CN102936018B - Preparation method for high stability mesoporous molecular sieve under ionothermal system - Google Patents
Preparation method for high stability mesoporous molecular sieve under ionothermal system Download PDFInfo
- Publication number
- CN102936018B CN102936018B CN201210397814.4A CN201210397814A CN102936018B CN 102936018 B CN102936018 B CN 102936018B CN 201210397814 A CN201210397814 A CN 201210397814A CN 102936018 B CN102936018 B CN 102936018B
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- molecular sieve
- crystallization
- hours
- acid functionalization
- 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
Abstract
The present invention discloses a method for preparing a high hydrothermal stability mesoporous molecular sieve by adopting an acid functionalized ion liquid as a medium and adopting a non-ionic surfactant or an ionic surfactant as a template agent. The preparation method comprises: sequentially adding sodium meta-aluminate, silica hydrosol (30%), sodium silicate and an acid functionalized ion liquid to a reaction kettle, uniformly mixing at a room temperature in the reaction kettle, transferring the mixed material to an autoclave, carrying out crystallization for 4-6 hours at a temperature of 120-140 DEG C, cooling to a room temperature after completing the reaction, adding an acid functionalized ion liquid and a template agent to the solution after the reaction, stirring for 20-24 hours at a temperature of 40-60 DEG to obtain a homogeneous phase gel mixture, transferring the gel mixture to the autoclave, carrying out crystallization for 24-48 hours at a temperature of 100-120 DEG C, cooling, adding deionized water to dilute and wash, carrying out suction filtration, and carrying out drying calcination to obtain the mesoporous molecular sieve product. The mesoporous molecular sieve prepared by the preparation method has good hydrothermal stability while the ion liquid can be recycled. The synthesis method has advantages of simpleness and environmental friendliness, and has important application values in the field of material science.
Description
Technical field
The present invention relates to the synthetic method of mesopore molecular sieve, specifically to take acid function voltinism ionic liquid be medium about a kind of, and nonionogenic tenside or ionogenic surfactant are the method that template is prepared the mesopore molecular sieve of high hydrothermal stability.
Background technology
Since New Mesoporous Molecular Sieves M41S or SBA-15 are developed successfully, because it has the pore passage structure of large homogeneous, as the catalyzer of macromolecular reaction, demonstrated good application prospect.But the hole wall of such mesopore molecular sieve is unbodied, hole wall is very easily because part hydrolysis or heat effect penetrate, and caving in of even whole molecular sieve lattice, causes its thermostability and hydrothermal stability very poor, thereby has restricted the industrial application of mesopore molecular sieve.In order to improve thermostability and the hydrothermal stability of mesopore molecular sieve, scientists has been carried out a large amount of research work.Wherein, make the technology of mesopore molecular sieve hole wall " crystallization ", i.e. the synthetic Jie's mesoporous-microporous composite molecular sieve of design, aspect its heat of increase and hydrothermal stability, be good technological line (CN1393403, J.Phys.Chem.B, 2001,105,7963-7966).At present, the mesopore molecular sieve with crystalline state hole wall be all water (solvent) thermal means under different condition (CNl208718, J.Phys.Chem.B, 2000,104,2817-2823) prepare.This water (solvent) hot system, unavoidably will adopt high-tension apparatus, produces a large amount of spent acid or salkali waste in preparation process simultaneously, and be subject to the restriction of the boiling point of water (solvent) own, in synthetic, easily cause skeleton structure loose, degree of crystallinity declines, and affects heat and the hydrothermal stability of material.2004, the people such as Russel E professor Morris of Britain University of St Andrews reported and have used ionic liquid as the method for solvent and the synthetic microporous aluminium phosphate molecular sieve of template, i.e. ion thermal synthesis method (Nature, 2004,430,1012).The proposition of ion process for thermosynthesizing is that new approach (CN200910248472.8 has been opened up in the development of molecular sieve, CN200710036633.8, CN200810105982.5), avoided reaction under high pressure, strengthened security, environmental friendliness, topmost feature has reduced the effect of solvent-skeleton structure and the competition of structure directing agent-skeleton structure effect, more easily obtain target product, and can obtain the molecular sieve of novel texture, improve the performance of molecular sieve.
Summary of the invention
Poor in order to solve existing mesopore molecular sieve hydrothermal stability, in preparation process, produce a large amount of spent acid or alkali lye, to problems such as environments, the invention provides that a kind of to take acid function voltinism ionic liquid be medium, nonionogenic tenside or ionogenic surfactant are the method that template is prepared the mesopore molecular sieve of high hydrothermal stability, mesopore molecular sieve prepared by the method is compared with the mesopore molecular sieve good hydrothermal stability making under hydrothermal system, and the ionic liquid of acid functionalization simultaneously can be reused.
Technical scheme of the present invention is achieved in that
A) by sodium metaaluminate, silica hydrosol (30%), water glass and acid functionalization ionic liquid, join in reactor successively, under room temperature, in reactor, mixes, and makes gel mixture, wherein Al
2o
3: SiO
2: Na
2o: H
2the mol ratio of O is 1.0: 5-30: 1-5: 500-800, and the 0.5-3 that the add-on of acid functionalization ionic liquid is solid masses is doubly;
B) gel mixture is proceeded in autoclave to sealing, crystallization 4-6 hour at 120-140 ℃;
C) after crystallization finishes, cool to room temperature, ionic liquid and the template of acid functionalization will be added again in solution after crystallization, at 40-60 ℃, stir 20-24 hour, obtain homogeneous phase gel mixture, doubly, template is nonionogenic tenside P to the 3.5-5 that wherein add-on of acid functionalization ionic liquid is solid masses
123or ionogenic surfactant cetyl trimethylammonium bromide, add-on is SiO
2the 0.01-0.02 of add-on mol ratio doubly;
D) this gel mixture is proceeded to autoclave, sealing, crystallization 24-48 hour at 100-120 ℃;
E), after crystallization finishes, cool to room temperature, adds deionized water dilution and washing, suction filtration, and 60 ℃ of dry 12-24 hour, roasting 6-8 hour at 550-600 ℃, makes high steady mesopore molecular sieve product.
F) collect washings, underpressure distillation dewaters, and acid functionalization ionic liquid is recyclable.
Acid functionalization ionic liquid of the present invention, for take imidazoles as parent, reacts it successively with 5 ring cycloalkanes sultoness, sulfuric acid, make the ionic liquid of acid functionalization, and general structure is as follows:
R
1fatty alkyl for carbon number 1～8; N is 3
Invention effect
1. the prepared mesopore molecular sieve of the present invention has crystalline state hole wall and good meso-hole structure, the mesopore molecular sieve good hydrothermal stability making under the more conventional hydrothermal system of hydrothermal stability.
2. adopting acid functionalization ionic liquid is crystallization medium, this ionic liquid stable performance, and thermostability is strong, and repeat performance is good, for the steady mesopore molecular sieve of height synthetic formulated an eco-friendly technique.
3. the steady mesopore molecular sieve of this height is synthetic, has expanded the scope of application of mesoporous material, for high-temperature high-voltage reaction provides potential catalytic material or carrier.
Embodiment
Below in conjunction with embodiment, further illustrate, but and unrestricted scope involved in the present invention.
Embodiment 1:
0.3 gram of sodium metaaluminate, 6.69 grams of silicon dioxde solutions (30%), 0.568 gram of water glass, 5 grams of acid functionalization ionic liquid 1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfate, in reactor, mix, then crystallization 4 hours at 140 ℃, then will in solution after crystallization, add 20 grams of acid functionalization ionic liquid 1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfates, 4 grams of P123 are blended at 40 ℃ and stir 20 hours.By crystallization at 100 ℃ of mixing solutionss after crystallization 24 hours.After crystallization finishes, cool to room temperature, adds deionized water dilution and washing, suction filtration, and by 60 ℃, powder dry 24 hours, at 550 ℃, roasting obtained product for 6 hours.
Embodiment 2:
0.3 gram of sodium metaaluminate, 6.69 grams of silicon dioxde solutions (30%), 0.568 gram of water glass, 5 grams of acid functionalization ionic liquid 1-ethyl-3-(3-sulfonic group propyl group) imidazole bisulfate, in reactor, mix, then crystallization 4 hours under 120 ℃ of degree, then will in solution after crystallization, add 20 grams of acid functionalization ionic liquid 1-ethyl-3-(3-sulfonic group propyl group) imidazole bisulfates, 4 grams of P123 are blended at 50 ℃ and stir 20 hours.At 100 ℃, crystallization is 24 hours.After crystallization finishes, cool to room temperature, adds deionized water dilution and washing, suction filtration, and by 60 ℃, powder dry 20 hours, at 600 ℃, roasting obtained product for 7 hours.
Embodiment 3:
0.3 gram of sodium metaaluminate, 13.92 grams of silicon dioxde solutions (30%), 1.14 gram water glass, 10 grams of acid functionalization ionic liquid 1-ethyl-3-(3-sulfonic group butyl) imidazole bisulfate mixes in reactor, then crystallization 5 hours at 130 ℃, cool to room temperature, then will in solution after crystallization, add 45 grams of acid functionalization ionic liquid 1-ethyl-3-(3-sulfonic group butyl) imidazole bisulfates, 4 grams of P123 are blended at 40 ℃ and stir 20 hours.At 100 ℃, crystallization is 24 hours.After crystallization finishes, cool to room temperature, adds deionized water dilution and washing, suction filtration, and by 60 ℃, powder dry 12 hours, at 550 ℃, roasting obtained product for 7 hours.
Embodiment 4:
0.3 gram of sodium metaaluminate, 13.92 grams of silicon dioxde solutions (30%), 1.14 gram water glass, 10 grams of acid functionalization ionic liquid 1-methyl-3-(3-sulfonic group butyl) imidazole bisulfate mixes in reactor, then crystallization 4 hours at 140 ℃, to in solution after crystallization, add 20 grams of acid functionalization ionic liquid 1-methyl-3-(3-sulfonic group butyl) imidazole bisulfates again, 4 grams of P123 mixing are directly put into 100 ℃ of crystallization of reactor 24 hours.After crystallization finishes, cool to room temperature, adds deionized water dilution and washing, suction filtration, and by 60 ℃, powder dry 24 hours, at 550 ℃, roasting obtained product for 7 hours.
Embodiment 5:
0.3 gram of sodium metaaluminate, 13.92 grams of silicon dioxde solutions (30%), 1.14 gram water glass, 10 grams of acid functionalization ionic liquid 1-propyl group-3-(3-sulfonic group butyl) imidazole bisulfate mixes in reactor, then crystallization 4 hours at 140 ℃, to in solution after crystallization, add acid functionalization ionic liquid 1-propyl group-3-(3-sulfonic group butyl) to narrow 20 grams of azoles hydrosulfates again, 1.2 grams of cetyl trimethylammonium bromides mix directly puts into 100 ℃ of crystallization of reactor 24 hours.After crystallization finishes, cool to room temperature, adds deionized water dilution and washing, suction filtration, and by 100 ℃, powder dry 12 hours, at 550 ℃, roasting obtained product for 7 hours.
Embodiment 6:
Washing water in embodiment 1 are reclaimed to 100 ℃ of underpressure distillation, recovered acid functionalized ion liquid 1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfate.3 grams of sodium metaaluminates, 6.69 grams of silicon dioxde solutions (30%), 0.568 gram of water glass, 5 grams of restored acid functionalized ion liquid 1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfate, in reactor, mix, then crystallization 4 hours at 140 ℃, then will in solution after crystallization, add 20 grams of restored acid functionalized ion liquid 1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfates, 4 grams of P123 are blended at 40 ℃ and stir 20 hours.By crystallization at 100 ℃ of mixing solutionss after crystallization 24 hours.After crystallization finishes, cool to room temperature, adds deionized water dilution and washing, suction filtration, and by 60 ℃, powder dry 24 hours, at 550 ℃, roasting obtained product for 6 hours.
Embodiment 7:
Under hydrothermal system, mesopore molecular sieve is synthetic: 0.3 gram of sodium metaaluminate, 0.16 gram of sodium hydroxide, 6.86 grams of silicon dioxde solutions (30%), 15.5 milliliters of tetraethyl ammonium hydroxides mix in autoclave, then crystallization 4 hours at 140 ℃, then will in solution after crystallization, add 100 ml waters, 25 milliliters of hydrochloric acid, 4 grams of P123 are blended at 40 ℃ and stir 20 hours, then under the condition of 100 ℃, continue crystallization 24 hours.After crystallization finishes, cool to room temperature, adds deionized water wash, suction filtration, and by 60 ℃, powder dry 24 hours, at 550 ℃, roasting obtained product for 6 hours.
By mesopore molecular sieve synthetic under this hydrothermal system with by embodiment 1 method synthetic mesopore molecular sieve under ion hot system, carry out respectively thermostability and hydrothermal stability test.For thermostability, two kinds of synthetic mesopore molecular sieves of different methods all have good stability, at 1000 ℃, roasting is after 10 hours, adopt X-ray powdery diffractometry technology to detect the meso-hole structure of material, two kinds of synthetic mesopore molecular sieves of different methods all keep good meso-hole structure and degree of crystallinity.For hydrothermal stability, synthetic mesopore molecular sieve under ion hot system, under the water vapor of 180 ℃, process after 96 hours, still can keep good meso-hole structure and degree of crystallinity, and synthetic mesopore molecular sieve was processed after 12 hours under the water vapor of 180 ℃ under hydrothermal system, meso-hole structure is substantially destroyed.Visible, under ion hot system, synthetic mesopore molecular sieve has good hydrothermal stability.
Claims (1)
1. take acid functionalization ionic liquid as a medium, nonionogenic tenside or ionogenic surfactant are the method that template is prepared the mesopore molecular sieve of high hydrothermal stability, it is characterized in that:
(1) the acid functionalization ionic liquid adopting, for take imidazoles as parent, reacts it successively with 5 ring cycloalkanes sultoness, sulfuric acid, make the ionic liquid of acid functionalization, and general structure is as follows:
R
1fatty alkyl for carbon number 1～8; N is 3;
(2) by sodium metaaluminate, 30% silica hydrosol, water glass and acid functionalization ionic liquid, join in reactor successively, under room temperature, in reactor, mixes, and makes gel mixture, wherein A1
2o
3: SiO
2: Na
2o: H
2the mol ratio of O is 1.0: 5-30: 1-5: 500-800, and the 0.5-3 that the add-on of acid functionalization ionic liquid is solid masses is doubly;
(3) gel mixture is proceeded in autoclave to sealing, crystallization 4-6 hour at 120-140 ℃;
(4) after crystallization finishes, cool to room temperature, ionic liquid and the template of acid functionalization will be added again in solution after reaction, at 40-60 ℃, stir 20-24 hour, obtain homogeneous phase gel mixture, doubly, template is nonionogenic tenside P to the 3.5-5 that wherein add-on of acid functionalization ionic liquid is solid masses
123or ionogenic surfactant cetyl trimethylammonium bromide, add-on is SiO
2the 0.01-0.02 of add-on mol ratio doubly;
(5) this gel mixture is proceeded to autoclave, sealing, crystallization 24-48 hour at 100-120 ℃;
(6), after crystallization finishes, cool to room temperature, adds deionized water dilution and washing, suction filtration, and 60 ℃ of dry 12-24 hour, roasting 6-8 hour at 550-600 ℃, makes high steady mesopore molecular sieve product;
(7) collect washings, underpressure distillation dewaters, and acid functionalization ionic liquid is recyclable.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210397814.4A CN102936018B (en) | 2012-10-07 | 2012-10-07 | Preparation method for high stability mesoporous molecular sieve under ionothermal system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210397814.4A CN102936018B (en) | 2012-10-07 | 2012-10-07 | Preparation method for high stability mesoporous molecular sieve under ionothermal system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102936018A CN102936018A (en) | 2013-02-20 |
| CN102936018B true CN102936018B (en) | 2014-10-15 |
Family
ID=47694954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210397814.4A Expired - Fee Related CN102936018B (en) | 2012-10-07 | 2012-10-07 | Preparation method for high stability mesoporous molecular sieve under ionothermal system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102936018B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923683B (en) * | 2014-04-12 | 2015-12-02 | 青岛科技大学 | A kind of novel method of ion thermal synthesis mesopore molecular sieve catalytic pyrolysis waste polyolefin recovering liquid fuel oil |
| CN104877762A (en) * | 2015-05-09 | 2015-09-02 | 青岛科技大学 | Method for catalyzing esterification reaction by means of high-stable-acidity mesoporous-microporous molecular sieve |
| CN105668581B (en) * | 2016-01-09 | 2018-01-09 | 青岛科技大学 | Method using acidic functionalized ionic liquid as template synthesizing new mesopore molecular sieve |
| CN108163869B (en) * | 2016-12-07 | 2020-04-10 | 中国石油天然气股份有限公司 | Method for improving hydrothermal stability of silicon-based mesoporous material |
| CN109650422A (en) * | 2017-10-12 | 2019-04-19 | 中国石油天然气股份有限公司 | A method of improving mesoporous aluminum oxide material hydrothermal stability |
| CN109647365A (en) * | 2017-10-12 | 2019-04-19 | 中国石油天然气股份有限公司 | A kind of preparation method of catalyst for heavy oil catalytic cracking |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005009602A2 (en) * | 2003-07-22 | 2005-02-03 | Iowa State University Research Foundation, Inc. | Capped mesoporous silicates |
| CN1609164A (en) * | 2004-09-16 | 2005-04-27 | 华东师范大学 | Process of preparing mesoporous molecular sieve with ionic liquid as template agent |
| CN1736867A (en) * | 2005-07-29 | 2006-02-22 | 华东师范大学 | Method for preparing MSU-S-Y mesoporous molecular screen using ion liquid as mould |
| CN1944255A (en) * | 2006-10-24 | 2007-04-11 | 南开大学 | Process for synthesizing nano zirconium-containing super micro porous molecular sieve using ionic liquid as template agent |
| CN101191035A (en) * | 2007-11-16 | 2008-06-04 | 青岛科技大学 | Brphinsted-Lewis acidic ionic liquid and application thereof in rosin polymerization reaction |
| CN101269818A (en) * | 2008-02-29 | 2008-09-24 | 上海大学 | Method for synthesizing nano-HMS mesoporous molecular sieve in ion liquid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100119736A1 (en) * | 2008-10-07 | 2010-05-13 | The Regents Of The University Of California | Ambient pressure synthesis of zeolite films and their application as corrosion resistant coatings |
-
2012
- 2012-10-07 CN CN201210397814.4A patent/CN102936018B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005009602A2 (en) * | 2003-07-22 | 2005-02-03 | Iowa State University Research Foundation, Inc. | Capped mesoporous silicates |
| CN1609164A (en) * | 2004-09-16 | 2005-04-27 | 华东师范大学 | Process of preparing mesoporous molecular sieve with ionic liquid as template agent |
| CN1736867A (en) * | 2005-07-29 | 2006-02-22 | 华东师范大学 | Method for preparing MSU-S-Y mesoporous molecular screen using ion liquid as mould |
| CN1944255A (en) * | 2006-10-24 | 2007-04-11 | 南开大学 | Process for synthesizing nano zirconium-containing super micro porous molecular sieve using ionic liquid as template agent |
| CN101191035A (en) * | 2007-11-16 | 2008-06-04 | 青岛科技大学 | Brphinsted-Lewis acidic ionic liquid and application thereof in rosin polymerization reaction |
| CN101269818A (en) * | 2008-02-29 | 2008-09-24 | 上海大学 | Method for synthesizing nano-HMS mesoporous molecular sieve in ion liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102936018A (en) | 2013-02-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102936018B (en) | Preparation method for high stability mesoporous molecular sieve under ionothermal system | |
| CN101643219B (en) | Preparation method of nano-ZSM-5 molecular sieve | |
| CN102502687A (en) | Method for greenly synthesizing Ti-Si molecular sieve | |
| CN104707648B (en) | A kind of ion hot post-synthesis of complex functionality hetero-atom molecular-sieve | |
| CN105800634B (en) | A kind of nanometer total silicon beta molecular sieves and preparation method thereof | |
| CN103274461B (en) | Method for modulating titanium dioxide crystalline phases by using fluoride ions | |
| CN107892309A (en) | A kind of preparation method of super big hole silicate molecular sieve | |
| CN104874419A (en) | Titanium silicalite molecular sieve catalyst and application of titanium silicalite molecular sieve in cyclohexanone ammoximation | |
| CN106395742A (en) | Hydrogen storage composite material MgH2-Ni-rGO and method for preparing same | |
| CN113880109A (en) | Method for solid-phase synthesis of morphology-controllable ZSM-5 molecular sieve by using fly ash | |
| CN104340987A (en) | Silicon aluminum phosphate molecular sieve with -CLO structure, and preparation method thereof | |
| CN103626788A (en) | Hybrid material with function of adsorbing and desorbing iodine and synthetic methods thereof | |
| CN105293516A (en) | Method for rapidly preparing ZSM-22 molecular sieve by means of seed crystal | |
| CN102527414B (en) | Fluorination catalyst for preparing difluoromethane or monochlorodifluoromethane, preparation method and application | |
| CN104556116B (en) | A kind of method of aerosol auxiliary synthesis TS-1 molecular sieve | |
| CN104876906A (en) | Synthetic method of propylene carbonate | |
| CN102728401B (en) | Post-processing modification method of Ti-Si molecular sieve | |
| CN102730712A (en) | Preparation method of nano GaZSM-5 molecular sieve | |
| CN107043111B (en) | A method of silica gel is prepared using silicon monosulfide hydrolysis | |
| CN100469694C (en) | Vanadium-substituted silicate molecular sieve and its preparing method | |
| CN112939003B (en) | Method for preparing SBA-15 molecular sieve by using fluorine-containing silicon slag and recovering fluorine | |
| CN102351207B (en) | Method for preparing nano attapulgite by solvothermal process | |
| CN108002403A (en) | A kind of synthetic method of CHA molecular sieves | |
| CN103922385A (en) | Preparation method of cerium oxide hexagonal nanometer sheet structure | |
| CN106276955B (en) | A kind of Ti-beta molecular sieves and its synthetic method and application |
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 |
Granted publication date: 20141015 Termination date: 20181007 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |