CN107686119A - A kind of multi-stage porous Si-Al molecular sieve nano-cluster and preparation method thereof - Google Patents
A kind of multi-stage porous Si-Al molecular sieve nano-cluster and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of multi-stage porous Si-Al molecular sieve nano-cluster and preparation method thereof.The multi-stage porous Si-Al molecular sieve nano-cluster is made up of molecular sieve nano particle, and containing mesoporous micropore hierarchical porous structure, wherein mesoporous pore size is 20~30nm.The present invention use vapor auxiliary crystallization method, using the mesoporous multi-stage porous carbon material of ordered big hole as hard mould agent, by obtaining having micropore, mesoporous and big pore volume multistage pore canal Si-Al molecular sieve after the adjustment of molecular sieve mother liquor and hard template dosage, crystallization.Mesopore orbit is introduced into nano molecular sieve by the multi-stage porous Si-Al molecular sieve nano-cluster prepared by the present invention, make gained molecular sieve that there is the property different from conventional nano molecular sieve, both there is superior Acidity, there is the multistage pore passage structure being distributed in structure again, cooperative effect and special catalytic performance are shown in catalytic reaction, and the preparation method simple possible being related to, synthesis condition is easily controllable and the cycle is short, is adapted to popularization and application.
Description
Technical field
The present invention relates to Zeolite synthesis technical field, and in particular to a kind of multi-stage porous Si-Al molecular sieve nano-cluster and its system
Preparation Method.
Background technology
In recent years, zeolite molecular sieve is as solid acid catalyst, is widely used in petrochemical industry, petroleum cracking and organic big
The key areas such as molecule synthesis.But the micropore canals size of zeolite molecular sieve greatly limit guest molecule in the catalyst
Mass transfer performance so that macromolecular can not reach the avtive spot inside microporous molecular sieve, so as to cause carbon distribution in duct to be urged
Agent deactivation prob, and then limit its practical application, therefore the circulation diffusion for improving zeolite molecular sieve turns into and improves it
One of important channel of catalytic performance.
Relative to micro porous molecular sieve, because crystal grain is smaller, transmission path shortens nano molecular sieve, is advantageous to reactant and production
The diffusion of thing molecule, so as to effectively improve the circulation diffusion of catalyst material.In nano molecular sieve structure exist due to
Grain piles up the intracrystalline pore to be formed, while its outer surface acid site is more, acid stronger so that nano molecular sieve has higher anti-
Should activity.Above-mentioned more special physico-chemical property determines that nano molecular sieve is improving molecular sieve catalyst frequency of use, improved
Selectivity, improvement macromolecular conversion capability, reduction deep reaction degree etc. performance all show excellent performance.Therefore,
Molecular sieve of Nano zeolite is as a kind of new catalysis material, in terms of synthesis, modified, physical and chemical performance sign and its catalytic performance
Research receives much attention, and substantial amounts of synthesis strategy has been successfully applied to prepare nano molecular sieve at present.But in catalytic reaction
In system, agglomeration easily occurs for nano molecular sieve and its separation process is relative complex, thus greatly limit it and widely should
With.
The content of the invention
In order to solve the shortcomings that prior art and weak point, primary and foremost purpose of the invention is to provide a kind of multi-stage porous silicon
Aluminum molecular screen nano-cluster and preparation method thereof, mesopore/macropore duct is introduced into nano molecular sieve so that this molecular sieve analog both had
There is a superior Acidity, there is the multistage pore passage structure being distributed in structure again, cooperative effect and special is shown in catalytic reaction
Catalytic performance.
The object of the invention is achieved through the following technical solutions：
A kind of multi-stage porous Si-Al molecular sieve nano-cluster, it is characterised in that its uniform particle diameter, is 1.3-1.8 μm, and pore volume is；
It is made up of molecular sieve nano particle, and molecular sieve nano particle size is 10~20nm, the multi-stage porous Si-Al molecular sieve nanometer
Cluster contains mesoporous-micropore hierarchical porous structure, and wherein mesoporous pore size is 20~30nm.
A kind of preparation method of above-mentioned multi-stage porous Si-Al molecular sieve nano-cluster, comprises the following steps：
1) structure directing agent, water, silicon source, silicon source and ethanol are mixed and are sufficiently stirred to obtain mixed solution, add hard template,
Aging is carried out at room temperature, obtains dry glue；
2) gained dry glue in step 1) is placed in reactor, water is left and taken at reactor bottom, carries out crystallization to dry glue, so
After washed and dried, obtain multistage pore canal Si-Al molecular sieve/ordered big hole-mesoporous multi-stage porous carbon mixing material；
3) multistage pore canal Si-Al molecular sieve/ordered big hole-mesoporous multi-stage porous carbon mixing material obtained by step 2) is roasted
Burn, remove carbon template, obtain the multi-stage porous Si-Al molecular sieve nano-cluster.
In such scheme, the molecular sieve structure directed agents are TPAOH；Hard template is ordered big hole-mesoporous
Multi-stage porous carbon material, wherein macropore diameter and mesoporous pore size are adjustable；Macropore diameter is 200~600nm, mesoporous pore size is 20~
40nm；Synthetic method reference literature [Chem.Mater.2010,22,3433-3440].
In such scheme, the silicon source is tetraethyl orthosilicate；Silicon source is sodium metaaluminate, aluminium isopropoxide or aluminum sulfate.
In such scheme, the aging temperature is 30~60 DEG C, and the time is 8~12h.
In such scheme, the silicon source, silicon source, the mol ratio of structure directing agent are 1:(0.001~0.02):(0.36~
0.8)。
In such scheme, the SiO of gained after the dosage of the hard template is hydrolyzed with silicon source2Quality be defined, SiO2Account for die
The 3~10% of plate quality.
In such scheme, the mass ratio of water described in step 2) and dry glue is (1~2):1.
In such scheme, the crystallization temperature is 150~200 DEG C, and the time is 8~16h.
In such scheme, the sintering temperature is 500~600 DEG C, and the time is 6~8h.
Compared with prior art, beneficial effects of the present invention are：
Mesopore orbit is introduced into nano molecular sieve by the present invention so that this kind of molecular sieve has different from conventional nano molecular sieve
Property, both with superior Acidity, and introduce in its structure the pore passage structure of multistage distribution, showed in catalytic reaction
Go out cooperative effect and special catalytic performance, anti-carbon deposition ability can be improved, improve the diffusion of product, improve catalytic reaction
The selectivity of activity and target product；Hydrocarbons catalytic conversion of the gained multi-stage porous Si-Al molecular sieve nano-cluster in petrochemical industry
There is important research and application value etc. process.
Brief description of the drawings
Fig. 1 be the embodiment of the present invention 1 prepare multi-stage porous Si-Al molecular sieve nano-cluster (a, b) scanning electron microscope (SEM) photograph and (c,
D) transmission electron microscope picture.
Fig. 2 is the X-ray diffractogram of multi-stage porous Si-Al molecular sieve nano-cluster prepared by the embodiment of the present invention 2.
Fig. 3 is (a) of multi-stage porous Si-Al molecular sieve nano-cluster prepared by the embodiment of the present invention 329Si nuclear magnetic resonance maps and
(b)27Al nuclear magnetic resonance figures spectrograms.
Fig. 4 is multi-stage porous Si-Al molecular sieve nano-cluster (a) nitrogen adsorption-desorption isotherm prepared by the embodiment of the present invention 4
Figure curve, (b) micropore size distribution map and (c) mesoporous pore size distribution map.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
In following examples, the hard template is ordered big hole-mesoporous multi-stage porous carbon material, synthetic method reference literature
[Chem.Mater.2010,22,3433-3440], macropore diameter 400nm, mesoporous pore size 20nm.
Embodiment 1
A kind of multi-stage porous Si-Al molecular sieve nano-cluster, silicon source, silicon source, the mol ratio of structure directing agent are in its preparation process
1:0.01:0.36, the SiO of gained after silicon source hydrolysis2Occupy the 3% of the foramen magnum-mesoporous multi-stage porous carbon quality of materials of sequence, specifically include
Following steps：
329 μ L TEOS and 0.00612g aluminium isopropoxides are added to the aqueous solution of 1.218g TPAOHs
(20wt.%), 1.35g deionized waters are with the mixed solution of 0.345g ethanol (traditional Chinese medicines), 3g is added after stirring 5h
Ordered big hole-mesoporous multi-stage porous carbon material (macropore diameter 400nm, mesoporous pore size 20nm) obtains mixed solution I, in 40 DEG C of bakings
Aging 10h is dried in case and obtains dry glue；Gained dry glue is placed in 150mL reactors, bottom takes 0.2g deionized waters, is heated to
180 DEG C of crystallization 10h, are then washed and are dried, and are obtained multistage pore canal Si-Al molecular sieve/ordered big hole-mesoporous multi-stage porous carbon and are mixed
Condensation material；Last 2 DEG C/min is warming up to 550 DEG C, and is incubated 6h, removes carbon template and obtains the multi-stage porous Si-Al molecular sieve nanometer
Cluster.
Fig. 1 (a, b) is the scanning electron microscope (SEM) photograph of this example products obtained therefrom, and Fig. 1 (c, d) is the transmission electricity that product is made in this example
Mirror figure.Understand that products obtained therefrom is made up of the molecular sieve nano-cluster of size uniformity with reference to Fig. 1, size is 1.5 μm or so；Each molecule
Sieve nano-cluster is made up of molecular sieve nano particle again, size 10-20nm.
Embodiment 2
A kind of multi-stage porous Si-Al molecular sieve nano-cluster, silicon source, silicon source, the mol ratio of structure directing agent are in its preparation process
1:0.001:0.5, the SiO of gained after silicon source hydrolysis2Occupy the 5% of the foramen magnum-mesoporous multi-stage porous carbon quality of materials of sequence, specifically include
Following steps：
548 μ L TEOS and 0.00051g aluminium isopropoxides are added to the aqueous solution of 1.2688g TPAOHs
In the mixed solution of (20wt.%), 2.25g deionized waters and 4.6g ethanol (traditional Chinese medicines), addition 3g has after stirring 5h
The foramen magnum-mesoporous multi-stage porous carbon material of sequence (macropore diameter 400nm, mesoporous pore size 20nm) obtains mixed solution I, in 40 DEG C of baking ovens
Middle dry aging 10h obtains dry glue；Gained dry glue is placed in 100mL reactors, bottom takes 0.2g deionized waters, is heated to 180
DEG C crystallization 10h, is then washed and is dried, obtain multistage pore canal Si-Al molecular sieve/ordered big hole-mesoporous multi-stage porous carbon mixing material
Material；Last 2 DEG C/min is warming up to 550 DEG C, and is incubated 6h, removes carbon template and obtains the multi-stage porous Si-Al molecular sieve nano-cluster.
Fig. 2 is the XRD that product is made in this example, in 2 θ is at 7.8 °, 8.8 °, 23.2 °, 23.8 °, 24.3 ° in spectrogram
There are five characteristic diffraction peaks of MFI type structure molecular screen, and peak intensity is high, the crystallinity of explanation is very high.
Embodiment 3
A kind of multi-stage porous Si-Al molecular sieve nano-cluster, silicon source, silicon source, the mol ratio of structure directing agent are in its preparation process
1:0.005:0.65, the SiO of gained after silicon source hydrolysis2Occupy the 10% of the foramen magnum-mesoporous multi-stage porous carbon quality of materials of sequence, specific bag
Include following steps：
1095 μ L TEOS and 0.0051g aluminium isopropoxides are added to the aqueous solution of 3.2988g TPAOHs
In the mixed solution of (20wt.%), 4.5g deionized waters and 4.6g ethanol (traditional Chinese medicines), addition 3g is orderly after stirring 5h
Foramen magnum-mesoporous multi-stage porous carbon material (macropore diameter 400nm, mesoporous pore size 20nm) obtains mixed solution I, in 40 DEG C of baking ovens
Dry aging 10h and obtain dry glue；Gained dry glue is placed in 150mL reactors, bottom takes 0.2g deionized waters, is heated to 150 DEG C
Crystallization 16h, is then washed and is dried, and obtains multistage pore canal Si-Al molecular sieve/ordered big hole-mesoporous multi-stage porous carbon mixing material
Material；Last 2 DEG C/min is warming up to 550 DEG C, and is incubated 6h, removes carbon template and obtains the multi-stage porous Si-Al molecular sieve nano-cluster.
Fig. 3 (a) and 3 (b) are respectively multi-stage porous Si-Al molecular sieve nano-cluster obtained by the present embodiment29Si nuclear magnetic resonance maps
With27Al nuclear magnetic resonance maps.Understood that Q is not present in the product after turning brilliant by Fig. 3 (a)2Species (the silicon of two terminal hydroxy groups of connection
Species, chemical shift is in -92ppm), mainly by Q4Species (silicon species for being not connected to terminal hydroxy group being condensed completely) are formed, and are existed
A small amount of Q3Species (silicon species of one terminal hydroxy group of connection).Illustrate that product crystallinity is very high, the polycondensation of products obtained therefrom silicon species
Degree is higher.Product is understood substantially so that the aluminium species (chemical shift 54ppm) of four-coordination are present and are not present six by Fig. 3 (b)
Aluminium (chemical shift 0ppm) is coordinated, because the aluminium of four-coordination is in the frame position of molecular sieve, and the aluminium of hexa-coordinate is in molecule
The non-bone rack position of sieve, illustrate that the aluminium in the product after turning brilliant is substantially present in a manner of four-coordination in the skeleton of molecular sieve.
Embodiment 4
A kind of multi-stage porous Si-Al molecular sieve nano-cluster, silicon source, silicon source, the mol ratio of structure directing agent are in its preparation process
1:0.02:0.8, the SiO of gained after silicon source hydrolysis2Occupy the 3% of the foramen magnum-mesoporous multi-stage porous carbon quality of materials of sequence, including it is following
Step：
329 μ L TEOS and 0.00306g aluminium isopropoxides are added to the aqueous solution of 0.5481g TPAOHs
In the mixed solution of (20wt.%), 1.35g deionized waters and 2.76g ethanol (traditional Chinese medicines), addition 3g has after stirring 5h
The foramen magnum-mesoporous multi-stage porous carbon material of sequence (macropore diameter 400nm, mesoporous pore size 20nm) obtains mixed solution I, in 60 DEG C of baking ovens
Middle dry aging 8h obtains dry glue；Gained dry glue is placed in reactor, bottom takes 0.2g deionized waters, is heated to 180 DEG C of crystallization
10h, then washed and dried, obtain multistage pore canal Si-Al molecular sieve/ordered big hole-mesoporous multi-stage porous carbon mixing material；Most
2 DEG C/min is warming up to 550 DEG C afterwards, and is incubated 6h, removes carbon template and obtains the multi-stage porous Si-Al molecular sieve nano-cluster.
Fig. 4 is nitrogen adsorption-desorption isotherm Fig. 4 (a), micropore size distribution map 4 (b) and Jie of this example products obtained therefrom
Hole pore-size distribution Fig. 4 (c).By Fig. 4 (a) understand product adsorption isothermal curve relative pressure be less than 0.02 when in the presence of very big
Absorption, illustrates substantial amounts of micropore canals structure in product be present；In relative pressure in 0.7~1 scope internal memory in this explanation product
In hysteresis loop, illustrate mesopore orbit structure in product be present.Understand that the micropore size of product is main with reference to Fig. 4 (b) and Fig. 4 (c)
0.45nm or so is concentrated on, while meso-hole structure and pore-size distribution relative narrower in material be present.The BET areas of product are
490m2/ g, micropore specific area 78m2/ g, total pore volume 1.05cm3/ g, further demonstrate in molecular screen material and exist greatly
The meso-hole structure of amount, pore volume caused by its intermediary hole are 1cm3/g。
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change or change therefore amplified
Move within still in the protection domain of the invention.
Claims (10)
1. a kind of multi-stage porous Si-Al molecular sieve nano-cluster, it is characterised in that its uniform particle diameter, be 1.3~1.8 μm；It is by molecule
Nano particle accumulation composition is sieved, wherein molecular sieve nano particle size is 10~20nm, the multi-stage porous Si-Al molecular sieve nanometer
Cluster contains mesoporous-micropore hierarchical porous structure, and wherein mesoporous pore size is 20~30nm.
2. the preparation method of multi-stage porous Si-Al molecular sieve nano-cluster described in claim 1, it is characterised in that comprise the following steps：
1) structure directing agent, water, silicon source, silicon source and ethanol are mixed and is sufficiently stirred to obtain mixed solution, hard template is added, in room
Temperature is lower to carry out aging, obtains dry glue；
2) gained dry glue in step 1) is placed in reactor, water is left and taken at reactor bottom, and crystallization, Ran Houjin are carried out to dry glue
Row is washed and dried, and obtains multistage pore canal Si-Al molecular sieve/ordered big hole-mesoporous multi-stage porous carbon mixing material；
3) multistage pore canal Si-Al molecular sieve/ordered big hole-mesoporous multi-stage porous carbon mixing material obtained by step 2) is calcined, gone
Except carbon template, the multi-stage porous Si-Al molecular sieve nano-cluster is obtained.
3. preparation method according to claim 2, it is characterised in that the structure directing agent is TPAOH；
Hard template is ordered big hole-mesoporous multi-stage porous carbon material, and wherein macropore diameter is 200~600nm, mesoporous pore size is 20~
40nm。
4. preparation method according to claim 2, it is characterised in that the silicon source is tetraethyl orthosilicate；Silicon source is inclined
Sodium aluminate, aluminium isopropoxide or aluminum sulfate.
5. preparation method according to claim 2, it is characterised in that silicon source described in step 1), silicon source, structure directing agent
Mol ratio be 1:(0.001~0.02):(0.36~0.82).
6. preparation method according to claim 2, it is characterised in that gained after the dosage of the hard template is hydrolyzed with silicon source
SiO2Quality be defined, SiO2Account for the 3~10% of hard template quality.
7. preparation method according to claim 2, it is characterised in that water described in step 2) and the mass ratio of dry glue are (1
~2):1.
8. preparation method according to claim 2, it is characterised in that the crystallization temperature is 150~200 DEG C, when
Between be 8~16h.
9. preparation method according to claim 2, it is characterised in that the sintering temperature is 500~600 DEG C, the time 6
~8h.
10. preparation method according to claim 2, it is characterised in that the aging temperature is 30~60 DEG C, the time 8
~12h.
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| CN116102030A (en) * | 2022-12-27 | 2023-05-12 | 瑞声科技（南京）有限公司 | Molecular sieve material for sound absorption and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012061A (en) * | 2007-01-09 | 2007-08-08 | 大连理工大学 | Mesoporous-microporous composite material and synthesis method thereof |
| CN101041428A (en) * | 2007-03-08 | 2007-09-26 | 复旦大学 | Multi-stage ordered medium hole/big hole composite material and preparation method thereof |
| CN102826565A (en) * | 2012-09-05 | 2012-12-19 | 北京化工大学 | Preparation method of multi-stage pore channel beta molecular screen |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012061A (en) * | 2007-01-09 | 2007-08-08 | 大连理工大学 | Mesoporous-microporous composite material and synthesis method thereof |
| CN101041428A (en) * | 2007-03-08 | 2007-09-26 | 复旦大学 | Multi-stage ordered medium hole/big hole composite material and preparation method thereof |
| CN102826565A (en) * | 2012-09-05 | 2012-12-19 | 北京化工大学 | Preparation method of multi-stage pore channel beta molecular screen |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102030A (en) * | 2022-12-27 | 2023-05-12 | 瑞声科技（南京）有限公司 | Molecular sieve material for sound absorption and preparation method thereof |
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