CN102126731A - Method for synthesizing highly-oriented MFI (Melt Flow Index) molecular sieve membrane through controlled secondary growth of twin crystal - Google Patents
Method for synthesizing highly-oriented MFI (Melt Flow Index) molecular sieve membrane through controlled secondary growth of twin crystal Download PDFInfo
- Publication number
- CN102126731A CN102126731A CN 201110033850 CN201110033850A CN102126731A CN 102126731 A CN102126731 A CN 102126731A CN 201110033850 CN201110033850 CN 201110033850 CN 201110033850 A CN201110033850 A CN 201110033850A CN 102126731 A CN102126731 A CN 102126731A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- screen membrane
- molecular screen
- oriented
- supporter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention discloses a method for synthesizing a highly-oriented MFI (Melt Flow Index) molecular sieve membrane through controlled secondary growth of a twin crystal. The method comprises the following steps of: (1) preparing secondary growth synthetic fluid consisting of ethyl orthosilicate, tetrapropyl ammonium hydroxide, sodium hydroxide and water in the molar ratio of 1:(0.001-0.60):(0.001-0.20):(10-1000); (2) stirring the synthetic fluid at room temperature for 1-10 hours, putting the stirred synthetic fluid into a synthesis kettle, putting a support body coated with a b axis oriented crystal seed layer into the synthesis kettle, sealing the synthesis kettle, heating, and synthesizing at the temperature of between 120 DEG C and 200 DEG C for 10-300 minutes; and (3) washing and drying to obtain the oriented MFI molecular sieve membrane from the support body. The MFI molecular sieve membrane synthesized by the method is highly oriented in a b axis, the method is easy to operate, a molecular sieve membrane layer has high orientation, the synthetic fluid can be recycled, cost is lowered, and pollution is reduced.
Description
Technical field
The present invention relates to the synthetic of MFI type molecular screen membrane, the method for the synthetic height-oriented property MFI type molecular screen membrane of the controlled diauxic growth of a kind of twin particularly is provided.
Background technology
Molecular screen membrane has machinery and the Electronic Performance and excellent thermostability, chemical stability and the biologically stable of regular pore passage structure, uniqueness, thereby is widely used in various fields such as separating substances, membrane reactor, chemical sensor, electrode, advanced low-k materials and corrosion protection coating.The molecular screen membrane of bibliographical information mainly contains LTA type, T type, MFI type, FAU type, MOR type etc. at present, and wherein MFI type molecular screen membrane receives much concern.This be because: the aperture size of (1) MFI type molecular sieve is suitable with the molecular dimension of a lot of essential industry chemical; (2) MFI type molecular sieve has complicated 3 D pore canal system,
bThe straight hole road of axle orientation 0.53 * 0.56 nm with
aThe sinusoidal duct of axle orientation 0.51 * 0.55 nm intersects mutually,
bAxle orientation MFI type molecular screen membrane has application prospect widely because of the straight hole road of its molecular sieve is vertical with supporting body surface.Up to now, most of research report has been had to the MFI type molecular screen membrane of unordered (random orientation).
Original position hydrothermal synthesis method and diauxic growth method (crystal seed method) are the common methods of synthetic orientation molecular screen membrane.(Chemistry of Materials, 2001,13:1101-1107 such as Wang; Microporous and Mesoporous Materials, 2001,48:229-238) make supporter with stainless steel substrates, adopt the original position hydrothermal synthesis method to prepare
bAxle orientation MFI type molecular screen membrane, and studied that synthetic liquid is formed in great detail and synthesis condition to the influence of molecular screen membrane orientation.That the advantage of original position hydrothermal synthesis method is is simple to operate, suitability is strong, cost is low; But the original position hydrothermal synthesis method forms on supporter in the molecular screen membrane, and body also generates a large amount of molecular sieve crystals in mutually, is difficult to avoid the generation of twin, thereby is difficult to the molecular screen membrane of synthetic height-oriented property.
The synthetic orientation molecular screen membrane of diauxic growth method can be controlled the orientation growth of molecular sieve crystal preferably owing to used the orientation crystal seed layer; But the diauxic growth method need obtain to apply uniform crystal seed layer, and operation steps is comparatively complicated, preparation cost is higher, and in the diauxic growth process also usually with the generation of other orientation twins, influence the orientation of molecular screen membrane.
Recently, the researchist developed some new methods synthesize the height
bThe MFI type molecular screen membrane of axle orientation.Lai etc. (Science, 2003,300:456-460) make supporter with αYang Hualv, at first applying one deck aperture in supporting body surface is the mesopore silicon oxide of 2 nm, applies on mesoporous layer again
bAxle orientation MFI type molecular sieve crystal seed layer carries out diauxic growth at last in the presence of complex construction directed agents (trimerization TPAOH), obtain
bAxle orientation MFI type molecular screen membrane.This molecular screen membrane is applied to the separation of xylene isomer, has obtained separating effect preferably.
Lee etc. (Microporous and Mesoporous Materials, 2009,122:288-293) adopt " μ-Tiles and mortar approach " method to prepare successive
bAxle orientation MFI type molecular sieve film.There is the supporting body surface that the connects agent PEI method by self-assembly and blade coating prepare an even compact in spin coating in advance
bAxle oriented seed crystal layer, high temperature are removed behind the structure directing agent in the crystal seed on crystal seed layer sputter one thin Au/Pd film with passivation crystal seed layer surface again, thereby make crystal seed can only grow in plane, crystal seed layer place in the diauxic growth process, and then obtain successive
bThe axle orientation molecular sieve membrane.
(Journal of the American Chemical Society, 2010,132:1768-1769 such as Liu; Chinese patent CN 200810012646.6) adopt a kind of improved diauxic growth method to obtain height
bThe MFI type molecular screen membrane of axle orientation.Drip an amount of water in clean supporting body surface earlier and make interim soft supporter, the careful afterwards oiliness molecular sieve crystal seed suspension liquid with formulated is expelled to water-air interface and forms a continuous individual layer crystal seed layer, carefully control velocity of evaporation again to remove liquid level, can make the height of a densification in supporting body surface
bThe MFI type molecular sieve crystal seed layer of axle orientation.And then this crystal seed layer carried out diauxic growth at the synthetic liquid of 150 ℃ of heating behind 2 h in advance with one, and then obtain height
bThe MFI type molecular screen membrane of axle orientation.In the diauxic growth process, pre-warmed synthetic liquid is crucial, if use fresh synthetic liquid then will generate on crystal seed in a large number
aAxle orientation twin can't obtain height
bThe MFI type molecular screen membrane of axle orientation.
Above-mentioned diauxic growth method or adopt special complex construction directed agents, or complex steps, or the energy consumption height, seriously polluted, cost is high.Because the suitability for industrialized production general requirement is simple to operate, material is easy to get, economically feasible, and it is more and more higher to environmental protection requirement, therefore, use cheap commercialized raw materials (such as TPAOH), synthesis step is simple and orientation molecular screen membrane synthetic method environmental protection receives much concern.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of simple to operate, raw material is easy to get, the method for the synthetic height-oriented property MFI type molecular screen membrane of the controlled diauxic growth of the twin of economic environmental protection.
The step of the method for the synthetic height-oriented property MFI type molecular screen membrane of the controlled diauxic growth of twin is as follows:
1) preparation of the synthetic liquid of diauxic growth, the mol ratio that synthetic liquid is formed is: tetraethoxy: TPAOH: sodium hydroxide: water=1:0.001-0.60:0.001-0.20:10-1000;
2) synthetic liquid chamber temperature stirs in the synthesis reactor of packing into after 1-10 hour, puts into to scribble
bThe supporter of axle oriented seed crystal layer heats syntheticly after the synthesis reactor sealing, synthesis temperature is 120-200 ℃, and generated time is 10-300 minute;
3) washing and drying obtains orientation MFI type molecular screen membrane on supporter.
Described
bAxle oriented seed crystal layer is directly crystal seed to be spread upon supporting body surface, perhaps spreads upon earlier on the flat film, then the film bag is arrived supporting body surface.
The method of the synthetic orientation MFI type molecular screen membrane of the controlled diauxic growth of twin of the present invention prepares height by the consumption of controlling TPAOH simply
bThe MFI molecular screen membrane of axle orientation, existing method have obtained better orientation, simple to operate and synthetic liquid can be recycled, and can see that from scanning electron microscope diagram and X ray diffracting spectrum synthetic MFI type molecular screen membrane is mainly height
bThe axle orientation, rete is continuous.
Description of drawings
Fig. 1 is the scanning electron microscope diagram of embodiment 1 preparation crystal seed layer;
Fig. 2 is the scanning electron microscope diagram of embodiment 2 synthesizing molecular sieve films;
Fig. 3 is the scanning electron microscope diagram of embodiment 3 synthesizing molecular sieve films;
Fig. 4 is the scanning electron microscope diagram of embodiment 4 synthesizing molecular sieve films;
Fig. 5 is the scanning electron microscope diagram of embodiment 5 synthesizing molecular sieve films;
Fig. 6 is the X-ray diffraction spectrogram of embodiment 5 synthesizing molecular sieve films;
Fig. 7 is the scanning electron microscope diagram of embodiment 6 synthesizing molecular sieve films;
Fig. 8 is the scanning electron microscope diagram of embodiment 7 synthesizing molecular sieve films;
Fig. 9 is the scanning electron microscope diagram of embodiment 8 synthesizing molecular sieve films;
Figure 10 is the scanning electron microscope diagram of embodiment 10 synthesizing molecular sieve films;
Figure 11 is the scanning electron microscope diagram of embodiment 11 synthesizing molecular sieve films.
Embodiment
For the method for the synthetic orientation MFI type molecular screen membrane of the controlled diauxic growth of twin is described better, enumerate the synthetic embodiment of some molecular screen membranes below, but the invention is not restricted to cited example.
Embodiment 1
MFI type molecular sieve crystal seed powder is coated onto smooth supporting body surface, slightly firmly pushes floatingly then, promptly get and scribble
bThe supporter of axle oriented seed crystal layer.The scanning electron microscope diagram sheet of crystal seed layer as shown in Figure 1.
Embodiment 2
With molar ratio is tetraethoxy: 40 milliliters of synthetic liquid of sodium hydroxide: water=1:0.20:165 at room temperature stirred 4 hours, obtain clear solution, then this synthetic liquid is put into one 100 milliliters with the supporter that scribbles crystal seed layer of embodiment 1 preparation and have the teflon-lined synthesis reactor, synthesis reactor after will sealing is subsequently put into 200 ℃ convection oven crystallization 10 minutes, at last the synthesis reactor after the crystallization is taken out, quenching is taken out supporter to room temperature, clean the back oven dry with deionized water.The scanning electron microscope diagram sheet of the molecular screen membrane after the oven dry as shown in Figure 2, the gained molecular screen membrane be the height
bThe MFI type molecular screen membrane of axle orientation, but discontinuous.
Embodiment 3
With molar ratio is tetraethoxy: 40 milliliters of synthetic liquid of TPAOH: sodium hydroxide: water=1:0.001:0.10:165 at room temperature stirred 10 hours, obtain clear solution, then this synthetic liquid is put into one 100 milliliters with the supporter that scribbles crystal seed layer of embodiment 1 preparation and have the teflon-lined synthesis reactor, synthesis reactor after will sealing is subsequently put into 150 ℃ convection oven crystallization 3 hours, at last the synthesis reactor after the crystallization is taken out, quenching is taken out supporter to room temperature, clean the back oven dry with deionized water.The scanning electron microscope diagram sheet of the molecular screen membrane after the oven dry as shown in Figure 3, the gained molecular screen membrane be the height
bThe MFI type molecular screen membrane of axle orientation.
Embodiment 4
With molar ratio is tetraethoxy: 40 milliliters of synthetic liquid of TPAOH: sodium hydroxide: water=1:0.005:0.095:165 at room temperature stirred 4 hours, obtain clear solution, then this synthetic liquid is put into one 100 milliliters with the supporter that scribbles crystal seed layer of embodiment 1 preparation and have the teflon-lined synthesis reactor, synthesis reactor after will sealing is subsequently put into 150 ℃ convection oven crystallization 3 hours, at last the synthesis reactor after the crystallization is taken out, quenching is taken out supporter to room temperature, clean the back oven dry with deionized water.The scanning electron microscope diagram sheet of the molecular screen membrane after the oven dry as shown in Figure 4, the gained molecular screen membrane is basic successive height
bThe MFI type molecular screen membrane of axle orientation.
Embodiment 5
With molar ratio is tetraethoxy: 40 milliliters of synthetic liquid of TPAOH: sodium hydroxide: water=1:0.05:0.05:165 at room temperature stirred 4 hours, obtain clear solution, then this synthetic liquid is put into one 100 milliliters with the supporter that scribbles crystal seed layer of embodiment 1 preparation and have the teflon-lined synthesis reactor, synthesis reactor after will sealing is subsequently put into 150 ℃ convection oven crystallization 3 hours, at last the synthesis reactor after the crystallization is taken out, quenching is taken out supporter to room temperature, clean the back oven dry with deionized water.The scanning electron microscope diagram sheet of the molecular screen membrane after the oven dry and X ray diffracting spectrum as shown in Figure 5 and Figure 6, the gained molecular screen membrane is the successive height
bThe MFI type molecular screen membrane of axle orientation.
Embodiment 6
With molar ratio is tetraethoxy: 40 milliliters of synthetic liquid of TPAOH: water=1:0.10:165 at room temperature stirred 4 hours, obtain clear solution, then this synthetic liquid is put into one 100 milliliters with the supporter that scribbles crystal seed layer of embodiment 1 preparation and have the teflon-lined synthesis reactor, synthesis reactor after will sealing is subsequently put into 150 ℃ convection oven crystallization 3 hours, at last the synthesis reactor after the crystallization is taken out, quenching is taken out supporter to room temperature, clean the back oven dry with deionized water.The scanning electron microscope diagram sheet of the molecular screen membrane after the oven dry as shown in Figure 7, the gained molecular screen membrane is a successive
bThe MFI type molecular screen membrane of axle orientation.
With molar ratio is tetraethoxy: 40 milliliters of synthetic liquid of TPAOH: water=1:0.32:165 at room temperature stirred 4 hours, obtain clear solution, then this synthetic liquid is put into one 100 milliliters with the supporter that scribbles crystal seed layer of embodiment 1 preparation and have the teflon-lined synthesis reactor, synthesis reactor after will sealing is subsequently put into 150 ℃ convection oven crystallization 3 hours, at last the synthesis reactor after the crystallization is taken out, quenching is taken out supporter to room temperature, clean the back oven dry with deionized water.The scanning electron microscope diagram sheet of the molecular screen membrane after the oven dry as shown in Figure 8, the gained molecular screen membrane is a successive MFI type molecular screen membrane, bottom is
bThe axle orientation, the second layer is
aThe axle orientation.
Embodiment 8
With molar ratio is tetraethoxy: 40 milliliters of synthetic liquid of TPAOH: water=1:0.60:1000 at room temperature stirred 1 hour, obtain clear solution, then this synthetic liquid is put into one 100 milliliters with the supporter that scribbles crystal seed layer of embodiment 1 preparation and have the teflon-lined synthesis reactor, synthesis reactor after will sealing is subsequently put into 150 ℃ convection oven crystallization 3 hours, at last the synthesis reactor after the crystallization is taken out, quenching is taken out supporter to room temperature, clean the back oven dry with deionized water.The scanning electron microscope diagram sheet of the molecular screen membrane after the oven dry as shown in Figure 9, the gained molecular screen membrane is the successive height
bThe MFI type molecular screen membrane of axle orientation.
Embodiment 9
With molar ratio is tetraethoxy: 40 milliliters of synthetic liquid of TPAOH: sodium hydroxide: water=1:0.05:0.001:10 at room temperature stirred 10 hours, then this synthetic liquid is put into one 100 milliliters with the supporter that scribbles crystal seed layer of embodiment 1 preparation and have the teflon-lined synthesis reactor, synthesis reactor after will sealing is subsequently put into 120 ℃ convection oven crystallization 5 hours, at last the synthesis reactor after the crystallization is taken out, quenching is taken out supporter to room temperature, clean the back oven dry with deionized water.The gained molecular screen membrane is a successive
bThe MFI type molecular screen membrane of axle orientation.
Synthetic liquid after embodiment 4 crystallization is put into one 100 milliliters with the supporter that scribbles crystal seed layer of embodiment 1 preparation have the teflon-lined synthesis reactor, synthesis reactor after will sealing is subsequently put into 150 ℃ convection oven crystallization 3 hours, at last the synthesis reactor after the crystallization is taken out, quenching is taken out supporter to room temperature, clean the back oven dry with deionized water.The scanning electron microscope diagram sheet of the molecular screen membrane after the oven dry as shown in figure 10, the gained molecular screen membrane is the successive height
bThe MFI type molecular screen membrane of axle orientation, synthetic liquid can recycle.
Embodiment 11 synthetic liquid recycle experiment 2
Synthetic liquid after embodiment 9 crystallization is put into one 100 milliliters with the supporter that scribbles crystal seed layer of embodiment 1 preparation have the teflon-lined synthesis reactor, synthesis reactor after will sealing is subsequently put into 150 ℃ convection oven crystallization 3 hours, at last the synthesis reactor after the crystallization is taken out, quenching is taken out supporter to room temperature, clean the back oven dry with deionized water.The scanning electron microscope diagram sheet of the molecular screen membrane after the oven dry as shown in figure 11, the gained molecular screen membrane is the successive height
bThe MFI type molecular screen membrane of axle orientation, synthetic liquid can recycle.
Embodiment 12
Earlier molecular sieve crystal seed powder is spread upon on the flat film and form
bThe MFI type molecular sieve crystal seed layer of axle orientation, again with the film bag to the porous supporting body surface.
With molar ratio is tetraethoxy: 40 milliliters of synthetic liquid of TPAOH: sodium hydroxide: water=1:0.05:0.05:165 at room temperature stirred 4 hours, obtain clear solution, then this synthetic liquid is put into one 100 milliliters with the supporter that is surrounded by film and have the teflon-lined synthesis reactor, synthesis reactor after will sealing is subsequently put into 150 ℃ convection oven crystallization 3 hours, at last the synthesis reactor after the crystallization is taken out, quenching is taken out supporter to room temperature, clean the back oven dry with deionized water.The gained molecular screen membrane is the successive height
bThe MFI type molecular screen membrane of axle orientation.
Claims (2)
1. the method for the synthetic height-oriented property MFI type molecular screen membrane of the controlled diauxic growth of twin is characterized in that its step is as follows:
1) preparation of the synthetic liquid of diauxic growth, the mol ratio that synthetic liquid is formed is: tetraethoxy: TPAOH: sodium hydroxide: water=1:0.001-0.60:0.001-0.20:10-1000;
2) synthetic liquid chamber temperature stirs in the synthesis reactor of packing into after 1-10 hour, puts into to scribble
bThe supporter of axle oriented seed crystal layer heats syntheticly after the synthesis reactor sealing, synthesis temperature is 120-200 ℃, and generated time is 10-300 minute;
3) washing and drying obtains orientation MFI type molecular screen membrane on supporter.
2. in accordance with the method for claim 1, it is characterized in that described
bAxle oriented seed crystal layer is directly crystal seed to be spread upon supporting body surface, perhaps spreads upon earlier on the flat film, then the film bag is arrived supporting body surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110033850 CN102126731B (en) | 2011-01-31 | 2011-01-31 | Method for synthesizing highly-oriented MFI (Melt Flow Index) molecular sieve membrane through controlled secondary growth of twin crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110033850 CN102126731B (en) | 2011-01-31 | 2011-01-31 | Method for synthesizing highly-oriented MFI (Melt Flow Index) molecular sieve membrane through controlled secondary growth of twin crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102126731A true CN102126731A (en) | 2011-07-20 |
| CN102126731B CN102126731B (en) | 2012-12-26 |
Family
ID=44265056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110033850 Expired - Fee Related CN102126731B (en) | 2011-01-31 | 2011-01-31 | Method for synthesizing highly-oriented MFI (Melt Flow Index) molecular sieve membrane through controlled secondary growth of twin crystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102126731B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583425A (en) * | 2012-03-01 | 2012-07-18 | 浙江大学 | Synthetic method of MFI (Mechanical Fuel Injection) type molecular sieve membrane |
| CN103132056A (en) * | 2013-03-15 | 2013-06-05 | 沈阳化工大学 | Method for carrying out corrosion resisting treatment on surface of aluminum or aluminum alloy |
| CN103601209A (en) * | 2013-08-23 | 2014-02-26 | 宁夏大学 | Method of orderly assembling molecular sieve crystal grain layer |
| CN104556107A (en) * | 2015-01-19 | 2015-04-29 | 浙江大学 | Method of preparing high-oriented MFI type zeolite membrane by virtue of secondary growth under neutral condition |
| CN104891519A (en) * | 2015-05-23 | 2015-09-09 | 浙江大学 | Method for preparing highly-oriented MFI-type molecular sieve membrane by secondary growth process |
| CN108726524A (en) * | 2018-07-11 | 2018-11-02 | 南昌工程学院 | The technique that MFI-type molecular screen membrane is prepared using the method for heat treatment seed layer |
| CN109822064A (en) * | 2019-04-09 | 2019-05-31 | 中冶赛迪工程技术股份有限公司 | In the method for continuous casting crystallizer copper plate surface growth inorganic coating |
| CN109942006A (en) * | 2019-04-24 | 2019-06-28 | 南昌工程学院 | A kind of method of hydro-thermal diauxic growth preparation orientation MFI-type molecular screen membrane |
| CN112707408A (en) * | 2020-12-29 | 2021-04-27 | 中国石油大学(华东) | Preparation method of core-shell type oriented titanium silicon molecular sieve membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004080889A2 (en) * | 2003-03-06 | 2004-09-23 | University Of Massachusetts | Crystalline membranes |
| CN101837990A (en) * | 2010-05-24 | 2010-09-22 | 江西师范大学 | Fluorine-containing all-silica MFI zeolite molecular sieve and preparation method thereof |
-
2011
- 2011-01-31 CN CN 201110033850 patent/CN102126731B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004080889A2 (en) * | 2003-03-06 | 2004-09-23 | University Of Massachusetts | Crystalline membranes |
| CN101837990A (en) * | 2010-05-24 | 2010-09-22 | 江西师范大学 | Fluorine-containing all-silica MFI zeolite molecular sieve and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 《Journal of the American Chemistry Society》 20100126 Yi Liu et al. Fabrication of Highly b-oriented MFI Film with Molecular Sieving Properties by Controlled In-Plane Secondary Growth 第1768-1769页 权利要求1-2 第132卷, 第6期 * |
| 《无机化学学报》 20061031 周明等 原位法合成有取向无过渡区域的MFI分子筛膜 第1750-1754页 权利要求1-2 第22卷, 第10期 * |
| 《无机化学学报》 20081031 刘秀凤等 无模板剂二次生长法制备取向MFI型分子筛膜 第1679-1683页 权利要求1-2 第24卷, 第10期 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583425A (en) * | 2012-03-01 | 2012-07-18 | 浙江大学 | Synthetic method of MFI (Mechanical Fuel Injection) type molecular sieve membrane |
| CN103132056A (en) * | 2013-03-15 | 2013-06-05 | 沈阳化工大学 | Method for carrying out corrosion resisting treatment on surface of aluminum or aluminum alloy |
| CN103601209A (en) * | 2013-08-23 | 2014-02-26 | 宁夏大学 | Method of orderly assembling molecular sieve crystal grain layer |
| CN104556107A (en) * | 2015-01-19 | 2015-04-29 | 浙江大学 | Method of preparing high-oriented MFI type zeolite membrane by virtue of secondary growth under neutral condition |
| CN104556107B (en) * | 2015-01-19 | 2016-06-01 | 浙江大学 | Under neutral condition, diauxic growth prepares the method for height-oriented property MFI-type molecular sieve film |
| CN104891519A (en) * | 2015-05-23 | 2015-09-09 | 浙江大学 | Method for preparing highly-oriented MFI-type molecular sieve membrane by secondary growth process |
| CN108726524A (en) * | 2018-07-11 | 2018-11-02 | 南昌工程学院 | The technique that MFI-type molecular screen membrane is prepared using the method for heat treatment seed layer |
| CN109822064A (en) * | 2019-04-09 | 2019-05-31 | 中冶赛迪工程技术股份有限公司 | In the method for continuous casting crystallizer copper plate surface growth inorganic coating |
| CN109942006A (en) * | 2019-04-24 | 2019-06-28 | 南昌工程学院 | A kind of method of hydro-thermal diauxic growth preparation orientation MFI-type molecular screen membrane |
| CN112707408A (en) * | 2020-12-29 | 2021-04-27 | 中国石油大学(华东) | Preparation method of core-shell type oriented titanium silicon molecular sieve membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102126731B (en) | 2012-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102126731B (en) | Method for synthesizing highly-oriented MFI (Melt Flow Index) molecular sieve membrane through controlled secondary growth of twin crystal | |
| CN101643218B (en) | Method for synthesizing oriented MFI type molecular sieve membrane by means of microwave heating | |
| CN103933871B (en) | A kind of preparation method of high stability all-silica MFI type molecular screen membrane | |
| CN101890306B (en) | Method for synthesizing NaA zeolite membrane on macroporous carrier | |
| CN105233702B (en) | A kind of utilization cobalt nano-array layer conversion forms the preparation method of the films of metal organic framework ZIF 67 | |
| CN101252983A (en) | Zeolitic separation membrane and process for producing the same | |
| CN108246122B (en) | Method for synthesizing NaA molecular sieve membrane | |
| CN101279207A (en) | Preparation of SAPO-34 molecular sieve film for selectively separating methane gas | |
| CN101544379A (en) | Method for synthesizing molecular sieve membrane by dip coating-rubbing crystal-coating method | |
| CN110627491B (en) | Synthesis method of molecular sieve membrane with sandwich structure and application of membrane | |
| CN104891519A (en) | Method for preparing highly-oriented MFI-type molecular sieve membrane by secondary growth process | |
| Li et al. | Continuity control of b-oriented MFI zeolite films by microwave synthesis | |
| CN101774607B (en) | Method for preparing oriented molecular sieve membrane by using diauxic growth method | |
| CN104906964B (en) | Preparation method for syntehsizing high-performance NaA molecular sieve membrane through seed self-self assembly supported support body | |
| CN103877865A (en) | Method for synthesizing NaA molecular sieve membrane | |
| CN105289323A (en) | Method for preparing high performance silicalite zeolite membrane | |
| CN107029561A (en) | A kind of preparation method of the MFI-type molecular screen membrane of h0h orientations | |
| CN104340993A (en) | Preparation method of SAPO-34 molecular sieve membrane | |
| CN105195029B (en) | Synthesize NaA types molecular sieve crystal and the method for synthesizing NaA type molecular screen membranes | |
| CN102500243A (en) | Preparation method for molecular sieve/organic composite permeable vaporization membrane | |
| CN109607681A (en) | A kind of Y-type zeolite molecular sieve film and preparation method thereof separating underwater gold category ion | |
| CN104556107A (en) | Method of preparing high-oriented MFI type zeolite membrane by virtue of secondary growth under neutral condition | |
| CN109970075B (en) | Method for synthesizing A-type molecular sieve membrane at low temperature | |
| CN108380059A (en) | A kind of method that microwave secondary growth method prepares MFI molecular screen membranes | |
| CN101654260A (en) | Method for preparing orientation molecular sieve membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121226 Termination date: 20160131 |
|
| EXPY | Termination of patent right or utility model |