CN108203101A - A kind of zeolite - Google Patents
A kind of zeolite Download PDFInfo
- Publication number
- CN108203101A CN108203101A CN201810299591.5A CN201810299591A CN108203101A CN 108203101 A CN108203101 A CN 108203101A CN 201810299591 A CN201810299591 A CN 201810299591A CN 108203101 A CN108203101 A CN 108203101A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- zeolite
- mesoporous
- porous
- silicon source
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to a kind of zeolites, the mesoporous hole with a certain size is formed by uniformly accumulating, it can be prepared into the sufficiently small MFI type molecular sieve of Nano zeolite of granularity by specific experiment condition, the granularity of its MFI type molecular sieve of Nano zeolite is less than 60nm, by effectively accumulating regulation and control, so that molecular sieve of Nano zeolite particle forms the aggregation (monolith) of relatively uniform accumulation, distribution of pores is in the mesoporous of 2~50nm and macropore more than 50nm between its particle, so as to form the multilevel hole material.The material has the advantages that micropore (0.5~1.5nm) zeolite, mesoporous (2~50nm) molecular sieve respectively simultaneously, also has the macropore more than 50nm, has a wide range of applications scene.
Description
Technical field
The present invention relates to a kind of porous materials in chemical field, and in particular to a kind of zeolite with MFI topological structures.
Background technology
The features such as zeolite molecular sieve is due to its special pore passage structure, Acidity and excellent hydrothermal stability, it is wide
General is applied in catalytic field.Zeolite molecular sieve (ZSM-5 zeolite molecular sieve and the total silicon zeolite molecular sieve of MFI topological structures
Silicalite-1) there is three dimensional intersection straight hole road, in a zigzag.Since its unique pore structure is not only that shape selective catalysis provides
Space restriction effect, and abundant access way is provided for reactants and products, also to prepare highly selective, high work
Property, the strong industrial catalyst of anti-carbon deposit inactivation performance provide crystal structure basis.Therefore, become shape-selective in petroleum industry
One of most important catalysis material in reaction.But since the zeolite molecular sieve of MFI topological structures belongs to micro-pore zeolite molecular sieve,
Aperture is smaller, therefore macromolecular enters that micropore canals are more difficult, and diffusional resistance is larger, is unfavorable for the interior unofficial biography of object macromolecular
It is defeated, so as to limit its application in bulky molecular catalysis field.And mesoporous zeolite molecular sieve has larger aperture, Gao Bibiao
The characteristics of area and orderly pore structure, but the unformed property of hole wall causes its catalytic activity and hydrothermally stable to be inferior to significantly
Micro-pore zeolite molecular sieve, this greatly affected application of these mesopore molecular sieves in PETROLEUM PROCESSING industry.Pure zeolite material simultaneously
Material has smaller micropore (0.5~1.5nm), limits the cracking of long-chain molecule, becomes the bottleneck of the deep development of oil product,
Therefore, in order to improve the utilization ratio of zeolite molecular sieve, while various long-chain molecule cracking are applicable in, are developed mesoporous material
It is combined with zeolite molecular sieve, makes the crystallization of amorphous hole wall or the partially crystallizable of mesoporous material, to form new composite construction molecule
Sieve fundamentally improves the performance of molecular sieve.Therefore with reference to the advantages of micro porous molecular sieve and mesopore molecular sieve, hierarchical zeolite
Molecular sieve comes into being.Hierarchical zeolite molecular sieve have simultaneously micropore (0.5~1.5nm) molecular sieve and it is mesoporous (2~
50nm) molecular sieve respectively the advantages of, can not only make up the deficiency of micro porous molecular sieve, advantageous space is provided for macromolecular reaction
Configuration has higher acidity, hydrothermal stability and meso-hole structure, and can have while Shape-selective is kept fine
Mass transfer ability, play an important role in petroleum catalytic cracking, bulky molecular catalysis reaction and the fields such as fine chemistry industry.
Up to the present, people have done many researchs, many subjects to synthesize the molecular sieve with multistage pore canal
Group has been reported, by the use of carbon mesoporous material of different morphologies etc. as hard mould agent, is added to the micropore of hydro-thermal method synthesis
In the Primogel of molecular sieve, to synthesize multi-stage pore canal molecular sieve, but this method, firstly the need of charcoal template is prepared, technique is multiple
Miscellaneous, cost is higher, and mesoporous being enclosed in micro porous molecular sieve crystal grain mostly of this method synthesis.Another common preparation
Method is that slough silicon in micro porous molecular sieve or aluminium by means such as high-temperature process, alkali process mesoporous to generate, but logical
The multi-stage pore canal molecular sieve that this method obtains is crossed, the controllability that aperture size is connected with hole is not ideal enough.Therefore one is found
Simple, the cheap method for preparing hierarchical zeolite molecular sieve of kind has become more and more urgent.
Invention content
In view of problems of the prior art, the object of the present invention is to provide a kind of zeolite, main purpose is to solve now
There is the defects of technology.
The purpose of the present invention is be achieved through the following technical solutions：
A kind of porous zeotile, including micropore, mesoporous and macropore, the porous zeotile is by based on MFI topological structures
Molecular sieve of Nano zeolite ZSM-5 build-up of particles forms, between adjacent molecular sieve of Nano zeolite particle hole formed it is described it is mesoporous and
Macropore, the mesoporous pore size are more than 50nm in 2~50nm ranges, the macropore diameter；The micropore is present in nano zeolite point
On son sieve particle；Any numerical value of the silica alumina ratio ranging from more than 10 of the porous zeotile ZSM-5, until infinitely great total silicon
Zeolite silicate-1 molecular sieves.
Further, the porous zeotile by granularity less than 60nm molecular sieve of Nano zeolite uniform particle accumulation and
Into.
Further, the mesoporous aperture is centrifuged by secondary monodisperse in water phase, and again by different rotating speeds
Or drying mode is adjusted；The number of its big hole number more than 50nm is adjusted by the addition of soluble starch.
Further, the raw material of the porous zeotile is：Silicon source, metal silicon source, alkali source, tetrapropyl ammonium, polyacrylamide
Amine and water.
Further, the molfraction of the raw material of the porous zeotile and various raw materials is：10 parts of silicon source, metallic aluminium
700~900 parts of 0~2 part of source, 5~6 parts of alkali source, 3~6 parts of tetrapropyl ammonium, 0.005~0.01 part of polyacrylamide and water.
Further, the silicon source is sodium metasilicate, methyl orthosilicate, ethyl orthosilicate, positive silicic acid propyl ester and positive silicon
One or more of acid butyl ester.
Further, the tetrapropyl ammonium is tetrapropylammonium hydroxide, 4-propyl ammonium chloride and 4-propyl bromide
One or more of.
Further, the metal silicon source is sodium metaaluminate；
Further, the polyacrylamide is at least one in anionic polyacrylamide and amphiprotic polyacrylamide
Kind.
A kind of preparation method of the porous zeotile, includes the following steps：
S1：Weigh raw material silicon source, metal silicon source, alkali source, tetrapropyl ammonium, polyacrylamide and water in proportion, and by its
Mixing, stirs evenly, obtains colloidal solution；
S2：By the colloidal solution obtained by step S1, aging 1~3 day, later reaction temperature control exist at 10 DEG C~35 DEG C
Between 70~100 DEG C, lower crystallization is stirred 2~7 days, obtain the molecular sieve of Nano zeolite particle emulsion with MFI topological structures；
S3：The molecular sieve of Nano zeolite particle with MFI topological structures obtained in step S2 is centrifuged, it should
Molecular sieve of Nano zeolite particle is scattered in water phase again after being centrifuged with mother liquor forms emulsion, and add under agitation
Enter soluble starch, ultrasound or stirring 30 minutes form colloidal sol；
S4：In step S3, after formation colloidal sol is uniformly dispersed again, receiving for accumulation is formed again by centrifugation or evaporation drying
Rice zeolite molecular sieve particle, that is, form nano zeolite aggregation；
S5：By the molecular sieve of Nano zeolite particle of the accumulation obtained in step S4 in 50 DEG C~90 DEG C dryings, 500 DEG C~
580 DEG C roast 5~8 hours；It is formed containing micropore and the mesoporous porous zeotile based on MFI topological structures, and mesoporous pore size
Can be 2~50nm ranges, macropore is more than 50nm any numbers.
Further, in step S3, the addition of the soluble starch for porous zeotile material quality 1% with
Interior, macropore increases with the increase of the addition of soluble starch.
Further, the rotating speed of the centrifugation described in step S3 and step S4 is 4000~25000r/min, the time for 3~
15min。
Further, in step S1, the mole proportioning of various raw materials is：SiO2:Al2O3:NaOH:TPAB:PAM:H2O
=10:0~1:5~6:3~6:0.005~0.01:700~900.
Beneficial effects of the present invention：
1st, the present invention is based on micro-pore zeolite molecular sieve particle, and the mesoporous hole with a certain size is formed by uniformly accumulating
Gap, therefore the multilevel hole material not only maintains the micropore feature of molecular sieve of Nano zeolite, can also regulate and control as needed 2~
Mesoporous and more than 50nm macropore in 50nm.And the silica alumina ratio compositing range of the multilevel hole material is wider, not only includes height
Silicone zeolite molecular sieve ZSM-5 and total silicon zeolite Silicate-1, further includes low silicon (SiO2/Al2O3=10) MFI type zeolite point
Son sieve.
2nd, multilevel hole material of the present invention can be prepared into the sufficiently small MFI of granularity by specific experiment condition
Type molecular sieve of Nano zeolite, the granularity of MFI type molecular sieve of Nano zeolite is less than 60nm, by effectively accumulating regulation and control so that
Molecular sieve of Nano zeolite particle forms the aggregation (monolith) of relatively uniform accumulation, between particle distribution of pores 2~
Mesoporous and more than 50nm the macropore of 50nm, so as to form the multilevel hole material.
3rd, the present invention is accumulated using twice dispersing during multilevel hole material is prepared and adds in the solvable of different content
Property starch adjust mesoporous and macropore hole, do not need to add in other mesoporous template mesoporous to generate, it is not required that use
The means such as high-temperature process, alkali process are mesoporous to generate to slough silicon in micro porous molecular sieve or aluminium, therefore the synthesis of the present invention
Method not only building-up process it is simple and easy to operate and also have the characteristics that it is cost-effective, environmental-friendly, while using this method synthesize
Multilevel hole material in mesoporous size and the number of macropore can arbitrarily regulate and control.
4th, MFI type multi-stage pore zeolite molecular sieve has micropore (0.5~1.5nm) zeolite, mesoporous (2~50nm) molecule simultaneously
It sieves the advantages of respective, also there is the macropore more than 50nm.It is mesoporous that advantageous space can be not only provided for macromolecular reaction, is also protected
The acidity and hydrothermal stability that zeolite is higher have been stayed, and there can be good mass transfer energy while Shape-selective is kept
Power, therefore can be adapted to the application of all catalysis of ZSM-5 and silicate-1.
Description of the drawings
The present invention is described in further detail below according to attached drawing.
Fig. 1 is a kind of multilevel hole material (SiO provided by the invention2/Al2O3=20) X-ray coatings；
Fig. 2 is a kind of multilevel hole material (SiO provided by the invention2/Al2O3=10,20) N2Adsorption isotherm and aperture
Distribution map；
Fig. 3 is a kind of multilevel hole material (SiO provided by the invention2/Al2O3=20) scanning electron microscope (SEM) photograph；
Fig. 4 is a kind of multilevel hole material (SiO provided by the invention2/Al2O3=20) transmission electron microscope picture.
Specific embodiment
The present invention provides a kind of porous zeotiles and preparation method thereof, illustrate have by taking specific experiment case as an example below
Body embodiment, it should be understood that the specific embodiments described herein are merely illustrative of the present invention, is not used to limit this hair
It is bright.
Embodiment 1
A kind of multilevel hole material, including mesoporous and micropore, the multilevel hole material is by the nano zeolite based on MFI topological structures
Molecular sieve particle is accumulated, and hole is formed mesoporous between adjacent molecular sieve of Nano zeolite particle, mesoporous pore size can 2~
It is arbitrarily adjusted in the range of 50nm；Micropore is present on molecular sieve of Nano zeolite particle；Mesoporous pore size can pass through zeolite nano-particle
Secondary monodisperse centrifuges accumulation into emulsion and again or evaporation drying accumulation is adjusted；It is adjusted by the addition of soluble starch
The number of macropore between section particle.
Sial (the SiO of multilevel hole material2/Al2O3) any numerical value than ranging from 10 and more than 10, for example, can be low
The molecular sieve of silicon MFI structure is (such as：SiO2:Al2O3=10), or high silicon (such as SiO2:Al2O3=100~300) ZSM-
5 zeolite molecular sieves and the total silicon zeolite molecular sieve (Silicate-1) of silica alumina ratio infinity etc..
As the preferred embodiment of above-described embodiment, multilevel hole material is less than the molecular sieve of Nano zeolite of 60nm by granularity
Uniform particle is accumulated, and it is the mesoporous of 2~50nm to form aperture.
As the preferred embodiment of above-described embodiment, the addition of soluble starch is multilevel hole material material quality
Within 1%.
Embodiment 2
A kind of multilevel hole material, the raw material of the multilevel hole material are：Silicon source, alkali source, tetrapropyl ammonium, is gathered at metal silicon source
Acrylamide and water.
As the preferred embodiment of above-described embodiment, the molfraction of the raw material of multilevel hole material and various raw materials
For：10 parts of silicon source, 0~2 part of metal silicon source, 5~6 parts of alkali source, 3~6 parts of tetrapropyl ammonium, 0.005~0.01 part of polyacrylamide
And 700~900 parts of water；For example, the molfraction of various raw materials can be：1. 10 parts of silicon source, 2 parts of metal silicon source, alkali source 5.5
Part, 4 parts of tetrapropyl ammonium, 0.005 part of polyacrylamide and 800 parts of water；2. 10 parts of silicon source, 0 part of metal silicon source, 5.5 parts of alkali source,
800 parts of 4 parts of tetrapropyl ammonium, 0.005 part of polyacrylamide and water；3. 10 parts of silicon source, 0.5 part of metal silicon source, 5 parts of alkali source, four
900 parts of 6 parts of propyl ammonium, 0.005 part of polyacrylamide and water；4. 10 parts of silicon source, 1 part of metal silicon source, 5.5 parts of alkali source, 4 third
700 parts of 3 parts of base ammonium, 0.01 part of polyacrylamide and water.
As the preferred embodiment of above-described embodiment, silicon source can be：1. sodium metasilicate；2. methyl orthosilicate；3. positive silicon
Acetoacetic ester；4. positive silicic acid propyl ester；5. butyl silicate；6. sodium metasilicate and methyl orthosilicate；7. ethyl orthosilicate and positive silicic acid third
Ester 8. sodium metasilicate, sodium metasilicate and methyl orthosilicate；9. sodium metasilicate, sodium metasilicate, methyl orthosilicate and positive silicic acid propyl ester；
Tetrapropyl ammonium can be：1. tetrapropylammonium hydroxide；2. 4-propyl bromide；3. 4-propyl ammonium chloride；4. 4 third
Base ammonium hydroxide and 4-propyl bromide；5. 4-propyl bromide and 4-propyl ammonium chloride；6. tetrapropylammonium hydroxide and 4 third
Ammonium chloride；
Metal silicon source is sodium metaaluminate；
Polyacrylamide can be (1) anionic polyacrylamide, (2) amphiprotic polyacrylamide.
Embodiment 3
The preparation method of porous zeotile:By 14.6 grams of (0.07mol) ethyl orthosilicates (TEOS) and 1.0 grams
(0.025mol) NaOH, 6.7g (0.025mol) 4-propyl bromide (TPABr), 0.1g anionic polyacrylamide (PAM) are molten
Solution A is formed in 50mL deionized waters；Again by 1.15g (0.014mol) sodium metaaluminates (NaAlO2) it is dissolved in 40mL deionized waters
Middle formation solution B.Then B solution is slowly dropped in solution A while stirring, aging 2 is stirred under the conditions of 10 DEG C~35 DEG C
My god, then isothermal reaction crystallization 7 days under 80 DEG C of stirrings, are made the molecular sieve of Nano zeolite particle with MFI topological structures, should
The granularity of particle is less than 60nm.Be then centrifuged for (5000r/min, 5min) and isolate reaction mother liquor, then again ultrasonic disperse in
Water phase adds in 0.5g soluble starches into emulsion, and ultrasound or stirring 30 minutes form colloidal sol, after being uniformly dispersed, by again
(15000r/min, 5min) or evaporation drying are centrifuged, by 80 DEG C of dryings, is roasted 6 hours using 550 DEG C, you can obtain
SiO2/Al2O3=10 MFI type porous zeotile, as shown in Figure 2.
Embodiment 4:
The preparation method of porous zeotile:By 14.6 grams of (0.07mol) ethyl orthosilicates (TEOS) and 1.0 grams
(0.025mol) NaOH, 6.7g (0.025mol) 4-propyl bromide (TPABr), 0.1g anionic polyacrylamide (PAM) are molten
Solution A is formed in 50mL deionized waters；Again by 0.575g (0.007mol) sodium metaaluminates (NaAlO2) it is dissolved in 40mL deionizations
Solution B is formed in water.Then B solution is slowly dropped in solution A while stirring, aging 2 is stirred under the conditions of 20 DEG C of room temperature
My god, then thermostatic crystallization 6 days under 90 DEG C of stirrings, are made the molecular sieve of Nano zeolite particle with MFI topological structures, the particle
Granularity be 50nm emulsion, be then centrifuged for (7000r/min, 8min) and isolate nano zeolite, be scattered in again therewith
In the deionized water of 50mL, the soluble starch of 0.3g is then slowly added in while stirring, is stirred 30 minutes, forms colloidal sol,
After being uniformly dispersed, volatilize moisture to the greatest extent in centrifugation (10000r/min, 4min) separation or air, by 80 DEG C of dryings, using 550
DEG C roasting 6 hours, you can obtain SiO2/Al2O3=20 MFI type multilevel hole material, as shown in Figure 1.
Embodiment 5
The preparation method of porous zeotile:By 14.6 grams of (0.07mol) ethyl orthosilicates (TEOS) and 1.0 grams
(0.025mol) sodium hydroxide (NaOH), 6.7g (0.025mol) 4-propyl bromide (TPABr), 0.1g anion pp acyls
Amine (PAM) is dissolved in 90mL deionized waters, and aging 3 days is stirred under the conditions of 20 DEG C of room temperature.Then in 70 DEG C of isothermal reactions, crystallization 5
My god, the molecular sieve of Nano zeolite particle with MFI topological structures is made, the granularity of the particle is 50~60nm.Then 5000r/
Min centrifugations, separation, and then by obtained nano zeolite, are scattered in the deionized water of 50mL, then while stirring again
0.8g soluble starches are slowly added in, are stirred 40 minutes, form colloidal sol, after being uniformly dispersed, 8000r/min centrifugations (8000r/
Min, 10min) separation or air in volatilize to the greatest extent moisture.It by 60 DEG C of dryings, is roasted 7 hours using 530 DEG C, you can obtain complete
Silicon (SiO2/Al2O3=∞) porous zeotile.
Finally it should be noted that：Above-described embodiments are merely to illustrate the technical scheme rather than to it
Limitation；Although the present invention is described in detail referring to the foregoing embodiments, it will be understood by those of ordinary skill in the art that：
It can still modify to the technical solution recorded in previous embodiment or to which part or all technical features into
Row equivalent replacement；And these modifications or substitutions, it does not separate the essence of the corresponding technical solution various embodiments of the present invention technical side
The range of case.
Claims (5)
1. a kind of porous zeotile, it is characterised in that：The porous zeotile includes micropore, mesoporous and macropore, the multi-stage porous
Zeolite is formed by the molecular sieve of Nano zeolite build-up of particles based on MFI topological structures, between adjacent molecular sieve of Nano zeolite particle
Hole forms described mesoporous and macropore, and the mesoporous pore size is more than 50nm in 2~50nm ranges, the macropore diameter；It is described micro-
Hole is present on molecular sieve of Nano zeolite particle；Any numerical value of the silica alumina ratio of the porous zeotile ranging from more than 10, directly
To infinitely great total silicon zeolite molecular sieve.
2. porous zeotile according to claim 1, which is characterized in that the porous zeotile is by granularity less than 60nm's
Molecular sieve of Nano zeolite uniform particle is accumulated, and the raw material of the porous zeotile is：Silicon source, metal silicon source, alkali source, 4 third
Base ammonium, polyacrylamide and water.
3. porous zeotile according to claim 3, which is characterized in that the raw material of the porous zeotile and various originals
The molfraction of material is：10 parts of silicon source, 0~2 part of metal silicon source, 5~6 parts of alkali source, 3~6 parts of tetrapropyl ammonium, polyacrylamide
0.005~0.01 part and 700~900 parts of water.
4. porous zeotile according to claim 4, which is characterized in that the silicon source for sodium metasilicate, methyl orthosilicate,
One or more of ethyl orthosilicate, positive silicic acid propyl ester and butyl silicate；The tetrapropyl ammonium is tetrapropyl hydrogen
One or more of amine-oxides, 4-propyl ammonium chloride and 4-propyl bromide；The metal silicon source is sodium metaaluminate；
The polyacrylamide is at least one of anionic polyacrylamide and amphiprotic polyacrylamide.
5. porous zeotile according to claim 1, which is characterized in that the number of the macropore passes through soluble starch
Addition regulates and controls.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810299591.5A CN108203101A (en) | 2018-04-04 | 2018-04-04 | A kind of zeolite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810299591.5A CN108203101A (en) | 2018-04-04 | 2018-04-04 | A kind of zeolite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108203101A true CN108203101A (en) | 2018-06-26 |
Family
ID=62606677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810299591.5A Withdrawn CN108203101A (en) | 2018-04-04 | 2018-04-04 | A kind of zeolite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108203101A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010146A (en) * | 2021-03-05 | 2022-09-06 | 中国石油化工股份有限公司 | Hierarchical pore ZSM-5 nano aggregate molecular sieve and preparation method thereof |
-
2018
- 2018-04-04 CN CN201810299591.5A patent/CN108203101A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010146A (en) * | 2021-03-05 | 2022-09-06 | 中国石油化工股份有限公司 | Hierarchical pore ZSM-5 nano aggregate molecular sieve and preparation method thereof |
| CN115010146B (en) * | 2021-03-05 | 2024-03-12 | 中国石油化工股份有限公司 | Multistage hole ZSM-5 nano aggregate molecular sieve and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104030314B (en) | A kind of ZSM-5 Quito level porous molecular sieve material and preparation method thereof | |
| JP5175428B2 (en) | Material with hierarchical porosity containing silicon | |
| CN101186311B (en) | Y/MCM-48 composite molecular screen and preparation method thereof | |
| WO2018086343A1 (en) | Method of preparing hierarchical porous channel molecular sieve membrane and application thereof | |
| CN109704355A (en) | A kind of porous zeotile and preparation method | |
| CN104760974B (en) | The method that one-step synthesis method has the zeolites of multi-stage artery structure ZSM 5 in open duct | |
| CN109368657A (en) | Framework metal high dispersive type multi-stage porous H-ZSM-5 molecular sieve preparation method | |
| CN105621445B (en) | A kind of NaY types molecular sieve and preparation method thereof | |
| CN102874843B (en) | Quick synthesis method for nano-scale ZSM-5 molecular sieve | |
| CN104556094B (en) | A kind of Y/Silicalite-1 composite molecular screen and preparation method thereof | |
| CN101613113A (en) | A kind of method of nanometer hierarchical pore MFI molecular sieve one-step synthesis | |
| CN103626203B (en) | A kind of preparation of nanometer of molecular sieve of ZSM 5 | |
| CN106830001A (en) | A kind of synthetic method of the molecular sieves of c axial directions Zn ZSM 5 with meso-hole structure | |
| JP7394972B2 (en) | Composite ZSM-5 molecular sieve, its manufacturing method, catalyst, and use | |
| CN101992126A (en) | Porous zeolite molecular sieve coating material on surface of silicon carbide ceramics and preparation method thereof | |
| WO2011047527A1 (en) | Double micro-mesoporous composite molecular sieve and preparation method thereof | |
| JP2014525389A (en) | Process for forming zeolite from homogeneous amorphous silica alumina | |
| CN107512725A (en) | With core shell structure TON MFI composite molecular screens and preparation method thereof | |
| CN108178163B (en) | A kind of low silicon multilevel structure ZSM-5 zeolite molecular sieve and its preparation method and application | |
| CN109437232A (en) | A kind of preparation method of the ZSM-5 molecular sieve of multilevel structure | |
| CN108203101A (en) | A kind of zeolite | |
| CN110330025B (en) | TS-1 molecular sieve single crystal with ordered hierarchical pores and adjustable silicon-titanium ratio and preparation method thereof | |
| CN107297220B (en) | Vermicular mesoporous Al2O3Molecular sieve composite material and preparation method thereof | |
| CN110467198A (en) | A kind of multi-stage porous ZSM-5 Micelle-like Nano-structure of Two microballoon and preparation method | |
| CN101417810A (en) | Mesoporous material and preparation method thereof |
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 | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180626 |
|
| WW01 | Invention patent application withdrawn after publication |