CN107601524A - A kind of synthetic method of the MFI molecular sieves of the microporous mesoporous structure containing aluminium - Google Patents
A kind of synthetic method of the MFI molecular sieves of the microporous mesoporous structure containing aluminium Download PDFInfo
- Publication number
- CN107601524A CN107601524A CN201711065281.9A CN201711065281A CN107601524A CN 107601524 A CN107601524 A CN 107601524A CN 201711065281 A CN201711065281 A CN 201711065281A CN 107601524 A CN107601524 A CN 107601524A
- Authority
- CN
- China
- Prior art keywords
- molecular sieves
- micropore
- containing aluminium
- synthetic method
- crystallization
- 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.)
- Pending
Links
Abstract
The present invention provides the synthetic method of the MFI molecular sieves of the microporous mesoporous structure containing aluminium, comprises the following steps：Silicon source, organic formwork agent, alkali source, ammonium salt, hard mould agent are weighed respectively, is put in successively in mortar, grinds 10~13min, obtain mixed-powder；The mixed-powder of acquisition is weighed, and deionized water is added according to weight, obtains gelatinous mixture；Gained gel is transferred to reactor, after 160 DEG C are heated 24h, 180 DEG C of heating 48h, last 160 DEG C of heating 2h, carries out crystallization；Treat that crystallization is completed, molecular sieve powder is put in after Muffle furnace Program is warming up to 550 DEG C of calcining 5h and obtains final zeolite product；Wherein silicon source needed for crystallization is with Al2O3Meter, alkali source is with Na2O is counted, and ammonium salt is with NH4 +Meter, crystallization material molar ratio are：Al2O3：Na2O：NH4 +：Organic template agent：Deionized water=1：0.48：1.1：0.8~1.1：8~10；The mass ratio of silicon source and hard template agent is 1：0.01；Molecular sieve crystallinity is high obtained by this law, and crystal formation is complete, and impurity is few.
Description
Technical field
The present invention relates to a kind of synthetic method of the MFI molecular sieves of micropore-mesopore structure containing aluminium.
Background technology
20th century the late sixties, Mobile oil companies of the U.S. have synthesized Microporous zeolite ZSM-5 molecular sieve.The zeolite
There is molecular sieve special 3-dimensional to intersect ten-ring duct, hydrothermal stability is high, good acid resistance, excellent selective activization
The advantages that, cause ZSM-5 molecular sieve to be widely used in petrochemical industry, field of fine chemical.But because its is less than one
Nanometer micropore aperture significantly limit the size of guest molecule and the diffusion velocity in duct.Therefore, it is mesoporous by introducing
Even macropore turns into current study hotspot to improve the accessibility of the permeability in duct and acid site.
The multi-stage porous forming method of molecular sieve is broadly divided into following a few classes：Soft template method, hard template method, post treatment method etc..
And hard template method is due to simple to operate, the features such as template is easy to get, has extensive scale to be combined to prospect.Jacobsen etc.
[J.Am.Chem.Soc., 2000,122,7116-7117, Chem.Mater. 2001,13,4416-4418] by
Carbon nano-particle is added in the crystallization process of ZSM-5 molecular sieve or CNT have successfully been obtained with transgranular as hard template
Mesoporous zeolite monocrystalline.Xiao Fengshou etc. [CN100439246C] uses rice husk, basicity styrene series ion exchange resin or mesoporous
Carbon etc. obtains mesoporous even macropore as hard mould agent.Chen Lihua etc. [CN106276957A, CN106283187A] uses
The compound of polymer microballoon, silica nanosphere and sucrose carbonized product prepares tool as macropore and mesoporous hard template
There are opal structural multi-stage porous Silicalite-1 and ZSM-5 molecular sieve, the PFI molecular sieve crystallinities of above method synthesis are low,
Poor crystal form, and impurity content is high, therefore, needs a kind of crystallinity height badly, crystal formation is good, the low knot of micropore-mesopore containing aluminium of impurity content
The synthetic method of the MFI molecular sieves of structure.
The content of the invention
It is an object of the invention to provide a kind of synthetic method of the MFI molecular sieves of micropore-mesopore structure containing aluminium.
A kind of synthetic method of the MFI molecular sieves of micropore-mesopore structure containing aluminium, comprises the following steps：
（1）A certain amount of silicon source, organic formwork agent, alkali source, ammonium salt, hard mould agent are weighed respectively, is put in successively in mortar, are ground
10~13min, obtain mixed-powder；
（2）The mixed-powder of acquisition is weighed, and adds deionized water according to weight or is put under infrared lamp and toast, is obtained
Gelatinous mixture；
（3）Gained gel is transferred to reactor, after 160 DEG C are heated 24h, 180 DEG C of heating 48h, last 160 DEG C of heating 2h,
Carry out crystallization；
（4）Treat that crystallization is completed, reactor is cooled to room temperature, open kettle and take out solid crystallized product and washed, in
Dried in 50 DEG C of baking ovens, obtain molecular sieve powder；
（5）Molecular sieve powder is put in after Muffle furnace Program is warming up to 550 DEG C of calcining 5h and obtains final zeolite product；
Wherein silicon source needed for crystallization is with Al2O3Meter, alkali source is with Na2O is counted, and ammonium salt is with NH4 +Meter, crystallization material molar ratio
For：Al2O3：Na2O：NH4 +：Organic template agent：Deionized water=1：0.48：1.1：0.8~1.1：8~10；Silicon source and hard template agent
Mass ratio be 1：0.01.
Preferably, silicon source is one kind in aluminum sulfate octadecahydrate, sodium aluminate.
Preferably, organic formwork agent is TPAOH, one kind of tetraethyl ammonium hydroxide.
While TPAOH, tetraethyl ammonium hydroxide are as organic template agent, in alkalescence, suppress the water of ammonium salt
Solution.
Preferably, alkali source is sodium hydroxide.
Preferably, ammonium salt is ammonium chloride.
Preferably, hard mould agent is stalk powder.
Beneficial effect：
A kind of synthetic method of the MFI molecular sieves of micropore-mesopore structure containing aluminium provided by the invention, reaction temperature is using special
Thermograde, attached gel solid-phase synthesis, the MFI molecular sieves of the micropore-mesopore structure containing aluminium of synthesis have crystallinity height, brilliant
Type is good, and impurity content is low.
Brief description of the drawings
Fig. 1 is the XRD spectra of the MFI molecular sieves of the micropore-mesopore structure containing aluminium in embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of the MFI molecular sieves of the micropore-mesopore structure containing aluminium in embodiment 1.
Fig. 3 is the XRD spectra of the MFI molecular sieves of the micropore-mesopore structure containing aluminium in embodiment 2.
Fig. 4 is the scanning electron microscope (SEM) photograph of the MFI molecular sieves of the micropore-mesopore structure containing aluminium in embodiment 2.
Fig. 5 is the XRD spectra of the MFI molecular sieves of the micropore-mesopore structure containing aluminium in embodiment 3.
Fig. 6 is the scanning electron microscope (SEM) photograph of the MFI molecular sieves of the micropore-mesopore structure containing aluminium in embodiment 3.
Embodiment
Embodiment 1
The present embodiment provides a kind of synthetic method of the MFI molecular sieves of the micropore-mesopore structure containing aluminium, comprises the following steps：
（1）Aluminum sulfate octadecahydrate 666.17g, sodium hydroxide 38.4g, ammonium chloride 58.84g, TPAOH are weighed respectively
162.69g, stalk powder 6.66g are put in mortar successively, grind 10~13min, obtain mixed-powder；
（2）Deionized water 144g is added into mixed-powder, obtains gelatinous mixture；
（3）Gained gel is transferred to reactor, after 160 DEG C are heated 24h, 180 DEG C of heating 48h, last 160 DEG C of heating 2h,
Carry out crystallization；
（4）Treat that crystallization is completed, reactor is cooled to room temperature, open kettle and take out solid crystallized product and washed, in
Dried in 50 DEG C of baking ovens, obtain molecular sieve powder；
（5）Molecular sieve powder is put in after Muffle furnace Program is warming up to 550 DEG C of calcining 5h and obtains final zeolite product；
Fig. 1 is that the XRD of the MFI molecular sieves of the present embodiment micropore-mesopore structure containing aluminium characterizes spectrogram, and what is produced under this method contains aluminium
The MFI molecular sieves of micropore-mesopore structure have typical MFI structure characteristic peak, and impurity peaks are few, and crystallinity is high.
Fig. 2 is the scanning electron microscope (SEM) photograph of the MFI molecular sieves of the present embodiment micropore-mesopore structure containing aluminium, and crystal formation is good.
Embodiment 2
The present embodiment provides a kind of synthetic method of the MFI molecular sieves of the micropore-mesopore structure containing aluminium, comprises the following steps：
（1）Sodium aluminate 163.94g, sodium hydroxide 38.4g, ammonium chloride 58.84g, tetraethyl ammonium hydroxide are weighed respectively
162.03g, stalk powder 1.64g are put in mortar successively, grind 10~13min, obtain mixed-powder；
（2）Deionized water 180g is added into mixed-powder, obtains gelatinous mixture；
（3）Gained gel is transferred to reactor, after 160 DEG C are heated 24h, 180 DEG C of heating 48h, last 160 DEG C of heating 2h,
Carry out crystallization；
（4）Treat that crystallization is completed, reactor is cooled to room temperature, open kettle and take out solid crystallized product and washed, in
Dried in 50 DEG C of baking ovens, obtain molecular sieve powder；
（5）Molecular sieve powder is put in after Muffle furnace Program is warming up to 550 DEG C of calcining 5h and obtains final zeolite product；
Fig. 3 is that the XRD of the MFI molecular sieves of the present embodiment micropore-mesopore structure containing aluminium characterizes spectrogram, and what is produced under this method contains aluminium
The MFI molecular sieves of micropore-mesopore structure have typical MFI structure characteristic peak, and impurity peaks are few, and crystallinity is high.
Fig. 4 is the scanning electron microscope (SEM) photograph of the MFI molecular sieves of the present embodiment micropore-mesopore structure containing aluminium, and crystal formation is good.
Embodiment 3
The present embodiment provides a kind of synthetic method of the MFI molecular sieves of the micropore-mesopore structure containing aluminium, comprises the following steps：
（1）Sodium aluminate 163.94g, sodium hydroxide 38.4g, ammonium chloride 58.84g, tetraethyl ammonium hydroxide are weighed respectively
139.94g, stalk powder 1.64g are put in mortar successively, grind 10~13min, obtain mixed-powder；
（2）Deionized water 162g is added into mixed-powder, obtains gelatinous mixture；
（3）Gained gel is transferred to reactor, after 160 DEG C are heated 24h, 180 DEG C of heating 48h, last 160 DEG C of heating 2h,
Carry out crystallization；
（4）Treat that crystallization is completed, reactor is cooled to room temperature, open kettle and take out solid crystallized product and washed, in
Dried in 50 DEG C of baking ovens, obtain molecular sieve powder；
（5）Molecular sieve powder is put in after Muffle furnace Program is warming up to 550 DEG C of calcining 5h and obtains final zeolite product；
Fig. 3 is that the XRD of the MFI molecular sieves of the present embodiment micropore-mesopore structure containing aluminium characterizes spectrogram, and what is produced under this method contains aluminium
The MFI molecular sieves of micropore-mesopore structure have typical MFI structure characteristic peak, and impurity peaks are few, and crystallinity is high.
Fig. 4 is the scanning electron microscope (SEM) photograph of the MFI molecular sieves of the present embodiment micropore-mesopore structure containing aluminium, and crystal formation is good.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of changes, modification can be carried out to these embodiments, replace without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (6)
1. a kind of synthetic method of the MFI molecular sieves of micropore-mesopore structure containing aluminium, comprises the following steps：
（1）A certain amount of silicon source, organic formwork agent, alkali source, ammonium salt, hard mould agent are weighed respectively, is put in successively in mortar, are ground
10~13min, obtain mixed-powder；
（2）The mixed-powder of acquisition is weighed, and adds deionized water according to weight or is put under infrared lamp and toast, is obtained
Gelatinous mixture；
（3）Gained gel is transferred to reactor, after 160 DEG C are heated 24h, 180 DEG C of heating 48h, last 160 DEG C of heating 2h,
Carry out crystallization；
（4）Treat that crystallization is completed, reactor is cooled to room temperature, open kettle and take out solid crystallized product and washed, in
Dried in 50 DEG C of baking ovens, obtain molecular sieve powder；
（5）Molecular sieve powder is put in after Muffle furnace Program is warming up to 550 DEG C of calcining 5h and obtains final zeolite product；
Wherein silicon source needed for crystallization is with Al2O3Meter, alkali source is with Na2O is counted, and ammonium salt is with NH4 +Meter, crystallization material molar ratio
For：Al2O3：Na2O：NH4 +：Organic template agent：Deionized water=1：0.48：1.1：0.8~1.1：8~10；Silicon source and hard template agent
Mass ratio be 1：0.01.
2. the synthetic method of the MFI molecular sieves of the micropore-mesopore structure according to claim 1 containing aluminium, it is characterised in that：Aluminium
Source is one kind in aluminum sulfate octadecahydrate, sodium aluminate.
3. the synthetic method of the MFI molecular sieves of the micropore-mesopore structure according to claim 1 containing aluminium, it is characterised in that：Have
Machine template is TPAOH, one kind of tetraethyl ammonium hydroxide.
4. the synthetic method of the MFI molecular sieves of the micropore-mesopore structure according to claim 1 containing aluminium, it is characterised in that：Alkali
Source is sodium hydroxide.
5. the synthetic method of the MFI molecular sieves of the micropore-mesopore structure according to claim 1 containing aluminium, it is characterised in that：Ammonium
Salt is ammonium chloride.
6. the synthetic method of the MFI molecular sieves of the micropore-mesopore structure according to claim 1 containing aluminium, it is characterised in that：Firmly
Template is stalk powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711065281.9A CN107601524A (en) | 2017-11-02 | 2017-11-02 | A kind of synthetic method of the MFI molecular sieves of the microporous mesoporous structure containing aluminium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711065281.9A CN107601524A (en) | 2017-11-02 | 2017-11-02 | A kind of synthetic method of the MFI molecular sieves of the microporous mesoporous structure containing aluminium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107601524A true CN107601524A (en) | 2018-01-19 |
Family
ID=61084495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711065281.9A Pending CN107601524A (en) | 2017-11-02 | 2017-11-02 | A kind of synthetic method of the MFI molecular sieves of the microporous mesoporous structure containing aluminium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107601524A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112573533A (en) * | 2020-12-25 | 2021-03-30 | 华中科技大学 | Method for preparing zeolite by directionally regulating and controlling biomass ash and application thereof |
-
2017
- 2017-11-02 CN CN201711065281.9A patent/CN107601524A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112573533A (en) * | 2020-12-25 | 2021-03-30 | 华中科技大学 | Method for preparing zeolite by directionally regulating and controlling biomass ash and application thereof |
| CN112573533B (en) * | 2020-12-25 | 2022-08-02 | 华中科技大学 | Method for preparing zeolite by directionally regulating and controlling biomass ash and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6034224B2 (en) | Beta-type zeolite and method for producing the same | |
| CN107640776B (en) | Preparation method of MFI molecular sieve with micro-mesoporous structure | |
| Guangyu et al. | Synthesis of SAPO-34 molecular sieves templated with diethylamine and their properties compared with other templates | |
| TWI544961B (en) | Hierarchically porous zeolites | |
| CN103601211B (en) | Synthesis method of molecular sieve SSZ-13 | |
| WO2016086362A1 (en) | Method for synthesizing multilevel pore zsm-5 zeolite | |
| TWI490167B (en) | Method of preparing zsm-5 zeolite using nanocrystalline zsm-5 seeds | |
| CN104030314B (en) | A kind of ZSM-5 Quito level porous molecular sieve material and preparation method thereof | |
| JP5960911B2 (en) | Method for preparing high silica LEV-type zeolite | |
| WO2015024380A1 (en) | Beta molecular sieve having mesoporous/microporous combined channel structure, and synthesizing method thereof | |
| CN109850906B (en) | Method for preparing hierarchical pore molecular sieve with nanoparticle close-packed structure by adopting silicon dioxide nano colloidal crystal solid phase conversion method | |
| WO2018205841A1 (en) | Method for preparing mesoporous nay-type zeolite molecular sieve | |
| CN107572548A (en) | A kind of method for the MFI molecular sieves for synthesizing the microporous mesoporous structure of pure silicon | |
| CN106185972A (en) | The preparation method of micro-meso-hole structure Beta molecular sieve | |
| CN106517239B (en) | A kind of pillared layered modenite and preparation method thereof | |
| CN107601524A (en) | A kind of synthetic method of the MFI molecular sieves of the microporous mesoporous structure containing aluminium | |
| CN113603110A (en) | Template-free preparation method of porous LSX zeolite molecular sieve | |
| JP6100361B2 (en) | Molecular sieve SSZ-87 and its synthesis | |
| CN112723380A (en) | Method for preparing hierarchical pore SAPO-20 molecular sieve from illite | |
| CN102515194B (en) | Method for directly synthesizing multi-stage ordered mesoporous molecular sieve | |
| CN105347358B (en) | A kind of preparation method that there is three-dimensional through the zeolite molecular sieve material of mesoporous multi-stage artery structure | |
| JP2018062450A (en) | Kfi zeolite and method for producing the same | |
| CN110407229B (en) | Method for synthesizing CHA structure molecular sieve and CHA structure molecular sieve | |
| CN108117089A (en) | A kind of chabazite molecular sieve and its application | |
| CN107973316B (en) | Preparation method of hierarchical pore mordenite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180119 |