CN101024187A - Super-strong acid mesoporous material synthesized in one pot and preparing method - Google Patents
Super-strong acid mesoporous material synthesized in one pot and preparing method Download PDFInfo
- Publication number
- CN101024187A CN101024187A CN 200710061628 CN200710061628A CN101024187A CN 101024187 A CN101024187 A CN 101024187A CN 200710061628 CN200710061628 CN 200710061628 CN 200710061628 A CN200710061628 A CN 200710061628A CN 101024187 A CN101024187 A CN 101024187A
- Authority
- CN
- China
- Prior art keywords
- super
- mesoporous material
- stir
- strong acid
- acid mesoporous
- 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.)
- Granted
Links
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a one-pot synthesis super acid mesoporous material and preparation method, specifically involved a SO42-/ZrO2-SiO2 super acid mesoporous material and preparation method. Its characteristic lie in Zr(NO3)4 . 3H2O and CTAB were separately dissolved in ethanol solution, mix stirring, calculated as A; At the same time, the mixture of concentration 1mol/LH2SO4 and 2 mol/LHCl into Polyoxyethylene - polyoxypropylene - Polyoxyethylene triblock copolymer, and add to silicate lipid mixing make it uniform, calculated as B; put A into reaction kettle loaded with Teflon-lined, heating 3-4h under the 95-100degree centigrade, and after its removal, after cooling joined into B, the mixture evenly loaded into reaction kettle, at 95 ~ 100 degree centigrade crystallization 45 ~ 48 h, it would complete after washing filtrating roasting to remove template. The method prepared super acid mesoporous materials has short synthesis lead time, and have structured mesoporous structure, good thermal stability, and it demonstrated a positive catalytic activity in positive pentane isomerization reaction, it will become the important catalytic material of fine chemical,petrochemical and other aspects.
Description
One, technical field
One pot of synthetic super-strong acid mesoporous material of the present invention and preparation method are a kind of synthetic methods about inorganic hole catalysis material, belong to field of fine chemical, more particularly, are a kind of easy SO
4 2-/ ZrO
2-SiO
2The synthetic method of super-strong acid mesoporous material.
Two, technical background
Since but Mobil company in 1992 at first successfully utilizes the alkyl quaternary ammonium salts cationic surfactant to synthesize the novel M41S series mesoporous SiO of aperture at 2-10nm scope modulation for the template agent
2After the material, the research of mesoporous material becomes international one big focus rapidly.It is big that such material has specific area, characteristics such as the narrow and high adsorption capacity of pore-size distribution, especially in recent years, along with constantly bringing forth new ideas of technology, emerge SBA, HMS equimolecular sieve series, its heat endurance and hydrothermal stability all improve a lot, and more cause the extensive concern of people to this material.
But a little less than this class pure silicon mesoporous material surface acidity, catalytic activity is low, must introduce metal heteroatom, increases its catalytic activity, so people expand to transition metal oxide (WO with thinking
3, TiO
2, ZrO
2Deng).And zirconia is unique acidity, alkalescence, oxidisability and reproducibility of having simultaneously, the catalyst of being made by it has unique catalytic activity and selectivity, but its poor heat stability, pore structure is caved in easily when removed template method and preparation super acids, has seriously hindered the application in PETROLEUM PROCESSING industry.
Adopting the synthetic zirconium mesoporous material that contains of direct synthesis technique is a feasibility method that addresses the above problem, but zirconic content very low (Zr/Si≤0.25) in the mesoporous material that is synthesized of oneself report, too high Zr/Si can not synthesize meso-porous material, therefore can't reach the theoretical preparation activity that requires and be equivalent to SO
4 2-/ ZrO
2The zirconium content of solid super-strong acid catalytic material.
With Heat stability is good, the regular pure silicon mesopore molecular sieve in duct is carrier, the SO that makes with infusion process
4 2-/ ZrO
2-SiO
2The type super acids also is a kind of method of studying at present, is distributed in the cubic phase ZrO in the mesopore molecular sieve hole in theory
2Has high SO
4 2-As long as load performance is ZrO
2 Content surpass 50%, crystal particle diameter≤5nm should be able to obtain greater than SO
4 2-/ ZrO
2The super acidic catalyst of type activity, but in fact work as ZrO
2Carrying capacity surpass 40%, ZrO in preparation process
2Move out of the crystal grain that formation is big outside the duct and pile up, will stop up the duct, specific area is descended, the SO that catalytic activity also prepares well below the precipitation method rapidly
4 2-/ ZrO
2Solid super acid catalyst.
The inventor successfully adopts direct method to synthesize SO high-ratio surface, highly acid
4 2-/ ZrO
2-SiO
2Super-strong acid mesoporous material (number of patent application: CN200410064502.7) (Li Fuxiang, Yu Feng, Li Yongli.Li Ruifeng, and Xie Kechang Microporous and Mesoporous Materials, 2007), and in n-pentane isomerization reaction, show good catalytic performance.But the zirconium mesoporous material needs that contain that this method is synthetic just possess superpower acidity through the post processing of sulfuric acid dipping again, thereby the Preparation of catalysts step is more, and the cycle is longer.If can adopt one kettle way to synthesize SO
4 2-/ ZrO
2-SiO
2Super-strong acid mesoporous material, promptly in the building-up process that contains the zirconium mesoporous material just with SO
4 2-Directly introduce, so just can reduce cost, simplify step, the shortening cycle.This certainly will will have great application prospect in petrochemical industry and field of fine chemical.
Three, summary of the invention
One pot of synthetic super-strong acid mesoporous material of the present invention and preparation method's purpose is in the building-up process that contains the zirconium mesoporous material SO
4 2-Introduce, directly synthesize SO by one kettle way
4 2-/ ZrO
2-SiO
2Super-strong acid mesoporous material, thus a kind of easy SO is disclosed
4 2-/ ZrO
2-SiO
2The synthetic method of super-strong acid mesoporous material.
One pot of synthetic super-strong acid mesoporous material of the present invention is characterized in that it being a kind of by the directly synthetic SO of one kettle way
4 2-/ ZrO
2-SiO
2Super-strong acid mesoporous material.
The preparation method of one pot of above-mentioned synthetic super-strong acid mesoporous material is characterized in that it being a kind of method by the direct synthesizing super-strong acid mesoporous material of one kettle way, and its concrete synthesis step is:
I. at first with Zr (NO
3)
43H
2O and softex kw are called for short CTAB and are dissolved in ethanolic solution respectively, after the dissolving, mix and stir, and count A; Simultaneously polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO) triblock copolymer abbreviation P123 being dissolved in concentration is: 1mol/LH
2SO
4In the HCl mixed liquor of 2mol/L, under 35~40 ℃, stir to triblock copolymer and dissolve fully, add tetraethoxysilance and be called for short TEOS, continue to stir 2~3h, count B;
II. then A is loaded on and has in the teflon-lined reactor,,, be cooled to room temperature then with its taking-up at 105~115 ℃ of heating 3~4h down, at room temperature stir 20~40min again, add B, mixed evenly after, reinstall reactor,, count C in 95~100 ℃ of following crystallization 45~48h;
III. last, with the C cooling, washing, suction filtration after the drying at room temperature, in 590~610 ℃ of roasting 2.5~3.5h, promptly gets Zr/Si than the SO that is 0.1~3.0
4 2-/ ZrO
2-SiO
2Super-strong acid mesoporous material.
One pot of synthetic super-strong acid mesoporous material of the present invention and preparation method's advantage is: the SO that this method makes
4 2-/ ZrO
2-SiO
2The super-strong acid mesoporous material step is few, and the cycle is short, and has regular meso-hole structure, Heat stability is good, and in n-pentane isomerization reaction, show good catalytic activity, will become the important catalysis materials in aspect such as fine chemistry industry, petrochemical industry.
Four, description of drawings
Fig. 1 is the SO of Zr/Si=1.1
4 2-/ ZrO
2-SiO
2The low angle of super-strong acid mesoporous material and high angle XRD diffraction pattern.
Five, the specific embodiment
At first with 4.4gZr (NO
3)
43H
2O and 1.63gCTAB are dissolved in the ethanolic solution of 40ml and 15ml respectively, after the dissolving, mix and stir 1h, count A; With 1gP123, be dissolved in 10ml 1mol/LH simultaneously
2SO
4With the mixed liquor of the HCl of 30ml2mol/L, stir 3h down in 40 ℃, after dissolving fully to P123, add 2.3mlTEOS, continue to stir 2.5h, count B;
Then A is loaded on 100ml and has in the teflon-lined reactor, pre-crystallization 3.5h under 110 ℃ then with its taking-up, is cooled to room temperature, at room temperature stirs 0.5h again, adds B, continues to stir 3h, and the dress still in 100 ℃ of following crystallization 48h, is counted C;
At last, with the C cooling, washing, suction filtration after the drying at room temperature, in 600 ℃ of roasting 3h, promptly gets SO
4 2-/ ZrO
2-SiO
2Super-strong acid mesoporous material, better through its degree of crystallinity of XRD analysis.
At first with 4.4gZr (NO
3)
43H
2O and 1.63gCTAB are dissolved in the ethanolic solution of 40ml and 15ml respectively, after the dissolving, mix and stir lh, count A; With 1gP123, be dissolved in 20ml 1mol/LH simultaneously
2SO
4With the mixed liquor of the HCl of 20ml2mol/L, stir 4h down in 40 ℃, after dissolving fully to P123, add 2.3mlTEOS, continue to stir 2h, count B;
Then A is loaded on 100ml and has in the teflon-lined reactor, pre-crystallization 4h under 110 ℃ then with its taking-up, is cooled to room temperature, at room temperature stirs 0.5h again, adds B, continues to stir 3h, and the dress still in 95 ℃ of following crystallization 48h, is counted C;
At last, with the C cooling, washing, suction filtration after the drying at room temperature, in 610 ℃ of roasting 2.5h, promptly gets SO
4 2/ ZrO
2-SiO
2Super-strong acid mesoporous material is more than two times of embodiment one gained sample through its degree of crystallinity of XRD analysis.
At first with 4.4gZr (NO
3)
43H
2O and 1.63gCTAB are dissolved in the ethanolic solution of 40ml and 15ml respectively, after the dissolving, mix and stir 1h, count A; With 1gP123, be dissolved in 30ml 1mol/LH simultaneously
2SO
4With the mixed liquor of the HCl of 10ml2mol/L, stir 3.5h down in 38 ℃, after dissolving fully to P123, add 2.3mlTEOS, continue to stir 3h, count B;
Then A is loaded on 100ml and has in the teflon-lined reactor, pre-crystallization 3h under 115 ℃ then with its taking-up, is cooled to room temperature, at room temperature stirs 0.5h again, adds B, continues to stir 3h, and the dress still in 100 ℃ of following crystallization 46h, is counted C;
At last, with the C cooling, washing, suction filtration after the drying at room temperature, in 590 ℃ of roasting 3.5h, promptly gets SO
4 2-/ ZrO
2-SiO
2Super-strong acid mesoporous material.Through its degree of crystallinity of XRD analysis is more than a times of degree of crystallinity of embodiment one gained sample.
At first with 4.4gZr (NO
3)
43H
2O and 1.63gCTAB are dissolved in the ethanolic solution of 40ml and 15ml respectively, after the dissolving, mix and stir 1h, count A; With 1gP123, be dissolved in 40ml 1mol/LH simultaneously
2SO
4Solution stirs 3h under 40 ℃, after dissolving fully to P123, add 2.3ml TEOS, continues to stir 2.5h, counts B;
Then A is loaded on 100ml and has in the teflon-lined reactor, pre-crystallization 4h under 105 ℃ then with its taking-up, is cooled to room temperature, at room temperature stirs 0.5h again, adds B, continues to stir 3h, and the dress still in 100 ℃ of following crystallization 45h, is counted C;
At last, with the C cooling, washing, suction filtration after the drying at room temperature, in 600 ℃ of roasting 3h, promptly gets SO
4 2-/ ZrO
2-SiO
2Super-strong acid mesoporous material.Through its degree of crystallinity of XRD analysis is about 90% of embodiment one gained sample.
At first with 0.4gZr (NO
3)
43H
2O and 0.15gCTAB are dissolved in the ethanolic solution of 40ml and 15ml respectively, after the dissolving, mix and stir 1h, count A; With 1gP123, be dissolved in 20ml 1mol/LH simultaneously
2SO
4With the mixed liquor of the HCl of 20ml2mol/L, stir 4h down in 35 ℃, after dissolving fully to P123, add 2.3mlTEOS, continue to stir 2.5h, count B;
Then A is loaded on 100ml and has in the teflon-lined reactor, pre-crystallization 3.5h under 110 ℃ then with its taking-up, is cooled to room temperature, at room temperature stirs 0.5h again, adds B, continues to stir 3h, and the dress still in 100 ℃ of following crystallization 48h, is counted C;
At last, with the C cooling, washing, suction filtration after the drying at room temperature, in 600 ℃ of roasting 3h, promptly gets SO
4 2-/ ZrO
2-SiO
2Super-strong acid mesoporous material.Through its degree of crystallinity of XRD analysis is more than 3 times of embodiment one gained sample.
Embodiment 6
At first with 5.2gZr (NO
3)
43H
2O and 1.93gCTAB are dissolved in the ethanolic solution of 40ml and 15ml respectively, after the dissolving, mix and stir 1h, count A; With 1gP123, be dissolved in 10ml 1mol/LH simultaneously
2SO
4With the mixed liquor of the HCl of 30ml2mol/L, in 38 ℃ stir 3h to P123 down and dissolve fully after, add 2.3ml TEOS, continue to stir 2h, count B;
Then A is loaded on 100ml and has in the teflon-lined reactor, pre-crystallization 3.5h under 110 ℃ then with its taking-up, is cooled to room temperature, at room temperature stirs 0.5h again, adds B, continues to stir 3h, and the dress still in 100 ℃ of following crystallization 48h, is counted C;
At last, with the C cooling, washing, suction filtration after the drying at room temperature, in 595 ℃ of roasting 3h, promptly gets SO
4 2-/ ZrO
2-SiO
2Super-strong acid mesoporous material.Through its degree of crystallinity of XRD analysis be embodiment one gained sample degree of crystallinity about 70%.
Embodiment 7
At first with 5.2gZr (NO
3)
43H
2O and 1.93gCTAB are dissolved in the ethanolic solution of 40ml and 15ml respectively, after the dissolving, mix and stir 1h, count A; With 1gP123, be dissolved in 20ml 1mol/LH simultaneously
2SO
4With the mixed liquor of the HCl of 20ml2mol/L, in 40 ℃ stir 4h to P123 down and dissolve fully after, add 2.3ml TEOS, continue to stir 2.5h, count B;
Then A is loaded on 100ml and has in the teflon-lined reactor, pre-crystallization 4h under 105 ℃ then with its taking-up, is cooled to room temperature, at room temperature stirs 0.5h again, adds B, continues to stir 3h, and the dress still in 100 ℃ of following crystallization 48h, is counted C;
At last, with the C cooling, washing, suction filtration after the drying at room temperature, in 600 ℃ of roasting 3h, promptly gets SO
4 2-/ ZrO
2-SiO
2Super-strong acid mesoporous material.Through its degree of crystallinity of XRD analysis about 1.5 times of embodiment one gained sample.
Embodiment 8
At first with 5.2gZr (NO
3)
43H
2O and 1.93gCTAB are dissolved in the ethanolic solution of 40ml and 15ml respectively, after the dissolving, mix and stir 1h, count A; With 1gP123, be dissolved in 30ml 1mol/LH simultaneously
2SO
4With the mixed liquor of the HCl of 10ml2mol/L, stir 3h down in 40 ℃, after dissolving fully to P123, add 2.3mlTEOS, continue to stir 2h, count B;
Then A is loaded on 100ml and has in the teflon-lined reactor, pre-crystallization 3.5h under 110 ℃ then with its taking-up, is cooled to room temperature, at room temperature stirs 0.5h again, adds B, continues to stir 3h, and the dress still in 100 ℃ of following crystallization 48h, is counted C;
At last, with the C cooling, washing, suction filtration after the drying at room temperature, in 610 ℃ of roasting 3.5h, promptly gets SO
4 2-/ ZrO
2-SiO
2Super-strong acid mesoporous material.About the same through its degree of crystallinity of XRD analysis with the degree of crystallinity of embodiment one gained sample.
Embodiment 9
At first with 5.2gZr (NO
3)
43H
2O and 1.93gCTAB are dissolved in the ethanolic solution of 40ml and 15ml respectively, after the dissolving, mix and stir 1h, count A; With 1gP123, be dissolved in 40ml 1mol/LH simultaneously
2SO
4Solution stirs 3h under 40 ℃, after dissolving fully to P123, add 2.3ml TEOS, continues to stir 3h, counts B;
Then A is loaded on 100ml and has in the teflon-lined reactor, pre-crystallization 3.5h under 110 ℃ then with its taking-up, is cooled to room temperature, at room temperature stirs 0.5h again, adds B, continues to stir 3h, and the dress still in 100 ℃ of following crystallization 48h, is counted C;
At last, with the C cooling, washing, suction filtration after the drying at room temperature, in 600 ℃ of roasting 3h, promptly gets SO
4 2-/ ZrO
2-SiO
2Super-strong acid mesoporous material.Through its degree of crystallinity of XRD analysis is about 80% of embodiment one gained sample.
Embodiment 10
At first with 12gZr (NO
3)
43H
2O and 4.45gCTAB are dissolved in the ethanolic solution of 75ml and 30ml respectively, after the dissolving, mix and stir 1h, count A; With 1gP123, be dissolved in 30ml 1mol/LH simultaneously
2SO
4With the mixed liquor of the HCl of 10ml2mol/L, in 35 ℃ stir 4h to P123 down and dissolve fully after, add 2.3mlTEOS, continue to stir 3h, count B;
Then A is loaded on 100ml and has in the teflon-lined reactor, pre-crystallization 3h under 110 ℃ then with its taking-up, is cooled to room temperature, at room temperature stirs 0.5h again, adds B, continues to stir 4h, and the dress still in 98 ℃ of following crystallization 48h, is counted C;
At last, with the C cooling, washing, suction filtration after the drying at room temperature, in 600 ℃ of roasting 3h, promptly gets SO
4 2-/ ZrO
2-SiO
2Super-strong acid mesoporous material.Through its degree of crystallinity of XRD analysis is about 70% of embodiment one gained sample.
Claims (2)
1. one pot of synthetic super-strong acid mesoporous material is characterized in that it being a kind of by the directly synthetic SO of one kettle way
4 2-/ ZrO
2-SiO
2Super-strong acid mesoporous material.
2. the preparation method of the described one pot of synthetic super-strong acid mesoporous material of claim 1 is characterized in that it being a kind of method by the direct synthesizing super-strong acid mesoporous material of one kettle way, and its concrete synthesis step is:
I. at first with Zr (NO
3)
43H
2O and softex kw are called for short CTAB and are dissolved in ethanolic solution respectively, after the dissolving, mix and stir, and count A; Simultaneously polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO) triblock copolymer abbreviation P123 being dissolved in concentration is: 1mol/LH
2SO
4In the HCl mixed liquor of 2mol/L, under 35~40 ℃, stir to triblock copolymer and dissolve fully, add tetraethoxysilance and be called for short TEOS, continue to stir 2~3h, count B;
II. then A is loaded on and has in the teflon-lined reactor,,, be cooled to room temperature then with its taking-up at 105~115 ℃ of heating 3~4h down, at room temperature stir 20~40min again, add B, mixed evenly after, reinstall reactor,, count C in 95~100 ℃ of following crystallization 45~48h;
III. last, with the C cooling, washing, suction filtration, after the drying at room temperature, in 590~610 ℃ of roasting 2.5~3.5h, promptly getting the Zr/Si ratio is 0.1~3.0 super-strong acid mesoporous material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2007100616282A CN100496722C (en) | 2007-03-24 | 2007-03-24 | Preparing method of super-strong acid mesoporous material synthesized in one pot |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2007100616282A CN100496722C (en) | 2007-03-24 | 2007-03-24 | Preparing method of super-strong acid mesoporous material synthesized in one pot |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101024187A true CN101024187A (en) | 2007-08-29 |
CN100496722C CN100496722C (en) | 2009-06-10 |
Family
ID=38743011
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2007100616282A Expired - Fee Related CN100496722C (en) | 2007-03-24 | 2007-03-24 | Preparing method of super-strong acid mesoporous material synthesized in one pot |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN100496722C (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102008968A (en) * | 2010-11-11 | 2011-04-13 | 太原理工大学 | Solid superacid mesoporous material and preparation method thereof |
CN102690202A (en) * | 2012-06-07 | 2012-09-26 | 河北工业大学 | Preparation method of dodecanol benzoate |
CN105344372A (en) * | 2015-11-09 | 2016-02-24 | 太原理工大学 | Preparation device and preparation method for mesoporous zirconium-based molecular sieve catalyst |
CN106242947A (en) * | 2016-08-02 | 2016-12-21 | 黄山市徽州天马化工有限公司 | A kind of method utilizing cerium modified zirconium-silicon molecular sieve catalyst to prepare dichlorohydrin |
CN106622286A (en) * | 2016-11-30 | 2017-05-10 | 浙江理工大学 | Preparation method of S2O8<2>/ZrO2-SiO2 solid super acid |
CN109879317A (en) * | 2019-04-15 | 2019-06-14 | 陕西科技大学 | A kind of multi-stage porous ZrO2Solid material, preparation method and applications |
-
2007
- 2007-03-24 CN CNB2007100616282A patent/CN100496722C/en not_active Expired - Fee Related
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102008968A (en) * | 2010-11-11 | 2011-04-13 | 太原理工大学 | Solid superacid mesoporous material and preparation method thereof |
CN102008968B (en) * | 2010-11-11 | 2012-11-07 | 太原理工大学 | Solid superacid mesoporous material and preparation method thereof |
CN102690202A (en) * | 2012-06-07 | 2012-09-26 | 河北工业大学 | Preparation method of dodecanol benzoate |
CN105344372A (en) * | 2015-11-09 | 2016-02-24 | 太原理工大学 | Preparation device and preparation method for mesoporous zirconium-based molecular sieve catalyst |
CN105344372B (en) * | 2015-11-09 | 2017-08-04 | 太原理工大学 | The preparation facilities and preparation method of a kind of mesoporous zirconium base molecular sieve catalyst |
CN106242947A (en) * | 2016-08-02 | 2016-12-21 | 黄山市徽州天马化工有限公司 | A kind of method utilizing cerium modified zirconium-silicon molecular sieve catalyst to prepare dichlorohydrin |
CN106622286A (en) * | 2016-11-30 | 2017-05-10 | 浙江理工大学 | Preparation method of S2O8<2>/ZrO2-SiO2 solid super acid |
CN109879317A (en) * | 2019-04-15 | 2019-06-14 | 陕西科技大学 | A kind of multi-stage porous ZrO2Solid material, preparation method and applications |
CN109879317B (en) * | 2019-04-15 | 2021-04-09 | 陕西科技大学 | Hierarchical hole ZrO2Solid material, preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN100496722C (en) | 2009-06-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN100496722C (en) | Preparing method of super-strong acid mesoporous material synthesized in one pot | |
CN112038648B (en) | Hollow-structure transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application thereof | |
CN101376506B (en) | Composite double microporous material and preparation thereof | |
CN106946282B (en) | A kind of preparation method of porous cerium-based composite oxides | |
CN101172240B (en) | Method for preparing propylene by butylene disproportionation | |
CN105457618A (en) | Carbon quantum dot and titanium codoped mesoporous silica composite photocatalyst | |
CN107089669B (en) | A kind of synthetic method of c- axis orientating type Zn-ZSM-5 molecular sieve under externally-applied magnetic field effect | |
CN1837053A (en) | Process for preparing mesoporous ceria | |
CN102008968B (en) | Solid superacid mesoporous material and preparation method thereof | |
CN109775716A (en) | A kind of multi-stage porous Y type molecular sieve and preparation method thereof rich in L acid | |
CN104959162A (en) | Preparation method for in-situ zirconium-doped molecular sieve solid superacid | |
CN104971770B (en) | A kind of preparation method of the solid super-strong acid containing zirconium | |
CN101979136A (en) | Mesoporous composite oxide type solid super acidic catalyst and preparation method thereof | |
CN108080000A (en) | A kind of hollow porous micro sphere catalysis material and preparation method thereof and degradation NO applications | |
CN110354895A (en) | A kind of oxide porous photochemical catalyst of molecular screen base Ce-Mn and its preparation method and application | |
CN106012018A (en) | Preparation method for bismuth vanadate mesoporous single crystal | |
CN106276958A (en) | A kind of ordered big hole-mesoporous multi-stage porous titanium-silicon molecular sieve TS-1 monocrystalline with opal structural and synthetic method thereof | |
CN101112683A (en) | Cerium zirconium aluminum composite oxides sosoloid with a mesopore structure and method for preparing the same | |
CN102627297A (en) | Synthetic method for SAPO (Silicoaluminophosphate)-34 molecular sieve | |
CN101269832A (en) | Process for producing nano-cerium dioxide with high-specific surface area and high hole capacity | |
CN113385198B (en) | Ordered mesoporous sulfated zirconium-aluminum composite oxide solid acid material and preparation and application thereof | |
CN108658087A (en) | A kind of multistage pore canal TS-1 zeolitic materials and preparation method thereof | |
CN110240177A (en) | A kind of laminated structure MFI type zeolite molecular sieve and preparation method thereof | |
CN102807252B (en) | Mesoporous cerium zirconium solid solution composite oxide nano material and preparation method thereof | |
CN104525180A (en) | Preparation method for cerium-zirconium-aluminum-lanthanum-based oxygen storage material of mesoporous structure |
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 | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090610 Termination date: 20100324 |