CN100436319C - Modified MCM-41 molecular sieve, and modified method - Google Patents
Modified MCM-41 molecular sieve, and modified method Download PDFInfo
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- CN100436319C CN100436319C CNB2005100908667A CN200510090866A CN100436319C CN 100436319 C CN100436319 C CN 100436319C CN B2005100908667 A CNB2005100908667 A CN B2005100908667A CN 200510090866 A CN200510090866 A CN 200510090866A CN 100436319 C CN100436319 C CN 100436319C
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- molecular sieve
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Abstract
This invention relates to a method for modifying MCM-41 molecular sieve with a layer of Si atoms on its inner surface. The method comprises: (1) adding Si-containing coupler into an organic solvent, and stirring evenly; (2) adding MCM-41 molecular sieve at a weight ratio of 10 : (2-10) to the coupler, and soaking for 1-20 h; (3) washing with an organic solvent for 2-6 times, drying at 100-150 deg.C for 2-20 h, and baking at 450-560 deg.C for 6-16 h to obtain modified MCM-41 molecular sieve. The stable time of the modified MCM-41 molecular sieve in 350 deg.C water vapor can be increased to 48-54 h compared with previous 4-6 h.
Description
Technical field
The present invention relates to a kind of MCM-41 molecular sieve of modification and the method for modification thereof.
Background technology
" nature " (Nature), 710 pages of 1992 359 phases, the reported first M41S of U.S. Mobil company series mesopore molecular sieve, because of it has the adjustable aperture of 2-10nm, arrange and high surface-area in orderly duct, in fields such as catalysis, absorption, separation good prospects for application is arranged, cause people's extensive concern.The MCM-41 molecular sieve is a member (MCM is the abbreviation of Mobil Crystalline Material) of M41S series molecular sieve, and it has six side's ordered arrangement ducts and very big specific surface area (〉=700m
2/ g) cause people's very big interest.But people such as Corma A show that in J.catal.1994 148 phases, 569 pages of results reported it is desirable that the thermostability of this molecular sieve analog can be said to be, but hydrothermal stability is relatively poor.
Summary of the invention
The purpose of this invention is to provide a kind of MCM-41 molecular sieve of modification, have high hydrothermal stability.
Assorted another purpose of the present invention provides a kind of method of modifying of the MCM-41 of raising hydrothermal stability of molecular sieve.
For achieving the above object, the present invention takes following technical scheme:
A kind of MCM-41 molecular sieve of modification is to cover one deck Siliciumatom on the MCM-41 inwall.
A kind of method of modifying that improves the MCM-41 hydrothermal stability of molecular sieve will contain silicone couplet and join in the organic solvent, stir; Then to wherein adding the MCM-41 molecular sieve, wherein, the weight ratio that contains silicone couplet and MCM-41 molecular sieve is 2～10: 10, flood after 1～20 hour, use organic solvent washing again 2～6 times, 100-150 ℃ of down oven dry 2-20 hour,, obtain the MCM-41 molecular sieve after the modification then at 450-560 ℃ of following roasting 6-16 hour.
The described silicone couplet that contains can be γ-methacryloyl propyl trimethoxy silicane, also can be γ-An Bingjisanyiyangjiguiwan.
Wherein, γ-methacryloyl propyl trimethoxy silicane, molecular formula: CH
2=C (CH
3) COO (CH
2)
3Si (OCH
3)
3This γ-methacryloyl propyl trimethoxy silicane is KH570 at the trade mark of the product of the Chinese Academy of Sciences; the trade mark at the product of U.S.'s union carbide corporation is A-174; the trade mark at the product of U.S. Dao Lianning company is Z-603, the Japanese KBM-503 of Shin-Etsu Chemial Co., Ltd.
γ-An Bingjisanyiyangjiguiwan, molecular formula: H
2NCH
2CH
2CH
2Si (OC
2H
5)
3This γ-An Bingjisanyiyangjiguiwan is KH550 at the trade mark of the product of the Chinese Academy of Sciences, is A-1100 at the trade mark of the product of U.S.'s union carbide corporation.
Described organic solvent is any one in ethanol, tetracol phenixin and the acetone.
Wherein, the kind of organic solvent and consumption are not limited fully, contain the silicone couplet dissolving, and the MCM-41 molecular sieve is flooded get final product in containing the organic solvent of silicone couplet as long as any organic solvent and consumption thereof can satisfy.
Advantage of the present invention is:
The purpose of MCM-41 molecular sieve exploitation is in industrial application, one of important indicator when hydrothermally stable is the solid catalyst industrial application.The present invention realizes a kind of MCM-41 molecular sieve of modification, and has found a kind of method of modifying that can improve the MCM-41 hydrothermal stability of molecular sieve.The sample that adopts method of the present invention to handle and does not have the comparison that experimentizes of treated sample, and contrast and experiment is as follows:
350 ℃ of steam treatment time is characterizing method as a result
The untreated samples x light that began to cave in 4 hours
X light begins to cave in when handling back sample 48-54
Wherein, untreated samples is the sample of handling without method of the present invention,, begins to cave in after 4 hours with 350 ℃ of steam treatment; Handle the sample of back sample for handling through method of the present invention, during with 350 ℃ of steam treatment 48-54 hour after, just begin to cave in, the time prolongs widely, and large increase has been arranged on the hydrothermal stability.
The present invention carries out modification by the MCM-41 that adopts KH series to contain behind the involutory one-tenth of silicone couplet, pass through high-temperature roasting again, remove the organic group in the coupling agent, make and increase one deck Siliciumatom on the MCM-41 inwall, remedied its lattice imperfection, increase the MCM-41 wall thickness, thereby also reach the purpose that strengthens its hydrothermal stability.Provide more wide prospect for after it in industrial application.
Embodiment
Embodiment 1
Take by weighing 2g KH570 and be dissolved in the 60ml ethanol, stir, then to the MCM-41 that wherein adds 10g roasting type, flood after 1 hour, more for several times, dried 2 hours down at 120 ℃ with washing with alcohol, then 540 ℃ of following roastings 6 hours, obtain the MCM-41 molecular sieve after the modification.Test result shows: the specific surface area of sample is 620m
2/ g, pore volume are 0.48ml/g, and mean pore size is 3.1nm, and sample was increased to 48 hours by original 6 hours the steady time under 350 ℃ of water vapour simultaneously.
Embodiment 2
Take by weighing 4g KH570 and be dissolved in the 60ml ethanol, stir, then to the MCM-41 that wherein adds 10g roasting type, flood after 1 hour, more for several times, dried 2 hours down at 120 ℃ with washing with alcohol, then 540 ℃ of following roastings 6 hours, obtain the MCM-41 molecular sieve after the modification.Test result shows: the specific surface area of sample is 642m
2/ g, pore volume are 0.44ml/g, and mean pore size is 2.7nm, and sample was increased to 54 hours by original 6 hours the steady time under 350 ℃ of water vapour simultaneously.
Embodiment 3
Take by weighing 10g KH570 and be dissolved in the 60ml ethanol, stir, then to the MCM-41 that wherein adds 10g roasting type, flood after 1 hour, more for several times, dried 2 hours down at 120 ℃ with washing with alcohol, then 540 ℃ of following roastings 6 hours, obtain the MCM-41 molecular sieve after the modification.Test result shows: the specific surface area of sample is 622m
2/ g, pore volume are 0.40ml/g, and mean pore size is 2.5nm, and sample was increased to 49 hours by original 6 hours the steady time under 350 ℃ of water vapour simultaneously.
Claims (4)
1, a kind of MCM-41 molecular sieve of modification is characterized in that: be to cover one deck Siliciumatom on the MCM-41 inwall.
2, the method for the modification of the MCM-41 molecular sieve of the described modification of a kind of claim 1 is characterized in that: will contain silicone couplet and join in the organic solvent, and stir; Then to wherein adding the MCM-41 molecular sieve, wherein, the weight ratio that contains silicone couplet and MCM-41 molecular sieve is 2～10: 10, flood after 1～20 hour, use organic solvent washing again 2～6 times, 100-150 ℃ of down oven dry 2-20 hour,, obtain the MCM-41 molecular sieve after the modification then at 450-560 ℃ of following roasting 6-16 hour.
3, method according to claim 2 is characterized in that: the described silicone couplet that contains is γ-methacryloyl propyl trimethoxy silicane, or γ-An Bingjisanyiyangjiguiwan.
4, method according to claim 2 is characterized in that: described organic solvent is any one in ethanol, tetracol phenixin and the acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100908667A CN100436319C (en) | 2005-08-18 | 2005-08-18 | Modified MCM-41 molecular sieve, and modified method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100908667A CN100436319C (en) | 2005-08-18 | 2005-08-18 | Modified MCM-41 molecular sieve, and modified method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1915815A CN1915815A (en) | 2007-02-21 |
| CN100436319C true CN100436319C (en) | 2008-11-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100908667A Expired - Fee Related CN100436319C (en) | 2005-08-18 | 2005-08-18 | Modified MCM-41 molecular sieve, and modified method |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964744B (en) * | 2012-12-10 | 2016-06-01 | 山东慧科助剂股份有限公司 | Thermal stabilizer for aluminate modified molecular sieve PVC and preparation method thereof |
| CN103819944B (en) * | 2014-03-03 | 2016-05-04 | 上海绿强新材料有限公司 | A kind of manufacture method of the active powder of molecular sieve that is applicable to polyurethane system |
| CN104387228B (en) * | 2014-09-29 | 2016-02-17 | 湖南湘易康制药有限公司 | A kind of preparation method of dehydrated alcohol |
| CN104387227B (en) * | 2014-09-29 | 2016-02-17 | 湖南湘易康制药有限公司 | A kind of preparation method of medicinal alcohol |
| CN112960679A (en) * | 2021-04-29 | 2021-06-15 | 钛纶新材料(昆山)有限公司 | Preparation method of modified MCM-41 molecular sieve |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6153798A (en) * | 1997-07-23 | 2000-11-28 | Mitsubishi Gas Chemical Co., Ltd. | Catalysts for methanol conversion reactions |
| US20050133052A1 (en) * | 2003-11-21 | 2005-06-23 | Philip Morris Usa Inc. | Cigarette filter |
-
2005
- 2005-08-18 CN CNB2005100908667A patent/CN100436319C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6153798A (en) * | 1997-07-23 | 2000-11-28 | Mitsubishi Gas Chemical Co., Ltd. | Catalysts for methanol conversion reactions |
| US20050133052A1 (en) * | 2003-11-21 | 2005-06-23 | Philip Morris Usa Inc. | Cigarette filter |
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| CN1915815A (en) | 2007-02-21 |
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