CN106006662B - The preparation method of multi-stage porous channel type molecular screen membrane - Google Patents
The preparation method of multi-stage porous channel type molecular screen membrane Download PDFInfo
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- CN106006662B CN106006662B CN201610330512.3A CN201610330512A CN106006662B CN 106006662 B CN106006662 B CN 106006662B CN 201610330512 A CN201610330512 A CN 201610330512A CN 106006662 B CN106006662 B CN 106006662B
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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
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
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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
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/087—Ferrosilicates
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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
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The present invention provides a kind of preparation method of multi-stage porous channel type molecular screen membrane.By carrying out alkali process to molecular screen membrane, so as to obtain microporous mesoporous/macroporous type multistage pore canal.Alkali process is that the corrosion of certain time is carried out to molecular screen membrane using containing molecular sieve, inorganic base or organic ammonium alkali and water mixed system, i.e. molecular sieve alkaline suspension liquid at a certain temperature.The crystal formation of molecular sieve and molecular screen membrane matches in molecular sieve alkaline suspension liquid.Gained multi-stage porous channel type molecular screen membrane of the invention has bigger gas permeation flux compared with traditional microporous molecular sieve membrane.In addition, the alkali process in the present invention can also form to molecular screen membrane element.This method process is simple, efficiently, has good repeatability and a high success rate, the chemical processes such as prepared multi-stage porous channel type molecular screen membrane is suitable for being catalyzed, separated.
Description
Technical field
The present invention relates to the preparation field of zeolite membrane material, specifically, is related to the system of multi-stage porous channel type molecular screen membrane
Preparation Method.
Background technology
Molecular screen membrane is a kind of Novel inorganic membrane developed in recent years.Molecular screen membrane is except with general inoranic membrane
Outside characteristic, the cation also with aperture in small and homogeneous, molecular sieve crystal can be by other ion exchanges (such as Ti, Fe), Si/
The characteristics such as Al is than can adjust, Si or Al atoms can be substituted by other hetero atoms.Wherein, the important prerequisite of molecular screen membrane application is it
With good compactness, to ensure its excellent properties.On the basis of compactness molecular screen membrane is obtained, molecular screen membrane is improved
Permeation flux be further lifting to molecular screen membrane performance.
The method for being presently used for improving molecular sieve film pervasion flux mainly reduces molecular sieve thickness.For example, by specific
Nanosized seeds layer guiding growth, can obtain thickness be less than 100nm molecular sieve film layer.But the less molecular screen membrane of thickness can
Can be cracked in follow-up heat treatment process, so as to influence the compactness of molecular screen membrane.Be worth using for reference is more in recent years
The preparation experience of level duct type molecular sieve.This multi-stage porous channel type molecular sieve has the multistage pore canal of micropore-mesopore, its intermediary hole
Be advantageous to improve the mass transfer flux in molecular sieve.
On the other hand, proposing that new preparation method is controlled by molecular screen membrane space structure, this leads to improving molecular screen membrane
Amount has great importance, and may advantageously facilitate the exploitation and application of zeolite membrane material.
The content of the invention
The present invention is directed to deficiency of the prior art, in order to obtain high-throughout molecular screen membrane, there is provided multi-stage porous channel type
The preparation method of molecular screen membrane, it can make that there is substantial amounts of mesopore/macropore in obtained molecular sieve film layer, itself and traditional list
One pore type molecular screen membrane is compared, and has more excellent permeation flux.
The technical scheme is that molecular screen membrane is carried out using the alkaline suspension liquid containing a certain amount of matching molecular sieve
The corrosion of certain time.Comprise the following steps that：
(1) alkaline suspension liquid containing molecular sieve is prepared：
Inorganic base or organic ammonium alkali are configured to the aqueous solution, sieve particle is added and obtains molecular sieve-alkaline suspension liquid；
(2) corrosion molecular screen membrane：
Molecular screen membrane is lain in a horizontal plane on support, the molecular sieve obtained with step (1)-alkaline suspension liquid submergence, film surface
Downwards, it is placed in the stainless steel crystallizing kettle of polytetrafluoroethyllining lining, stainless steel crystallizing kettle is placed in insulating box, temperature programming is extremely
120-170 DEG C, constant temperature corrosion 16-48h；Molecular screen membrane is taken out after corrosion, is washed with deionized water to neutrality, dries, i.e., much
Level duct type molecular screen membrane.
Molecular sieve, alkali, the mass ratio of water are in molecular sieve-alkaline suspension liquid described in step (1)：0.1-0.5：0.5-
1.0：10.0-15.0.
Alkali inorganic base or organic ammonium alkali described in step (1) in molecular sieve-alkaline suspension liquid, it is preferred that alkali is hydrogen
Sodium oxide molybdena or TPAOH.
Sieve particle used in molecular sieve-alkaline suspension liquid and molecular screen membrane crystal formation phase during alkali process in step (1)
Matching.
The preparation method of above-mentioned multi-stage porous channel type molecular screen membrane, in second step, the same patent of preparation method of molecular screen membrane
CN201310411136.7 or CN201510121411.0.
The above method can obtained molecular screen membrane type be MFI, beta type molecular screen membrane, but be not limited to this crystalline substance
Body structure type, it is particularly applicable to a variety of molecular screen membranes with pure silicon structure.
The present invention has the advantages that：
1st, preparation method of the invention utilizes the mode of alkali process, forms multi-stage porous channel type molecular screen membrane, has good
Permeation flux.2nd, preparation method of the invention utilizes the mode of alkali process, can regulate and control element in original molecular screen membrane and form, gained
To multi-stage porous channel type molecular screen membrane, there is lower aluminium content, so that the superficial layer of molecular screen membrane has pure silicon property, have
Excellent hydrophobic performance.3rd, the present invention, which prepares compactness molecular screen membrane, has success rate repeatable and very high well, fits
In industrialization amplification application.
Brief description of the drawings
Accompanying drawing 1 is the SEM front elevations of the gained multi-stage porous channel type TS-1 molecular screen membranes of embodiment 1；
Accompanying drawing 2 is the SEM sectional drawings of the gained multi-stage porous channel type TS-1 molecular screen membranes of embodiment 1；
Accompanying drawing 3 is the XRD spectra of the gained multi-stage porous channel type TS-1 molecular screen membranes of embodiment 1；
Accompanying drawing 4 is the surface SEM figures of the gained TS-1 molecular screen membranes of comparative example 1；
Accompanying drawing 5 is the section SEM figures of the gained TS-1 molecular screen membranes of comparative example 1；
Embodiment
The embodiment of the present invention is as follows：
Embodiment 1：The preparation of MFI type HTS (TS-1) type molecular screen membrane
(1) alkaline suspension liquid containing molecular sieve is prepared：
0.15g TS-1 molecular sieves are scattered in 0.75g TPAOH (TPAOH, 25wt.%) and 11.25g surpasses
In the mixed liquor of pure water, ultrasonic 30min, molecular sieve-alkaline suspension liquid is made；
(2) corrosion molecular screen membrane：
The TS-1 molecular screen membranes prepared are placed horizontally on support, the molecular sieve obtained with step (1)-alkalescence suspends
Liquid submerges, and film surface is downward, is placed in the stainless steel crystallizing kettle of polytetrafluoroethyllining lining, and stainless steel crystallizing kettle is placed in into insulating box
In, temperature programming is to 160 DEG C, constant temperature corrosion 48h；TS-1 molecular screen membranes are taken out after corrosion, are washed with deionized water to neutrality, are done
It is dry, produce multi-stage porous channel type molecular screen membrane.
Prepared by TS-1 molecular screen membranes to the above method and carries out repeated experiment, in triplicate, each 10 films of batch are made
Standby film has same compactness hierarchical porous structure.EDX elementary analyses show before alkali process Ti in TS-1 molecular screen membranes:Al:
Si mol ratio=1.01:2.45:100, Ti in TS-1 molecular screen membranes after alkali process:Al:Si mol ratio=2.21:0.72:100,
Illustrate that element forms in alkali process energy regulatory molecule sieve membrane.
He gas one-component permeability test shows under 0.1MPa：TS-1 molecular sieve film pervasions flux is 0.3 × 10 before alkali process- 7mol/(m2SPa), TS-1 molecular sieve film pervasions flux is 1.7 × 10 after alkali process-7mol/(m2SPa), alkali is illustrated
Gained multi-stage porous channel type molecular screen membrane has bigger mass transfer flux after processing.
Comparative example 1：
Preparation method same as Example 1, difference are the ratio of molecular sieve-alkaline suspension liquid.In the first step,
1.0g TS-1 molecular sieves are scattered in the mixed liquor of 0.75g TPAOH and 11.25g ultra-pure waters, ultrasonic 30min, molecule is made
Sieve-alkaline suspension liquid.TS-1 molecular screen membranes do not possess hierarchical porous structure after alkali process, referring to accompanying drawing 4 and accompanying drawing 5.
Comparative example 2：
The preparation method same as Example 1 of this comparative example 1, difference are the proportioning of molecular sieve-alkaline suspension liquid.
In the first step, not using the TS-1 molecular sieves to match, only by the mixed liquor of 0.75g TPAOH and 11.25g ultra-pure waters, obtain
To alkali lye.TS-1 molecular screen membranes disappear after XRD and EDX elementary analyses show alkali process.
Embodiment 2：
Specific steps are with embodiment 1, the difference is that the molecular screen membrane used is type ZSM 5 molecular sieve film.This example uses
The method of alkali process corrosion obtains multi-stage porous channel type ZSM-5 molecular sieve film.
(1) alkaline suspension liquid containing molecular sieve is prepared：
0.15g ZSM-5 molecular sieves are scattered in 0.75g TPAOH (TPAOH, 25wt.%) and 10g is ultrapure
In the mixed liquor of water, ultrasonic 30min, molecular sieve-alkaline suspension liquid is made；
(2) corrosion molecular screen membrane：
The ZSM-5 molecular sieve film prepared is placed horizontally on support, the molecular sieve-alkalescence obtained with step (1) is outstanding
Supernatant liquid submerges, and film surface is downward, is placed in the stainless steel crystallizing kettle of polytetrafluoroethyllining lining, and stainless steel crystallizing kettle is placed in into insulating box
In, temperature programming is to 140 DEG C, constant temperature corrosion 48h；ZSM-5 molecular sieve film is taken out after corrosion, is washed with deionized water to neutrality,
Dry, produce multi-stage porous channel type molecular screen membrane.
ZSM-5 molecular sieve film is prepared to the above method and carries out repeated experiment, in triplicate, each 10 films of batch, institute
The film of preparation has same compactness hierarchical porous structure.
Embodiment 3：
Specific steps are with embodiment 2, the difference is that the alkali in molecular sieve-alkaline suspension liquid is sodium hydroxide.Step (1),
Prepare the alkaline suspension liquid containing molecular sieve：0.50g ZSM-5 molecular sieves are scattered in 1.00g NaOH and 15.00g ultra-pure waters
In mixed liquor, ultrasonic 30min, molecular sieve-alkaline suspension liquid is made.Corrosion temperature is 120 DEG C in step (2), and processing time is
24h。
Embodiment 4：
Specific steps are with embodiment 1, the difference is that the molecular screen membrane used is beta type molecular screen membrane.It is molten using alkali process
The method of erosion obtains multi-stage porous channel type beta molecular screen membranes.
(1) alkaline suspension liquid containing molecular sieve is prepared：
0.10g beta molecular sieves are scattered in 0.70g TEAOH (tetraethyl ammonium hydroxide, 25wt.%) and 12.00g surpasses
In the mixed liquor of pure water, ultrasonic 30min, molecular sieve-alkaline suspension liquid is made；
(2) corrosion molecular screen membrane：
The beta molecular screen membranes prepared are placed horizontally on support, the molecular sieve obtained with step (1)-alkalescence suspends
Liquid submerges, and film surface is downward, is placed in the stainless steel crystallizing kettle of polytetrafluoroethyllining lining, and stainless steel crystallizing kettle is placed in into insulating box
In, temperature programming is to 120 DEG C, constant temperature corrosion 48h；Beta molecular screen membranes are taken out after corrosion, are washed with deionized water to neutrality, are done
It is dry, produce multi-stage porous channel type molecular screen membrane.
Embodiment 5：
For specific steps with embodiment 1, the molecular screen membrane used is molten using alkali process for Fe-Silicalite molecular screen membranes
The method of erosion obtains multi-stage porous channel type Fe-Silicalite molecular screen membranes.
(1) alkaline suspension liquid containing molecular sieve is prepared：
By 0.50g Fe-Silicalite-1 molecular sieves be scattered in 1.00g TPAOH (TPAOH,
25wt.%) and in the mixed liquor of 15.00g ultra-pure waters, ultrasonic 30min, molecular sieve-alkaline suspension liquid is made.
(2) corrosion molecular screen membrane：
Corrosion molecular screen membrane is with the step of embodiment 1 (2), but corrosion temperature is 170 DEG C, processing time 16h.
It is described above, it is only the preferred embodiments of the present invention, not limits the present invention,
Any person skilled in the art is changed or is modified as equivalent variations possibly also with the technology contents of the disclosure above
Equivalent embodiment.But it is every without departing from the present invention program content, the technical spirit according to the present invention is done to above example
Any simple modification, equivalent variations and remodeling, still fall within protection scope of the present invention.
Claims (4)
1. the preparation method of multi-stage porous channel type molecular screen membrane, it is characterised in that alkali process is carried out to molecular screen membrane, so that molecule
Sieve membrane has the multistage pore canal of micropore-mesopore/macropore, comprises the following steps that：
(1) alkaline suspension liquid containing molecular sieve is prepared：
Inorganic base or organic ammonium alkali are configured to the aqueous solution, sieve particle is added and obtains molecular sieve-alkaline suspension liquid；Described point
Molecular sieve, alkali, the mass ratio of water are in sub- sieve-alkaline suspension liquid：0.1-0.5：0.5-1.0：10.0-15.0；The molecular sieve
Particle matches with molecular screen membrane crystal formation；
(2) corrosion molecular screen membrane：
Molecular screen membrane is lain in a horizontal plane on support, the molecular sieve obtained with step (1)-alkaline suspension liquid submergence, film surface is downward,
It is placed in the stainless steel crystallizing kettle of polytetrafluoroethyllining lining, stainless steel crystallizing kettle is placed in insulating box, temperature programming to 120-
170 DEG C, constant temperature corrosion 16-48h；Molecular screen membrane is taken out after corrosion, is washed with deionized water to neutrality, is dried, produce multi-stage porous
Channel type molecular screen membrane.
2. the preparation method of multi-stage porous channel type molecular screen membrane according to claim 1, it is characterised in that：The molecular sieve-
Alkali in alkaline suspension liquid is sodium hydroxide or TPAOH.
3. a kind of utilize requires the molecular screen membrane that the preparation method described in 1 is prepared, it is characterised in that the molecular screen membrane has
Multistage pore canal.
4. the preparation method of the multi-stage porous channel type molecular screen membrane described in claim 1 answering in regulatory molecule sieve membrane element composition
With.
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