CN104150504B - A kind of preparation method of SAPO-34 molecular screen membrane - Google Patents
A kind of preparation method of SAPO-34 molecular screen membrane Download PDFInfo
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Abstract
The invention provides a kind of preparation method of SAPO-34 molecular screen membrane.It is characterized in that adopting particular zeolite molecular sieve to be silicon source, define SAPO-34 molecular sieve film fine and close continuously on porous ceramic support surface and namely grow one deck SAPO-34 molecular screen membrane with crystalline zeolitic molecular sieve for silicon comes from porous ceramic support, this zeolite molecular sieve has the structural unit identical with SAPO-34, for SAPO-34 Crystallization of Zeolite provides nucleus, shorten film generated time, and in SAPO-34 rete, silicone content can adjust in a big way.The film of synthesis is to CO
2there is preferred selectivity, at separation of C O
2/ CH
4there is during mixed system high permeation flux and separation selectivity.
Description
Technical field
The invention provides a kind of preparation method of SAPO-34 molecular screen membrane, belong to zeolite membrane material preparation and application field.
Background technology
Carbonic acid gas is the major impurity gas of Sweet natural gas (effective constituent is methane), not only reduces the combustion heat value of Sweet natural gas, and cause corrosion to gas pipe line under moisture conditions.There is the shortcomings such as the high and reagent dosage of energy consumption is large in common organic amine (as methyldiethanolamine) absorption extraction process.Use membrane technique separating carbon dioxide from Sweet natural gas can reduce the cost of purification of natural gas.There is CO
2optionally polymeric film is separated as cellulose acetate membrane and polyimide film are used for natural gas of industry.As far back as the eighties in 20th century, the European and American developed countries such as the U.S. have used and have established CO in cellulose acetate membrane separating natural gas
2full scale plant, the processing power of largest device set up in the U.S. has reached 7,000 ten thousand standard cubic feet/sky.But in production easily there is the phenomenons such as carbon is crisp in organic membrane under high carbon dioxide concentration and high-carbon hydrocarbon exist, and affects separation performance and the stability of film.Recent two decades comes, and mineral membrane particularly molecular screen membrane has obtained the extensive concern of investigator owing to having high hydrothermal stability, chemical stability and the characteristic such as withstand voltage.Some molecular screen membranes have been reported as SAPO-34, DDR and T equimolecular sieve membrane and have been applied to CO
2/ CH
4be separated.There is relevant report aspect.NGK company of Japan (EP2198948A1, JP2009214075A, CN102695674A, US2012213696A, US2004173094A1, JP2003159518A and CN101301589A) discloses the method for preparing DDR molecular screen membrane on single tube and hyperchannel ceramic supporting body and at CO
2/ CH
4separation performance in mixed system.Mountain pass university of Japan [JournalofMaterialsChemistry, 2004,14 (5): 924] reports preparation and the separation of C O of type T molecular sieve film
2/ CH
4and CO
2/ N
2the separation performance of mixture.The CO of T-shaped and DDR molecular screen membrane
2infiltration rate is on the low side.
SAPO-34 molecular sieve has CHA type topological framework and three-dimensional 8 membered ring channels communicated; Molecular sieve crystal duct size is 0.38nm, between CO
2(0.33nm) and CH
4(0.38nm), between, the display of absorption test simultaneously SAPO-34 molecular sieve has obvious CO
2/ CH
4and CO
2/ N
2preferential adsorption selectivity.Therefore, SAPO-34 molecular screen membrane is at separation of C O
2/ CH
4and CO
2/ N
2can show obviously high preferred absorption and molecule sieving action during system, be a kind of desirable separation of C O
2zeolite membrane material.SAPO-34 molecular sieve is the one of silicoaluminophosphamolecular molecular sieves.Silicoaluminophosphamolecular molecular sieves replaces phosphorus oxygen tetrahedron by silicon-oxy tetrahedron or aluminum-oxygen tetrahedron is formed, and generally speaking, the substitution amount of silicon is higher, and crystal crystallization velocity is about slow, synthesizes more difficult.
Univ Colorado-Boulder USA discloses the method preparing SAPO-34 molecular screen membrane at asymmetric alumina tube inwall in WO2011072215A1 patent.This molecular screen membrane has following features: synthesis colloidal sol contains bad environmental and is difficult to the amine substance (diethylamine) of removal; The silicon source used is amorphous silicon colloidal sol; Use expensive asymmetric alumina support, active coating forms inner membrance at inwall; React 6 hours under the synthesis temperature of 220 DEG C high.Patent US2011015057A1 discloses the method preparing SAPO-34 molecular screen membrane at asymmetric alumina tube inwall, although synthesis temperature is reduced to 200 DEG C, generated time still needs 20 hours.Above-mentioned SAPO-34 molecular screen membrane all adopts asymmetric alumina support, expensive, constrains the through engineering approaches application of film.And these SAPO-34 molecular screen membranes all grow the inwall at porous supporting body, exist in large-scale membrane module uses and detect a difficult problem: when namely going wrong when a film pipe, the component due to infiltration mixes and can not detect problematic film pipe well.
Summary of the invention
The object of the invention is the preparation method providing a kind of SAPO-34 molecular screen membrane in order to improve the deficiencies in the prior art.This patent adopts crystalline zeolitic molecular sieve to be silicon source, and the symmetrical ceramic support of the macropore of cheapness defines SAPO-34 molecular screen membrane fast.Because nucleation is played at film crystallization process in this special silicon source, greatly improve crystallization velocity, under lower synthesis temperature (170 ~ 190 DEG C), generated time foreshortens to 2 ~ 5 hours, reduce further preparation cost.Do not contain organic amine reagent, more environmental protection in preparation method provided by the invention simultaneously.The present invention also developed a kind of method utilizing electric charge independently to fill method to prepare high quality crystal seed layer, improves synthesis repeatability.
Technical scheme of the present invention is: a kind of preparation method of SAPO-34 molecular screen membrane, it is characterized in that growing one deck SAPO-34 molecular screen membrane with crystalline zeolitic molecular sieve for silicon comes from porous ceramic support, and its concrete steps are:
(1) JZPD capsule: template tetraethyl ammonium hydroxide is called for short TEAOH, aluminium source, phosphoric acid, silicon source chabazite and water mixing, stir aging 1 ~ 12 hour, each component molar ratio of the colloidal sol formed is: P
2o
5/ Al
2o
3=0.7 ~ 0.9, SiO
2/ Al
2o
3=0.02 ~ 0.5, TEAOH/Al
2o
3=1.5 ~ 2.5, H
2o/Al
2o
3=40 ~ 80, Hydrothermal Synthesis 2 ~ 4 hours under 160 ~ 190 DEG C of synthesis temperatures, by obtaining SAPO-34 phosphate aluminium molecular sieve crystal after eccentric cleaning;
(2) supporter pre-treatment: porous supporting body is after polishing, ultrasonic cleaning and drying, to be immersed in the cationic polymerizable compound aqueous solution 0.5 ~ 1 hour, for subsequent use after seasoning, the SAPO-34 phosphate aluminium molecular sieve crystal preparation of synthesis in step (1) is become crystal seed aqueous suspension, alkali lye is adopted to regulate seed-solution pH value to be 9 ~ 10, supporter after seasoning is immersed in crystal seed suspension, act on supporter outer wall by electric charge assembling and form uniform crystal seed layer, then at 350 ~ 500 DEG C, calcine 4 ~ 6 hours to obtain seeding supporter;
(3) SAPO-34 molecular screen membrane synthesis: by tetraethyl ammonium hydroxide, aluminium source, phosphoric acid, silicon source chabazite and water mixing, stir aging 1 ~ 12 hour, each component molar ratio of the colloidal sol formed is: P
2o
5/ Al
2o
3=0.7 ~ 0.9, SiO
2/ Al
2o
3=0.02 ~ 0.5, TEAOH/Al
2o
3=1.5 ~ 2.5, H
2o/Al
2o
3=80 ~ 200; Insert the seeding supporter that obtains through step (2) in the stainless steel cauldron that colloidal sol is housed, hydrothermal crystallizing 4 ~ 7 hours under 160 ~ 190 DEG C of temperature condition, one deck SAPO-34 film is formed at porous supporting body pipe outer wall, then through cleaning, dry and calcination processing; Obtained SAPO-34 molecular screen membrane.
Aluminium source in preferred steps (1) and step (3) is aluminium hydroxide, metallic aluminium, aluminum isopropylate, Tributyl aluminate or aluminate.
The cationic polymerizable compound aqueous solution described in preferred steps (2) is the aqueous solution of diallyl dimethyl amine hydrochlorate or diallyl dimethyl amine vitriol; The mass concentration of the cationic polymerizable compound aqueous solution is 0.5 ~ 5%.
In preferred steps (2), in crystal seed aqueous suspension, the mass percentage concentration of crystal seed is 0.2 ~ 2%; The time that supporter after seasoning immerses in crystal seed suspension is 1-5 minute; More preferably 2-3 minute.
In preferred steps (2), alkali lye is ammoniacal liquor, caustic-alkali aqueous solution or the quaternary ammonium hydroxide aqueous solution.
The porous supporting body adopted in preferred steps (2) is tubulose mullite or alumina support.
In preferred steps (3), the temperature of calcination processing is 350 ~ 600 DEG C; Calcination time is 2 ~ 10 hours; Temperature rise rate is 0.2 ~ 2 DEG C/min.
In preferred steps (1), in preparation SAPO-34 molecular sieve crystal, Si/Al is 0.05 ~ 0.2.
The present invention, when using mullite pipe for supporter, because supporter contains silicon, for SAPO-34 molecular screen membrane layer growth provides silicon source, when also can not add silicon source in film synthesis lyosol, contains silicon in SAPO-34 molecular sieve rete.
In SAPO-34 molecular screen membrane building-up process of the present invention, step (1) and the middle silicon source chabazite reference used of step (3)
www.IZA-online.orgdisclosed synthetic method is prepared and obtains.
Beneficial effect:
The present invention adopts crystal form chabazite to be silicon source, significantly improves film crystallization velocity, substantially reduces generated time; Cheap symmetrical mullite or alumina support is adopted to reduce film synthesis cost; Adopt the physical structure of adventitia can realize the on-line checkingi of film in application process; Adopt self-assembly crystal seed mode of loading to substantially increase the homogeneity of crystal seed layer, improve the quality that film is formed.Present method is prepared the SAPO-34 film thickness that film synthesizes and is less than 5 microns.Film is synthesized at separation of C O under optimal conditions
2/ CH
4during mixture, infiltration rate is greater than 2 × 10
-7mol/ (m
2.s.pa), separation selectivity is greater than 200 (probe temperature be 25 DEG C, pressure be 0.2Mpa).
Accompanying drawing explanation
X-ray diffraction (XRD) figure of SAPO-34 molecular sieve prepared by Fig. 1 embodiment 1;
Scanning electronic microscope (SEM) figure of SAPO-34 molecular sieve prepared by Fig. 2 embodiment 1;
Fig. 3 embodiment 1 is that supporter prepares SAPO-34 molecular screen membrane surface SEM figure at symmetrical mullite pipe;
Fig. 4 embodiment 1 is that supporter is prepared SAPO-34 molecular screen membrane section S EM and schemed at symmetrical mullite pipe;
Fig. 5 embodiment 6 prepares SAPO-34 molecular screen membrane surface SEM figure at symmetrical alumina tube;
The symmetrical alumina tube of Fig. 6 embodiment 6 prepares SAPO-34 molecular screen membrane surface SEM figure.
Embodiment
In order to further describe the present invention, shown below is several concrete case study on implementation, but patent claim is not limited to these examples.
The present invention uses chabazite for silicon source, and it prepares reference
www.IZA-online.orgdisclosed synthetic method is prepared and obtains, and chabazite consists of KAlSi
no
2 (n+1), n equals 1 ~ 4.Obtain H type chabazite by ion-exchange, consist of HAlSi
no
2 (n+1), n equals 1 ~ 4.Because crystalline framework is made up of silicon-oxy tetrahedron and aluminum-oxygen tetrahedron, in crystal, aluminium and silicone content are the important indicator of crystalline structure.In the chabazite crystal of the use in the embodiment of the present invention, Si/Al ratio (n value) is 2.
Embodiment 1
(1) SAPO-34 JZPD capsule: template tetraethyl ammonium hydroxide is called for short the mixing of TEAOH, Tributyl aluminate, phosphoric acid, silicon source chabazite and water, after at room temperature aging 1 hour, each component molar ratio of the colloidal sol formed is: P
2o
5/ Al
2o
3=0.7, SiO
2/ Al
2o
3=0.5, TEAOH/Al
2o
3=1.8, H
2o/Al
2o
3=70.Added by colloidal sol in the stainless steel cauldron of teflon lined, Hydrothermal Synthesis 2 hours under 190 DEG C of synthesis temperatures, by obtaining SAPO-34 molecular sieve after eccentric cleaning.
(2) supporter pre-treatment: adopt the supporter that porous mullite pipe synthesizes as film, consisting of mol ratio is 66%Al
2o
3with 34% SiO
2.Internal diameter and external diameter are respectively 9mm and 12mm, and length is 100mm, and mean pore size is about 1.0 μm, and porosity is about 30%.After supporter outer wall dries after the pre-treatment such as 800 order sand paperings and ultrasonic cleaning, carry out seeding process, be specially: supporter being immersed in mass concentration is in the diallyl dimethyl amine hydrochlorate aqueous solution of 0.5% of solution total mass 1 hour, supporting body surface is made to form uniform cationic polymers, the SAPO-34 crystal preparation of preparation in step (1) is become mass ratio be 0.2% crystal seed aqueous suspension, ammoniacal liquor is adopted to regulate seed-solution pH 9 to make plane of crystal carry negative charge, supporter is immersed in crystal seed suspension, uniform crystal seed layer is obtained by electric charge assembling effect, 6 hours are calcined again to obtain seeding supporter at 350 DEG C.
(3) SAPO-34 molecular screen membrane synthesis: tetraethyl ammonium hydroxide, Tributyl aluminate, phosphoric acid, chabazite and water are mixed, each component molar ratio of the colloidal sol formed after at room temperature aging 1 hour is: P
2o
5/ Al
2o
3=0.7, SiO
2/ Al
2o
3=0.5, TEAOH/Al
2o
3=2.0, H
2o/Al
2o
3=120.Insert the porous pipe type supporter processed through step (2), hydrothermal crystallizing 4 hours under 190 DEG C of temperature condition, defines one deck SAPO-34 molecular screen membrane in supporter outer wall surface.Extremely neutral with deionized water wash again, under 440 DEG C of conditions, roasting removes template (it is 0.5 DEG C/min that intensification and rate of temperature fall are) for 6 hours and obtains SAPO-34 molecular screen membrane.
The XRD figure of crystal as shown in Figure 1, is pure SAPO-34 crystal.As shown in Figure 2, crystal seed size is about 500 nanometers to the SEM figure of crystal seed.In the SAPO-34 molecular sieve crystal of ICP ultimate analysis display synthesis, the mol ratio of Si/Al/P is 0.4/0.85/1.
Fig. 3 shows the surface microstructure of the SAPO-34 film synthesized on porous mullite supporter.Supporting body surface is covered by one deck SAPO-34 crystal, molecular sieve crystal compact growth.
Fig. 4 shows the section face microtexture of the chabazite film synthesized on porous mullite supporter.Coating growth is fine and close continuously, and thickness is about 5 microns.
The gas separating property of film is by the CO of equimolar ratio
2/ CH
4mixed gas tests separation performance.Gas permeation rate P and gas selectivity α two parametric representations.By the gas gross of the film of unit surface under gas permeation rate P representation unit time, unit pressure, P=N/ (A × t × △ P), unit is mol/ (m
2.s.pa); Gas selectivity α is used for the height of evaluated for film separation efficiency, α=P
a/ P
b.
The film M1 of preparation is used for 25 DEG C, CO
2/ CH
4(50/50) carry out gas separating property sign in system, what gas delivery was tested the results are shown in Table 1.
Embodiment 2
(1) JZPD capsule: preparation process is as identical in embodiment 1 step (1), unlike selecting aluminium foil as aluminium source, and colloidal sol mol ratio is P
2o
5/ Al
2o
3=0.9, SiO
2/ Al
2o
3=0.05, TEAOH/Al
2o
3=1.5, H
2o/Al
2o
3=40.
(2) supporter pre-treatment: preparation process is as identical in embodiment 1 step (2), is 2% of solution quality unlike seed count in crystal seed suspension, and adopt aqueous sodium hydroxide solution adjust ph to be 10.
(3) SAPO-34 molecular screen membrane synthesis: preparation process is as identical in embodiment 1 step (3), unlike selecting aluminium powder as aluminium source.
The film M2 of preparation is used for 25 DEG C, CO
2/ CH
4(50/50) carry out gas separating property sign in system, what gas delivery was tested the results are shown in Table 1.
Embodiment 3
(1) JZPD capsule: preparation process is as identical in embodiment 1 step (1), unlike selecting aluminium hydroxide as aluminium source, and colloidal sol at room temperature aging 12 hours.
(2) supporter pre-treatment: preparation process is as identical in embodiment 1 step (2), be 5% diallyl dimethyl amine sulfate liquor of solution total mass unlike employing mass concentration, dipping time is 0.5 hour.
(3) SAPO-34 molecular screen membrane synthesis: preparation process is as identical in embodiment 1 step (3), unlike selecting aluminum isopropylate as aluminium source.
The film M3 of preparation is used for 25 DEG C, CO
2/ CH
4(50/50) carry out gas separating property sign in system, what gas delivery was tested the results are shown in Table 1.
Embodiment 4
(1) JZPD capsule: preparation process is as identical in embodiment 1 step (1), is P unlike colloidal sol mol ratio
2o
5/ Al
2o
3=0.9, SiO
2/ Al
2o
3=0.25, TEAOH/Al
2o
3=2.0, H
2o/Al
2o
3=80; And Hydrothermal Synthesis temperature is 170 DEG C, generated time is 4 hours.
(2) supporter pre-treatment: preparation process is as identical in embodiment 1 step (2), is 1% of solution quality unlike seed count in crystal seed suspension, and adopt tetraethyl ammonium hydroxide aqueous solution adjust ph to be 9.
(3) SAPO-34 molecular screen membrane synthesis: preparation process is as identical in embodiment 1 step (3), is P unlike colloidal sol mol ratio
2o
5/ Al
2o
3=0.9, SiO
2/ Al
2o
3=0.05, TEAOH/Al
2o
3=2.5, H
2o/Al
2o
3=90; And Hydrothermal Synthesis is 170 DEG C, generated time is 6 hours.
The film M4 of preparation is used for 25 DEG C, CO
2/ CH
4(50/50) carry out gas separating property sign in system, what gas delivery was tested the results are shown in Table 1.
Embodiment 5
(1) JZPD capsule: preparation process is as identical in embodiment 1 step (1).
(2) supporter pre-treatment: preparation process is as identical in embodiment 1 step (2), calcines 4 hours at 500 DEG C unlike crystal seed layer.
(3) SAPO-34 molecular screen membrane synthesis: preparation process is as identical in embodiment 1 step (3), unlike colloidal sol at room temperature digestion time be 12 hours, colloidal sol mol ratio is: P
2o
5/ Al
2o
3=0.7, SiO
2/ Al
2o
3=0.3, TEAOH/Al
2o
3=1.6, H
2o/Al
2o
3=180.
The film M5 of preparation is used for 25 DEG C, CO
2/ CH
4(50/50) carry out gas separating property sign in system, what gas delivery was tested the results are shown in Table 1.
Embodiment 6
(1) JZPD capsule: preparation process is as identical in embodiment 1 step (1).
(2) supporter pre-treatment: preparation process is as identical in embodiment 1 step (2).
(3) SAPO-34 molecular screen membrane synthesis: preparation process is as identical in embodiment 1 step (3), unlike adopting macroporous aluminium oxide pipe to be supporter, internal diameter and the external diameter of supporter are respectively 9mm and 12mm, length is 100mm, mean pore size is about 1.3 μm, and porosity is about 35%; And film roasting 4 hours removing template (heat up and rate of temperature fall be 1.5 DEG C/min) under 550 DEG C of conditions obtains SAPO-34 molecular screen membrane.
The film M6 of preparation is used for 25 DEG C, CO
2/ CH
4(50/50) carry out gas separating property sign in system, what gas delivery was tested the results are shown in Table 1.Film surface and section SEM scheme respectively as shown in Figure 5 and Figure 6, and crystal is in crosslinked growth, and rete is fine and close continuously, and thickness is about 5 microns.
Comparative example 1
(1) JZPD capsule: preparation process is as identical in embodiment 1 step (1), unlike employing amorphous silicon colloidal sol as silicon source, generated time extends to 12 hours, and the crystal of synthesis is the mixed crystal composition of SAPO-34 and SAPO-5.
(2) supporter pre-treatment: preparation process is as identical in embodiment 1 step (2).
(3) SAPO-18 molecular screen membrane synthesis: preparation process is as identical in embodiment 1 step (3), unlike employing amorphous silicon colloidal sol as silicon source, generated time extends to 12 hours.
The film M7 of preparation is used for 25 DEG C, CO
2/ CH
4(50/50) carry out gas separating property sign in system, what gas delivery was tested the results are shown in Table 1.
Comparative example 2
(1) JZPD capsule: preparation process is as identical in embodiment 1 step (1).
(2) supporter pre-treatment: preparation process is as identical in embodiment 1 step (2), unlike employing direct dip-coating method coating crystal seed, namely do not use diallyl dimethyl amine hydrochlorate aqueous solution process supporting body surface, do not use alkali lye to regulate seed-solution pH value simultaneously yet.
(3) SAPO-34 molecular screen membrane synthesis: preparation process is as identical in embodiment 1 step (3).
The film M8 of preparation is used for 25 DEG C, CO
2/ CH
4(50/50) carry out gas separating property sign in system, what gas delivery was tested the results are shown in Table 1.
The CO of table 1SAPO-34 molecular screen membrane
2/ CH
4(50/50) separation performance (25 DEG C, feed pressure is 0.2Mpa)
Claims (7)
1. a preparation method for SAPO-34 molecular screen membrane, it is characterized in that growing one deck SAPO-34 molecular screen membrane with crystalline zeolitic molecular sieve for silicon comes from porous ceramic support, its concrete steps are:
(1) JZPD capsule: template tetraethyl ammonium hydroxide is called for short TEAOH, aluminium source, phosphoric acid, silicon source chabazite and water mixing, stir aging 1 ~ 12 hour, each component molar ratio of the colloidal sol formed is:
P
2o
5/ Al
2o
3=0.7 ~ 0.9, SiO
2/ Al
2o
3=0.02 ~ 0.5, TEAOH/Al
2o
3=1.5 ~ 2.5, H
2o/Al
2o
3=40 ~ 80, Hydrothermal Synthesis 2 ~ 4 hours under 160 ~ 190 DEG C of synthesis temperatures, by obtaining SAPO-34 phosphate aluminium molecular sieve crystal after eccentric cleaning;
(2) supporter pre-treatment: porous supporting body is after polishing, ultrasonic cleaning and drying, to be immersed in the cationic polymerizable compound aqueous solution 0.5 ~ 1 hour, for subsequent use after seasoning, the SAPO-34 phosphate aluminium molecular sieve crystal preparation of synthesis in step (1) is become crystal seed aqueous suspension, alkali lye is adopted to regulate seed-solution pH value to be 9 ~ 10, supporter after seasoning is immersed in crystal seed suspension, act on supporter outer wall by electric charge assembling and form uniform crystal seed layer, then at 350 ~ 500 DEG C, calcine 4 ~ 6 hours to obtain seeding supporter;
(3) SAPO-34 molecular screen membrane synthesis: by tetraethyl ammonium hydroxide, aluminium source, phosphoric acid, silicon source chabazite and water mixing, stir aging 1 ~ 12 hour, each component molar ratio of the colloidal sol formed is: P
2o
5/ Al
2o
3=0.7 ~ 0.9, SiO
2/ Al
2o
3=0.02 ~ 0.5, TEAOH/Al
2o
3=1.5 ~ 2.5, H
2o/Al
2o
3=80 ~ 200; Insert the seeding supporter that obtains through step (2) in the stainless steel cauldron that colloidal sol is housed, hydrothermal crystallizing 4 ~ 7 hours under 160 ~ 190 DEG C of temperature condition, one deck SAPO-34 film is formed at porous supporting body pipe outer wall, then through cleaning, dry and calcination processing; Obtained SAPO-34 molecular screen membrane.
2. preparation method according to claim 1, is characterized in that the aluminium source in step (1) and step (3) is aluminium hydroxide, metallic aluminium, aluminum isopropylate, Tributyl aluminate or aluminate.
3. preparation method according to claim 1, is characterized in that the cationic polymerizable compound aqueous solution described in step (2) is the aqueous solution of diallyl dimethyl amine hydrochlorate or diallyl dimethyl amine vitriol; The mass concentration of the cationic polymerizable compound aqueous solution is 0.5 ~ 5%.
4. preparation method according to claim 1, is characterized in that the mass percentage concentration of crystal seed in crystal seed aqueous suspension in step (2) is 0.2 ~ 2%; The time that supporter after seasoning immerses in crystal seed suspension is 1-5 minute.
5. preparation method according to claim 1, is characterized in that in step (2), alkali lye is ammoniacal liquor, caustic-alkali aqueous solution or the quaternary ammonium hydroxide aqueous solution.
6. preparation method according to claim 1, is characterized in that the porous supporting body adopted in step (2) is tubulose mullite or alumina support.
7. preparation method according to claim 1, is characterized in that the temperature of calcination processing in step (3) is 350 ~ 600 DEG C; Calcination time is 2 ~ 10 hours; Temperature rise rate is 0.2 ~ 2 DEG C/min.
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| CN106278368A (en) * | 2016-08-15 | 2017-01-04 | 北京大学深圳研究生院 | A kind of composite molecular sieve film and its preparation method and application |
| CN106943889B (en) * | 2017-04-08 | 2018-02-23 | 郝至臻 | A kind of preparation method of chip film |
| 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 |
| CN107746065A (en) * | 2017-12-06 | 2018-03-02 | 武汉工程大学 | A kind of method for preparing the molecular screen membrane of high-performance SAPO 34 |
| CN109663509B (en) * | 2019-01-18 | 2022-01-21 | 中国科学院上海高等研究院 | Preparation method of hierarchical pore SAPO-34 molecular sieve membrane |
| EP3938099A1 (en) | 2019-03-14 | 2022-01-19 | Johnson Matthey Public Limited Company | Jmz-1s, a cha-containing molecular sieve and methods of preparation |
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| CN103922361A (en) * | 2014-04-25 | 2014-07-16 | 江西师范大学 | Preparation method of SAPO-17 molecular sieves |
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