CN103172080A - Method for preparing mesoporous molecular sieve - Google Patents
Method for preparing mesoporous molecular sieve Download PDFInfo
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- CN103172080A CN103172080A CN2013101016464A CN201310101646A CN103172080A CN 103172080 A CN103172080 A CN 103172080A CN 2013101016464 A CN2013101016464 A CN 2013101016464A CN 201310101646 A CN201310101646 A CN 201310101646A CN 103172080 A CN103172080 A CN 103172080A
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Abstract
The invention discloses a method for preparing a mesoporous molecular sieve MCM-48. The method comprises the steps of extracting effective ingredients in coal ash as silicon sources by adopting a single template agent cetyl trimethyl ammonium bromide (CTAB); and synthetizing MCM-48 under alkaline medium by a hydrothermal method. The synthetized mesoporous material is regular in ducts, single in aperture distribution, high in order degree, and large in specific surface area. The method is simple and feasible in actual operation, economic and environment-friendly, and can provide a new path for 'recycling' utilization of the coal ash; and the synthetized sample has practical application value.
Description
Technical field
The present invention relates to a kind of preparation method of molecular sieve, particularly the preparation method of a kind of mesopore molecular sieve MCM-48.
Background technology
U.S. Mobil company reported first in 1992 mesopore molecular sieve of M41S series.This class material has homogeneous adjustable aperture and high-specific surface area, has become the study hotspot in environmental improvement field at present.M41S family material, it comprises the MCM-41 of six side's phases, the MCM-48 of Emission in Cubic and the MCM-50 of lamellar phase.But MCM-48 is due to the pore passage structure with three-dimensional spiral, higher specific surface area and the higher performances such as duct of the general character, and more be conducive to the diffusion of reaction molecular, no matter be to be applied to environmental improvement, or the assembling aspect of catalysis, nanocluster all has tempting prospect.
Up to now, forefathers' patent is 201010107602.9 to be that silicon used in 200510111245.2 source is the chemical reagent of purchase or synthetic silicon source with announcing in the number of patent application on May 24th, 2006 such as announcing in the number of patent application on July 14th, 2010, and this not only can cause the loss that also has raw material in the raising of cost but also building-up process.
Summary of the invention
The solid waste coal ash that the object of the invention is to utilize power plant emission prepares the MCM-48 molecular sieve as the silicon source, and the preparation method of a kind of simple and easy, low-cost, mesopore molecular sieve MCM-48 that actually operating is feasible is provided.
The technical solution that realizes the object of the invention is:
The preparation method of a kind of mesopore molecular sieve MCM-48 is characterized in that adopting single template CTAB, and the effective constituent in the extract powder coal ash is as the silicon source, and under the effect of ethanol activation, with the synthetic MCM-48 of hydrothermal method, concrete steps are as follows under alkaline medium:
(1) will comprise that the mixture that siliceous supernatant liquor, template CTAB, dehydrated alcohol and water form is placed in reactor, slowly stir under 30 ~ 40 ℃ until all dissolvings were reacted after 2 ~ 3 hours, use H
2SO
4The pH that solution is regulated mixed solution is 10 ~ 11, continues to stir 2 ~ 3h, obtains white gels;
(2) the gained white gels is placed in reactor, controlling temperature is 100 ~ 110 ℃, crystallization 60 ~ 72h, and after reaction finishes, filtration washing, oven dry obtains pulverulent solids, and 500 ℃ of roasting sample 5h of retort furnace get the MCM-48 sample.
Wherein, siliceous supernatant liquor be extract from flyash and in step (1) mol ratio of each reactant be siliceous supernatant liquor: masterplate agent CTAB=1:0.5 ~ 1:1; Siliceous supernatant liquor: dehydrated alcohol=1:4 ~ 1:5; Siliceous supernatant liquor: water=1:100 ~ 1:200.
Preferred version is siliceous supernatant liquor: nog plate agent CTAB: dehydrated alcohol: water=1:0.5:4.5:100; Step is used 5mol/LH in (1)
2SO
4The pH that regulates mixed solution is 10.5; In step (2), the crystallization temperature is 100 ℃, and the crystallization time is 72h.
The present invention compared with prior art, its remarkable advantage:
(1) raw material is flyash, therefrom extracts the silicon source, has reduced synthetic cost, can reach the resource utilization purpose of the treatment of wastes with processes of wastes against one another simultaneously, has avoided simultaneously using the toxic of the expensive organosilicon such as TEOS source;
(2) room temperature is synthetic, and operation is simple and feasible, uses simultaneously single template can overcome synthetic difficulty, further reduces preparation cost, greatly reduced the usage quantity of tensio-active agent, good reproducibility;
(3) every characterization method shows that the product thermostability is high, and the degree of order is good, and synthesizing the material specific surface area is 1256.95 m
2/ g, the aperture is 2.88 nm, has potential industrial application value.
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Description of drawings
Fig. 1 is the XRD spectra of the prepared MCM-48 of the present invention;
Fig. 2 is the N of the prepared MCM-48 of the present invention
2Absorption/desorption curve;
Fig. 3 is the infrared spectrogram of the prepared MCM-48 of the present invention;
Fig. 4 be the prepared MCM-48 of the present invention thermogravimetric/differential thermal figure.
Embodiment
The preparation method of a kind of mesopore molecular sieve MCM-48 is characterized in that adopting single template CTAB, and the effective constituent in the extract powder coal ash is as the silicon source, and under the effect of ethanol activation, with the synthetic MCM-48 of hydrothermal method, concrete steps are as follows under alkaline medium:
(1) will comprise that the mixture that siliceous supernatant liquor, template CTAB, dehydrated alcohol and water form is placed in reactor, slowly stir under 30 ~ 40 ℃ until all dissolvings were reacted after 2 ~ 3 hours, use H
2SO
4The pH that solution is regulated mixed solution is 10.5, continues to stir 2 ~ 3h, obtains white gels;
(2) the gained white gels is placed in reactor, controlling temperature is 100 ~ 110 ℃, crystallization 60 ~ 72h, and after reaction finishes, filtration washing, oven dry obtains pulverulent solids, and 500 ℃ of roasting sample 5h of retort furnace get the MCM-48 sample.
Wherein, siliceous supernatant liquor be extract from flyash and in step (1) mol ratio of each reactant be siliceous supernatant liquor: masterplate agent CTAB=1:0.5 ~ 1:1; Siliceous supernatant liquor: dehydrated alcohol=1:4 ~ 1:5; Siliceous supernatant liquor: water=1:100 ~ 1:200.
The deironing pre-treatment of flyash: flyash is dried to constant weight under 100 ℃, after mixing take liquid-solid ratio (mL/g) as the 20:1 proportioning with 20% hydrochloric acid soln and xeraphium coal ash, after stirring 4 h, 80 ℃ of lower constant speed (300 r/min) filter, be neutral with deionized water wash to filtrate, oven dry, be placed in vacuum drier standby under 100 ℃.
Extraction silicon source in flyash: pretreated flyash is mixed with the NaOH solution of different concns 5mol/L, after 80 ℃ of lower stirring and refluxing 4h of normal pressure, filter and obtain siliceous supernatant liquor, utilize ICP-AES to measure the concentration of silicon in supernatant liquor.
Reagent and instrument: the cetyl trimethylammonium bromide that uses is from the Chengdu Long Huagongshijichang of section, ethanol is analytical pure, from Nanjing Chemistry Reagent Co., Ltd., Optima 7000DV type inductive coupling plasma emission spectrograph (ICP-AES) is U.S. Perkin Elmer company.
Configuration 1000ml massfraction is 20% hydrochloric acid soln, adds 50g flyash, stirs 4h 80 ℃ of lower constant speed, filters, and washing is to neutral, and oven dry 40g flyash is standby.Get 20gNaOH, the concentration of configuration 100ml is 5mol/L solution, adds 10g iron power removing coal ash, after 80 ℃ of lower stirring and refluxing 4h of normal pressure, filters and obtains siliceous supernatant liquor (with the silicone content in ICP-AES mensuration supernatant liquor), places standby.According to the siliceous supernatant liquor of mol ratio: nog plate agent CTAB: dehydrated alcohol: water=1:0.5:4.5:100 adds reagent mix and stirs, during with the H of 5mol/L
2SO
4The pH that solution is regulated mixed solution is 10.5.The gained white gels is placed in crystallizing kettle, and controlling temperature is 100 ℃, and crystallization 72h takes out naturally cooling, filtration washing, and oven dry obtains pulverulent solids, and retort furnace is warming up to 500 ℃ with 1 ℃/min, and constant temperature calcining sample 5h namely gets the MCM-48 sample.
Embodiment 2
Get the mesoporous material 0.05g of preparation in embodiment 1, be added in the aqueous solution that the 25mL lead concentration is 100mg/L.Finally can obtain 95% plumbous clearance, obtain decontamination effect improving preferably.
Embodiment 3
Configuration 1000ml massfraction is 20% hydrochloric acid soln, adds 50g flyash, stirs 4h 80 ℃ of lower constant speed, filters, and washing is to neutral, and oven dry 40g flyash is standby.Get 20gNaOH, the concentration of configuration 100ml is 5mol/L solution, adds 10g iron power removing coal ash, after 80 ℃ of lower stirring and refluxing 4h of normal pressure, filters and obtains siliceous supernatant liquor (with the silicone content in ICP-AES mensuration supernatant liquor), places standby.According to the siliceous supernatant liquor of mol ratio: nog plate agent CTAB: dehydrated alcohol: water=1:1:5:100 adds reagent mix and stirs, during with the H of 5mol/L
2SO
4The pH that solution is regulated mixed solution is 10.5.The gained white gels is placed in crystallizing kettle, and controlling temperature is 110 ℃, and crystallization 60h takes out naturally cooling, filtration washing, and oven dry obtains pulverulent solids, and retort furnace is warming up to 500 ℃ with 1 ℃/min, and constant temperature calcining sample 5h namely gets the MCM-48 sample.
Embodiment 4
Get the mesoporous material 0.05g of preparation in embodiment 3, be added in the aqueous solution that the 25mL lead concentration is 100mg/L.Finally can obtain 90% plumbous clearance, obtain good decontamination effect improving.
Claims (5)
1. the preparation method of a mesopore molecular sieve MCM-48, is characterized in that adopting single template CTAB, and the effective constituent in the extract powder coal ash is as the silicon source, and under the effect of ethanol activation, with the synthetic MCM-48 of hydrothermal method, concrete steps are as follows under alkaline medium:
(1) will comprise that the mixture that siliceous supernatant liquor, template CTAB, dehydrated alcohol and water form is placed in reactor, slowly stir under 30 ~ 40 ℃ until all dissolvings were reacted after 2 ~ 3 hours, use H
2SO
4The pH that solution is regulated mixed solution is 10 ~ 11, continues to stir 2 ~ 3h, obtains white gels;
(2) the gained white gels is placed in reactor, controlling temperature is 100 ~ 110 ℃, crystallization 60 ~ 72h, and after reaction finishes, filtration washing, oven dry obtains pulverulent solids, and 500 ℃ of roasting sample 5h of retort furnace get the MCM-48 sample.
2. the preparation method of mesopore molecular sieve MCM-48 according to claim 1, it is characterized in that: in step (1), the mol ratio of each reactant is siliceous supernatant liquor: masterplate agent CTAB=1:0.5 ~ 1:1; Siliceous supernatant liquor: dehydrated alcohol=1:4 ~ 1:5; Siliceous supernatant liquor: water=1:100 ~ 1:200.
3. the preparation method of mesopore molecular sieve MCM-48 according to claim 1 is characterized in that siliceous supernatant liquor is to extract and get from flyash.
4. the preparation method of mesopore molecular sieve MCM-48 according to claim 1, it is characterized in that: step is used 5mol/LH in (1)
2SO
4The pH that regulates mixed solution is 10.5.
5. the preparation method of mesopore molecular sieve MCM-48 according to claim 1 is characterized in that: in step (2), the crystallization temperature is 100 ℃, and the crystallization time is 72h.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103738977A (en) * | 2013-12-27 | 2014-04-23 | 中国神华能源股份有限公司 | Method for preparing 4A type molecular sieve by taking white mud as raw material and product prepared by same |
| CN103818920A (en) * | 2013-12-24 | 2014-05-28 | 淮南师范学院 | Method for preparing Si-Al ordered mesoporous molecular sieve |
| CN104150941A (en) * | 2014-07-18 | 2014-11-19 | 西安建筑科技大学 | Steel slag-based mesoporous material and preparation method thereof |
| CN105692651A (en) * | 2016-04-07 | 2016-06-22 | 陕西大秦钾业有限公司 | Method for preparing 13X molecular sieve by using potash feldspar as raw material and 13X molecular sieve prepared by method |
| CN108928834A (en) * | 2017-05-24 | 2018-12-04 | 神华集团有限责任公司 | MCM-41 mesopore molecular sieve and its preparation method and application |
| CN108993457A (en) * | 2018-07-27 | 2018-12-14 | 河北科技大学 | A method of adsorbent is prepared by raw material of flyash |
| CN110668458A (en) * | 2018-07-02 | 2020-01-10 | 国家能源投资集团有限责任公司 | Al-SBA-15 mesoporous molecular sieve, denitration catalyst, preparation methods of Al-SBA-15 mesoporous molecular sieve and denitration catalyst, and application of Al-SBA-15 mesoporous molecular sieve and denitration catalyst |
| CN114985000A (en) * | 2022-05-05 | 2022-09-02 | 宁夏医科大学 | Preparation method and application of MCM-48 composite catalyst |
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| CN1180044A (en) * | 1996-10-15 | 1998-04-29 | 李泽民 | Method for producing molecular sieve material by using flyash |
| CN1775674A (en) * | 2005-12-08 | 2006-05-24 | 华东理工大学 | Method for preparing mesoporous molecular sieve |
| CN101381086A (en) * | 2008-10-20 | 2009-03-11 | 西安建筑科技大学 | Method for preparing Si-MCM-41 mesopore molecular sieve |
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2013
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Patent Citations (4)
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103818920A (en) * | 2013-12-24 | 2014-05-28 | 淮南师范学院 | Method for preparing Si-Al ordered mesoporous molecular sieve |
| CN103738977A (en) * | 2013-12-27 | 2014-04-23 | 中国神华能源股份有限公司 | Method for preparing 4A type molecular sieve by taking white mud as raw material and product prepared by same |
| CN103738977B (en) * | 2013-12-27 | 2016-03-23 | 中国神华能源股份有限公司 | A kind of take white clay as the method that 4A type molecular sieve prepared by raw material and the product prepared by the method |
| CN104150941A (en) * | 2014-07-18 | 2014-11-19 | 西安建筑科技大学 | Steel slag-based mesoporous material and preparation method thereof |
| CN104150941B (en) * | 2014-07-18 | 2015-10-21 | 西安建筑科技大学 | A kind of slag based mesoporous material and preparation method thereof |
| CN105692651A (en) * | 2016-04-07 | 2016-06-22 | 陕西大秦钾业有限公司 | Method for preparing 13X molecular sieve by using potash feldspar as raw material and 13X molecular sieve prepared by method |
| CN108928834A (en) * | 2017-05-24 | 2018-12-04 | 神华集团有限责任公司 | MCM-41 mesopore molecular sieve and its preparation method and application |
| CN108928834B (en) * | 2017-05-24 | 2020-07-10 | 神华集团有限责任公司 | MCM-41 mesoporous molecular sieve, and preparation method and application thereof |
| CN110668458A (en) * | 2018-07-02 | 2020-01-10 | 国家能源投资集团有限责任公司 | Al-SBA-15 mesoporous molecular sieve, denitration catalyst, preparation methods of Al-SBA-15 mesoporous molecular sieve and denitration catalyst, and application of Al-SBA-15 mesoporous molecular sieve and denitration catalyst |
| CN108993457A (en) * | 2018-07-27 | 2018-12-14 | 河北科技大学 | A method of adsorbent is prepared by raw material of flyash |
| CN114985000A (en) * | 2022-05-05 | 2022-09-02 | 宁夏医科大学 | Preparation method and application of MCM-48 composite catalyst |
| CN114985000B (en) * | 2022-05-05 | 2023-10-03 | 宁夏大学 | Preparation method and application of MCM-48 composite catalyst |
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Application publication date: 20130626 |