaction medium with template, and porous alumina carrier reacts with phosphorus-containing compound, at the synthetic AFO structure microporous aluminophosphates molecular screen membrane of alumina carrier surface. The AFO molecular screen membrane of preparing by this method has good gas permeation separating property. The feature of the inventive method is carry out molecular screen membrane in ionic liquid synthetic, has overcome the spontaneous high pressure of system in conventional Hydrothermal Synthesis molecular screen membrane process. The inventive method has environmental friendliness, advantage easy and simple to handle.
Description
Technical field
The invention relates to a kind of ion process for thermosynthesizing of microporous aluminophosphates molecular screen membrane, more precisely about oneKind have the zeolite structured aluminium phosphate molecular sieve film of AFO type with and preparation method thereof.
Background technology
Molecular sieve is the inorganic microporous material that a class has regular pore canal structure. In decades, researcher and engineering staffBe devoted to the molecular sieve of research and synthetic different ducts feature as the catalyst of specific chemical reaction process always. Along with scienceThe continuous progress of technology, if recognize gradually can be by molecular sieve film forming for people, just can binding molecule sieve material and filmThe feature that material has, greatly widen its application: utilize the accurate molecule screening function in microporous molecular sieve duct, withTime combination film material efficiency is high during as separating film, energy consumption is low, continuous production, flexibility strong with the feature such as environmental protection, realizationEfficient, the continuous separate of blending ingredients from. Even to this day, because molecular screen material has diversified skeleton pore passage structure, thenIn addition the adjustable sex change of membrane material microstructure, increasing about the research report of molecular screen membrane, this field also will be continuedShine vitality.
AFO type molecular sieve is the one of aluminium phosphate molecular sieve, has the oval 10 ring straight hole roads of one dimension, and aperture size is0.70nm × 0.43nm. This molecular sieve separates in gas absorption, and the aspects such as catalysis are with a wide range of applications. Traditional dividesSub-sieve membrane is prepared synthetic method and is mainly contained: (1) in situ synthesis, by substrate direct impregnation, in synthetic liquid, crystallization obtains after processingTo molecular screen membrane; (2) diauxic growth method, be also the most frequently used a kind of masking strategy, first adheres to one deck pre-synthesis in substrateNano-class molecular sieve crystal is as crystal seed, then immerses in synthetic liquid and continue crystallization, forms continuous molecular screen membrane. Above-mentioned preparation sideAll there is certain weak point in method: in-situ synthesis is stricter to the requirement of substrate and synthesis condition; Secondary synthetic method is notEvitablely want previously prepared nano-class molecular sieve crystal as crystal seed, be coated with membrane process heavy complexity thereupon; In addition, due to this twoKind method is all based on Hydrothermal Synthesis technology, and the system self-generated 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 professor RusselEMorris of University of St Andrews of Britain reported use ionic liquidAs the ion thermal synthesis method of solvent and the synthetic microporous aluminium phosphate molecular sieve of template, i.e. ion thermal synthesis method. Ionic liquid isFusing point, at a low temperature molten salt near room temperature, is generally made up of organic cation and inorganic anion. With traditional moleculeType solvent phase ratio, ionic liquid vapour pressure is almost nil, is non-volatile liquid; Therefore with conventional Hydrothermal Synthesis and solventProcess for thermosynthesizing is compared, and ion thermal synthesis reaction can be carried out under normal pressure, so just can eliminate due to molten in course of reactionThe potential safety hazard that the spontaneous high pressure of agent brings. In addition,, in the process of the hot method synthetic inorganic material of ion, ionic liquid not onlyCan be used as solvent, sometimes can also participate in synthetic reaction as template, these features all meet Green Chemistry requirement very much,Building-up process is fool proof, environmental protection.
From finding out the introduction of molecular screen membrane and ion thermal synthesis above, if hot ion method can be applied to moleculeThe synthetic field of sieve 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 the system of the AFO structure aluminium phosphate molecular sieve film that proposes a kind of porous alumina carrier supportPreparation Method.
Synthetic method provided by the present invention adopts synthetic method feature to be: taking ionic liquid as reaction medium with templateAgent, taking porous alumina carrier as supporter, at the synthetic AFO type microporous aluminophosphates molecular screen membrane of supporting body surface.
Specific operation process is as follows,
1) prepare precursors reaction solution: in ionic liquid, add phosphorous raw material, after stirring, form precursors reaction moltenLiquid, P in reaction solution2O5: the molar ratio of ionic liquid is 1: 10～400;
For under normal temperature for liquid or through with reactant mix and blend after can be formed directly in the ionic liquid of solution, precursor is anti-Answer in solution preparation process and do not need to heat; For being still solid-state ionic liquid after mix and blend, should be higher than its fusing pointAt temperature, prepare precursors reaction liquid (temperature can be 80～120 DEG C);
2) porous alumina carrier is inserted to above-mentioned precursors reaction solution, at 100～300 DEG C, carry out crystallization, crystalline substanceChange reaction time >=1 minute;
3) crystallization finishes, and takes out porous alumina carrier, removes after organic formwork, obtains AFO aluminium phosphate molecular sieve film.
The AFO aluminium phosphate molecular sieve film of preparing with said method is by comparing really with XRD powder diffraction data storehouse cardFixed its structure has the AFO structure that International Zeolite Association confirms, the molecular sieve crystal that forms this molecular screen membrane has one dimension ellipse10 ring straight hole roads, aperture size is 0.70nm × 0.43nm; Its X-ray diffraction spectrogram has at least following listed diffraction maximum(2 θ value representation diffraction maximum position): 2 θ/°: 6.80 ± 0.2; 9.77 ± 0.2; 13.63 ± 0.2; 18.35 ± 0.2; 20.52 ±0.2；21.27±0.2；22.33±0.2；22.95±0.2；23.45±0.2；25.40±0.2；25.81±0.2；28.16±0.2；29.56±0.2；
Above-mentioned synthetic method intermediate ion liquid is for having following cation: quaternary ammonium alkyl salt ion [NR4]+, alkyl quaternary phosphine fromSon [PR4]+, the imidazol ion [Rim] that alkyl replaces+, the pyridinium ion [Rpy] that alkyl replaces+In a kind of ionic liquid, RFor the alkyl of C1-C16; The anion of ionic liquid can be: Br-、Cl-、I-、BF4 -、PF6 -、PO4 3-、NO3 -、SO4 2-In one.
Phosphorous raw material is the one in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate (ADP), is preferably 85% phosphorusAcid.
Taking porous alumina carrier as supporter. Porous alumina carrier is prepared by extrusion, casting method or Method for bonding; ItsBe shaped as the various shapes such as round sheet, polygon sheet or cylindrical; Its material be gama-alumina, δ-aluminium oxide orθ-aluminium oxide.
P in precursors reaction solution in precursors reaction solution in above-mentioned synthetic method2O5: the preferred molar ratio example of ionic liquidBe 1: 20～200.
In above-mentioned synthetic method step, preferred crystallization temperature is 120～280 DEG C, 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 at sheetSynthetic molecular screen membrane on shape carrier, can directly characterize its surface; For molecular screen membrane synthetic on tubular carrier,The molecular sieve crystal of carrier surface need be scraped and characterizes.
Removing the method for template in molecular screen membrane duct is: under air atmosphere with the heating rate of 0.2～1K/minRise to 500～550 DEG C from room temperature, and keep 4～8h; Or under inert gas (nitrogen) atmosphere with the intensification of 0.2～1K/minSpeed rises to 500～550 DEG C from room temperature, and keeps 4～8h; Or under ozone atmosphere with the heating rate of 1～5K/min from chamberTemperature rise to 150～250 DEG C, and keep 4～8h.
Adopt the experiment of one-component gas permeation to carry out permeance property analysis to the AFO molecular screen membrane of removing template, existUnder uniform temperature and pressure condition, in measurement unit's time, gas with various passes through the flow of certain molecular screen membrane respectively, by comparingGas with various determines by the ratio of flow and the size of corresponding Knudsen diffusion coefficient whether surveyed molecular screen membrane possesses betterGas permeation separating property.
The present invention can prepare and under hydrothermal condition, fail so far to prepare AFO type aluminum phosphate molecule with ionic liquid and cooperationSieve membrane. Porous alumina carrier is participated in synthetic reaction directly as supporter and aluminium source simultaneously, has overcome under ion heat condition, becomesThe required molecular sieve crystal seed of film is difficult to be attached to the difficulty of carrier surface. Ionic liquid vapour pressure is almost nil, and the present invention is in systemIn standby process, do not produce the spontaneous high pressure of system. The molecular screen membrane of synthesized possesses good gas and separates permeance property. The present inventionMethod has environmental friendliness, and advantage easy and simple to handle is particularly advantageous in the large-scale production of molecular screen membrane.
Brief description of the drawings
Fig. 1 is the XRD spectra of the AFO type aluminium phosphate molecular sieve film of the embodiment of the present invention 1 synthesized;
Fig. 2 is the SEM electromicroscopic photograph of the AFO type aluminium phosphate molecular sieve film of the embodiment of the present invention 1 synthesized;
Fig. 3 is the one-component gas permeation experiment number of the AFO type aluminium phosphate molecular sieve film of the embodiment of the present invention 1 synthesizedAccording to.
Detailed description of the invention
Embodiment 1
57.3 grams of 1-ethyl-3-methyl bromination imidazole ion liquids are added in 100 ml beakers, be warming up to 100 DEG C, toWherein drip the phosphoric acid that 1.15 gram mass concentration are 85%, P2O5: the molar ratio of ionic liquid is 1: 60, stirs 2 hours to equalEven, then reactant liquor is poured in the reactor of having placed in advance δ-round sheet alumina support, notice that carrier need soak completelySubmerge in reactant liquor, the amount ratio of supporter and precursors reaction solution is 0.4 (cm2·ml-1Supporting body surface is long-pending), by reactorBe warming up to 140 DEG C, keep 48 hours, subsequently reactor is down to room temperature, take out carrier, in deionized water for ultrasonic washing threeInferior, and use acetone washing by soaking. Washing carrier is later placed in to 110 DEG C of baking ovens dries. In air atmosphere with 1K/minHeating rate rise to 550 DEG C, and keep 6h, remove the organic matter in molecular screen membrane duct, thereby obtain AFO type molecular sieveFilm.
As seen from Figure 1, the molecular screen membrane of preparing is pure phase, not containing stray crystal; As seen from Figure 2, prepareMolecular screen membrane densification, complete, continuously; Thickness is 20 microns of left and right; As seen from Figure 3, prepared molecular screen membrane possessesGood gas permeability.
Embodiment 2
57.3 grams of 1-ethyl-3-methyl bromination imidazole ion liquids are added in 100 ml beakers, be warming up to 100 DEG C, toWherein drip the phosphoric acid that 2.30 gram mass concentration are 85%, P2O5: the molar ratio of ionic liquid is 1: 30, stirs 2 hours to equalEven, then reactant liquor is poured in the reactor of having placed in advance δ-round sheet alumina support, notice that carrier need soak completelySubmerge in reactant liquor, the amount ratio of supporter and precursors reaction solution is 0.6 (cm2·ml-1Supporting body surface is long-pending), by reactorBe warming up to 160 DEG C, keep 24 hours, subsequently reactor is down to room temperature, take out carrier, in deionized water for ultrasonic washing threeInferior, and use acetone washing by soaking. Washing carrier is later placed in to 110 DEG C of baking ovens dries. In air atmosphere with 1K/minHeating rate rise to 550 DEG C, and keep 6h, remove the organic matter in molecular screen membrane duct, thereby obtain AFO type molecular sieveFilm.
Embodiment 3
57.3 grams of 1-ethyl-3-methyl bromination imidazole ion liquids are added in 100 ml beakers, be warming up to 90 DEG C, toWherein drip the phosphoric acid that 3.45 gram mass concentration are 85%, P2O5: the molar ratio of ionic liquid is 1: 20, stirs 2 hours to equalEven, then reactant liquor is poured in the reactor of having placed in advance 0-round sheet alumina support, notice that carrier need soak completelySubmerge in reactant liquor, the amount ratio of supporter and precursors reaction solution is 0.8 (cm2·ml-1Supporting body surface is long-pending), by reactorBe warming up to 160 DEG C, keep 24 hours, subsequently reactor is down to room temperature, take out carrier, in deionized water for ultrasonic washing threeInferior, and use acetone washing by soaking. Washing carrier is later placed in to 110 DEG C of baking ovens dries. In air atmosphere with 1K/minHeating rate rise to 550 DEG C, and keep 6h, remove the organic matter in molecular screen membrane duct, thereby obtain AFO type molecular sieveFilm.
Embodiment 4
57.3 grams of 1-ethyl-3-methyl bromination imidazole ion liquids are added in 100 ml beakers, be warming up to 120 DEG C, toWherein drip the phosphoric acid that 0.35 gram mass concentration is 85%, P2O5: the molar ratio of ionic liquid is 1: 200, stirs 2 hours extremelyEvenly, then reactant liquor is poured in the reactor of having placed in advance 0-cylindrical alumina support, noticed that carrier has neededEntirely be submerged in reactant liquor, the amount ratio of supporter and precursors reaction solution is 0.3 (cm2·ml-1Supporting body surface is long-pending), will be anti-Answer device to be warming up to 140 DEG C, keep 240 hours, subsequently reactor is down to room temperature, take out carrier, wash in deionized water for ultrasonicWash three times, and use acetone washing by soaking. Washing carrier is later placed in to 110 DEG C of baking ovens dries. In nitrogen atmosphere with 1K/The heating rate of min rises to 550 DEG C, and keeps 6h, removes the organic matter in molecular screen membrane duct, thereby obtains AFO type moleculeSieve membrane.
Embodiment 5
65.7 grams of 1-butyl-3-methyl bromination imidazole ion liquids are added in 100 ml beakers, be warming up to 100 DEG C, toWherein drip the phosphoric acid that 0.58 gram mass concentration is 85%, P2O5: the molar ratio of ionic liquid is 1: 120, stirs 2 hours extremelyEvenly, then reactant liquor is poured in the reactor of having placed in advance δ-round sheet alumina support, noticed that carrier needs completelyBe submerged in reactant liquor, the amount ratio of supporter and precursors reaction solution is 0.5 (cm2·ml-1Supporting body surface is long-pending) will reactDevice is warming up to 180 DEG C, keeps 12 hours, subsequently reactor is down to room temperature, takes out carrier, in deionized water for ultrasonic washing threeInferior, and use acetone washing by soaking. Washing carrier is later placed in to 110 DEG C of baking ovens dries. In nitrogen atmosphere with 1K/minHeating rate rise to 550 DEG C, and keep 6h, remove the organic matter in molecular screen membrane duct, thereby obtain AFO type molecular sieveFilm.
Embodiment 6
57.3 grams of 1-ethyl-3-methyl bromination imidazole ion liquids are added in 100 ml beakers, be warming up to 90 DEG C, toWherein drip the phosphoric acid that 0.70 gram mass concentration is 85%, P2O5: the molar ratio of ionic liquid is 1: 100, stirs 2 hours extremelyEvenly, then reactant liquor is poured in the reactor of having placed in advance δ-square sheet alumina support, noticed that carrier needs completelyBe submerged in reactant liquor, the amount ratio of supporter and precursors reaction solution is 0.5 (cm2·ml-1Supporting body surface is long-pending) will reactDevice is warming up to 280 DEG C, keeps 0.5 hour, subsequently reactor is down to room temperature, takes out carrier, washs in deionized water for ultrasonicThree times, and use acetone washing by soaking. Washing carrier is later placed in to 110 DEG C of baking ovens dries. At the sky containing ozone 50mg/LIn gas atmosphere, rise to 140 DEG C with the heating rate of 4K/min, and keep 8h, remove the organic matter in molecular screen membrane duct, therebyObtain AFO type molecular screen membrane.
The XRD diffraction maximum 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 this method, all can prepare the AFO type aluminum phosphate of pure phaseMolecular screen membrane.
Claims (9)
1. the preparation method of AFO structure aluminium phosphate molecular sieve film that porous alumina carrier supports, is characterized in that: with fromSub-liquid is reaction medium and template, taking porous alumina carrier as supporter, at the synthetic AFO type micropore phosphorus of supporting body surfaceAcid aluminum molecular screen film;
Specific operation process is as follows,
1) prepare precursors reaction solution: ionic liquid is mixed with phosphorous raw material, after stirring, form precursors reaction solution, anti-Answer P in solution2O5: the molar ratio of ionic liquid is 1:10～400;
2) porous alumina carrier is inserted to above-mentioned precursors reaction solution, carry out crystallization at 100～300 DEG C, crystallization is anti-Between seasonable >=1 minute;
3) crystallization finishes, and takes out porous alumina carrier, removes after organic formwork, obtains AFO aluminium phosphate molecular sieve film.
2. it is characterized in that in accordance with the method for claim 1: the molecular sieve crystal that forms this molecular screen membrane has the world and boilsThe AFO structure that stone association confirms, AFO structure aluminium phosphate molecular sieve has the oval 10 ring straight hole roads of one dimension, and aperture size is0.70nm × 0.43nm, its X-ray diffraction spectrogram has at least following listed diffraction maximum:
2 θ value representation diffraction maximum positions, 2 θ/°: 6.80 ± 0.2; 9.77 ± 0.2; 13.63 ± 0.2; 18.35 ± 0.2; 20.52 ±0.2；21.27±0.2；22.33±0.2；22.95±0.2；23.45±0.2；25.40±0.2；25.81±0.2；28.16±0.2；29.56±0.2。
3. according to preparation method claimed in claim 1, it is characterized in that: reaction medium is ionic liquid; This ionic liquid toolThere is following cation: quaternary ammonium alkyl salt ion [NR4]+, alkyl quaternary phosphine ion [PR4]+, the imidazol ion [Rim] that alkyl replaces+，The pyridinium ion [Rpy] that alkyl replaces+In one, the alkyl that R is C1-C16; Wherein the anion of ionic liquid is: Br-、Cl-、I-、BF4 -、PF6 -、PO4 3-、NO3 -、SO4 2-In one.
4. according to preparation method claimed in claim 1, it is characterized in that: phosphorous raw material is phosphoric acid, ammonium phosphate, ammonium hydrogen phosphateOr one or more in ammonium dihydrogen phosphate (ADP).
5. according to preparation method claimed in claim 1, it is characterized in that: taking porous alumina carrier as supporter, porous oxygenThe aluminium oxide crystalline phase of changing alumina supporter is the one in gama-alumina, δ-aluminium oxide or θ-aluminium oxide;
Supporter is long-pending by surface area and the precursors reaction liquid of the supporter contacting with solution with the amount ratio of precursors reaction solutionRatio calculate, be 0.2～0.8cm corresponding to every mL solution2The surface area of supporter.
6. according to preparation method claimed in claim 1, it is characterized in that: P in precursors reaction solution2O5: ionic liquid moleRatio is 1:20～200.
7. according to preparation method claimed in claim 1, it is characterized in that: crystallization temperature is 120～280 DEG C, crystallization time 0.5～480h。
8. according to preparation method claimed in claim 1, it is characterized in that: in described precursors reaction solution, the water yield is precursors reactionThe 0-10wt% of solution weight.
9. according to preparation method claimed in claim 8, it is characterized in that: the water in described precursors reaction solution is by raw bandEnter, or additionally add.
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| CN201210076754.6A CN103318915B (en) | 2012-03-21 | 2012-03-21 | The preparation of the AFO structure aluminium phosphate molecular sieve film that porous alumina carrier supports |
| 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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| CN102139889A (en) * | 2010-01-29 | 2011-08-03 | 中国科学院大连化学物理研究所 | Synthesis method of silicoaluminophosphate molecular sieve with AFO structure |
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