CN104108721B - The preparation of the AEL structure aluminophosphate molecular sieve membrane that porous alumina carrier supports - Google Patents
The preparation of the AEL structure aluminophosphate molecular sieve membrane that porous alumina carrier supports Download PDFInfo
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Abstract
The invention discloses a kind of ion process for thermosynthesizing of microporous aluminophosphates molecular screen membrane, is solvent with imidazolium ionic liquid, at alumina carrier surface, by the method for ion heat two step synthesis, and synthesis AlPO
4-11 molecular screen membranes.The feature of the method adopts ionic liquid as solvent and template, carries out crystallization at ambient pressure, overcome in molecular screen membrane conventional synthetic procedures, the potential safety hazard that system autogenous pressure brings; Without acid-base waste fluid discharge, environmental friendliness; Easy and simple to handle, aging without the need to carrying out synthesis liquid, without the need to introducing crystal seed, be easy to industrialization expanding production.
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 aluminium phosphate molecular sieve (AlPO of AEL type
4-11) and its 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 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 the most separating film time efficiency high, 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.
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 professor RusselEMorris 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.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.
The preparation method of the AEL structure aluminophosphate molecular sieve membrane that a kind of porous alumina carrier supports, it is characterized in that: take ionic liquid as reaction medium, ionic liquid cation is template, take porous alumina carrier as supporter, in two steps at supporting body surface order synthesis AEL type microporous aluminophosphates molecular screen membrane:
(1) take ionic liquid as reaction medium, mineralizer is added obtained mineralizer ionic liquid solution in ionic liquid under certain temperature and violent stirring, its mol ratio is: 1HF:1 ~ 800ILs;
(2) take ionic liquid as reaction medium, the precursor compound of phosphorus is added obtained phosphorous ionic liquid solution in 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 the reactor containing hydrofluoric acid ionic liquid solution, temperature of reaction is 100 DEG C ~ 300 DEG C, 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 DEG C ~ 300 DEG C, reaction times >=1 minute;
(5) after second step reaction terminates, by reactor cooling to room temperature, substrate is taken out, by acetone and deionized water repetitive scrubbing extremely neutrality, dry at 100 ~ 120 DEG C, obtain AEL molecular screen membrane.
(6) in air atmosphere, be warming up to 500 ~ 600 DEG C with the temperature rise rate of 0.5 ~ 2K/min, and keep 4-16h, to slough the organism in molecular sieve fenestra.
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 crystal structure of molecular sieve forming this molecular screen membrane comprises the chabazite cage connected by two six-ring, has octatomic ring window and the neighbour tetracyclic structure be connected; Its X-ray diffraction spectrogram has at least following listed diffraction peak (2 θ values represent 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, 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%.
Fluorine-containing raw material 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.
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, the first step reacts preferred crystallization temperature is 120 ~ 280 DEG C, and preferred crystallization time is 0.5 ~ 480h; It is 120 ~ 280 DEG C that second step reacts preferred crystallization temperature, 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 0.4 × 0.65nm.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; A: the reacted XRD spectra of the first step; B: the reacted XRD spectra of second step.
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
76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids are added respectively in two 100 ml beakers, be warming up to 100 DEG C, evenly drip respectively 0.5 gram mass concentration be 40% hydrofluoric acid and 1.15 gram mass concentration be the phosphoric acid of 85%, stir 2 little of evenly respectively, 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 being poured into by hydrofluoric acid ionic liquid solution placed in the reactor of alumina supporter in advance, and 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 210 DEG C, keeps 1 hour, subsequently carrier is taken out, put into another reactor, pour phosphate ion liquor wherein into, reactor is warming up to 210 DEG C, keep 3 hours, subsequently by reactor cooling 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 0.2K/min, and keep 8h, 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; As seen from Figure 3, prepared molecular screen membrane possesses good gas permeability.
Embodiment 2
76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids are added respectively in two 100 ml beakers, be warming up to 100 DEG C, evenly drip respectively 2 gram mass concentration be 40% hydrofluoric acid and 1.15 gram mass concentration be the phosphoric acid of 85%, stir 2 little of evenly respectively, 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 being poured into by hydrofluoric acid ionic liquid solution placed in the reactor of alumina supporter in advance, and 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 carrier is taken out, put into another reactor, pour phosphate ion liquor wherein into, reactor is warming up to 280 DEG C, keep 0.5 hour, subsequently by reactor cooling 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 500 DEG C with the temperature rise rate of 1K/min, and keep 4h, the organism in removing molecular screen membrane duct, thus obtain AEL type molecular screen membrane.
Embodiment 3
76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids are added respectively in two 100 ml beakers, be warming up to 100 DEG C, evenly drip respectively 0.5 gram mass concentration be 40% hydrofluoric acid and 4.6 gram mass concentration be the phosphoric acid of 85%, stir 2 little of evenly respectively, 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 being poured into by hydrofluoric acid ionic liquid solution placed in the reactor of alumina supporter in advance, and 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 120 DEG C, keeps 3 hours, subsequently carrier is taken out, put into another reactor, pour phosphate ion liquor wherein into, reactor is warming up to 120 DEG C, keep 3 hours, subsequently by reactor cooling 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 0.2K/min, and keep 8h, the organism in removing molecular screen membrane duct, thus obtain AEL type molecular screen membrane.
Embodiment 4
76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids are added respectively in two 100 ml beakers, be warming up to 100 DEG C, evenly drip respectively 0.5 gram mass concentration be 40% hydrofluoric acid and 1.15 gram mass concentration be the phosphoric acid of 85%, stir 2 little of evenly respectively, 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 being poured into by hydrofluoric acid ionic liquid solution placed in the reactor of alumina supporter in advance, and 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 480 DEG C, keeps 3 hours, subsequently carrier is taken out, put into another reactor, pour phosphate ion liquor wherein into, reactor is warming up to 160 DEG C, keep 480 hours, subsequently by reactor cooling 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 500 DEG C with the temperature rise rate of 1K/min, and keep 4h, the organism in removing molecular screen membrane duct, thus obtain AEL type molecular screen membrane.
Embodiment 5
76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids are added respectively in two 100 ml beakers, be warming up to 100 DEG C, evenly drip respectively 0.05 gram mass concentration be 40% hydrofluoric acid and 0.115 gram mass concentration be the phosphoric acid of 85%, stir 2 little of evenly respectively, 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 being poured into by hydrofluoric acid ionic liquid solution placed in the reactor of alumina supporter in advance, and 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 120 DEG C, keeps 3 hours, subsequently carrier is taken out, put into another reactor, pour phosphate ion liquor wherein into, reactor is warming up to 120 DEG C, keep 3 hours, subsequently by reactor cooling 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 6
76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids are added respectively in two 100 ml beakers, be warming up to 100 DEG C, evenly drip hydrofluoric acid and 0.66 gram of ammonium hydrogen phosphate that 0.25 gram mass concentration is 40% respectively, stir 2 little of evenly respectively, 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 being poured into by hydrofluoric acid ionic liquid solution placed in the reactor of alumina supporter in advance, and 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 120 DEG C, keeps 3 hours, subsequently carrier is taken out, put into another reactor, pour phosphate ion liquor wherein into, reactor is warming up to 120 DEG C, keep 3 hours, subsequently by reactor cooling 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 6
76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids are added respectively in two 100 ml beakers, be warming up to 100 DEG C, respectively evenly drip 0.21 gram of Sodium Fluoride and 0.575 gram of primary ammonium phosphate, stir 2 little of evenly respectively, 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 being poured into by hydrofluoric acid ionic liquid solution placed in the reactor of alumina supporter in advance, and 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 120 DEG C, keeps 3 hours, subsequently carrier is taken out, put into another reactor, pour phosphate ion liquor wherein into, reactor is warming up to 120 DEG C, keep 3 hours, subsequently by reactor cooling 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 7
76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids are added respectively in two 100 ml beakers, be warming up to 100 DEG C, evenly dripping 0.185 gram of Neutral ammonium fluoride and 0.575 gram mass concentration is respectively the phosphoric acid of 85%, stirs 2 little of evenly respectively, 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 being poured into by hydrofluoric acid ionic liquid solution placed in the reactor of alumina supporter in advance, and 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 120 DEG C, keeps 3 hours, subsequently carrier is taken out, put into another reactor, pour phosphate ion liquor wherein into, reactor is warming up to 120 DEG C, keep 3 hours, subsequently by reactor cooling 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 150 DEG C with the temperature rise rate of 1K/min, and keep 4h, the organism in removing molecular screen membrane duct, thus obtain AEL type molecular screen membrane.
Embodiment 8
76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids are added respectively in two 100 ml beakers, be warming up to 100 DEG C, evenly drip 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 respectively, stir 2 little of evenly respectively, 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 being poured into by hydrofluoric acid ionic liquid solution placed in the reactor of alumina supporter in advance, and 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 120 DEG C, keeps 3 hours, subsequently carrier is taken out, put into another reactor, pour phosphate ion liquor wherein into, reactor is warming up to 120 DEG C, keep 3 hours, subsequently by reactor cooling 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 250 DEG C with the temperature rise rate of 5K/min, and keep 8h, 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 (7)
1. the preparation method of the AEL structure aluminophosphate molecular sieve membrane of porous alumina carrier support, it is characterized in that: take ionic liquid as reaction medium, ionic liquid cation is template, take porous alumina carrier as supporter, in two steps at supporting body surface order synthesis AEL type microporous aluminophosphates molecular screen membrane:
(1) take ionic liquid as reaction medium, under agitation mineralizer is added obtained mineralizer ionic liquid solution in ionic liquid (ILs), 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 phosphorous raw material is added obtained phosphorous ionic liquid solution in ionic liquid (ILs), phosphorous raw material is with P
2o
5meter, the mol ratio of phosphorous raw material and ionic liquid is: 1P
2o
5: 2 ~ 1600ILs;
Phosphorous raw material is one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate or primary ammonium phosphate;
(3) building-up process is divided into two steps, the first step reaction is carried out in mineralizer ionic liquid solution: the alumina substrate after roasting is inserted the reactor containing mineralizer ionic liquid solution, temperature of reaction is 100 DEG C ~ 300 DEG C, 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 DEG C ~ 300 DEG C, reaction times >=1 minute;
(5) after second step reaction terminates, by reactor cooling to room temperature, substrate is taken out, by acetone and deionized water repetitive scrubbing extremely neutrality, dry at 100 ~ 120 DEG C, obtain AEL structure aluminophosphate molecular sieve membrane;
(6) in air atmosphere with the temperature rise rate of 0.5 ~ 2K/min from room temperature to 500 ~ 600 DEG C, and keep 4-16h, to slough the organism in molecular sieve fenestra;
The mineralizer added is for containing F
-compound.
2. according to preparation method 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 method according to 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 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.
4. according to preparation method according to claim 1, it is characterized in that: described mineralizer is one or more in hydrofluoric acid, Neutral ammonium fluoride or Sodium Fluoride.
5. according to preparation method 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.
6., according to preparation method according to 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.
7., according to preparation method according to claim 1, it is characterized in that:
Reaction times 0.5 ~ the 480h of the first step reaction; Temperature of reaction is 120 ~ 280 DEG C;
Reaction times 0.5 ~ the 480h of second step reaction; Temperature of reaction is 120 ~ 280 DEG C.
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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 |
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| Ionothermal Synthesis of Oriented Zeolite AEL Films and Their Application as Corrosion-Resistant Coatings;Rui Cai et al.;《Angewandte Chemie》;20071031;第47卷;第525-528页 * |
| 分子筛膜合成方法与条件的探讨;纪君美等;《无机材料学报》;19950331;第10卷(第1期);第100-104页 * |
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