CN104192858A - Method for preparing zeolite membrane by introducing crystal seeds with hot impregnation method - Google Patents
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Abstract
The invention belongs to the technical field of new fields and relates to a method for preparing zeolite membrane by introducing crystal seeds with a hot impregnation method. The method comprises the following steps: by taking a porous material as a carrier, carrying out pretreatment on the carrier, and drying the carrier to keep the surface of the carrier clean; and drying at a drying temperature of 150-400 DEG C, wherein zeolite with a particle size 1/10-3/4 the average channel diameter of the carrier is selected as crystal seeds; preparing 0.5-30wt.% crystal seed aqueous liquor, impregnating the carrier treated in the step (1) into the crystal seed aqueous liquor for 5-100 seconds at a temperature of 50-100 DEG C, carrying out preliminary dehydration at 30-90 DEG C and then carrying out deep dehydration at 200-500 DEG C, curing a crystal seed coating on the carrier to complete pre-coating of the crystal seeds; cooling to-be-precoated crystal seeds to the room temperature, adding the cooled to-be-precoated crystal seeds into the prepared zeolite membrane crystallization liquor to carry out crystallization, and then drying, washing and roasting to obtain the high-performance zeolite membrane.
Description
Technical field
The invention belongs to new material technology field, relate to a kind of preparation method of molecular screen membrane, particularly a kind of hot pickling process is introduced the method that crystal seed is prepared molecular screen membrane.
Background technology
Molecular sieve has regular pore passage structure, and surperficial positively charged ion can exchange, and pore size is adjustable, in gas delivery, liquid separation, catalytic process, have a wide range of applications, prepared film forming, can have the dual nature of molecular sieve and film, range of application is wider.
At present, the preparation of molecular screen membrane becomes better and approaching perfection day by day, multiple high performance molecular screen membrane, and as NaA type, Y type, ZSM-5 equimolecular sieve membrane all successfully prepare, but most of film is to be all prepared in specific support tube.And molecular screen membrane will drop into industrial applications, the porous material that the business of must take is used is carrier.At present, the porous support that business is used, because it is prepared on a large scale, so its surface ratio is more coarse, channel diameter is bigger than normal, unstable properties, cannot stablize in the above and synthesize high-quality molecular screen membrane.For can be in business with preparing high-quality molecular screen membrane on macropore carrier, inventor has just proposed first hot pickling process and has introduced crystal seed in 2004, and on macropore carrier, prepare high performance NaA type molecular screen membrane (Lu Jinming, on macropore carrier, prepare the research [D] of NaA molecular screen membrane, Dalian University of Technology, 2004).Afterwards, again this method is applied to y-type zeolite membrane (You Xin, the separated benzene/cyclohexane [D] of the preparation of NaY zeolite membrane and infiltration evaporation thereof, Dalian University of Technology, 2007), type T molecular sieve film (Chen little Xia, the preparation of T-shaped zeolite membrane and pervaporation applied research [D], Dalian University of Technology, 2012) and mesoporous MCM-48 film (Liu Chunyan, Liu Jiale, Wang Jin canal, Lu Jinming etc., back diffusion legal system is for mesoporous MCM-48[J] molecular screen membrane, membrane science and technology, 2012,32 (6): preparation process 55-63), has all obtained desirable result.And this method is amplified to preparation NaA type film for industrialization, although also obtained good result, but because carrier bulk becomes greatly, surface roughness increases, homogeneity declines, and causes the molecular screen membrane of synthesized still to there will be stability bad, degradation problem under repetition rate.Analyze reason wherein, three problems of main existence: the one, hot steeping process is that the high support tube of temperature is flooded in normal temperature seed-solution, when hot support tube contacts with solution, although support tube is in high dry state, water can be adsorbed in duct, but because temperature is higher, its adsorptive power declines, affected the adsorption rate of water, formation on crystal seed layer has caused impact, simultaneously, because bed temperature is higher, surpass sometimes 150 degree, when contacting with seed-solution, can make the water molecules temperature in seed-solution raise, fugacity increases, may cause part water vapor, the water molecules of vaporization is when to external diffusion, to crystal seed layer, can produce destruction, affect the formation of seed coat.The 2nd, dipping time is partially long, can cause that the crystal seed layer having formed is corroded by the aqueous solution again and produces to cave in; The 3rd, the selection of crystal seed and carrier hole matching degree are lower, have selected too much little crystal grain as crystal seed, and when larger with carrier hole difference, cannot form builds bridge holds back, and can not form high-quality crystal seed layer.
Summary of the invention
The object of the invention is to overcome the shortcoming and defect of prior art, provide a kind of new hot pickling process on carrier, to introduce crystal seed and prepare roughness, repair surface defects inducing molecule sieve that seed coat reduces carrier surface and concentrate on carrier surface and form, prepare the method for the molecular screen membrane of high-repetition-rate, high permeability and high separation performance.For addressing the above problem, the present invention improves original method, and its advantage is that seed coat more easily forms on commercial carrier, and the repetition rate of synthesized film is high, performance is more stable.
Hot pickling process is introduced the method that crystal seed is prepared molecular screen membrane, first take porous material as carrier, first carrier is carried out to pre-treatment, dry, keeps carrier surface clean; 150～400 ℃ of drying temperatures are then cooled to room temperature under dry or vacuum condition.Selecting grain size is that the molecular sieve of the average channel diameter 1/10～3/4 of carrier is as crystal seed again; Configuration quality percentage concentration is the crystal seed aqueous solution of 0.5～30wt.%, in temperature, be under the condition of 50～100 ℃, the carrier of handling well is immersed in the crystal seed aqueous solution, dipping time is 5～100s, then preliminary hydro-extraction under 30～90 ℃ of conditions, deep dehydration, the seed coat above solidified carrier under 200～500 ℃ of conditions, complete seeded again; Treat the cooling room temperature of seeded, joined in the molecular screen membrane crystallization liquid configuring, carry out crystallization, then through super-dry, washing, roasting, obtain high performance molecular screen membrane.
Concrete steps are as follows:
(1) pre-treatment of carrier
To remove carrier surface, affect the dust, oil stain of crystal seed absorption etc., keep carrier surface clean.In this step, carrier is polished gently with 800～1500# fine sandpaper, remove significantly projection of carrier surface, then, according to the pollution level of carrier surface, select the hydrochloric acid of 0.1～1M to carry out acid treatment, the treatment time is 1～5 hour; After cleaning with clear water, then select to carry out alkaline purification in the sodium hydroxide solution of 0.1～1M, the treatment time is 1～5 hour; After cleaning with clear water, film pipe is put into ultrasonic cleaner, clean concussion 5～30 minutes.Through peracid, alkali and supersound process, the microorganism that can farthest carrier surface be adhered to, oil stain and dust etc. are processed clean.When handled carrier wetting ability is weak (as carbon support pipe), can introduces some hydrophilic functional groups (as hydroxyl) at carrier surface and improve its surperficial hydrophilicity.
(2) carrier is carried out to drying treatment, guarantee that carrier has the ability of maximum planar water.In this step, pore size distribution situation for carrier, by drying temperature scope control at 150～400 ℃, be controlled at 1～5 hour time of drying, moisture removal in carrier surface and duct is clean, make the state of carrier in high dry, and be cooled to room temperature under vacuum or dry condition, standby.
(3) screening crystal seed.In this step, select grain size be the molecular sieve of carrier surface mean pore size 1/10～3/4 as crystal seed, the type of molecular sieve is identical with the type of molecular sieve that will synthesize film.
(4) the configuration crystal seed aqueous solution.In this step, in order to guarantee that crystal seed is uniformly dispersed and can makes crystal seed more stably be adsorbed on carrier in solution, form seed coat, can in solution, increase additive (as silicon sol, water glass, tensio-active agent etc.).The mass percent concentration of the crystal seed aqueous solution is controlled at 0.5～30% (wt.), and the size of concentration is decided by the size of crystal seed: the particle diameter of crystal seed is less, and concentration is lower.
(5) adopt hot pickling process to introduce crystal seed, on carrier, prepare seed coat.In this step, first the crystal seed aqueous solution configuring is heated between 50～100 degree, dried carrier (if tubular carrier need seal two ends by polytetrafluoro) is immersed rapidly in hot seed-solution, impregnation method can be selected to be dipped vertically into or level immerses mode again; When the aperture of carrier surface is larger, its crystal seed particle diameter is larger, and the concentration of seed-solution is higher, and dipping time is at 5～50 seconds, when the aperture of carrier surface hour, its crystal seed particle diameter is less, the concentration of seed-solution is lower, dipping time was at 50～100 seconds.After having flooded, rapidly carrier is shifted out to seed-solution, put into low-temperature bake oven (30～90 degree) 5～10 hours (if tubular carriers of preliminary hydro-extraction, need first the polytetrafluoro that seals two ends to be unloaded and pour out the water in pipe), and then put into retort furnace, 200～500, spend deep dehydration 1～5 hour, and the further seed coat above solidified carrier, be down to normal temperature, complete seeded, standby.The mechanism that adopts hot pickling process to introduce crystal seed is: porous support is after depth drying, and especially, when normal temperature, adsorptive power is stronger, so carrier is now for water, similar one " vacuum body ", has the ability of strong planar water; And seed-solution is mainly comprised of water and crystal seed, when carrier contacts with seed-solution, because the strong absorptive of carrier, the internal surface that can make water molecules diffuse to rapidly micropore is adsorbed, and crystal seed is diffusion thereupon also, " taken out " outside surface of carrier, because the rate of diffusion of water is much larger than the speed of crystal seed diffusion, therefore, crystal seed can be adsorbed, concentrate, assemble at carrier outside surface, in mechanical retention, absorption, hold back and build bridge under the effect of holding back, forming seed coat.Because the degree of drying of carrier is homogeneous relatively, so the coating of formation is also uniform; Especially when carrier surface aperture is inhomogeneous, because the resistance of aperture is larger, water diffusion is relatively slow, so near the crystal seed of assembling aperture is less, the seed coat of formation is thinner, and scope is less; And the resistance of macropore is less, water diffusion phase, to comparatively fast, therefore, can be assembled more crystal seed near large aperture, forms thicker, fairly large seed coat.So just can overcome the problem that business carrier surface pore size differs, form more even and continuous seed coat.In steeping process, improve the temperature of seed-solution, can make the kinetic energy of reduced viscosity, seed particles and water molecules of solution larger, be conducive to the rapid diffusion in solution of crystal seed and water molecules, and when contacting with carrier, because the temperature of carrier is lower than the temperature of seed-solution, can make its temperature decline, activity reduces, and promotes crystal seed to reunite, more easily form seed coat, so seed-solution is at higher temperature, dipping effect is better, therefore, present method is named as hot pickling process.
(6) crystallization film forming.In this step, by the carrier of seeded after dropping to room temperature, put into the Crystallization of Zeolite liquid having configured according to a certain percentage, hydrothermal crystallizing or microwave crystallization under certain condition, in seed coat, synthesize molecular screen membrane, the molecular screen membrane of synthesized through washing, dry, roasting, finally obtains high performance molecular screen membrane again.Synthetic molecular screen membrane comprises micro porous molecular sieve film, mesopore molecular sieve film and micro-mesoporous composite molecular sieve film.
Effect of the present invention and benefit are:
1, the invention is to be immersed in high temperature seed-solution in the low temperature support tube with high dry, under the strong water sorption of carrier, make crystal seed at carrier surface, form the seed coat of homogeneous, the defect that the commercial carrier surface of Efficient software patching is coarse, pore size distribution is inhomogeneous, prepares high performance molecular screen membrane.
2, the invention is that the molecular sieve of selecting grain-size and carrier surface aperture to match is crystal seed, can form more stable seed coat, makes coarse carrier surface leveling.
3, the present invention introduces crystal seed by hot pickling process, utilize the difference of aqueous solvent and crystal seed rate of diffusion, make seed particles only at the outside surface of carrier, form rapidly seed coat, and can not enter in large quantities the inner duct of stopping up, duct of carrier, affect film forming permeation flux afterwards.
Embodiment
Below in conjunction with technical scheme, further illustrate the specific embodiment of the present invention.
Example executes 1
In surperficial mean pore size, be to prepare NaA type molecular screen membrane in 10 microns of left and right, the commercial support tube of long 250 millimeters
(1) with the 1000# fine sandpaper carrier of polishing gently, remove significantly projection of carrier surface, then with clear water, clean; (2) by the salt acid soak support tube of 0.5M, after 1 hour, with clear water, be washed till neutrality;
(3) with the NaOH solution dipping carrier pipe of 1M, after 1 hour, takes out, put into the container that clear water is housed and put into together ultrasonic cleaner, clean and shake 10 minutes, support tube is weakly alkaline;
(4) support tube is put into the retort furnace drying and roasting 3 hours that temperature is 400 degree, and be cooled to room temperature under vacuum condition, and the two ends of pipe are sealed by polytetrafluoro, standby;
(5) select grain size be the NaA type molecular sieve of 1～2 micron as crystal seed, configuration seed-solution, solution quality proportioning is crystal seed: silicon sol: water=1:0.4:8;
(6) seed-solution configuring is heated to after 80 degree while stirring, more dried carrier is immersed in hot seed-solution rapidly with horizontal mode of entrance, flood 10 seconds;
(7) after having flooded, rapidly carrier is shifted out to seed-solution, unload the polytetrafluoro of sealing both ends, pour out the water in pipe, then put into the baking oven preliminary hydro-extraction 8 hours of 80 degree, and then put into retort furnace, at 400 degree deep dehydrations, after 2 hours, be down to normal temperature, then the two ends of pipe sealed rear standby by polytetrafluoro;
(8) according to Al
2o
3: SiO
2: NaOH:H
2o=1:1.2:6:200 proportioning (mol ratio) configuration crystallization solution, violent stirring 3 as a child, is poured crystallizing kettle into.Then, the support tube of seeded is also put into crystallizing kettle, under 100 degree, hydrothermal crystallizing is 5 hours, synthesizes molecular screen membrane in seed coat, and the molecular screen membrane of synthesized through washing, dry, roasting, finally obtains high performance molecular screen membrane again.
Example executes 2
In surperficial mean pore size, be to prepare MCM-48 mesopore molecular sieve film in about 2-4 micron, the commercial support tube of long 250 millimeters
(1) with the 1200# fine sandpaper carrier of polishing gently, remove significantly projection of carrier surface, then with clear water, clean;
(2) by the salt acid soak support tube of 0.5M, after 1 hour, with clear water, be washed till neutrality;
(3) with the NaOH solution dipping carrier pipe of 1M, after 1 hour, takes out, put into the container that clear water is housed and put into together ultrasonic cleaner, clean and shake 10 minutes, support tube is weakly alkaline;
(4) support tube is put into the retort furnace drying and roasting 3 hours that temperature is 400 degree, and be cooled to room temperature under vacuum condition, and the two ends of pipe are sealed by polytetrafluoro, standby;
(5) select grain size be the MCM-48 molecular sieve of 0.4～1 micron as crystal seed, configuration seed-solution, solution quality proportioning is crystal seed: silicon sol: CTAB: water=1:0.2:0.1:8;
(6) seed-solution configuring is heated to after 90 degree while stirring, more dried carrier is immersed in hot seed-solution rapidly with horizontal mode of entrance, flood 30 seconds;
(7) after having flooded, rapidly carrier is shifted out to seed-solution, unload the polytetrafluoro of sealing both ends, pour out the water in pipe, then put into the baking oven preliminary hydro-extraction 8 hours of 80 degree, and then put into retort furnace, at 400 degree deep dehydrations, after 1 hour, be down to normal temperature, then the two ends of pipe sealed rear standby by polytetrafluoro;
(8) according to SiO
2: NaOH:CTAB:H
2o:NaF=1:0.5:0.1:70:0.1 proportioning (mol ratio) configuration crystallization solution: the deionized water of first NaOH and CTAB being put into 35 degree, under agitation dissolve, when becoming clarification, solution adds NaF, violent stirring 1 as a child, add silicon source TEOS, continue to stir 4 hours, obtain the synthetic liquid of MCM-48 mesopore molecular sieve.Then, the support tube of seeded is put into crystallizing kettle, after sealing, puts into the baking oven crystallization of 150 degree and take out after 12 hours, after chilling after, take out film pipe, with deionized water, be washed till neutrality, at room temperature dry, afterwards, put into 50 degree baking ovens further dry.Then put into retort furnace, adopt temperature programming to rise to 550 degree roastings 3 as a child, programmed cooling takes out to normal temperature, obtains high performance mesoporous MCM-48 molecular screen membrane.
Claims (5)
1. hot pickling process is introduced the method that crystal seed is prepared molecular screen membrane, it is characterized in that step is as follows:
(1) pre-treatment of carrier: take porous material as carrier, first carrier is carried out to pre-treatment, dry, keep carrier surface clean; 150～400 ℃ of drying temperatures are then cooled to room temperature under dry or vacuum condition, standby;
(2) preparation of the selection of crystal seed, crystal seed liquid and crystallization film forming: selecting grain size is that the molecular sieve of the average channel diameter 1/10～3/4 of carrier is as crystal seed; Configuration quality percentage concentration is the crystal seed aqueous solution of 0.5～30wt.%, in temperature, be under the condition of 50～100 ℃, the carrier that step (1) is handled well is immersed in the crystal seed aqueous solution, dipping time is 5～100s, then preliminary hydro-extraction under 30～90 ℃ of conditions, deep dehydration, the seed coat above solidified carrier under 200～500 ℃ of conditions, complete seeded again; Treat the cooling room temperature of seeded, joined in the molecular screen membrane crystallization liquid configuring, carry out crystallization, then through super-dry, washing, roasting, obtain high performance molecular screen membrane.
2. method according to claim 1, is characterized in that step is as follows:
(1) pre-treatment of carrier
Carrier is polished gently with 800～1500# fine sandpaper, remove significantly projection of carrier surface, then, according to the pollution level of carrier surface, select the hydrochloric acid of 0.1～1M to carry out acid treatment, the treatment time is 1～5 hour; After cleaning with clear water, then select to carry out alkaline purification in the sodium hydroxide solution of 0.1～1M, the treatment time is 1～5 hour; After cleaning with clear water, film pipe is put into ultrasonic cleaner, clean concussion 5～30 minutes;
(2) carrier is carried out to drying treatment
Drying temperature scope control, at 150～400 ℃, is controlled to 1～5 hour time of drying, the moisture removal in carrier surface and duct is clean, make the state of carrier in high dry, and be cooled to room temperature under vacuum or dry condition;
(3) screening crystal seed
Select grain size be the molecular sieve of carrier surface mean pore size 1/10～3/4 as crystal seed, the type of molecular sieve is identical with the type of molecular sieve that will synthesize film;
(4) the configuration crystal seed aqueous solution
In order to guarantee that crystal seed is uniformly dispersed and can makes crystal seed more stably be adsorbed on carrier in solution, form seed coat, in solution, increase additive; The mass percent concentration of the crystal seed aqueous solution is controlled at 0.5～30% (wt.), and the size of concentration is decided by the size of crystal seed: the particle diameter of crystal seed is less, and concentration is lower;
(5) adopt hot pickling process to introduce crystal seed, on carrier, prepare seed coat
First the crystal seed aqueous solution configuring is heated between 50～100 degree, more dried carrier is immersed rapidly in hot seed-solution; When the aperture of carrier surface is larger, its crystal seed particle diameter is larger, and the concentration of seed-solution is higher, and dipping time is at 5～50 seconds, when the aperture of carrier surface hour, its crystal seed particle diameter is less, the concentration of seed-solution is lower, dipping time was at 50～100 seconds; After having flooded, rapidly carrier is shifted out to seed-solution, put into low-temperature bake oven preliminary hydro-extraction 5～10 hours, and then put into retort furnace, 200～500 degree deep dehydration 1～5 hour, and the further seed coat above solidified carrier, be down to normal temperature, complete seeded;
(6) crystallization film forming
By the carrier of seeded after dropping to room temperature, put into the Crystallization of Zeolite liquid proportionally having configured, at hydrothermal crystallizing or microwave crystallization, in seed coat, synthesize molecular screen membrane, the molecular screen membrane of synthesized through washing, dry, roasting, finally obtains high performance molecular screen membrane again.
3. method according to claim 1 and 2, is characterized in that, when carrier floods in the crystal seed aqueous solution, adopts vertical mode to immerse or horizontal mode immersion.
4. method according to claim 1 and 2, is characterized in that, the crystallization described in step (2) is hydrothermal crystallizing or microwave crystallization.
5. method according to claim 3, is characterized in that, the crystallization described in step (2) is hydrothermal crystallizing or microwave crystallization.
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| CN112999890A (en) * | 2021-03-03 | 2021-06-22 | 大连理工大学 | Organic-inorganic hybrid SiO of flat plate2Composite membrane and preparation method and application thereof |
| CN114225718A (en) * | 2021-12-24 | 2022-03-25 | 中国科学院上海硅酸盐研究所 | NaA molecular sieve membrane on surface of porous silicon nitride ceramic and preparation method thereof |
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