CN1180877C - Method for synthesizing molecular sieve film using vacuum crystal method - Google Patents
Method for synthesizing molecular sieve film using vacuum crystal method Download PDFInfo
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- CN1180877C CN1180877C CNB021411972A CN02141197A CN1180877C CN 1180877 C CN1180877 C CN 1180877C CN B021411972 A CNB021411972 A CN B021411972A CN 02141197 A CN02141197 A CN 02141197A CN 1180877 C CN1180877 C CN 1180877C
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Abstract
The present invention relates to a method for synthesizing an A-shaped molecular sieve membrane by a vacuum pumping and crystal coating method. The method comprises the following steps: 1. one layer of molecular sieve crystal seeds uniformly distributed is introduced on a base membrane through a vacuum pumping method by a vacuum pump or a compression method by a compressor, wherein the vacuum pumping pressure or the compression pressure is from 0.0010 to 0.0500Mpa, the soaking and coating time is from 30 to 300S, the concentration of soaking and coating liquid is from 1 g/l to 20 g/l, and the crystal size is from 0.20 to 10 mum; 2. the A-shaped molecular sieve membrane is synthesized by a hydrothermal synthesis method and a microwave synthesis method, and a solution for synthesizing the A-shaped molecular sieve membrane is prepared from 20 to 100 portions of aNa2O, 0.5 to 5 portions of bAl2O3, 5SiO2 and 500 to 4000 portions of cH2O. In hydrothermal synthesis or microwave synthesis, the temperature of hydrothermal synthesis is from 323K to 373K, and the synthesis time of the hydrothermal synthesis is from 2h to 60h; the temperature of microwave synthesis is from 323K to 373K, and the synthesis time of the microwave synthesis is from 30 to 120 min. A molecular sieve membrane synthesized by the method has the advantages of good separation performance and high repeatability, and is suitable for industrial amplification.
Description
Technical field
The present invention relates to a kind of synthetic method of molecular screen membrane, particularly adopt the method for the synthetic A type molecular sieve film of crystal method of finding time.
Background technology
Molecular sieve be a kind of be the microporous inorganic crystalline material that basic framework forms with silicon-oxy tetrahedron and aluminum-oxygen tetrahedron.Molecular sieve has the following advantages as inorganic material film: 1) molecular sieve has the neat duct of standard, and pore-size distribution is single; And the molecular dimension size of the duct size of molecular sieve and many important raw materials of industry is close, and molecule can or be selected the type diffusion by the molecule screening and obtain separating.2) molecular sieve has good chemical stability and heat endurance.3) diversity of molecular sieve structure causes the diversity of its character, as different pore sizes, and different hydrophilic and hydrophobics, thereby, can select suitable molecular sieve as membrane material according to different separation requirement.4) modifiability of molecular sieve pore passage and hole outer surface causes the adjustable sex change of molecular sieve bore diameter and absorption property, thereby can realize the accurate control that separates.5) catalytic activity of molecular sieve can realization response-isolation integral.So molecular screen membrane has a wide range of applications, molecular screen membrane all can be applied in various fields such as gas separation, steam separation, the separation of liquid infiltration evaporation, membrane catalytic reaction, Subjective and Objective reaction, environmental protection, life engineering, electrode and sensors.
Just because of molecular screen membrane has unique characteristic and application prospects, the research of molecular screen membrane causes people's extensive concern and interest, since people such as Suzuki reported since the molecular screen membrane that has synthesized ultra-thin (1nm) on the porous carrier with the patent form first in 1987, the research of molecular screen membrane has obtained great progress, till now, people have successfully synthesized MFI, FER, MOR, A type, Y type, SAPO-5, SAPO-34, AlPO4-5, L type, P type, TS-1, UTD-1 equimolecular sieve membrane on variety carrier.
The synthetic basic step of molecular screen membrane comprises: 1) processing and the preparation of carrier (or claiming basement membrane); 2) reactant liquor preparation; 3) basement membrane and reactant liquor react film forming under certain condition; 4) post-reaction treatment.The synthetic method of molecular screen membrane has a lot, can be divided into three kinds substantially: a) direct method, be meant directly basement membrane is dipped in the reactant liquor for preparing, and react film forming under certain condition; B) indirect method is meant earlier and introduces the homodisperse molecular sieve crystal seed of one deck in membrane surface, hydro-thermal synthesizing molecular sieve film then, and this method is also referred to as the secondary synthetic method usually; C) chemical gaseous phase transfer method.Synthesizing molecular sieve film the simplest the most direct method is a direct method, also is synthetic method commonly used at present.But the performance of the molecular screen membrane that the employing direct method is synthetic relies on the performance of basement membrane to a great extent, is difficult to obtain flawless molecular screen membrane, especially is difficult to the tracheary element sieve membrane of synthesized high-performance, so lacks industrial application value.The chemical gaseous phase transfer method is mainly used to the molecular screen membrane of synthesizing high-silicon content, and is poor for applicability, and the condition harshness, complex process, few of industrial application value.The secondary synthetic method is meant introduces layer of even molecular sieve crystal seed earlier on basement membrane, directly provide nuclearing centre in membrane surface, then crystal seed basement membrane hydro-thermal synthesizing molecular sieve film in synthetic liquid.The most significant advantage of secondary synthetic method is to separate nucleation process and crystal growing process, suppresses nucleus and is transformed into other crystal, improves the purity of molecular screen membrane.In addition, the secondary synthetic method can shorten nucleation and crystal growth time, accelerates the membrane surface molecular screen membrane and forms, and improves degree of crystallinity.
The formation mechanism of molecular screen membrane is a very complicated problems, briefly, mainly contains two kinds of ripe viewpoints at present: i.e. homogeneous nucleation mechanism and heterogeneous nucleation mechanism, in fact these two kinds of mechanism are normally simultaneous.People are of long duration to the research that molecular screen membrane forms mechanism, though the viewpoint of now not reaching an agreement as yet, but everybody generally believes: aluminate ion in the synthetic liquid and silicate ion are after combination forms sial amorphous phase under the inducing of nucleus, be adsorbed to membrane surface, crystalline film then by the ion migration.The secondary synthetic method is introduced layer of even molecular sieve crystal seed earlier on basement membrane, directly provide nuclearing centre in membrane surface, induces aluminate ion and silicate ion in the synthetic liquid to move to membrane surface, then crystalline film.The most significant advantage of secondary synthetic method is to separate nucleation process and crystal growing process, thereby the Artificial Control molecular screen membrane is synthetic to a certain extent.
Secondary synthetic method synthesizing molecular sieve film has two problems the most challenging, and one is the molecular sieve crystal seed that how to prepare homogeneous grain size, and another is how the molecular sieve crystal seed to be introduced membrane surface, to obtain homodisperse crystal seed basement membrane.About first problem, have many reports at present both at home and abroad.For second problem, the researcher has done a large amount of research both at home and abroad, numerous methods (technology) of the molecular sieve crystal seed being introduced membrane surface have been invented, comprise: (1) dipping crystal method (Dip coating method), promptly flood the regular hour to membrane surface and the method for crystal seed introducing membrane surface in preparing molecular sieve crystal seed sol-gel; (2) obliterating crystal method (Rubbing coating method) promptly adopts the method for mechanical friction directly to be coated with the method for last layer molecular sieve powder as crystal seed in membrane surface; (3) spraying crystal method (Spraying coatingmethod or sputtering coating method) promptly adopts the method for spray gun at membrane surface spraying last layer molecular sieve crystal seed; (4) pulsed laser deposition crystal method (Plused-laser depositioncoating method), the pulse of promptly adopting laser instrument to send deposits the method for one deck molecular sieve crystal seed in membrane surface.In addition, the pH value of people such as Tsapatsis by changing solution is with adjustment Al
2O
3Basement membrane and SiO
2The zata electromotive force of crystal seed is introduced crystal seed in membrane surface; Hedlund and Sterte introduce crystal seed by the electrostatic interaction membrane surface and synthesize the ZSM-5 film.These molecular sieve crystal seeds are introduced membrane surface method (technology) and are helped the synthetic of molecular screen membrane to a certain extent, but defective is separately all arranged.The dipping crystal method is the at present the most frequently used crystal method that is coated with, but is coated with in the brilliant process at dipping, and molecular sieve crystal seed sol-gel is difficult to closely and membrane surface combines and drop down stream easily, therefore is difficult to form evenly continuous crystal seed film.The operation of obliterating crystal method is the easiest, introduces evenly continuous crystal seed of one deck but in fact be difficult in membrane surface.Though the spraying crystal method can be introduced evenly continuous crystal seed film of one deck in the tabular membrane surface, is difficult in evenly continuous crystal seed film of tubulose membrane surface one deck, therefore is unsuitable for industry and amplifies, and does not have industrial application value.Though the pulsed laser deposition crystal method can be introduced evenly continuous crystal seed film of one deck in membrane surface, needs expensive laser instrument, does not therefore have industrial application value.And by adjusting Al
2O
3Basement membrane and SiO
2The zata electromotive force of crystal seed or introduce the method for crystal seed film in membrane surface by electrostatic interaction, complicated operation, wayward, be unsuitable for industry and amplify.These reasons have restricted the synthetic of molecular screen membrane to a certain extent, thus also restricted molecular screen membrane in industrial application.
Summary of the invention
The object of the present invention is to provide a kind of method of the crystal method synthesizing molecular sieve film of finding time, the present invention is easy and simple to handle, and is widely applicable, and repeatability is high, and function admirable is suitable for industry and amplifies.
For achieving the above object, the method for the crystal method synthesizing molecular sieve film of finding time provided by the invention, its key step is as follows:
(A) preparation crystal seed basement membrane
The A type molecular sieve crystal seed is dissolved in distilled water and in ultrasonic wave vibrating dispersion become uniform molecular sieve suspension, its suspension concentration is 1-20g/L, grain size is 0.02-10 μ m, by vavuum pump the pressure reduction of both sides inside and outside the basement membrane is adjusted to 0.0010-0.0500MPa, also can use water pump or compressor to adjust the pressure reduction of the inside and outside both sides of basement membrane, with basement membrane in molecular sieve suspension, find time to take out behind the dip-coating 30-300s dry solidify the crystal seed basement membrane.α-the Al of basement membrane tubulose or sheet
2O
3Basement membrane or other are as glass or stainless steel basement membrane.
(B) synthetic A type molecular sieve film
NaOH is dissolved in the distilled water, and the clarification back adds aluminium oxide or aluminium foil, stirs and forms aluminum solutions; To be added to as the Ludox of crystal seed in the pre-heated distilled water and fully stir, and pre-heated aluminum solutions be added in the Ludox stir, the solution composition of the synthetic A type molecular sieve film of making is: aNa
2O: bAl
2O
3: 5SiO
2: cH
2O, a=20-100 wherein, b=0.5-5, c=500-4000; Vertically be placed in the autoclave after the crystal seed basement membrane is fixing, pour the solution of synthetic A type molecular sieve film into, synthetic or the microwave synthesizing molecular sieve film of hydro-thermal, synthesis temperature is 323-373K, and the hydro-thermal generated time is 2-60h, and the microwave time is 30-120min, taking-up is cooled to room temperature, be washed with distilled water to neutrality, oven dry gets the A type molecular sieve film.Can repeat the step of synthesizing molecular sieve film if desired.
Adopt the synthetic molecular screen membrane separating property of the inventive method good, repeatability is high, is suitable for industry and amplifies.Method with A type molecular sieve film of high selectivity high osmosis high duplication,
The A type molecular sieve film that adopts the present invention to synthesize shows do not have stray crystal to generate through SEM and XRD detection, and membrane surface generates the fine and close continuous films of one deck.
The molecular screen membrane that adopts the present invention to synthesize is used for infiltration evaporation, and the result shows that the selection separation factor of this film all surpasses 10 in 95wt% isopropanol system when temperature is 323K and 343K
4, its flux is respectively 1.45Kg/m at 323K and 343K
2H and 1.75Kg/m
2H.Fine separation selectivity and permeability are arranged.
Adopt synthesizing molecular sieve film of the present invention to compare with domestic and international synthesizing molecular sieve film reported method, have easy and simple to handlely, film forming repeatability is high, and function admirable is suitable for the advantage that industry is amplified.
The method of the molecular sieve crystal seed being introduced the membrane surface synthesizing molecular sieve film that the present invention reports relatively at present both at home and abroad, mainly contain following advantage: (1) the present invention adopts vavuum pump to find time or method both sides inside and outside basement membrane of compressor compresses produce a pressure reduction, the molecular sieve crystal seed is just moved to membrane surface and is formed evenly continuous crystal seed film of one deck under the effect of pressure like this, experiment shows adopts the present invention only to need a few minutes just can form evenly continuous crystal seed film of one deck in membrane surface, and this can save the brilliant time that is coated with greatly than the crystal method of reporting in the past; (2) the present invention is suitable for the synthetic of tracheary element sieve membrane fully, therefore is suitable for industry and amplifies, and has very high industrial application value; (3) the present invention is easy and simple to handle, does not need to be coated with especially brilliant device; (4) adopt synthesizing molecular sieve film repeatability of the present invention high, function admirable is suitable for industry and amplifies.
Description of drawings
Fig. 1 is the find time schematic diagram of crystal method of the present invention, 1-molecular sieve crystal seed wherein, 2-basement membrane, the interface of 3-water pump or compressor.
Fig. 2 is the schematic flow sheet of synthesizing molecular sieve film of the present invention.
Find time for the present invention the adopts x-ray diffraction pattern of the synthetic molecular screen membrane of crystal method of Fig. 3, curve a is a basement membrane among the figure, and b is the crystal seed basement membrane, and c is the A type molecular sieve film.
Find time for the present invention the adopts scanning electron microscope diagram of the synthetic molecular screen membrane of crystal method of Fig. 4, wherein Fig. 4 a is the crystal seed basement membrane, b is the A type molecular sieve film.
Fig. 5 carries out infiltration evaporation test device schematic diagram for the involutory film forming of the present invention, 9-thermostat wherein, 10-raw material tank, 11-circulating pump, 4-membrane reactor, 5-gatherer, 6-triple valve, 7-separator tube, 8-vavuum pump.
Isopropyl alcohol concentration is to isopropanol system infiltration evaporation Effect on Performance figure in the material liquid when 343K for the present invention for Fig. 6, and curve b is a separation among the figure, the c amount of being.
Fig. 7 600 gram initial concentrations when the 343K are the isopropanol system concentration of raw material of 95wt% and the penetrating fluid concentration Changing Pattern figure with dewatering time, and curve b is a concentration of raw material among the figure, and c is a penetrating fluid concentration.
The specific embodiment
The synthetic embodiment 1 of tubulose A type molecular sieve film
The preparation of step 1 crystal seed basement membrane
Take by weighing 1.0 gram A type molecular sieve crystal seeds, add 300 ml distilled waters, stir back abundant vibrating dispersion in ultrasonic wave, after the filtration again in ultrasonic wave fully vibrating dispersion become uniform molecular sieve crystal seed suspension 1.By water pump 3 pressure reduction of basement membrane 2 inside and outside both sides is adjusted to 0.0050MPa, with tubulose α-Al
2O
3Basement membrane finds time to take out behind the dip-coating 120s in the molecular sieve crystal seed suspension that makes.After drying at a certain temperature baking and curing get the crystal seed basement membrane.
Synthesizing of step 2 A type molecular sieve film
Take by weighing 156 gram NaOH and be dissolved in 300 ml distilled waters, the clarification back adds 2.1 gram aluminium foils, stirs and forms aluminum solutions; Measure 43.5 milliliters of Ludox (SiO
227wt%, ρ=1.16g/l) be added in pre-heated 390 ml distilled waters fully stirs; Pre-heated aluminum solutions is slowly added in the Ludox, continue to stir 10 minutes.The composition (mol ratio) of each component is 50Na in the last solution
2O: Al
2O
3: 5SiO
2: 1000H
2O.Vertically be placed in the autoclave after the crystal seed basement membrane is fixing, pour reactant liquor into, under 343K, take out behind the reaction 10h, be cooled to room temperature, be washed with distilled water to neutrality, be used for after the oven dry characterizing and the infiltration evaporation experiment.
The synthetic embodiment 2 of tubulose A type molecular sieve film
The preparation of step 1 crystal seed basement membrane
Take by weighing 1.5 gram A type molecular sieve crystal seeds, add 300 ml distilled waters, stir back abundant vibrating dispersion in ultrasonic wave, after the filtration again in ultrasonic wave fully vibrating dispersion become uniform molecular sieve suspension.The pressure reduction of both sides inside and outside the basement membrane is adjusted to 0.0050MPa, basement membrane is found time to take out behind the dip-coating 120sec in the molecular sieve suspension that makes.After drying at a certain temperature baking and curing get the crystal seed basement membrane.
Synthesizing of step 2 A type molecular sieve film is with embodiment 1 step 2.
The synthetic embodiment 3 of tubulose A type molecular sieve film
The preparation of step 1 crystal seed basement membrane
Take by weighing 1.0 gram A type molecular sieve crystal seeds, add 300 ml distilled waters, stir back abundant vibrating dispersion in ultrasonic wave, after the filtration again in ultrasonic wave fully vibrating dispersion become uniform molecular sieve suspension.Vacuum is adjusted to 0.0150MPa, basement membrane is found time to take out behind the dip-coating 120sec in the molecular sieve suspension that makes.After drying at a certain temperature baking and curing get the crystal seed basement membrane.
Synthesizing of step 2 A type molecular sieve film is with embodiment 1 step 2.
Following table is the find time result of the synthetic A type molecular sieve film of crystal method of embodiment 1,2,3.
Embodiment crystal seed basement membrane thickness total flux separation
Quality (μ m) (Kg/m
2H) (α) (water/isopropyl alcohol)
1 is evenly continuous more than 9 1.72 10000
2 even continuous 14 1.14 5000
3 is evenly continuous more than 10 1.47 10000
The synthetic embodiment 4 of tubulose A type molecular sieve film
The preparation of step 1 crystal seed basement membrane
Take by weighing 1.0 gram A type molecular sieve crystal seeds, add 300 ml distilled waters, stir back abundant vibrating dispersion in ultrasonic wave, after the filtration again in ultrasonic wave fully vibrating dispersion become uniform molecular sieve suspension.The pressure reduction of both sides inside and outside the basement membrane is adjusted to 0.0050MPa, basement membrane is found time to take out behind the dip-coating 120sec in the molecular sieve suspension that makes.After drying at a certain temperature baking and curing get the crystal seed basement membrane.
Synthesizing of step 2 A type molecular sieve film
Take by weighing 156 gram NaOH and be dissolved in 300 ml distilled waters, the clarification back adds 2.1 gram aluminium foils, stirs and forms aluminum solutions; Measure 43.5 milliliters of Ludox (SiO
227wt%, ρ=1.16) be added in pre-heated 390 ml distilled waters, fully stir; Pre-heated aluminum solutions is slowly added in the Ludox, continue to stir 10 minutes.The composition (mol ratio) of each component is 50Na in the last solution
2O: Al
2O
3: 5SiO
2: 1000H
2O.Vertically be placed in the autoclave after the crystal seed basement membrane is fixing, pour reactant liquor into, heating using microwave 373K is synthetic to be taken out after 60 minutes, was cooled to room temperature, was washed with distilled water to neutrality, was used for after the oven dry characterizing and the infiltration evaporation experiment.
The synthetic embodiment 5 of tubulose A type molecular sieve film
The preparation of step 1 crystal seed basement membrane is with embodiment 3 steps 1.
Synthesizing of step 2 A type molecular sieve film is with embodiment 4 steps 2.
The synthetic embodiment 6 of tubulose A type molecular sieve film
The preparation of step 1 crystal seed basement membrane is with embodiment 3 steps 1.
Synthesizing of step 2 A type molecular sieve film
Take by weighing 156 gram NaOH and be dissolved in 300 ml distilled waters, the clarification back adds 2.1 gram aluminium foils, stirs and forms aluminum solutions; Measure 43.5 milliliters of Ludox (SiO
227wt%, ρ=1.16g/l) be added in pre-heated 390 ml distilled waters fully stirs; Pre-heated aluminum solutions is slowly added in the Ludox, continue to stir 10 minutes.The composition (mol ratio) of each component is 50Na in the last solution
2O: Al
2O
3: 5SiO
2: 1000H
2O.Vertically be placed in the autoclave after the crystal seed basement membrane is fixing, pour reactant liquor into, under 343K, take out behind the reaction 10h, be cooled to room temperature, be washed with distilled water to the oven dry of neutral back.
A type molecular sieve film repeating step 2 after the oven dry is synthesized.The oven dry of reaction back is used for characterizing and the infiltration evaporation experiment.
The synthetic embodiment 7 of sheet A type molecular sieve film
The preparation of step 1 crystal seed basement membrane
Take by weighing 1.0 gram A type molecular sieve crystal seeds, add 300 ml distilled waters, stir back abundant vibrating dispersion in ultrasonic wave, after the filtration again in ultrasonic wave fully vibrating dispersion become uniform molecular sieve suspension.With the sheet basement membrane fixing after, the pressure reduction of both sides inside and outside the basement membrane is adjusted to 0.0050MPa, basement membrane is found time to take out behind the dip-coating 120sec in the molecular sieve suspension that makes.After drying at a certain temperature baking and curing get the crystal seed basement membrane.
Synthesizing of step 2 A type molecular sieve film is with embodiment 4 steps 2.
Following table is the find time result of the synthetic A type molecular sieve film of crystal method of embodiment 4,5,6,7 and 1,3
Embodiment crystal seed basement membrane thickness total flux separation
Quality (μ m) (Kg/m
2H) (α) (water/isopropyl alcohol)
1 is evenly continuous more than 9 1.72 10000
4 evenly continuous 5 //
3 is evenly continuous more than 10 1.47 10000
6 is evenly continuous more than 14 1.29 10000
5 evenly continuous 7 //
7 evenly continuous 4 //
Claims (9)
1, a kind of method of the synthetic A type molecular sieve film of crystal method of finding time, its key step is as follows:
(A) preparation crystal seed basement membrane
The A type molecular sieve crystal seed is dissolved in distilled water and in ultrasonic wave vibrating dispersion become uniform molecular sieve suspension, its suspension concentration is 1-20g/L, grain size is 0.02-10 μ m, by vavuum pump the pressure reduction of both sides inside and outside the basement membrane is adjusted to 0.0010-0.0500MPa, with basement membrane in molecular sieve suspension, find time to take out behind the dip-coating 30-300s dry solidify the crystal seed basement membrane;
(B) synthetic A type molecular sieve film
NaOH is dissolved in the distilled water, and the clarification back adds aluminium oxide, stirs and forms aluminum solutions; Ludox is added to fully stirring in the pre-heated distilled water, will stirs in the pre-heated aluminum solutions adding Ludox, the solution composition of the synthetic A type molecular sieve film of making is: aNa
2O: bAl
2O
3: 5SiO
2: cH
2O, a=20-100 wherein, b=0.5-5, c=500-4000; Vertically be placed in the autoclave after the crystal seed basement membrane is fixing, pour the solution of synthetic A type molecular sieve film into, the synthetic temperature of hydro-thermal is 323-373K, and generated time is to take out behind the 2-60h to be cooled to room temperature, is washed with distilled water to neutral oven dry.
2, in accordance with the method for claim 1, it is characterized in that using water pump to find time to adjust the pressure reduction of the inside and outside both sides of basement membrane.
3, in accordance with the method for claim 1, it is characterized in that using compressor compresses to adjust the pressure reduction of the inside and outside both sides of basement membrane.
4, in accordance with the method for claim 1, it is characterized in that basement membrane is α-Al
2O
3, glass or stainless steel basement membrane.
5,, it is characterized in that described basement membrane is tubulose or sheet according to claim 1 or 4 described methods.
6, in accordance with the method for claim 1, it is characterized in that hydro-thermal synthesizes the microwave synthesizing molecular sieve film, generated time is 30-120min.
7, in accordance with the method for claim 1, it is characterized in that aluminium oxide described in the step B is an aluminium foil.
8, in accordance with the method for claim 1, it is characterized in that repeating the hydro-thermal synthesizing molecular sieve film.
9, in accordance with the method for claim 6, it is characterized in that repeating the synthetic or microwave synthesizing molecular sieve film of hydro-thermal.
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| CNB021411972A CN1180877C (en) | 2002-07-08 | 2002-07-08 | Method for synthesizing molecular sieve film using vacuum crystal method |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100337918C (en) * | 2004-11-17 | 2007-09-19 | 中国科学院大连化学物理研究所 | Method for synthesizing molecular screen membrane from in-site aging-microwave heat |
| CN100463714C (en) * | 2005-12-26 | 2009-02-25 | 浙江师范大学 | Manufacturing method of catalysis-isolation integral mini-size membrane reactor |
| CN101397142B (en) * | 2007-09-24 | 2011-06-15 | 中国科学院大连化学物理研究所 | Microwave apparatus and method for synthesizing molecular sieve film |
| CN101279210B (en) * | 2008-05-20 | 2010-12-08 | 吉林大学 | ZSM-5 molecular sieve film and use thereof in aspect of processing arsenic |
| CN104174300B (en) * | 2014-08-21 | 2016-03-02 | 上海如杰电子科技有限公司 | The preparation method of the sieved filter membrane of a kind of flexible molecule for purification of air |
| CN105311972A (en) * | 2015-11-14 | 2016-02-10 | 大连理工大学 | Method for synthesizing hydrophilic ZSM-5 zeolite molecular sieve membrane |
| CN105457502B (en) * | 2015-12-31 | 2017-10-10 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method and applications of MOFs films |
| CN107337472B (en) * | 2016-12-02 | 2020-03-31 | 上海绿强新材料有限公司 | Preparation method of FAU type zeolite molecular sieve membrane |
| CN111921390A (en) * | 2020-07-15 | 2020-11-13 | 上海念诺膜技术有限公司 | Method for synthesizing compact LTA type molecular sieve membrane by covalent bonding hydrothermal method |
| CN113731485A (en) * | 2021-09-29 | 2021-12-03 | 江西师范大学 | Preparation method of supported hierarchical pore titanium silicalite molecular sieve |
| CN115057452A (en) * | 2022-07-10 | 2022-09-16 | 苏州科技大学 | Method for rapidly preparing molecular sieve and molecular sieve membrane by using 'clean' crystal seeds |
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