CN108726524A - The technique that MFI-type molecular screen membrane is prepared using the method for heat treatment seed layer - Google Patents
The technique that MFI-type molecular screen membrane is prepared using the method for heat treatment seed layer Download PDFInfo
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- CN108726524A CN108726524A CN201810757409.6A CN201810757409A CN108726524A CN 108726524 A CN108726524 A CN 108726524A CN 201810757409 A CN201810757409 A CN 201810757409A CN 108726524 A CN108726524 A CN 108726524A
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- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/181—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process
- C01B33/185—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process of crystalline silica-polymorphs having molecular sieve properties, e.g. silicalites
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract
The invention discloses the techniques that the method using heat treatment seed layer prepares MFI-type molecular screen membrane, the specially synthesis technical field of MFI-type molecular screen membrane.The MFI molecular sieve seed layers of b axis orientation are coated on supporter using manual self-assembly method；It is placed in baking oven, certain time is handled, by tetrapropylammonium hydroxide:Tetraethoxysilane:Water is according to 0.2:1:2000 molar ratio, it is fitted into synthesis reactor after ageing, places into the seed layer after heat treatment, Synthesis liquid submerges supporter, it is synthesized 4 hours at 150 DEG C after synthesis reactor sealing, obtains the b axis orientation MFI-type molecular screen membranes of the smooth densification of height after washing and drying on supporter.Present invention enhances the active force between supporter and seed layer, processing method is simple and efficient.The MFI-type molecular screen membrane that can see synthesis from scanning electron microscope diagram piece and X ray diffracting spectrum is that height b axis is orientated, and film layer is smooth and fine and close.
Description
Technical field
The present invention relates to the techniques that the method using heat treatment seed layer prepares MFI-type molecular screen membrane, specially MFI type point
The synthesis technical field of sub- sieve membrane.
Background technology
The molecular sieve of MFI type has a wide range of applications in the fields such as catalysis and absorption, and pore canal system is by b axis directions
The straight hole road of 0.53 × 0.56 nm and the sinusoidal duct of 0.51 × 0.55 nm of a axis directions intersect to form.MFI-type molecular sieve
The form i.e. MFI molecular screen membranes of film can be fabricated to, by many researchs for being used as separation material, membrane reactor, preventing
Rotten coating, chemical sensor and advanced low-k materials etc..Preferred orientation, grain boundary structure and the thickness of MFI molecular sieve film layers
Degree etc. has a great impact to its performance.Since the MFI molecular screen membranes that preferential b axis is orientated have perpendicular to the straight-through of supporter
Type hole road and diffusion admittance is shorter, therefore show more excellent performance.
Currently, secondary growth method（That is crystal seed method）Have become the common method that synthesis b axis is orientated MFI molecular screen membranes.The party
Method is that the MFI molecular sieve seed layers that there is b axis to be orientated first are prepared on supporter, is then made and is taken with hydro-thermal method secondary synthesis again
To molecular screen membrane.Current research is mainly concentrated in the condition of control diauxic growth to obtain the height of not two-ling
DegreebThe film layer that axis is orientated（Chinese patent CN 200810012646.6, CN200910101819.6,
CN201110033850.8,CN 201510025076.4, CN201510265492.1, CN201610311050.0, CN
201710187937.8）.But it can see from complete building-up process, uniform, close oriented seed crystal layer right and wrong be prepared
Often important step is smooth, the fine and close precondition of the film layer that ensures subsequently to synthesize.
There are many methods for preparing b axis oriented seed crystal layers, including phase separation induction construction from part（Chinese patent CN
200810012646.6）, chemical bonding construction from part, manual self-assembly method, dynamic interface construction from part and LB methods etc..Wherein, hand
Work self-assembly method is in contrast easy, time saving.This method is the hydroxyl using supporting body surface and MFI seed surfaces, in hand
Refer to and form hydrogen bond under conditions of firmly pressing, to which MFI crystal seeds to be coated in the form of b axis preferred orientations on supporter
（Angewandte Chemie International Edition, 2007,46：3087-3090）.This method can also be applied
In preparing other kinds of molecular sieve seed layer, such as ETS-10 and Si-BEA.
Although manual self-assembly method is easy to be time saving, since the active force of hydrogen bond is weaker, in Synthesis liquid when diauxic growth
It has part to be broken, causes finally obtained MFI molecular screen membranes planarization and compactness poor, destroy whole b axis
It is orientated.Therefore, it is necessary to carry out processing appropriate to seed layer, to reinforce the effect between supporter and crystal seed, so that it is guaranteed that taking
To the smooth densification of film layer.
Invention content
The purpose of the present invention is to provide a kind of methods of heat treatment seed layer to prepare MFI-type molecular screen membrane.
To achieve the above object, the present invention provides the following technical solutions：MFI type is prepared using the method for heat treatment seed layer
The processing step of molecular screen membrane is as follows：
Step 1: the MFI molecular sieve seed layers of b axis orientation are coated on supporter using manual self-assembly method；
Step 2: the supporter that step 1 is coated to b axis MFI molecular sieve seed layers is placed in baking oven, handled under certain temperature
Certain time；
Step 3: preparing the Synthesis liquid of diauxic growth：By tetrapropylammonium hydroxide:Tetraethoxysilane:Water is according to 0.2:1:
2000 molar ratio is fitted into after ageing in synthesis reactor, places into the seed layer after heat treatment, and Synthesis liquid submerges supporter,
It is synthesized 4 hours at 150 DEG C after synthesis reactor sealing, the b axis for obtaining the smooth densification of height after washing and drying on supporter is orientated
Property MFI-type molecular screen membrane.
Preferably, the supporter in the step 1 includes but not limited to stainless steel substrates, sheet glass, silicon chip and quartz
Piece.
Preferably, the treatment temperature in the step 2 is 90 DEG C -200 DEG C.
Preferably, the processing time in the step 2 is -10 hours 0.5 hour.
Compared with prior art, beneficial effects of the present invention are as follows：Heat treatment seed layer of the present invention is to prepare height
The method for spending the orientation MFI molecular screen membranes of smooth densification strengthens active force between supporter and seed layer, processing method
It is simple and efficient.The MFI-type molecular screen membrane that can see synthesis from scanning electron microscope diagram piece and X ray diffracting spectrum is heightbAxis is orientated, and film layer is smooth and fine and close.
Description of the drawings
Fig. 1 is the scanning electron microscope diagram of oriented seed crystal layer prepared by embodiment 1；
Fig. 2 is the X-ray diffraction spectrogram of oriented seed crystal layer prepared by embodiment 1；
Fig. 3 is the scanning electron microscope diagram for the molecular screen membrane that embodiment 1 synthesizes；
Fig. 4 is the X-ray diffraction spectrogram for the molecular screen membrane that embodiment 1 synthesizes；
Fig. 5 is the scanning electron microscope diagram of the orientation molecular sieve membrane for the smooth densification that embodiment 1 synthesizes；
Fig. 6 is the X-ray diffraction spectrogram of the orientation molecular sieve membrane for the smooth densification that embodiment 1 synthesizes；
Fig. 7 is the scanning electron microscope diagram of the orientation molecular sieve membrane for the smooth densification that embodiment 2 synthesizes；
Fig. 8 is the scanning electron microscope diagram of the orientation molecular sieve membrane for the smooth densification that embodiment 4 synthesizes.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
Self-assembly method is by MFI-type molecular sieve crystal seed powder by hand（About 1 micron of size）It is coated to sheet glass supporting body surface, i.e.,
It is carriedbThe sheet glass of axis oriented seed crystal layer, the scanning electron microscope diagram piece of the seed layer is as shown in Figure 1, X-ray diffraction
Collection of illustrative plates is as shown in Figure 2.Above-mentioned crystal seed is placed in baking oven, processing 3 hours under 150 degree.It is tetrapropyl hydrogen by molar ratio
Amine-oxides:Tetraethoxysilane:Water=0.2:1:It is fitted into synthesis reactor, is placed into not through overheat after 2000 Synthesis liquid ageing
Processing and the seed layer after Overheating Treatment, Synthesis liquid submerge supporter, are synthesized 4 hours in 150 DEG C after synthesis reactor sealing, washing
MFI-type molecular screen membrane is obtained after drying on supporter.The MFI film surfaces not obtained after the growth of the seed layer of Overheating Treatment
Planarization and compactness are poor, and scanning electron microscope diagram piece is as shown in figure 3, X ray diffracting spectrum is as shown in Figure 4；Through overheat
The smooth densification of MFI film surfaces obtained after the seed layer growth of processing, scanning electron microscope diagram piece is as shown in figure 5, X-ray is spread out
It is as shown in Figure 6 to penetrate collection of illustrative plates.
Embodiment 2
The preparation method is the same as that of Example 1 for seed layer, and supporter is stainless steel substrates.Above-mentioned crystal seed is placed in baking oven, under 180 degree
Processing 1 hour.It is tetrapropylammonium hydroxide by molar ratio:Tetraethoxysilane:Water=0.2:1:After 2000 Synthesis liquid ageing
It is fitted into synthesis reactor, places into the seed layer after Overheating Treatment, Synthesis liquid submerges supporter, in 150 DEG C after synthesis reactor sealing
Synthesis 4 hours, obtains the MFI-type molecular screen membrane of smooth densification, scanning electron microscope diagram piece on supporter after washing and drying
As shown in Figure 7.
Embodiment 3
The preparation method is the same as that of Example 1 for seed layer, and supporter is stainless steel substrates.Above-mentioned crystal seed is placed in baking oven, under 120 degree
Processing 8 hours.It is tetrapropylammonium hydroxide by molar ratio:Tetraethoxysilane:Water=0.2:1:After 2000 Synthesis liquid ageing
It is fitted into synthesis reactor, places into the seed layer after Overheating Treatment, Synthesis liquid submerges supporter, in 150 DEG C after synthesis reactor sealing
Synthesis 4 hours, obtains the MFI-type molecular screen membrane of smooth densification on supporter after washing and drying.
Embodiment 4
The preparation method is the same as that of Example 1 for seed layer, and supporter is silicon chip and quartz plate.Above-mentioned crystal seed is placed in baking oven, in 120
The lower processing of degree 1 hour.It is tetrapropylammonium hydroxide by molar ratio:Tetraethoxysilane:Water=0.2:1:2000 Synthesis liquid is old
Be fitted into synthesis reactor after change, place into the seed layer after Overheating Treatment, Synthesis liquid submerges supporter, after synthesis reactor sealing in
150 DEG C synthesize 4 hours, obtain the MFI-type molecular screen membrane of smooth densification after washing and drying on supporter.Film layer sweeps on silicon chip
It is as shown in Figure 8 to retouch electron microscope picture.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (4)
1. the technique for preparing MFI-type molecular screen membrane using the method for heat treatment seed layer, it is characterised in that：Specific processing step
It is as follows：
Step 1: the MFI molecular sieve seed layers of b axis orientation are coated on supporter using manual self-assembly method；
Step 2: the supporter that step 1 is coated to b axis MFI molecular sieve seed layers is placed in baking oven, handled under certain temperature
Certain time；
Step 3: preparing the Synthesis liquid of diauxic growth：By tetrapropylammonium hydroxide:Tetraethoxysilane:Water is according to 0.2:1:
2000 molar ratio is fitted into after ageing in synthesis reactor, places into the seed layer after heat treatment, and Synthesis liquid submerges supporter,
It is synthesized 4 hours at 150 DEG C after synthesis reactor sealing, the b axis for obtaining the smooth densification of height after washing and drying on supporter is orientated
Property MFI-type molecular screen membrane.
2. the method according to claim 1 using heat treatment seed layer prepares the technique of MFI-type molecular screen membrane, feature
It is：Supporter in the step 1 includes but not limited to stainless steel substrates, sheet glass, silicon chip and quartz plate.
3. the method according to claim 1 using heat treatment seed layer prepares the technique of MFI-type molecular screen membrane, feature
It is：Treatment temperature in the step 2 is 90 DEG C -200 DEG C.
4. the method according to claim 1 using heat treatment seed layer prepares the technique of MFI-type molecular screen membrane, feature
It is：Processing time in the step 2 is -10 hours 0.5 hour.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| US7476635B2 (en) * | 2002-06-03 | 2009-01-13 | Institut Francais Du Petrole | Process for making supported thin zeolite membrane |
| US20100071559A1 (en) * | 2008-09-19 | 2010-03-25 | Sylvain Miachon | Membranes and devices for gas separation |
| CN102126731A (en) * | 2011-01-31 | 2011-07-20 | 浙江大学 | Method for synthesizing highly-oriented MFI (Melt Flow Index) molecular sieve membrane through controlled secondary growth of twin crystal |
| CN102583425A (en) * | 2012-03-01 | 2012-07-18 | 浙江大学 | Synthetic method of MFI (Mechanical Fuel Injection) type molecular sieve membrane |
| JP2015150527A (en) * | 2014-02-17 | 2015-08-24 | 東ソー株式会社 | Zeolite membrane for amine compound separation, method of producing the same and separation method |
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2018
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US7476635B2 (en) * | 2002-06-03 | 2009-01-13 | Institut Francais Du Petrole | Process for making supported thin zeolite membrane |
| US20100071559A1 (en) * | 2008-09-19 | 2010-03-25 | Sylvain Miachon | Membranes and devices for gas separation |
| CN102126731A (en) * | 2011-01-31 | 2011-07-20 | 浙江大学 | Method for synthesizing highly-oriented MFI (Melt Flow Index) molecular sieve membrane through controlled secondary growth of twin crystal |
| CN102583425A (en) * | 2012-03-01 | 2012-07-18 | 浙江大学 | Synthetic method of MFI (Mechanical Fuel Injection) type molecular sieve membrane |
| JP2015150527A (en) * | 2014-02-17 | 2015-08-24 | 東ソー株式会社 | Zeolite membrane for amine compound separation, method of producing the same and separation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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