CN104709915A - Ionothermal synthesis method of CHA type microporous aluminum phosphate molecular sieve membrane - Google Patents

Ionothermal synthesis method of CHA type microporous aluminum phosphate molecular sieve membrane Download PDF

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CN104709915A
CN104709915A CN201310691126.3A CN201310691126A CN104709915A CN 104709915 A CN104709915 A CN 104709915A CN 201310691126 A CN201310691126 A CN 201310691126A CN 104709915 A CN104709915 A CN 104709915A
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ionic liquid
reaction
methylimidazole
mineralizer
molecular sieve
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田志坚
厉晓蕾
李科达
马怀军
徐仁顺
王炳春
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

The present invention discloses an ionothermal synthesis method of a CHA type microporous aluminum phosphate molecular sieve membrane, wherein an imidazole-based ionic liquid is used as a solvent to synthesize an AlPO4-34 molecular sieve membrane on the surface of an alumina carrier through an ionothermal two-step synthesis method. The method of the present invention has the following characteristics that: the ionic liquid is used as the solvent and the template agent to carry out the crystallization reaction under the normal pressure, such that the safe hidden danger caused by the system self-pressure during the conventional molecular sieve membrane synthesis process is overcome; acid-alkali waste liquid emission does not exist, and the environment protection property is provided; and the operation is simple, the synthesis liquid aging is not required, the crystal seed introducing is not required, and the industrial expanding production is easily achieved.

Description

A kind of ion process for thermosynthesizing of CHA type microporous aluminophosphates molecular screen membrane
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 CHA type 4-34) 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 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.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 CHA structure aluminophosphate molecular sieve membrane that a kind of porous alumina carrier supports.
The preparation method of the CHA 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 and N-Methylimidazole are template, take porous alumina carrier as supporter, in two steps at supporting body surface order synthesis CHA type microporous aluminophosphates molecular screen membrane:
(1) step (1) take ionic liquid as reaction medium, and 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) step (2) take ionic liquid as reaction medium, and the precursor compound of phosphorus and N-Methylimidazole are added obtained reaction soln in ionic liquid under certain temperature and strong stirring, its mol ratio is: 1P 2o 5: 0.1 ~ 10N-Methylimidazole: 2 ~ 1600ILs;
(3) building-up process is divided into two steps, step (1) 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) step (2) 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, and temperature of reaction is 100 DEG C ~ 300 DEG C, reaction times >=1 minute;
(5) after step (2) terminates, by reactor cooling to room temperature, substrate is taken out, by acetone and deionized water repetitive scrubbing extremely neutrality, dry at 90 ~ 120 DEG C, obtain CHA 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 CHA aluminophosphate molecular sieve membrane prepared with aforesaid method is by determining with the card comparison of XRD powder diffraction data storehouse the CHA 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/°：9.40±0.2；12.05±0.2；13.81±0.2；15.20±0.2；15.53±0.2；17.87±0.2；18.45±0.2；19.35±0.2；19.75±0.2；21.31±0.2；21.74±0.2；22.50±0.2；23.23±0.2；23.85±0.2；24.28±0.2；25.06±0.2；26.15±0.2。
The positively charged ion of above-mentioned synthetic method intermediate ion 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; The negatively charged ion of ionic liquid has following negatively charged ion: 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.
F in preferred mineralizer ionic liquid solution in above-mentioned synthetic method -: the molar ratio of ionic liquid is 1:10 ~ 400; Preferably P in phosphorous and N-Methylimidazole ionic liquid solution 2o 5: the molar ratio of ionic liquid is 1:20 ~ 800; Preferably P in phosphorous and N-Methylimidazole ionic liquid solution 2o 5be 1:0.1 ~ 10 with etamon chloride mol ratio, be preferably 1:0.2 ~ 5.
In above-mentioned synthetic method, the preferred crystallization temperature of step (1) is 120 ~ 280 DEG C, and preferred crystallization time is 0.5 ~ 480h; The preferred crystallization temperature of step (1) 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 ~ 16h.
The CHA 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.
From Sweet natural gas (methane), separating carbon dioxide is a significant process in gas conditioning, because carbonic acid gas can reduce ignition energy value, has acid and corrodibility and be unfavorable for storing and transporting under aqueous conditions.CHA type molecular sieve is the one of aluminium phosphate molecular sieve, is structurally similar to chabazite; The aperture of its 0.38nm is close in the kinetic diameter of methane, is greater than the kinetic diameter of carbonic acid gas, if be prepared into molecular screen membrane, has application prospect in the separation of therefore CHA molecular screen membrane carbonic acid gas in gas industry.The feature of this synthetic method is in ionic liquid, carry out the synthesis of molecular screen membrane, overcomes the spontaneous high pressure of system in conventional hydrothermal synthesis of molecular sieve membrane 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.
The present invention is that reaction medium prepares the CHA 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 AFI type aluminophosphate molecular sieve membrane of Fig. 1 synthesized by the embodiment of the present invention 1.Wherein, a: the reacted XRD spectra of the first step, b: the reacted XRD spectra of second step;
The SEM electromicroscopic photograph of the CHA 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 CHA type aluminophosphate molecular sieve membrane of Fig. 3 synthesized by the embodiment of the present invention 1.
Embodiment
Embodiment 1
In 100 ml beakers, add 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%, stirs 0.5 little of evenly, F in gained mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:40; Then poured into by mineralizer ionic liquid solution in the reactor that placed δ-alumina supporter in advance, notice that carrier need be submerged in reaction solution completely, the amount ratio of supporter and mineralizer ionic liquid 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; In another 100 ml beaker, add 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 100 DEG C, evenly drip phosphoric acid and 0.41 gram of N-Methylimidazole that 1.15 gram mass concentration are 85%, P in phosphorous and N-Methylimidazole ionic liquid solution 2o 5: N-Methylimidazole: the molar ratio of ionic liquid is 1:1:80, alumina supporter reacted in mineralizer ionic liquid is put into another reactor, pour phosphorous N-Methylimidazole ionic liquid solution wherein into, 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 3 hours, subsequently by reactor cooling to room temperature, taking-up 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 CHA 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
In 100 ml beakers, add 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%, stirs 0.5 little of evenly, F in gained mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:400; Then poured into by mineralizer ionic liquid solution in the reactor that placed δ-alumina supporter in advance, notice that carrier need be submerged in reaction solution completely, the amount ratio of supporter and mineralizer ionic liquid solution is 0.8(cm 2ml -1supporting body surface is amassed), reactor is warming up to 120 DEG C, keeps 480 hours, subsequently carrier is taken out; In another 100 ml beaker, add 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 100 DEG C, evenly drip phosphoric acid and 0.21 gram of N-Methylimidazole that 0.12 gram mass concentration is 85%, P in phosphorous and N-Methylimidazole ionic liquid solution 2o 5: N-Methylimidazole: the molar ratio of ionic liquid is 1:5:800, alumina supporter reacted in mineralizer ionic liquid is put into another reactor, pour phosphorous and N-Methylimidazole ionic liquid solution wherein into, the amount ratio of supporter and precursors reaction solution is 0.8(cm 2ml -1supporting body surface is amassed), reactor is warming up to 120 DEG C, keeps 480 hours, subsequently by reactor cooling to room temperature, taking-up carrier, in deionized water supersound washing three times, and use acetone washing by soaking.Carrier after washed is placed in 90 DEG C of baking ovens dry.In air atmosphere, rise to 500 DEG C with the temperature rise rate of 0.2K/min, and keep 16h, the organism in removing molecular screen membrane duct, thus obtain CHA type molecular screen membrane.
Embodiment 3
In 100 ml beakers, add 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 100 DEG C, evenly dripping 1.0 gram mass concentration is the hydrofluoric acid of 40%, stirs 0.5 little of evenly, F in gained mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:20; Then poured into by mineralizer ionic liquid solution in the reactor that placed θ-alumina supporter in advance, notice that carrier need be submerged in reaction solution completely, the amount ratio of supporter and mineralizer ionic liquid solution is 0.4(cm 2ml -1supporting body surface is amassed), reactor is warming up to 160 DEG C, keeps 4 hours, subsequently carrier is taken out; In another 100 ml beaker, add 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 100 DEG C, evenly drip phosphoric acid and 0.41 gram of N-Methylimidazole that 2.30 gram mass concentration are 85%, P in phosphorous and N-Methylimidazole ionic liquid solution 2o 5: N-Methylimidazole: the molar ratio of ionic liquid is 1:0.5:40, alumina supporter reacted in mineralizer ionic liquid is put into another reactor, pour phosphorus and N-Methylimidazole ionic liquid solution wherein into, the amount ratio of supporter and precursors reaction solution is 0.4(cm 2ml -1supporting body surface is amassed), reactor is warming up to 160 DEG C, keeps 6 hours, subsequently by reactor cooling to room temperature, taking-up carrier, in deionized water supersound washing three times, and use acetone washing by soaking.Carrier after washed is placed in 120 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 CHA type molecular screen membrane.
Embodiment 4
In 100 ml beakers, add 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 100 DEG C, evenly dripping 2.0 gram mass concentration is the hydrofluoric acid of 40%, stirs 0.5 little of evenly, F in gained mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:10; Then poured into by mineralizer ionic liquid solution in the reactor that placed δ-alumina supporter in advance, notice that carrier need be submerged in reaction solution completely, the amount ratio of supporter and mineralizer ionic liquid solution is 0.2(cm 2ml -1supporting body surface is amassed), reactor is warming up to 280 DEG C, keeps 0.5 hour, subsequently carrier is taken out; In another 100 ml beaker, add 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 100 DEG C, evenly drip phosphoric acid and 0.51 gram of N-Methylimidazole that 4.60 gram mass concentration are 85%, P in phosphorous and N-Methylimidazole ionic liquid solution 2o 5: N-Methylimidazole: the molar ratio of ionic liquid is 1:0.2:20, alumina supporter reacted in mineralizer ionic liquid is put into another reactor, pour phosphorous and N-Methylimidazole ionic liquid solution wherein into, the amount ratio of supporter and precursors reaction solution is 0.2(cm 2ml -1supporting body surface is amassed), reactor is warming up to 280 DEG C, keeps 0.5 hour, subsequently by reactor cooling to room temperature, taking-up carrier, in deionized water supersound washing three times, and use acetone washing by soaking.Carrier after washed is placed in 120 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 CHA type molecular screen membrane.
Embodiment 5
In 100 ml beakers, add 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 100 DEG C, evenly dripping 1.0 gram mass concentration is the hydrofluoric acid of 40%, stirs 0.5 little of evenly, F in gained mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:20; Then being poured into by mineralizer ionic liquid solution placed in the reactor of gamma-aluminium oxide carrier in advance, and notice that carrier need be submerged in reaction solution completely, the amount ratio of supporter and mineralizer ionic liquid solution is 0.4(cm 2ml -1supporting body surface is amassed), reactor is warming up to 160 DEG C, keeps 12 hours, subsequently carrier is taken out; In another 100 ml beaker, add 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 100 DEG C, evenly drip phosphoric acid and 0.41 gram of N-Methylimidazole that 1.15 gram mass concentration are 85%, P in phosphorous and N-Methylimidazole ionic liquid solution 2o 5: N-Methylimidazole: the molar ratio of ionic liquid is 1:1:80, alumina supporter reacted in mineralizer ionic liquid is put into another reactor, pour phosphorous and N-Methylimidazole ionic liquid solution wherein into, 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 24 hours, subsequently by reactor cooling to room temperature, taking-up carrier, in deionized water supersound washing three times, and use acetone washing by soaking.Carrier after washed is placed in 120 DEG C of baking ovens dry.In air atmosphere, rise to 550 DEG C with the temperature rise rate of 1K/min, and keep 4h, the organism in removing molecular screen membrane duct, thus obtain CHA type molecular screen membrane.
Embodiment 6
In 100 ml beakers, add 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 100 DEG C, evenly dripping 0.10 gram mass concentration is the hydrofluoric acid of 40%, stirs 0.5 little of evenly, F in gained mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:200; Then being poured into by mineralizer ionic liquid solution placed in the reactor of gamma-aluminium oxide carrier in advance, and notice that carrier need be submerged in reaction solution completely, the amount ratio of supporter and mineralizer ionic liquid solution is 0.6(cm 2ml -1supporting body surface is amassed), reactor is warming up to 200 DEG C, keeps 8 hours, subsequently carrier is taken out; In another 100 ml beaker, add 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 100 DEG C, evenly drip phosphoric acid and 0.41 gram of N-Methylimidazole that 0.24 gram mass concentration is 85%, P in phosphorous and N-Methylimidazole ionic liquid solution 2o 5: N-Methylimidazole: the molar ratio of ionic liquid is 1:5:400, alumina supporter reacted in mineralizer ionic liquid is put into another reactor, pour phosphorous and N-Methylimidazole ionic liquid solution wherein into, the amount ratio of supporter and precursors reaction solution is 0.6(cm 2ml -1supporting body surface is amassed), reactor is warming up to 200 DEG C, keeps 8 hours, subsequently by reactor cooling to room temperature, taking-up carrier, in deionized water supersound washing three times, and use acetone washing by soaking.Carrier after washed is placed in 90 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 CHA type molecular screen membrane.
Embodiment 7
In 100 ml beakers, add 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 100 DEG C, evenly drip 0.185 gram of Neutral ammonium fluoride, stir 2 little of evenly, F in gained mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:80; Then poured into by mineralizer ionic liquid solution in the reactor that placed δ-alumina supporter in advance, notice that carrier need be submerged in reaction solution completely, the amount ratio of supporter and mineralizer ionic liquid solution is 0.5(cm 2ml -1supporting body surface is amassed), reactor is warming up to 200 DEG C, keeps 8 hours, subsequently carrier is taken out; In another 100 ml beaker, add 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 100 DEG C, evenly drip phosphoric acid and 0.41 gram of N-Methylimidazole that 0.575 gram mass concentration is 85%, P in phosphorous and N-Methylimidazole ionic liquid solution 2o 5: N-Methylimidazole: the molar ratio of ionic liquid is 1:1:80, alumina supporter reacted in mineralizer ionic liquid is put into another reactor, pour phosphorous and N-Methylimidazole ionic liquid solution wherein into, the amount ratio of supporter and precursors reaction solution is 0.5(cm 2ml -1supporting body surface is amassed), reactor is warming up to 200 DEG C, keeps 12 hours, subsequently by reactor cooling to room temperature, taking-up carrier, in deionized water supersound washing three times, and use acetone washing by soaking.Carrier after washed is placed in 120 DEG C of baking ovens dry.In air atmosphere, rise to 600 DEG C with the temperature rise rate of 1K/min, and keep 4h, the organism in removing molecular screen membrane duct, thus obtain CHA type molecular screen membrane.
Embodiment 8
In 100 ml beakers, add 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids, be warming up to 100 DEG C, evenly drip 0.0925 gram of Neutral ammonium fluoride, 0.105 gram of Sodium Fluoride, stir 2 little of evenly, F in gained mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:80; Then being poured into by mineralizer ionic liquid solution placed in the reactor of gamma-aluminium oxide carrier in advance, and notice that carrier need be submerged in reaction solution completely, the amount ratio of supporter and mineralizer ionic liquid solution is 0.5(cm 2ml -1supporting body surface is amassed), reactor is warming up to 200 DEG C, keeps 8 hours, subsequently carrier is taken out; 76.4 grams of 1-ethyl-3-methy limidazolium ionic liquids are added in another 100 ml beaker, be warming up to 100 DEG C, even dropping 0.33 gram of ammonium hydrogen phosphate, 0.29 gram of primary ammonium phosphate and 0.41 gram of N-Methylimidazole, P in phosphorous and N-Methylimidazole ionic liquid solution 2o 5: N-Methylimidazole: the molar ratio of ionic liquid is 1:1:80, alumina supporter reacted in mineralizer ionic liquid is put into another reactor, pour phosphorous and N-Methylimidazole ionic liquid solution wherein into, the amount ratio of supporter and precursors reaction solution is 0.5(cm 2ml -1supporting body surface is amassed), reactor is warming up to 200 DEG C, keeps 12 hours, subsequently by reactor cooling to room temperature, taking-up carrier, in deionized water supersound washing three times, and use acetone washing by soaking.Carrier after washed is placed in 120 DEG C of baking ovens dry.In air atmosphere, rise to 500 DEG C with the temperature rise rate of 1K/min, and keep 12h, the organism in removing molecular screen membrane duct, thus obtain CHA 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 CHA type aluminophosphate molecular sieve membrane of pure phase.

Claims (10)

1. the preparation method of the CHA structure aluminophosphate molecular sieve membrane of a porous alumina carrier support, it is characterized in that: take ionic liquid as reaction medium, N-Methylimidazole is template, take porous alumina carrier as supporter, in two steps at supporting body surface synthesis CHA type microporous aluminophosphates molecular screen membrane:
Step (1) take ionic liquid as reaction medium, mineralizer is added the obtained ionic liquid solution containing mineralizer in ionic liquid under certain temperature and violent stirring;
Step (2) take ionic liquid as reaction medium, and phosphorous raw material and N-Methylimidazole are added obtained reaction soln in ionic liquid under certain temperature and strong stirring, its mol ratio is: 1P 2o 5: 0.1 ~ 1N-Methylimidazole: 2 ~ 1600ILs;
Building-up process is divided into two steps, step (1) reaction is carried out in containing the ionic liquid solution of mineralizer: the alumina substrate after roasting is vertically inserted the reactor containing mineralizer ionic liquid solution, temperature of reaction is 100 DEG C ~ 300 DEG C, reaction times >=1 minute;
Step (2) reaction is carried out in the ionic liquid solution of phosphorous and N-Methylimidazole: will carry out step (1) reacted alumina substrate and insert phosphorous with N-Methylimidazole ionic liquid solution, temperature of reaction is 100 DEG C ~ 300 DEG C, reaction times >=1 minute;
After step (2) reaction terminates, by reactor cooling to room temperature, take out substrate, by acetone and deionized water repetitive scrubbing extremely neutrality, dry at 90 ~ 120 DEG C, obtain CHA molecular screen membrane.
500 ~ 600 DEG C of calcining 4-16h in air atmosphere, to slough the organism in molecular sieve fenestra.
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 CHA structure of International Zeolite Association's confirmation, the molecular sieve crystal forming this molecular screen membrane has octatomic ring aperture, and its X-ray diffraction spectrogram has at least following listed diffraction peak:
2 θ values represent diffraction peak position, 2 θ/°: 9.40 ± 0.2; 12.05 ± 0.2; 13.81 ± 0.2; 15.20 ± 0.2; 15.53 ± 0.2; 17.87 ± 0.2; 18.45 ± 0.2; 19.35 ± 0.2; 19.75 ± 0.2; 21.31 ± 0.2; 21.74 ± 0.2; 22.50 ± 0.2; 23.23 ± 0.2; 23.85 ± 0.2; 24.28 ± 0.2; 25.06 ± 0.2; 26.15 ± 0.2.
3. according to preparation method according to claim 1, it is characterized in that: the mineralizer added is for containing F -compound, F in containing mineralizer ionic liquid solution -be 1:1 ~ 1600 with the mol ratio of ionic liquid.
4. according to preparation method according to claim 1, it is characterized in that: reaction medium is ionic liquid.The positively charged ion of 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 has following negatively charged ion: Br -, Cl -, I -, BF 4 -, PF 6 -, PO 4 3-, NO 3 -, SO 4 2-in one.
5. according to preparation method according to claim 1, it is characterized in that: described phosphorous raw material is one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate or primary ammonium phosphate;
Described mineralizer is fluorine-containing raw material, comprises one or both in hydrofluoric acid, Neutral ammonium fluoride or Sodium Fluoride
Above.
6. 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;
Supporter and the amount ratio of precursors reaction solution are the long-pending ratio of the surface-area of supporter and precursors reaction liquid, are 0.2 ~ 0.8cm that every ml solution is corresponding 2the surface-area of supporter.
7., according to preparation method according to claim 3, it is characterized in that:
F in mineralizer ionic liquid solution -: the molar ratio of ionic liquid is 1:10 ~ 400.
8., according to preparation method according to claim 5, it is characterized in that:
P in the ionic liquid solution of phosphorous and N-Methylimidazole 2o 5: the molar ratio of ionic liquid is 1:20 ~ 800.
P in the ionic liquid solution of phosphorous and N-Methylimidazole 2o 5: the molar ratio of N-Methylimidazole is 1:0.1 ~ 1.
9., according to preparation method according to claim 1, it is characterized in that:
The temperature of reaction that step (1) is reacted is 120 ~ 280 DEG C, crystallization time 0.5 ~ 480h;
The temperature of reaction that step (2) is reacted is 120 ~ 280 DEG C, crystallization time 0.5 ~ 480h.
10. according to preparation method according to claim 1, it is characterized in that: in the ionic liquid solution of described phosphorous and N-Methylimidazole, water content is the 0-10wt% of solution weight.
CN201310691126.3A 2013-12-13 2013-12-13 Ionothermal synthesis method of CHA type microporous aluminum phosphate molecular sieve membrane Pending CN104709915A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106957062A (en) * 2017-05-05 2017-07-18 南京工业大学 A kind of preparation method of the orientation molecular screen membranes of SAPO 34
CN108147428A (en) * 2016-12-05 2018-06-12 中国科学院大连化学物理研究所 A kind of aluminium phosphate molecular sieve with CHA structure and preforming synthetic method
CN110496637A (en) * 2018-05-17 2019-11-26 中国石油化工股份有限公司 The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108147428A (en) * 2016-12-05 2018-06-12 中国科学院大连化学物理研究所 A kind of aluminium phosphate molecular sieve with CHA structure and preforming synthetic method
CN106957062A (en) * 2017-05-05 2017-07-18 南京工业大学 A kind of preparation method of the orientation molecular screen membranes of SAPO 34
CN106957062B (en) * 2017-05-05 2019-11-01 南京膜材料产业技术研究院有限公司 A kind of preparation method being orientated SAPO-34 molecular screen membrane
CN110496637A (en) * 2018-05-17 2019-11-26 中国石油化工股份有限公司 The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane
CN110496637B (en) * 2018-05-17 2021-10-19 中国石油化工股份有限公司 Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation

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