CN102167350B - Method for preparing ordered mesoporous aluminosilicate hollow sphere - Google Patents
Method for preparing ordered mesoporous aluminosilicate hollow sphere Download PDFInfo
- Publication number
- CN102167350B CN102167350B CN2011100692121A CN201110069212A CN102167350B CN 102167350 B CN102167350 B CN 102167350B CN 2011100692121 A CN2011100692121 A CN 2011100692121A CN 201110069212 A CN201110069212 A CN 201110069212A CN 102167350 B CN102167350 B CN 102167350B
- Authority
- CN
- China
- Prior art keywords
- ordered mesoporous
- hollow ball
- mesoporous silicon
- preparation
- dispersion liquid
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention discloses a method for preparing an ordered mesoporous aluminosilicate hollow sphere, and relates to mesoporous materials. The method comprises the following steps of: adding a silicon dioxide sphere into water, and performing ultrasonic treatment to obtain silicon dioxide sphere dispersion liquid; adding the silicon dioxide sphere dispersion liquid into cationic surfactant; adding an alkali source and an aluminum source and etching, and after etching, collecting precipitate; and dispersing the obtained precipitate in water to form dispersion liquid, transferring the dispersion liquid into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in a reaction kettle and reacting, collecting precipitates, washing and airing to obtain white powder, and removing cationic surfactant to obtain the ordered mesoporous aluminosilicate hollow sphere. The silicon dioxide sphere is used as a template for alkali etching, and an ordered mesoporous aluminosilicate layer is deposited on the surface of the template by synergistic assembling of the added cationic surfactant, the dissolved silicon dioxide sphere component, and the aluminum source, and the ordered mesoporous aluminosilicate hollow sphere is prepared by an etching and assembling process.
Description
Technical field
The present invention relates to mesoporous material, particularly a kind of preparation method of ordered mesoporous silicon aluminate hollow ball.
Background technology
1992, people such as the scientist Beck of Mobil company and Kresge (1, C.T.Kresge, M.E.Leonowicz; W.J.Roth, J.C.Vartuli, J.S.Beck; Nature; 1992,359,710-712) in alkaline medium, make template first with cats product; It is the M41s mesopore molecular sieve series material of orderly pore passage structure of having of representative and narrow pore size distribution that hydrothermal crystallizing silicate or dehydrated form one-step synthesis go out with the MCM-41 molecular sieve, starts the mesoporous material research boom.Because the hole wall of mesoporous M41s molecular sieve is thinner, and is in unbodied state, this just makes its hydrothermal stability not high, has limited their application.Simultaneously, because pure silicon M41s molecular sieve has the neutral skeleton structure, defective is few, and ion-exchange capacity is little, and acid content and strength of acid are low, reactive behavior is low, so has limited their application at aspects such as catalysis, absorption, separation and environmental protection.Research shows the skeleton that the A1 ion is incorporated into mesopore molecular sieve, not only can improve the hydrothermal stability of mesopore molecular sieve, and after introducing its A1 ion in the skeleton; Can increase defects count, improve the absorption property on surface, acid-basicity; Thereby improve its catalytic performance, improve reactive behavior.Therefore the ordered mesoporous Si-Al silicate material has received investigator's extensive concern.
In recent years, along with going deep into of synthetic and applied research, the synthesize meso-porous material of design controllable pattern becomes the focus of a research.Wherein, because its using value in confinement catalysis and drug delivery, be that the synthetic of order mesoporous hollow ball of representative has broad application prospects with the ordered mesoporous silica dioxide hollow ball.At present, owing to lack effective compound method, the controlledly synthesis with ordered mesoporous silicon aluminate hollow ball of high hydrothermal stability and catalytic performance becomes a difficult problem that needs to be resolved hurrily.The preparation method of existing ordered mesoporous silicon aluminate hollow ball (2, Y.S.Li, J.L.Shi, Z.L.Hua; H.R.Chen, M.L.Ruan, and D.S.Yan; Nano Letters, 2003,3; Be soft template 609-612) for utilizing two tensio-active agents (hydroxide tetrapropyl amine and cetyl trimethylammonium bromide); With tetraethoxysilance and Tai-Ace S 150 is silicon source and aluminium source, and under the effect of sodium hydroxide, is hydrolyzed, and has obtained having the ordered mesoporous silicon aluminate hollow ball of MCM-48 type pore passage structure at last.Owing to adopt the soft template synthesis method; The maximum defective of above compound method is: the ordered mesoporous silicon aluminate hollow ball that is difficult to synthetic size homogeneous; While also is difficult to regulate and control effectively to the size of ordered mesoporous silicon aluminate hollow ball, has therefore limited the applicability of this method.
Summary of the invention
The objective of the invention is to be directed against the problem that exists in the compound method of existing ordered mesoporous silicon aluminate hollow ball, a kind of preparation method of ordered mesoporous silicon aluminate hollow ball is provided.
The preparation method of said a kind of ordered mesoporous silicon aluminate hollow ball may further comprise the steps:
1) silica spheres is added in the entry, obtain the silica spheres dispersion liquid after ultrasonic;
2) cats product is added the silica spheres dispersion liquid of step 1) gained, add alkali source and aluminium source after the stirring again, carry out etching then, etching is accomplished the back and is collected deposition and clean the 1st time;
3) get step 2) the 1st precipitation of gained be dispersed in and form dispersion liquid in the water; The dispersion liquid of gained is transferred in the polytetrafluoroethyllining lining; After then polytetrafluoroethyllining lining being placed reaction kettle reaction, collect deposition the 2nd time, clean dry white powder; Decationize tensio-active agent from white powder promptly gets ordered mesoporous silicon aluminate hollow ball.
In step 1), the mass ratio of said silica spheres and water can be 1: (25～200); The said ultransonic time can be 10～30min, preferred 30min.
In step 2) in; The mass ratio of said silica spheres and cats product can be 25: (3～5); Said cats product tensio-active agent can be the quaternary ammonium salt of chain alkyl etc., is preferably cetyl trimethylammonium bromide or palmityl trimethyl ammonium chloride etc.; The mass ratio of said alkali source, aluminium source and silica spheres can be 1: 1: (1.66～3.32) are preferably 1: 1: 3.32; Said alkali source is preferably soda ash light etc., and said aluminium source is preferably sodium metaaluminate etc.; The condition of said etching is: 50～90 ℃ of the temperature of etching, and the time 3～24h of etching, the temperature of preferred etching is 90 ℃, the time of etching is 3h.
In step 3), the mass ratio of said the 1st deposition and water can be 1: (25～200); Said dispersion liquid and said teflon-lined volume ratio can be 1: (2～3); The temperature of said reaction can be 100～150 ℃, is preferably 150 ℃; The time of reaction can be 24～72h, is preferably 48h; Said clean water successively and ethanol clean 1～3 time, and said decationize tensio-active agent can adopt the method for acetone extract.
Gained ordered mesoporous silicon aluminate hollow ball of the present invention is typical silico-aluminate, and wherein the ratio of Si and Al is 1: (0.1～0.37); Gained ordered mesoporous silicon aluminate hollow ball has the absorption behavior of typical mesoporous material, and specific surface can reach 400～650m
2/ g; Have the mesopore orbit of homogeneous, the aperture can be 2.1～2.5nm, and pore volume reaches 0.48～0.6cm
3/ g.
The present invention utilizes silica spheres to carry out alkaline etching as template; The cats product that passes through to be added and the dissolved silica spheres component and the collaborative assembling in aluminium source; Deposit orderly mesoporous aluminoshilicate layer at template surface, realize preparation ordered mesoporous silicon aluminate hollow ball through " etching-assembling " process.Relatively and the compound method of other mesoporous aluminoshilicate, the invention has the advantages that:
(1) the present invention uses cheap dioxide pellet as template and silicon source, just can obtain high-quality ordered mesoporous silicon aluminate hollow ball.
(2) the present invention just can regulate the ordered mesoporous silicon aluminate hollow ball size of gained through the control to dioxide pellet.
(3) the present invention can select gentle solvent extration to remove tensio-active agent; The hydroxy functional group that can keep orderly mesoporous aluminoshilicate hollow ball surface effectively; This just makes it possible to it is carried out surface or duct modification, and progressive one obtains the ordered mesoporous silicon aluminate hollow ball of functionalization.
(4) the ordered mesoporous silicon aluminate hollow ball that the present invention obtained has high Al/Si ratio, has strengthened its acidity as lewis acid catalyst, makes ordered mesoporous silicon aluminate hollow ball that good prospects for application can be arranged.
(5) the ordered mesoporous silicon aluminate hollow ball through the present invention preparation, its pore passage structure high-sequential, and communicate with internal cavities is vertical, good using value is arranged.
(6) the present invention have that workable, with low cost, reaction unit is simple, preparation process condition gentleness, reaction process cleanliness without any pollution, reaction efficiency advantages of higher, comparing other compound methods has favorable industrial application prospect.
Description of drawings
Fig. 1 is the SEM figure of the ordered mesoporous silicon aluminate hollow ball of the embodiment of the invention 1 preparation.In Fig. 1, a is the low power SEM figure of ordered mesoporous silicon aluminate hollow ball, and scale is 5 μ m, and wherein illustration is the SEM figure of used silicon-dioxide ball template, and the illustration scale is 500nm; B is the high power SEM figure of ordered mesoporous silicon aluminate hollow ball, and scale is 2 μ m.
Fig. 2 is the SEM figure of the ordered mesoporous silicon aluminate hollow ball of embodiment of the invention preparation.In Fig. 2, a is the low power SEM figure of ordered mesoporous silicon aluminate hollow ball, and scale is 0.5 μ m; B is the high power SEM figure of single ordered mesoporous silicon aluminate hollow ball, and scale is 50nm.
Fig. 3 is the EDX figure of the ordered mesoporous silicon aluminate hollow ball of embodiment of the invention preparation.In Fig. 3, X-coordinate is energy (kV), and ordinate zou is intensity (a.u.).
Fig. 4 for the ordered mesoporous silicon aluminate hollow ball of embodiment of the invention preparation the nitrogen adsorption graphic representation.In Fig. 4, X-coordinate is relative pressure (P/Po), and ordinate zou is adsorptive capacity (cm
3g
-1STP).
Fig. 5 for the ordered mesoporous silicon aluminate hollow ball of embodiment of the invention preparation pore size distribution curve figure.In Fig. 5, X-coordinate is aperture (nm), and ordinate zou is loading capacity (cm
3g
-1Nm
-1).
Fig. 6 is the SEM figure of the ordered mesoporous silicon aluminate hollow ball of embodiment of the invention preparation.In Fig. 6, a is the low power SEM figure of ordered mesoporous silicon aluminate hollow ball, and scale is 2 μ m; B is the high power SEM figure of ordered mesoporous silicon aluminate hollow ball, and scale is 1 μ m.
Embodiment
Combine accompanying drawing that the present invention is described further through embodiment below.
(1) in vial, the 50mg silica spheres is added in the 10mL water, and ultrasonic 30min.
(2) the 12.5mg CTAB is added in the vial in the step (1); Add 20.5mg sodium metaaluminate and 26.5mg soda ash light successively after stirring 30min; Continue to stir 1min again, stir etching 3h down at 90 ℃ then, at room temperature leave standstill cooling at last.
(3) extracting waste deposition water and ethanol clean 2 times repeatedly, are dispersed in again then in the water of 15mL and form dispersion liquid.
(4) dispersion liquid with step (3) gained shifts as in the middle of the 20mL polytetrafluoroethyllining lining, places reaction kettle at 150 ℃ of following constant temperature 48h polytetrafluoroethyllining lining then, at last cooling at room temperature.
(5) white precipitate water and the ethanol handled through step (4) clean 2 times repeatedly, dry naturally then to obtain white powder.
(6) after being removed, the cats product that uses promptly gets title product from white powder.
Prepared ordered mesoporous silicon aluminate hollow ball has hollow structure (referring to Fig. 1); The product that behind over etching, obtains has the pore passage structure of high-sequential; Gained mesopore orbit and inner cavity vertical (referring to Fig. 2), compare its size increases with silica spheres to some extent.This is because add the effect of the component of cats product and aluminium source and dissolved silica spheres, on template surface, deposits the mesoporous aluminoshilicate layer.Resulting product consists of typical silico-aluminate (referring to Fig. 3), and wherein the molar ratio of Al and Si is 0.37: 1; Based on the nitrogen adsorption curve (referring to Figure 4 and 5) of silicon-dioxide ball template and hollow mesoporous silica spheres, can find out that hollow mesoporous silica spheres has the absorption behavior of typical mesoporous material, calculate through the BET method, its specific surface reaches 428m
2/ g; Calculate through the BJH method, the hollow mesoporous silica spheres of gained has the mesopore orbit (aperture is 2.1nm) of homogeneous, and its pore volume reaches 0.48cm
3/ g.
(1) in vial, the 50mg silica spheres is added in the 10mL water, and ultrasonic 30min.
(2) 15mg cetyl trimethyl ammonia chloride is added in the vial in the step (1); Add 20.5mg sodium metaaluminate and 26.5mg soda ash light successively after stirring 30min; Continue to stir 1min again, stir etching 3h down at 90 ℃ then, at room temperature leave standstill cooling at last.
(3) extracting waste deposition water and ethanol clean 2 times repeatedly, are dispersed in again then in the water of 15mL and form dispersion liquid.
(4) dispersion liquid with step (3) gained shifts as in the middle of the 20mL polytetrafluoroethyllining lining, places reaction kettle at 150 ℃ of following constant temperature 48h polytetrafluoroethyllining lining then, at last cooling at room temperature.
(5) white precipitate water and the ethanol handled through step (4) clean 2 times repeatedly, dry naturally then to obtain white powder.
(6) after being removed, the cats product that uses promptly gets title product from white powder.
Select for use the cetyl trimethyl ammonia chloride can obtain high-quality hollow mesoporous silica spheres (referring to Fig. 6) too.
Embodiment 3
(1) in vial, the 50mg silica spheres is added in the 10mL water, and ultrasonic 30min.
(2) the 12.5mg CTAB is added in the vial in the step (1); Add 41mg sodium metaaluminate and 26.5mg soda ash light successively after stirring 10min; Continue to stir 1min again, stir etching 2h down at 90 ℃ then, at room temperature leave standstill cooling at last.
(3) extracting waste deposition water and ethanol clean 2 times repeatedly, are dispersed in again then in the water of 15mL and form dispersion liquid.
(4) dispersion liquid with step (3) gained shifts as in the middle of the 20mL polytetrafluoroethyllining lining, places reaction kettle at 100 ℃ of following constant temperature 72h polytetrafluoroethyllining lining then, at last cooling at room temperature.
(5) white precipitate water and the ethanol handled through step (4) clean 1 time repeatedly, dry naturally then to obtain white powder.
(6) after being removed, the cats product that uses promptly gets title product from white powder.
Embodiment 4
(1) in vial, the 50mg silica spheres is added in the 10mL water, and ultrasonic 30min.
(2) the 12.5mg CTAB is added in the vial in the step (1); Add 20.5mg sodium metaaluminate and 53mg soda ash light successively after stirring 30min; Continue to stir 1min again, stir etching 3h down at 90 ℃ then, at room temperature leave standstill cooling at last.
(3) extracting waste deposition water and ethanol clean 2 times repeatedly, are dispersed in again then in the water of 15mL and form dispersion liquid.
(4) dispersion liquid with step (3) gained shifts as in the middle of the 20mL polytetrafluoroethyllining lining, places reaction kettle at 120 ℃ of following constant temperature 24h polytetrafluoroethyllining lining then, at last cooling at room temperature.
(5) white precipitate water and the ethanol handled through step (4) clean to 2 times repeatedly, dry naturally then to obtain white powder.
(6) after being removed, the cats product that uses promptly gets title product from white powder.
Embodiment 5
(1) in vial, the 50mg silica spheres is added in the 10mL water, and ultrasonic 30min.
(2) the 6mg CTAB is added in the vial in the step (1); Add 20.5mg sodium metaaluminate and 26.5mg soda ash light successively after stirring 30min; Continue to stir 1min again, stir etching 3h down at 90 ℃ then, at room temperature leave standstill cooling at last.
(3) extracting waste deposition water and ethanol clean 2 times repeatedly, are dispersed in again then in the water of 15mL and form dispersion liquid.
(4) dispersion liquid with step (3) gained shifts as in the middle of the 20mL polytetrafluoroethyllining lining, places reaction kettle at 140 ℃ of following constant temperature 48h polytetrafluoroethyllining lining then, at last cooling at room temperature.
(5) white precipitate water and the ethanol handled through step (4) clean to 2 times repeatedly, dry naturally then to obtain white powder.
(6) after being removed, the cats product that uses promptly gets title product from white powder.
(1) in vial, the 50mg silica spheres is added in the 10mL water, and ultrasonic 20min.
(2) the 15mg CTAB is added in the vial in the step (1); Add 20.5mg sodium metaaluminate and 26.5mg soda ash light successively after stirring 10min; Continue to stir 1min again, stir etching 3h down at 90 ℃ then, at room temperature leave standstill cooling at last.
(3) extracting waste deposition water and ethanol clean 2 times repeatedly, are dispersed in again then in the water of 15mL and form dispersion liquid.
(4) dispersion liquid with step (3) gained shifts as in the middle of the 20mL polytetrafluoroethyllining lining, places reaction kettle at 150 ℃ of following constant temperature 48h polytetrafluoroethyllining lining then, at last cooling at room temperature.
(5) white precipitate water and the ethanol handled through step (4) clean to 2 times repeatedly, dry naturally then to obtain white powder.
(6) after being removed, the cats product that uses promptly gets title product from white powder.
Embodiment 7
(1) in vial, the 50mg silica spheres is added in the 10mL water, and ultrasonic 30min.
(2) the 12.5mg CTAB is added in the vial in the step (1); Add 20.5mg sodium metaaluminate and 26.5mg soda ash light successively after stirring 20min; Continue to stir 1min again, stir etching 12h down at 50 ℃ then, at room temperature leave standstill cooling at last.
(3) extracting waste deposition water and ethanol clean 2 times repeatedly, are dispersed in again then in the water of 15mL and form dispersion liquid.
(4) dispersion liquid with step (3) gained shifts as in the middle of the 20mL polytetrafluoroethyllining lining, places reaction kettle at 150 ℃ of following constant temperature 72h polytetrafluoroethyllining lining then, at last cooling at room temperature.
(5) white precipitate water and the ethanol handled through step (4) clean to 2 times repeatedly, dry naturally then to obtain white powder.
(6) after being removed, the cats product that uses promptly gets title product from white powder.
Embodiment 7
(1) in vial, the 50mg silica spheres is added in the 10mL water, and ultrasonic 10min.
(2) the 12.5mg CTAB is added in the vial in the step (1); Add 20.5mg sodium metaaluminate and 26.5mg soda ash light successively after stirring 30min; Continue to stir 1min again, stir etching 16h down at 50 ℃ then, at room temperature leave standstill cooling at last.
(3) extracting waste deposition water and ethanol clean 2 times repeatedly, are dispersed in again then in the water of 15mL and form dispersion liquid.
(4) dispersion liquid with step (3) gained shifts as in the middle of the 20mL polytetrafluoroethyllining lining, places reaction kettle at 130 ℃ of following constant temperature 72h polytetrafluoroethyllining lining then, at last cooling at room temperature.
(5) white precipitate water and the ethanol handled through step (4) clean to 2 times repeatedly, dry naturally then to obtain white powder.
(6) after being removed, the cats product that uses promptly gets title product from white powder.
Claims (10)
1. the preparation method of an ordered mesoporous silicon aluminate hollow ball is characterized in that it may further comprise the steps:
1) silica spheres is added in the entry, obtain the silica spheres dispersion liquid after ultrasonic;
2) cats product is added the silica spheres dispersion liquid of step 1) gained, add alkali source and aluminium source after the stirring again, carry out etching then, etching is accomplished the back and is collected deposition and clean the 1st time;
3) get step 2) the 1st precipitation of gained be dispersed in and form dispersion liquid in the water; The gained dispersion liquid is transferred in the polytetrafluoroethyllining lining; Place reaction kettle reaction back to collect deposition the 2nd time polytetrafluoroethyllining lining then; Clean dry white powder, decationize tensio-active agent from white powder promptly gets ordered mesoporous silicon aluminate hollow ball.
2. the preparation method of a kind of ordered mesoporous silicon aluminate hollow ball as claimed in claim 1 is characterized in that in step 1), and the mass ratio of said silica spheres and water is 1: 25～200.
3. the preparation method of a kind of ordered mesoporous silicon aluminate hollow ball as claimed in claim 1 is characterized in that in the said ultransonic time of step 1) be 10～30min.
4. the preparation method of a kind of ordered mesoporous silicon aluminate hollow ball as claimed in claim 1; It is characterized in that in step 2) in; The mass ratio of said silica spheres and cats product is 25: 3～5, and the mass ratio of said alkali source, aluminium source and silica spheres is 1: 1: 1.66～3.32.
5. the preparation method of a kind of ordered mesoporous silicon aluminate hollow ball as claimed in claim 1 is characterized in that said cats product is cetyl trimethylammonium bromide or palmityl trimethyl ammonium chloride.
6. the preparation method of a kind of ordered mesoporous silicon aluminate hollow ball as claimed in claim 1 is characterized in that said alkali source is a soda ash light, and said aluminium source is a sodium metaaluminate.
7. the preparation method of a kind of ordered mesoporous silicon aluminate hollow ball as claimed in claim 1 is characterized in that in step 2) condition of said etching is: 50～90 ℃ of etching temperatures, etching time 3～24h.
8. the preparation method of a kind of ordered mesoporous silicon aluminate hollow ball as claimed in claim 1 is characterized in that in step 3), and the mass ratio of said the 1st deposition and water is 1: 25～200; The temperature of said reaction is 100～150 ℃, and the time of reaction is 24～72h, and said dispersion liquid and said teflon-lined volume ratio are 1: 2～3.
9. the preparation method of a kind of ordered mesoporous silicon aluminate hollow ball as claimed in claim 8, the temperature that it is characterized in that said reaction is 150 ℃; The time of reaction is 48h.
10. the preparation method of a kind of ordered mesoporous silicon aluminate hollow ball as claimed in claim 1 is characterized in that in step 3), and said decationize tensio-active agent is the method that adopts acetone extract.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100692121A CN102167350B (en) | 2011-03-21 | 2011-03-21 | Method for preparing ordered mesoporous aluminosilicate hollow sphere |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100692121A CN102167350B (en) | 2011-03-21 | 2011-03-21 | Method for preparing ordered mesoporous aluminosilicate hollow sphere |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102167350A CN102167350A (en) | 2011-08-31 |
| CN102167350B true CN102167350B (en) | 2012-11-14 |
Family
ID=44488705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100692121A Expired - Fee Related CN102167350B (en) | 2011-03-21 | 2011-03-21 | Method for preparing ordered mesoporous aluminosilicate hollow sphere |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102167350B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529523A (en) * | 2018-11-26 | 2019-03-29 | 吉林大学 | Molecular sieve core-mesoporous organosilicon hollow shell multi-stage porous composite material and preparation method |
| CN111232984B (en) * | 2020-03-09 | 2021-06-25 | 常熟理工学院 | Method for preparing sintering-free high-stability mesoporous silica-alumina material by using silica fume and aluminum fume and product |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6319486B1 (en) * | 1999-09-22 | 2001-11-20 | Chinese Petroleum Corp. | Control of morphology of mesoporous aluminosilicate or pure-silica molecular sieves by effect of alcohol |
| CN100406382C (en) * | 2003-10-15 | 2008-07-30 | 中国科学院上海硅酸盐研究所 | Water thermostable cube phase medium aperture aluminosilicate hollow ball and preparation method thereof |
| CN101618336B (en) * | 2009-08-03 | 2012-05-23 | 大连理工大学 | Metal supported MCM-22 molecular sieve hollow sphere bifunctional catalyst preparation method and application thereof |
-
2011
- 2011-03-21 CN CN2011100692121A patent/CN102167350B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102167350A (en) | 2011-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5175428B2 (en) | Material with hierarchical porosity containing silicon | |
| CN103318911B (en) | Preparation method of beta zeolite with multilevel pore canals | |
| CN101890363B (en) | Preparation method for mesopore-micropore core-shell composite molecular sieve catalyst | |
| CN102167336A (en) | Preparation method of mesoporous silicon dioxide hollow sphere | |
| DK3166910T3 (en) | LIKE USING A RECYCLABLE AND RECYCLABLE MESOPORE TEMPLATE AGENT | |
| CN103539153B (en) | The preparation method of nanometer hierarchical pore ZSM-11/ZSM-5 eutectic zeolite | |
| CN104707542B (en) | A kind of photochemical catalyst/SiO2aerogel composite and preparation method thereof | |
| CN101795968B (en) | Crystallised material containing silicon with hierarchised and organised porosity | |
| CN104030314A (en) | ZSM-5-based hierarchical porous molecular sieve material and preparation method thereof | |
| Song et al. | Synthesis and catalytic characterization of ZSM-5 zeolite with uniform mesopores prepared in the presence of a novel organosiloxane | |
| CN101549279A (en) | Method for improving specific surface area of diatomite | |
| CN101746775B (en) | Preparation method for organic functional ordered mesoporous titanium oxide silicon molecular sieve | |
| CN102001681A (en) | Method for synthesizing ZSM-5 zeolite | |
| Guo et al. | Design of MoS2/MMT bi-layered aerogels integrated with phase change materials for sustained and efficient solar desalination | |
| CN103693693A (en) | Preparation method for synthesizing molybdenum sulfide nanospheres by microwave-assisted liquid phase deposition | |
| CN102167350B (en) | Method for preparing ordered mesoporous aluminosilicate hollow sphere | |
| JP5767977B2 (en) | Method for forming an aluminosilicate-zeolite layer on a metal substrate, coated substrate and use thereof | |
| Lin et al. | Aerosol processing of low-cost mesoporous silica spherical particles from photonic industrial waste powder for CO2 capture | |
| CN109694087A (en) | A kind of synthetic method of nano-ZSM-5 molecular sieve aggregation | |
| CN102942193A (en) | Method for synthesizing novel thin layer ZSM-5 zeolite with boron-containing framework | |
| CN100500564C (en) | Method for preparing mesoporous material by non-surface activator process | |
| CN100406382C (en) | Water thermostable cube phase medium aperture aluminosilicate hollow ball and preparation method thereof | |
| US8568882B2 (en) | Mesostructured material having a high aluminium content and consisting of spherical particles of specific size | |
| CN102285659B (en) | Ordered mesoporous silicon-dioxide material and preparation method thereof | |
| CN101475589B (en) | Preparation and use of mesoporous-macroporous structure aluminum organophosphonate material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121114 Termination date: 20190321 |