CN102259887A - Method for improving regularity of porous channels of mesoporous molecular sieve synthesized in alkali environment - Google Patents
Method for improving regularity of porous channels of mesoporous molecular sieve synthesized in alkali environment Download PDFInfo
- Publication number
- CN102259887A CN102259887A CN 201110148621 CN201110148621A CN102259887A CN 102259887 A CN102259887 A CN 102259887A CN 201110148621 CN201110148621 CN 201110148621 CN 201110148621 A CN201110148621 A CN 201110148621A CN 102259887 A CN102259887 A CN 102259887A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- hours
- regularity
- mesoporous molecular
- mcm
- 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.)
- Pending
Links
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for improving regularity of porous channels of a mesoporous molecular sieve synthesized in an alkali environment. The method comprises the following steps of: (1) firstly synthesizing a mesoporous molecular sieve MCM-41, sequentially adding a silicon source, a template agent, deionized water and hydrochloric acid into a container, then carrying out hydrothermal crystallization reaction, and finally washing and drying products of the hydrothermal crystallization reaction to obtain mesoporous molecular sieve MCM-41 raw powder solid; and (2) impregnating the solid obtained in the step (1) into ammonium salt solution, and then drying and roasting to obtain a mesoporous molecular sieve with high porous channel regularity. By adopting the method provided by the invention, the regularity of the porous channels of the mesoporous molecular sieve is obviously improved, meanwhile the whole preparation process is simple and feasible and reaction repeatability is good.
Description
Technical field
The present invention relates to a kind of method that can significantly improve synthetic gained mesopore molecular sieve duct regularity under the alkali environment, belong to the synthetic field of molecular sieve, be characterized in improving technology and carry out after synthetic, technology is simple, and effect is obvious.
Background technology
Because mesoporous material is in catalysis, separation, as the application potential aspect nano-cluster and embedding object carrier, the medicament slow release, over past ten years, it has been subjected to extensive concern.Though its kind has obtained continuous expansion, as a member in the initial family of mesoporous material, MCM-41 is because it has bigger serface, homogeneous duct and relative characteristics such as stability, and still the research focus as Materials science exists.The internal structure of MCM-41 is arranged by parallel one dimension hexagonal hole road and is formed, and pore size is between 1.6～10nm, and by the change of surfactant templates agent, solubilizing agent and other synthesis conditions, its aperture is adjustable.These characteristics make the carrier of its reactor that is suitable as molecular level and synthetic regular nano material.But the MCM-41 meso-hole structure distortion that obtains usually is more, and regularity is poor, can't guarantee the consistence of reaction environment as the Subjective and Objective reactor; And the meso-hole structure of MCM-41 is under the aqueous solution is handled, as forfeiture easily under the conditions such as ion-exchange, shaping of catalyst.
More document is mentioned to add auxiliary agent or to carry out compound with regular structure degree and the stability of the method improvement MCM-41 of secondary treatment.Khushalani etc. handle the synthetic former powder of MCM-41 one day in synthesis mother liquid under 423K, and discovery can make mesoporous duct all once be enhanced, and in 0.3～0.4nm scope modulation d100 parameter; The research of Pan etc. is thought can strengthen the diffraction peak intensity and the stability of mesoporous material by adding an amount of salt; Ryoo etc. add different metal-salts at the MCM-41 hydrothermal crystallization process, as sodium-chlor, Repone K, sodium-acetate, sodium ethylene diamine tetracetate etc., find that the hydrothermal stability of material has obtained enhancing.But generally speaking,, particularly do not appear in the newspapers by the method improvement mesoporous material regularity and the stability of adding salt about by synthetic aftertreatment.
Summary of the invention
The object of the invention is that the mesopore molecular sieve duct regularity that improves synthetic gained under the present alkali environment is not high, and the defective that degree of crystallinity is relatively poor provides a kind of method that improves mesopore molecular sieve duct regularity.After hydrothermal crystallization process was finished, the molecular screen primary powder that obtains impregnated in certain density ammonium salt solution, and the duct regularity of the improvement product that obtains after the drying roasting significantly is better than the product without the ammonium salt processing.Be characterized in and can select to carry out in synthetic back that effect is obvious, technology is simple.
For achieving the above object, the present invention takes following technical scheme:
A kind of method that improves synthetic mesopore molecular sieve duct regularity under the alkali environment comprises the steps:
(1) at first synthesising mesoporous molecular sieve MCM-41, silicon source, template, deionized water and hydrochloric acid are placed container successively, carry out the hydrothermal crystallizing reaction then, the product that hydrothermal crystallizing is reacted obtains the former powder solid of mesopore molecular sieve MCM-41 after washing, drying at last;
(2) solid impregnating that step (1) is obtained flooded 4～8 hours in ammonium salt solution, preferably flooded 6 hours, got the high mesopore molecular sieve of duct regularity then behind drying, the roast.
In the aforesaid method, described silicon source is a water glass, and described template is cetyl trimethylammonium bromide (CTAB).
In the aforesaid method, when carrying out the hydrothermal crystallizing reaction, the mol ratio of reactive material is: 1CTAB: 15.7SiO
2: 4.76Na
2O: 22.4HCl: 2.56H
2O.
In the aforesaid method, the temperature of described hydrothermal crystallizing reaction is 100～150 ℃, and the reaction times is 16～32 hours.
In the aforesaid method, the concrete steps of described synthesising mesoporous molecular sieve MCM-41 are: CTAB, water glass are dissolved in the deionized water, dropwise add hydrochloric acid after reaching the pH value and being 11, introduce and carry out the hydrothermal crystallizing reaction in the still, with the solid phase prod washing, filter and collect after the crystallization, dry naturally.
In the aforesaid method, described ammonium salt is ammonium chloride (NH4Cl), brometo de amonio (NH4Br), ammonium iodide (NH4I) or Neutral ammonium fluoride (NH4F) etc.
In the aforesaid method, the concentration of described ammonium salt solution is 1～10wt%.
In the aforesaid method, in the step (2), descended slowly dry 2 hours at 60 ℃ behind the described solid impregnating, slowly be warming up to 550 ℃, and, obtain modified product 550 ℃ of following roastings 6 hours.Described slow intensification is meant 16～20 hours and is warming up to 550 ℃, is warming up to 550 ℃ in for example preferred 18 hours.
According to aforesaid method, a kind of concrete steps that improve the method for synthetic mesopore molecular sieve duct regularity under the alkali environment comprise:
(1) 2.64 gram CTAB, 18.46g water glass are dissolved in the 35ml deionized water under constantly stirring;
(2) hydrochloric acid that dropwise adds 1.0M reaches 11 until the pH of latex gel value.The mol ratio of various materials is in the final gel: 1CTAB: 15.7SiO
2: 4.76Na
2O: 22.4HCl: 2.56H
2O;
(3) hydrothermal treatment consists 24 hours under the 393K, then with the solid phase prod washing, filter and collect, at the air at room temperature evaporate to dryness;
(4) the said products be impregnated in the ammonium salt solution of 1～10wt%, the above-mentioned sample of gained 60 ℃ dry 2 hours down slowly, 550 ℃ of following roastings 6 hours obtain target product.
The preparation of the said mesopore molecular sieve MCM-41 of the present invention and improving one's methods is the silicon source with water glass, and cetyl trimethylammonium bromide (CTAB) is a structure directing agent, synthetic preparation MCM-41 sample in alkaline environment.The said products be impregnated in the salts solution of a small amount of some specific concentrations, the above-mentioned sample of gained is slow dry 2hr under 60 ℃, slowly is warming up to 550 ℃, and at 550 ℃ of following roasting 6hr, obtains modified product.
The present invention compared with prior art has following characteristics:
1) improved the duct regularity of mesopore molecular sieve MCM-41, characterized through transmission electron microscope, its structure has more significantly to be improved.
2) whole process of preparation is simple and reaction repeatability good.
The present invention will be further described below by the drawings and specific embodiments, but and do not mean that limiting the scope of the invention.
Description of drawings
Fig. 1 is NH
4The Cl consumption is to the influence (a:0.0wt% of MCM-41 regularity; B:2.0wt%; 5.0wt%).
Fig. 2 is NH
4The Br consumption is to the influence (a:0.0wt% of MCM-41 regularity; B:2.0wt%; 5.0wt%).
Fig. 3 is that (JEM-2100F 200KeV) characterizes TEM, and Fig. 3-1 and Fig. 3-2 is respectively unprocessed and through 5%NH
4Br handles also and obtains the mesoporous phase of MCM-41 material after the roasting.
Embodiment
With water glass (SiO
2: 28.2%, Na
2O:8.7%) be the silicon source, cetyl trimethylammonium bromide (CTAB) is a structure directing agent, synthetic preparation MCM-41 sample in alkaline environment: 2.64 gram CTAB, 18.46g water glass are dissolved in the 35ml deionized water under constantly stirring, and the hydrochloric acid that dropwise adds 1.0M reaches 11 until the pH of latex gel value.The mol ratio of various materials is in the final gel: 1CTAB: 15.7SiO
2: 4.76Na
2O: 22.4HCl: 2.56H
2O.Hydrothermal treatment consists 24hr under the 393K then with the solid phase prod deionized water wash, filters and collects, and at the air at room temperature evaporate to dryness, obtains the not former powder of mesopore molecular sieve of removed template method.
Embodiment 2
Gained powder among the embodiment 1 was promptly got mesopore molecular sieve MCM-41 in 6 hours at 550 ℃ of following roasts.
Adopt X-ray diffraction method to identify the thing phase of product, the power at the peak of the characteristic peak that is gone out from the X-ray diffraction spectrogram is judged the structure quality of product: characteristic peak is weak more, and pore passage structure is poor more; Characteristic peak is strong more, and the duct is regular more.Can investigate the duct alignment degree intuitively by transmission electron microscope in addition.
The X-ray diffractogram of the mesopore molecular sieve MCM-41 product of the non-modified of present embodiment gained, shown in a and a among Fig. 2 among Fig. 1, characteristic peak a little less than, pore passage structure is relatively poor.Fig. 3-1 is the transmission electron microscope photo of mesopore molecular sieve MCM-41 product of the non-modified of present embodiment gained, and the duct regularity of mesopore molecular sieve is lower as can be seen.
Embodiment 3
Products obtained therefrom 10g among the embodiment 1 be impregnated in the 10ml 2wt% aqueous ammonium chloride solution, flood 6 hours gained sample slow dry 2hr under 60 ℃, the gained powder slowly was warming up to 550 ℃ with 18 hours, promptly got the mesopore molecular sieve of modification in 6 hours at 550 ℃ of following roasts, its X-ray diffractogram is shown in the b among Fig. 1, characteristic peak is stronger, and the duct is more regular.
Embodiment 4
Products obtained therefrom 10g among the embodiment 1 be impregnated in the 10ml 5.0wt% aqueous ammonium chloride solution, flood 6 hours gained sample slow dry 2hr under 60 ℃, the gained powder slowly was warming up to 550 ℃ with 17 hours, promptly got the mesopore molecular sieve of modification in 6 hours at 550 ℃ of following roasts, its X-ray diffractogram is shown in the c among Fig. 1, characteristic peak is stronger, and the duct is more regular.
Embodiment 5
Products obtained therefrom 10g among the embodiment 1 be impregnated in the 10ml 2.0wt% bromize ammonium solution, flood 6 hours gained sample slow dry 2hr under 60 ℃, the gained powder slowly was warming up to 550 ℃ with 18 hours, promptly got the mesopore molecular sieve of modification in 6 hours at 550 ℃ of following roasts, its X-ray diffractogram is shown in the b among Fig. 2, characteristic peak is stronger, and the duct is more regular.
Embodiment 6
Products obtained therefrom 10g among the embodiment 1 be impregnated in the 10ml 5.0wt% bromize ammonium solution, flood 6 hours gained sample slow dry 2hr under 60 ℃, the gained powder slowly was warming up to 550 ℃ with 18 hours, promptly got the mesopore molecular sieve of modification in 6 hours at 550 ℃ of following roasts, its X-ray diffractogram is shown in the c among Fig. 2, characteristic peak is stronger, and the duct is more regular.Fig. 3-2 is the transmission electron microscope photo of the mesopore molecular sieve MCM-41 product of present embodiment gained modification, and the duct regularity of mesopore molecular sieve is higher as can be seen.
Embodiment 7
With water glass (SiO
2: 28.2%, Na
2O:8.7%) be the silicon source, cetyl trimethylammonium bromide (CTAB) is a structure directing agent, synthetic preparation MCM-41 sample in alkaline environment: 2.64 gram CTAB, 18.46g water glass (SG) are dissolved in the 35ml deionized water under constantly stirring, and the hydrochloric acid that dropwise adds 1.0M reaches 11 until the pH of latex gel value.The mol ratio of various materials is in the final gel: 1CTAB: 15.7SiO
2: 4.76Na
2O: 22.4HCl: 2.56H
2O.150 ℃ of following hydrothermal treatment consists 16hr then with the solid phase prod deionized water wash, filter and collect, and at the air at room temperature evaporate to dryness, obtain the not former powder of mesopore molecular sieve of removed template method.
Products obtained therefrom 10g be impregnated in the 10ml 10.0wt% ammonium iodide aqueous solution, flood 4 hours gained sample slow dry 2hr under 60 ℃, the gained powder slowly was warming up to 550 ℃ with 16 hours, promptly got the mesopore molecular sieve of modification in 6 hours at 550 ℃ of following roasts, its X-ray diffractogram indicating characteristic peak is stronger, and the duct is more regular.
Embodiment 8
With water glass (SiO
2: 28.2%, Na
2O:8.7%) be the silicon source, cetyl trimethylammonium bromide (CTAB) is a structure directing agent, synthetic preparation MCM-41 sample in alkaline environment: 2.64 gram CTAB, 18.46g water glass (SG) are dissolved in the 35ml deionized water under constantly stirring, and the hydrochloric acid that dropwise adds 1.0M reaches 11 until the pH of latex gel value.The mol ratio of various materials is in the final gel: 1CTAB: 15.7SiO
2: 4.76Na
2O: 22.4HCl: 2.56H
2O.100 ℃ of following hydrothermal treatment consists 32hr then with the solid phase prod deionized water wash, filter and collect, and at the air at room temperature evaporate to dryness, obtain the not former powder of mesopore molecular sieve of removed template method.
Products obtained therefrom 10g be impregnated in the 10ml 1.0wt% aqueous ammonium chloride solution, flood 6 hours gained sample slow dry 2hr under 60 ℃, the gained powder was promptly got the mesopore molecular sieve of modification in 6 hours at 550 ℃ of following roasts, and its X-ray diffractogram indicating characteristic peak is stronger, and the duct is more regular.
Claims (10)
1. a method that improves synthetic mesopore molecular sieve duct regularity under the alkali environment comprises the steps:
(1) at first synthesising mesoporous molecular sieve MCM-41, silicon source, template, deionized water and hydrochloric acid are placed container successively, carry out the hydrothermal crystallizing reaction then, the product that hydrothermal crystallizing is reacted obtains the former powder solid of mesopore molecular sieve MCM-41 after washing, drying at last;
(2) solid impregnating that step (1) is obtained flooded 4～8 hours in ammonium salt solution, got the high mesopore molecular sieve of duct regularity then behind drying, the roast.
2. the method for claim 1, it is characterized in that: described silicon source is a water glass, described template is a cetyl trimethylammonium bromide.
3. the method for claim 1 is characterized in that: when carrying out the hydrothermal crystallizing reaction, the mol ratio of reactive material is: 1CTAB: 15.7SiO
2: 4.76Na
2O: 22.4HCl: 2.56H
2O.
4. method as claimed in claim 3 is characterized in that: the temperature of described hydrothermal crystallizing reaction is 100～150 ℃, and the reaction times is 16～32 hours.
5. the method for claim 1, it is characterized in that: the concrete steps of described synthesising mesoporous molecular sieve MCM-41 are: CTAB, water glass are dissolved in the deionized water, dropwise add hydrochloric acid after reaching the pH value and being 11, introduce and carry out the hydrothermal crystallizing reaction in the still, after the crystallization solid phase prod is washed, filter and collect, dry naturally.
6. the method for claim 1, it is characterized in that: described ammonium salt is ammonium chloride, brometo de amonio, ammonium iodide or Neutral ammonium fluoride.
7. method as claimed in claim 6 is characterized in that: the concentration of described ammonium salt solution is 1～10wt%.
8. the method for claim 1, it is characterized in that: the time of described dipping is 6 hours.
9. the method for claim 1 is characterized in that: in the step (2), descended dry 2 hours at 60 ℃ behind the described solid impregnating, slowly be warming up to 550 ℃, and 550 ℃ of following roastings 6 hours, obtain product.
10. method as claimed in claim 9 is characterized in that: described slow intensification is meant 16～20 hours and is warming up to 550 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110148621 CN102259887A (en) | 2011-06-03 | 2011-06-03 | Method for improving regularity of porous channels of mesoporous molecular sieve synthesized in alkali environment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110148621 CN102259887A (en) | 2011-06-03 | 2011-06-03 | Method for improving regularity of porous channels of mesoporous molecular sieve synthesized in alkali environment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102259887A true CN102259887A (en) | 2011-11-30 |
Family
ID=45006762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110148621 Pending CN102259887A (en) | 2011-06-03 | 2011-06-03 | Method for improving regularity of porous channels of mesoporous molecular sieve synthesized in alkali environment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102259887A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974382A (en) * | 2012-11-22 | 2013-03-20 | 天津大学 | Catalyst for preparing ethanol by virtue of acetate hydrogenation and preparation method thereof |
| CN105948071A (en) * | 2016-04-29 | 2016-09-21 | 辽宁工程技术大学 | Method for preparing meso-porous material from natural mordenite |
| CN109748294A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | The method of spherical mesoporous molecular screen material and preparation method thereof and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN110627085A (en) * | 2018-06-25 | 2019-12-31 | 中国石油化工股份有限公司 | Preparation method and application of sulfydryl functionalized MCM (mesoporous crystalline silica) molecular sieve |
-
2011
- 2011-06-03 CN CN 201110148621 patent/CN102259887A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《材料科学与工程学报》 20070831 殷立峰等 盐处理对介孔MCM-41结构和稳定性的调变 第620-623、633页 1-10 第25卷, 第4期 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974382A (en) * | 2012-11-22 | 2013-03-20 | 天津大学 | Catalyst for preparing ethanol by virtue of acetate hydrogenation and preparation method thereof |
| CN102974382B (en) * | 2012-11-22 | 2014-09-17 | 天津大学 | Catalyst for preparing ethanol by virtue of acetate hydrogenation and preparation method thereof |
| CN105948071A (en) * | 2016-04-29 | 2016-09-21 | 辽宁工程技术大学 | Method for preparing meso-porous material from natural mordenite |
| CN109748294A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | The method of spherical mesoporous molecular screen material and preparation method thereof and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN110627085A (en) * | 2018-06-25 | 2019-12-31 | 中国石油化工股份有限公司 | Preparation method and application of sulfydryl functionalized MCM (mesoporous crystalline silica) molecular sieve |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103025658B (en) | The manufacture method of zeolite | |
| CN105668548B (en) | The method that core shell structure customizes high dispersive codope porous carbon | |
| EP2322479A1 (en) | Amorphous aluminum silicate salt manufacturing method, aluminum silicate salt obtained with said method, and adsorption agent using same | |
| KR20150005538A (en) | Beta zeolite and method for producing same | |
| CN102259887A (en) | Method for improving regularity of porous channels of mesoporous molecular sieve synthesized in alkali environment | |
| WO2020056838A1 (en) | Molecular sieve with hierarchical pore fau structure and preparation method therefor | |
| CN103318911A (en) | Preparation method of beta zeolite with multilevel pore canals | |
| CN102633282B (en) | Method for preparing mesoporous titanium silicon molecular sieve nanoparticles | |
| CN113149026B (en) | Preparation method of molecular sieve with stepped hole structure | |
| CN105214734B (en) | The preparation method of illite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals | |
| CN105153204B (en) | Micro-diplopore metal-organic framework materials and preparation method in a kind of CuBTC types | |
| JP5467432B2 (en) | Method for producing plate-like hydroxyapatite single crystal | |
| CN106573787B (en) | Composition and its manufacturing method including the silicotitanate with SITINAKITE structure | |
| CN114655963B (en) | Preparation method of SSZ-13 molecular sieve composite material | |
| CN103140445B (en) | Using the zeolite of modified mixed hydroxides or the Hydrothermal Synthesiss of Zeolite-like materials | |
| CN109928406A (en) | A kind of analcime and its synthetic method | |
| CN108946754B (en) | SBA-15 mesoporous molecular sieve, preparation method and application thereof, and method for producing alumina and SBA-15 mesoporous molecular sieve from fly ash | |
| CN110407229B (en) | Method for synthesizing CHA structure molecular sieve and CHA structure molecular sieve | |
| CN107601525B (en) | Preparation method and application of bi-hemispherical W zeolite | |
| CN104925827A (en) | Transition-metal-including crystal-structure mesoporous molecular sieve Cry-Fe and preparation method thereof | |
| CN102963905A (en) | Method for synthetizing Al-SBA-15 containing plug type silicon/aluminum structure in pore channel | |
| CN112808296B (en) | Catalyst containing Y-type molecular sieve and preparation method thereof | |
| CN110407231B (en) | Method for synthesizing copper-containing CHA structure molecular sieve and copper-containing CHA structure molecular sieve | |
| JP6814433B2 (en) | Method for producing beta-type zeolite | |
| JP6727884B2 (en) | ZSM-5 type zeolite having almond-like shape and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20111130 |