CN101863499A - Preparation method of macroporous-mesoporous alumina - Google Patents
Preparation method of macroporous-mesoporous alumina Download PDFInfo
- Publication number
- CN101863499A CN101863499A CN201010187094A CN201010187094A CN101863499A CN 101863499 A CN101863499 A CN 101863499A CN 201010187094 A CN201010187094 A CN 201010187094A CN 201010187094 A CN201010187094 A CN 201010187094A CN 101863499 A CN101863499 A CN 101863499A
- Authority
- CN
- China
- Prior art keywords
- mesoporous
- preparation
- foramen magnum
- aluminum oxide
- solution
- 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
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of macroporous-mesoporous alumina, which comprises the following steps: a, dissolving reaction assistants and aluminum salts into solution of an organic solvent, wherein the molar ratio of the reaction assistants and aluminum ions is (3-5): 1, dissolving a template agent into the solution, wherein the molar ratio of the aluminum ions and the template agent is 1: (0.015-0.025), and finally controlling the PH value of the solution to be 3.5-6.0; b, aging the solution prepared in Step a to gradually remove the organic solvent and water in the system, thereby obtaining a macroporous-mesoporous alumina precursor; c, calcinating at the temperature of 400-800 DEG C, thereby obtaining macroporous-mesoporous alumina powder. The invention has the advantages of simple process, regular pore canals and centralized pore size distribution, and can realize controlled regulation according to specific application conditions. Therefore, the invention has significant value of application in heterogeneous catalysis and adsorptive separation in the petrochemical industry and the use as the catalyst carrier, energy material and the like.
Description
Technical field
The present invention relates to a kind of preparation method of foramen magnum-mesoporous aluminum oxide.
Background technology
Activated alumina can be widely used as catalytic material, as acid catalyst, support of the catalyst and be used for fields such as absorption, separation.Compare with conventional aluminium oxide, outstanding features such as specific surface area is big owing to having for the alumina pore material, compound with regular structure, aperture are big, the surface has acid sites are expected to replace traditional activated alumina and are applied to petrochemical industry heterogeneous catalyst, fractionation by adsorption, and as aspects such as support of the catalyst and energy and materials.
At present, Chinese scholars is in the exploratory stage for the synthetic of porous alumina, mainly concentrates on the duct ordering of single meso-porous alumina, the preparation and the regulation and control of pattern aspects such as aperture regularization.Foramen magnum-mesoporous composite holes alumina material than the alumina material of single mesoporous component in oil heterogeneous catalyst, the cracking of heavy oil bulky molecular catalysis and aspect catalyzer, catalytic carrier, have more advantage.This be because: 1, meso-hole structure is between the macropore hole wall, macropore, mesoporous interval produce and connect with macropore and mesopore orbit in material matrix inside, and Du Te pore structure is better than single mesoporous component aluminum oxide to macromolecular selectivity of heavy oil and assembly catalyze like this.2, aspect catalyzer and catalytic carrier, the alumina material that possesses foramen magnum-mesoporous compound pass more helps catalyzer in its surperficial useful load based on its unique pore structure, is not prone to hole plug, hole phenomenon such as cave in.3, foramen magnum-mesoporous its thermostability of composite holes aluminum oxide obviously is better than single mesoporous component alumina material, thereby it is stronger to be applied to the adaptability of heterogeneous catalyst under higher temperature conditions.
(Langmuir such as Tie-Zhen Ren, 2004,20:1531-1534) adopt nonionogenic tenside Brij 56 aluminium secondary butylates under acidic conditions, to adopt hydrothermal method and the synthetic foramen magnum-mesoporous aluminum oxide of microwave-assisted, synthetic porous alumina powder macropore diameter 0.8-2 μ m, mesoporous aperture 5-8nm, the aluminum oxide of hole wall 0.4-1.4 μ m.Its deficiency is that aluminium-alcohol salt costs an arm and a leg, and the foramen magnum-mesoporous aluminum oxide pore volume of synthetic is little, the duct is irregular, pore size distribution is excessive and can't realize effective adjusting of pore structure, thereby, on result of use and scope, significant limitation is arranged.(J.Am.Chem.Soc. such as Jean-Philippe Dacquin, 2009,131:12896-12897) adopting sol-gel method is that template is introduced the formation that the polystyrene small droplets with single disperse phase is realized macropore in the foramen magnum-mesoporous aluminum oxide with P123 in mixing solutions.Weak point is macropore diameter size (300nm or 400nm) is introduced the polystyrene drop fully by secondary size decision, and promptly the macropore diameter size depends on polystyrene drop size.Can't by the part of solution self component is changed and system in organic molecule interact and realize the adjustment in aperture.(Inorganic Chemistry such as Huining Li, 2009,48:4421) adopting sol-gel method equally is that template is introduced the formation that polymethylmethacrylate (PMMA) small droplets with single disperse phase is realized macropore in the foramen magnum-mesoporous aluminum oxide with F127 in mixing solutions, weak point is that the macropore diameter size is also introduced the decision of polymethylmethacrylate drop size by secondary fully, can't change the formation that the adjustment that realizes the aperture realizes foramen magnum-mesoporous composite pore structural by part to solution system self component, thereby also can't realize the controllable adjustment in foramen magnum-mesoporous aperture, in use, especially be subjected to significant limitation in the bulky molecular catalysis process at complicated ingredient.
Summary of the invention
The preparation method who the purpose of this invention is to provide the foramen magnum-mesoporous aluminum oxide in a kind of energy controllable adjustment aperture.
In order to achieve the above object, the present invention includes:
A. earlier reaction promoter and aluminium salt are dissolved in the organic solvent solution, reaction promoter: two kinds of material mol ratios of aluminum ion are 3～5: 1, template is added above-mentioned solution and dissolving, aluminum ion and template mol ratio are 1: 0.015～0.025 again, and the pH value of final solution is controlled at 3.5～6.0; B. the solution with a step preparation carries out burin-in process, makes it remove progressively that organic solvent and moisture obtain foramen magnum-mesoporous alumina precursor in the system; C. obtain foramen magnum-mesoporous alumina powder jointed through 400～800 ℃ of calcination process.
As improvement of the present invention, reaction promoter is an organic acid, and aluminium salt is inorganic aluminate.
Template is a triblock copolymer.
The dissolution process of described a step is to carry out under 30～60 ℃ of water bath condition.
The burin-in process temperature of b step is 50～80 ℃.
The calcination process temperature rise rate of c step is 0.5～2 ℃/min.
Preferably, organic solvent is anhydrous alcohols, ethers or ketones solvent.
Organic acid is citric acid or lauric acid.
Triblock copolymer is P123 or F127.
The technology of the present invention in aperture is simple, make full use of the space frame effect and the coordination of reaction promoter and template, and intermediary's organic polymer, reaction promoter be to the complexing action of mineral ion, thereby a step is prepared the adjustable foramen magnum-mesoporous alumina material in aperture.The specific surface area of prepared foramen magnum-mesoporous alumina material is up to 250～320m
2/ g, the duct rule, pore size distribution is at mesoporous 5～40nm, macropore 50～150nm, and can realize regulating according to practical situation.Thereby there is important use to be worth at petrochemical industry heterogeneous catalyst, fractionation by adsorption and as aspects such as support of the catalyst, energy and materials.As adopt inorganic aluminate can reduce preparation cost greatly.
Embodiment
Embodiment 1
Take by weighing 1.7g citric acid and 7.5g Al (NO
3)
39H
2O is dissolved in the ethanol solution of 40mL, at the uniform velocity stirs 0.5h under the room temperature, and solution is water white transparency, then 2.0g P123 is added above-mentioned solution, stirs 24h under 60 ℃ of water bath condition.Above-mentioned mixing solutions is moved to 60 ℃ of baking ovens continue burin-in process, and the ethanol and the moisture that progressively remove in the system obtain foramen magnum-mesoporous alumina precursor, the foramen magnum-mesoporous alumina precursor that removes ethanol and moisture fully becomes yellowish transparence, grind to form white powder and be placed on pyroprocessing in the program control retort furnace, 1 ℃/min of temperature rise rate, 400 ℃ the insulation 4h after naturally cooling obtain foramen magnum-mesoporous alumina material.
Transmission microscopy shows the foramen magnum-mesoporous alumina material macropore diameter 60～80nm that obtains, mesoporous aperture 20～40nm.N
2Aspiration desorption analysis result shows its specific surface area 290m
2/ g, mesoporous concentrating is distributed in 30nm, and macropore is concentrated and is distributed in 70nm.
Embodiment 2
Take by weighing 1.3g lauric acid and 5.0g AlCl
36H
2O is dissolved in the ethanol solution of 40mL, at the uniform velocity stirs 0.5h under the room temperature, and solution is water white transparency, then 1.6g P123 is added above-mentioned solution, stirs 24h under 30 ℃ of water bath condition.Above-mentioned mixing solutions is moved to 60 ℃ of baking ovens continue burin-in process, and the ethanol and the moisture that progressively remove in the system obtain foramen magnum-mesoporous alumina precursor, the foramen magnum-mesoporous alumina precursor that removes ethanol and moisture fully becomes yellowish transparence, grind to form white powder and be placed on pyroprocessing in the program control retort furnace, 1 ℃/min of temperature rise rate obtains foramen magnum-mesoporous alumina material behind 400 ℃ of insulation 4h.
Transmission microscopy shows the foramen magnum-mesoporous alumina material macropore diameter 50～80nm that obtains, mesoporous aperture 3～5nm.N2 aspiration desorption analysis result shows its specific surface area 320m
2/ g, mesoporous concentrating is distributed in 3.7nm, and macropore is concentrated and is distributed in 55nm.
Embodiment 3
Take by weighing 1.5g citric acid and 7.5g Al (NO
3)
39H
2O is dissolved in the ethanol solution of 40mL, at the uniform velocity stirs 0.5h under the room temperature, and solution is water white transparency, then 2.4g F127 is added above-mentioned solution, stirs 24h under 50 ℃ of water bath condition.Above-mentioned mixing solutions is moved to 60 ℃ of baking ovens continue burin-in process, and the ethanol and the moisture that progressively remove in the system obtain foramen magnum-mesoporous alumina precursor, the foramen magnum-mesoporous alumina precursor that removes ethanol and moisture fully becomes yellowish transparence, grind to form white powder and be placed on pyroprocessing in the program control retort furnace, 1 ℃/min of temperature rise rate obtains foramen magnum-mesoporous alumina material behind 400 ℃ of insulation 4h.
Transmission microscopy shows the foramen magnum-mesoporous alumina material macropore diameter 50～80nm that obtains, mesoporous aperture 10～30nm.N
2Aspiration desorption analysis result shows its specific surface area 260m
2/ g, mesoporous concentrating is distributed in 15nm, and macropore is concentrated and is distributed in 80nm.
Embodiment 4
Take by weighing 1.8g lauric acid and 5.0g AlCl
36H
2O is dissolved in the butanol solution of 40mL, at the uniform velocity stirs 0.5h under the room temperature, and solution is water white transparency, then 1.8g P123 is added above-mentioned solution, stirs 24h under 50 ℃ of water bath condition.Above-mentioned mixing solutions is moved to 60 ℃ of baking ovens continue burin-in process, and the ethanol and the moisture that progressively remove in the system obtain foramen magnum-mesoporous alumina precursor, the foramen magnum-mesoporous alumina precursor that removes propyl carbinol and moisture fully becomes yellowish transparence, grind to form white powder and be placed on pyroprocessing in the program control retort furnace, 1 ℃/min of temperature rise rate obtains foramen magnum-mesoporous alumina material behind 400 ℃ of insulation 4h.
At this moment, transmission microscopy shows the foramen magnum-mesoporous alumina material macropore diameter 50～80nm that obtains, mesoporous aperture 3～5nm.N
2Aspiration desorption analysis result shows its specific surface area 290m
2/ g, mesoporous concentrating is distributed in 6.5nm, and macropore is concentrated and is distributed in 60nm.
Claims (9)
1. the preparation method of a foramen magnum-mesoporous aluminum oxide may further comprise the steps:
A. earlier reaction promoter and aluminium salt are dissolved in the organic solvent solution, reaction promoter: two kinds of material mol ratios of aluminum ion are 3～5: 1, template is added above-mentioned solution and dissolving, aluminum ion and template mol ratio are 1: 0.015～0.025 again, and the pH value of final solution is controlled at 3.5～6.0; B. the solution with a step preparation carries out burin-in process, makes it remove progressively that organic solvent and moisture obtain foramen magnum-mesoporous alumina precursor in the system; C. obtain foramen magnum-mesoporous alumina powder jointed through 400～800 ℃ of calcination process.
2. according to the preparation method of a kind of foramen magnum-mesoporous aluminum oxide of claim 1, reaction promoter is an organic acid, and aluminium salt is inorganic aluminate.
3. according to the preparation method of a kind of foramen magnum-mesoporous aluminum oxide of claim 1, template is a triblock copolymer.
4. according to the preparation method of a kind of foramen magnum-mesoporous aluminum oxide of claim 1, the dissolution process of described a step is to carry out under 30～60 ℃ of water bath condition.
5. according to the preparation method of a kind of foramen magnum-mesoporous aluminum oxide of claim 1, the burin-in process temperature of b step is 50～80 ℃.
6. according to the preparation method of a kind of foramen magnum-mesoporous aluminum oxide of claim 1, the calcination process temperature rise rate of step is 0.5～2 ℃/min.
7. according to the preparation method of a kind of foramen magnum-mesoporous aluminum oxide of claim 1, organic solvent is anhydrous alcohols, ethers or ketones solvent.
8. according to the preparation method of a kind of foramen magnum-mesoporous aluminum oxide of claim 2, organic acid is citric acid or lauric acid.
9. according to the preparation method of a kind of foramen magnum-mesoporous aluminum oxide of claim 3, triblock copolymer is P123 or F127.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010187094A CN101863499B (en) | 2010-05-31 | 2010-05-31 | Preparation method of macroporous-mesoporous alumina |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010187094A CN101863499B (en) | 2010-05-31 | 2010-05-31 | Preparation method of macroporous-mesoporous alumina |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101863499A true CN101863499A (en) | 2010-10-20 |
| CN101863499B CN101863499B (en) | 2012-10-24 |
Family
ID=42955472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010187094A Expired - Fee Related CN101863499B (en) | 2010-05-31 | 2010-05-31 | Preparation method of macroporous-mesoporous alumina |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101863499B (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173390A (en) * | 2011-01-20 | 2011-09-07 | 复旦大学 | Ordered mesoporous metal oxide material with ultra-large aperture and preparation method thereof |
| CN102614934A (en) * | 2011-01-30 | 2012-08-01 | 中国石油化工股份有限公司 | Alumina carrier with composite pore structure and preparation method thereof |
| CN102659151A (en) * | 2012-04-24 | 2012-09-12 | 中国铝业股份有限公司 | Method for preparing spherical porous alumina carrier |
| CN102701247A (en) * | 2012-05-08 | 2012-10-03 | 山东大学 | Preparation method of mesoporous spherical aluminum oxide |
| CN102765737A (en) * | 2011-05-06 | 2012-11-07 | 北京化工大学 | Mesoporous spherical alumina prepared by guiding of template and preparation method thereof |
| CN103048363A (en) * | 2011-10-12 | 2013-04-17 | 中国科学院合肥物质科学研究院 | Metallic oxide material with mesoporous-macroporous composite structure as well as preparation method and application thereof |
| WO2014120037A1 (en) * | 2013-02-04 | 2014-08-07 | Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" | Aluminum oxide |
| CN105565351A (en) * | 2015-12-11 | 2016-05-11 | 李金秀 | Preparing method of high thermal stability aluminum oxide |
| CN106861665A (en) * | 2017-03-02 | 2017-06-20 | 太原理工大学 | Aluminum oxide hydrolytic catalyst of carbonyl sulfur and preparation method thereof |
| CN106984303A (en) * | 2017-04-28 | 2017-07-28 | 武汉理工大学 | A kind of mesoporous γ Al of grade hole macropore for supporting noble metal2O3Catalyst and preparation method thereof |
| CN107096552A (en) * | 2017-06-02 | 2017-08-29 | 钦州学院 | A kind of catalyst and preparation method for FCC gasoline removal of mercaptans |
| CN107159279A (en) * | 2017-06-02 | 2017-09-15 | 钦州学院 | A kind of one-stage selective hydrogenation of gasoline splitting catalyst and preparation method thereof |
| CN107185567A (en) * | 2017-06-02 | 2017-09-22 | 钦州学院 | A kind of nickel system selective hydrocatalyst and preparation method thereof |
| CN108793211A (en) * | 2017-05-02 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of macroporous aluminium oxide and preparation method thereof of dual pore size distribution |
| CN109052358A (en) * | 2018-10-09 | 2018-12-21 | 湖南雅城新材料有限公司 | A kind of preparation method of mesopore-macropore ferric phosphate |
| CN112490427A (en) * | 2020-11-30 | 2021-03-12 | 湖北亿纬动力有限公司 | Cathode material and preparation method and application thereof |
| CN114054037A (en) * | 2020-08-03 | 2022-02-18 | 中国石油天然气股份有限公司 | Paraffin hydrogenation catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346801A (en) * | 2001-09-26 | 2002-05-01 | 复旦大学 | Process for preparing nano-size uniform mesoporous aluminium oxide ball separating agent |
| KR20020083235A (en) * | 2001-04-26 | 2002-11-02 | 이종협 | Production Method of Mesoporous Alumina using Templates |
| CN1958450A (en) * | 2006-10-13 | 2007-05-09 | 广东工业大学 | Method for synthesizing mesoporous molecular sieve of alumina |
-
2010
- 2010-05-31 CN CN201010187094A patent/CN101863499B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020083235A (en) * | 2001-04-26 | 2002-11-02 | 이종협 | Production Method of Mesoporous Alumina using Templates |
| CN1346801A (en) * | 2001-09-26 | 2002-05-01 | 复旦大学 | Process for preparing nano-size uniform mesoporous aluminium oxide ball separating agent |
| CN1958450A (en) * | 2006-10-13 | 2007-05-09 | 广东工业大学 | Method for synthesizing mesoporous molecular sieve of alumina |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173390A (en) * | 2011-01-20 | 2011-09-07 | 复旦大学 | Ordered mesoporous metal oxide material with ultra-large aperture and preparation method thereof |
| CN102614934B (en) * | 2011-01-30 | 2015-08-19 | 中国石油化工股份有限公司 | Alumina support of a kind of composite pore structural and preparation method thereof |
| CN102614934A (en) * | 2011-01-30 | 2012-08-01 | 中国石油化工股份有限公司 | Alumina carrier with composite pore structure and preparation method thereof |
| CN102765737A (en) * | 2011-05-06 | 2012-11-07 | 北京化工大学 | Mesoporous spherical alumina prepared by guiding of template and preparation method thereof |
| CN103048363A (en) * | 2011-10-12 | 2013-04-17 | 中国科学院合肥物质科学研究院 | Metallic oxide material with mesoporous-macroporous composite structure as well as preparation method and application thereof |
| CN102659151A (en) * | 2012-04-24 | 2012-09-12 | 中国铝业股份有限公司 | Method for preparing spherical porous alumina carrier |
| CN102659151B (en) * | 2012-04-24 | 2013-08-14 | 中国铝业股份有限公司 | Method for preparing spherical porous alumina carrier |
| CN102701247A (en) * | 2012-05-08 | 2012-10-03 | 山东大学 | Preparation method of mesoporous spherical aluminum oxide |
| WO2014120037A1 (en) * | 2013-02-04 | 2014-08-07 | Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" | Aluminum oxide |
| CN105121347A (en) * | 2013-02-04 | 2015-12-02 | 俄罗斯工程技术中心 | Aluminum oxide |
| CN105565351A (en) * | 2015-12-11 | 2016-05-11 | 李金秀 | Preparing method of high thermal stability aluminum oxide |
| CN105565351B (en) * | 2015-12-11 | 2018-06-26 | 李金秀 | The preparation method of high thermal stability aluminum oxide |
| CN106861665A (en) * | 2017-03-02 | 2017-06-20 | 太原理工大学 | Aluminum oxide hydrolytic catalyst of carbonyl sulfur and preparation method thereof |
| CN106861665B (en) * | 2017-03-02 | 2019-10-15 | 太原理工大学 | The preparation method of aluminium oxide hydrolytic catalyst of carbonyl sulfur |
| CN106984303A (en) * | 2017-04-28 | 2017-07-28 | 武汉理工大学 | A kind of mesoporous γ Al of grade hole macropore for supporting noble metal2O3Catalyst and preparation method thereof |
| CN106984303B (en) * | 2017-04-28 | 2019-09-10 | 武汉理工大学 | A kind of foramen magnum-mesoporous γ-Al in grade hole supporting noble metal2O3Catalyst and preparation method thereof |
| CN108793211A (en) * | 2017-05-02 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of macroporous aluminium oxide and preparation method thereof of dual pore size distribution |
| CN107185567A (en) * | 2017-06-02 | 2017-09-22 | 钦州学院 | A kind of nickel system selective hydrocatalyst and preparation method thereof |
| CN107159279A (en) * | 2017-06-02 | 2017-09-15 | 钦州学院 | A kind of one-stage selective hydrogenation of gasoline splitting catalyst and preparation method thereof |
| CN107159279B (en) * | 2017-06-02 | 2019-05-17 | 钦州学院 | A kind of one-stage selective hydrogenation of gasoline splitting catalyst and preparation method thereof |
| CN107185567B (en) * | 2017-06-02 | 2019-05-17 | 钦州学院 | A kind of nickel system selective hydrocatalyst and preparation method thereof |
| CN107096552A (en) * | 2017-06-02 | 2017-08-29 | 钦州学院 | A kind of catalyst and preparation method for FCC gasoline removal of mercaptans |
| CN109052358A (en) * | 2018-10-09 | 2018-12-21 | 湖南雅城新材料有限公司 | A kind of preparation method of mesopore-macropore ferric phosphate |
| CN114054037A (en) * | 2020-08-03 | 2022-02-18 | 中国石油天然气股份有限公司 | Paraffin hydrogenation catalyst and preparation method thereof |
| CN114054037B (en) * | 2020-08-03 | 2024-06-28 | 中国石油天然气股份有限公司 | Paraffin hydrogenation catalyst and preparation method thereof |
| CN112490427A (en) * | 2020-11-30 | 2021-03-12 | 湖北亿纬动力有限公司 | Cathode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101863499B (en) | 2012-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101863499B (en) | Preparation method of macroporous-mesoporous alumina | |
| Yu et al. | Microstructures and photoactivity of mesoporous anatase hollow microspheres fabricated by fluoride-mediated self-transformation | |
| Shang et al. | Template-free fabrication of TiO2 hollow spheres and their photocatalytic properties | |
| CN108745274B (en) | Rectorite mesoporous material and preparation method and application thereof | |
| Cheng et al. | SiO2/TiO2 composite aerogels: preparation via ambient pressure drying and photocatalytic performance | |
| Yang et al. | Influence of synthesis variables of a sol-gel process on the properties of mesoporous alumina and their fluoride adsorption | |
| CN102614819A (en) | Method for preparing magnetic mesoporous carbon nanometer microspheres with high adsorption property | |
| Xu et al. | Synthesis, characterization, and catalytic application of highly ordered mesoporous alumina-carbon nanocomposites | |
| CN103191771A (en) | Core-shell USY@SBA-15 composite material as well as preparation method and application thereof | |
| CN104261427B (en) | A kind of preparation method of " plug-in card " type multi-stage porous ZSM-5 molecular sieve | |
| CN104001471B (en) | Preparation method of silicon dioxide immobilized hydroxyapatite material | |
| CN106946282B (en) | A kind of preparation method of porous cerium-based composite oxides | |
| CN106145132B (en) | A method of ordered mesoporous material Al-MCM-41 is prepared using attapulgite | |
| CN104874385B (en) | A kind of TiO2Nanotube/SiO2Compound catalysis material of aeroge and preparation method thereof | |
| CN101559954B (en) | Method for preparing mesoporous molecular sieve with high hydrothermal stability by taking ionic liquid as template agent | |
| Kim et al. | Synthesis of tailored porous alumina with a bimodal pore size distribution | |
| CN107651693B (en) | A kind of direct synthesis method of multi-stage ordered mesoporous molecular sieve | |
| CN104528814B (en) | A kind of layer structure CaTi2O4(OH)2The preparation method of rhombus nanometer sheet and product | |
| Liu et al. | Template-free synthesis of carbon doped TiO2 mesoporous microplates for enhanced visible light photodegradation | |
| Meng et al. | Pd NPs supported on N-doped carbon layer coated ZrSBA-15 for efficient heterogeneous catalysis reactions | |
| CN105347358B (en) | A kind of preparation method that there is three-dimensional through the zeolite molecular sieve material of mesoporous multi-stage artery structure | |
| CN104001432A (en) | Titanium dioxide/polyvinylidene fluoride composite mesoporous membrane, and preparation method and application thereof | |
| Dong et al. | Preparation of three-dimensional interconnected mesoporous anatase TiO2-SiO2 nanocomposites with high photocatalytic activities | |
| CN107297220B (en) | Vermicular mesoporous Al2O3Molecular sieve composite material and preparation method thereof | |
| Zhong et al. | Meso/micro-porosity and phase separation in TiO2/SiO2/C nanocomposites |
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: 20121024 Termination date: 20130531 |