CN1515490A - Method for removing organic-inorganic composite porous material organic template agent - Google Patents
Method for removing organic-inorganic composite porous material organic template agent Download PDFInfo
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Abstract
The present invention relates to a method for removing organic template agent from organic-inorganic composite porous material. It adopts microwave heating counteracting system, and uses the cheap oxidizing inorganic acid and aqueous hydrogen peroxide as solvent, and utilize self-produced pressure in the system to remove the organic template agent. Said method is high-effective, quick and small in damage to inorganic skeleton, and the prepared ordered silicon oxide material has higher specific area, pore volume and structure ordered degree. Said invention can be used for removing organic material from various acid-resistant inorganic materials.
Description
Technical field
The invention belongs to the inorganic porous material technical field, be specifically related to a kind of removal methods of organic and inorganic composite porous material organic formwork agent.
Technical background
Inorganic hole material has big specific surface area and pore volume, adjustable aperture, the surface properties that can modify and the pattern that can control or the like, thereby all has very large application potential in separation, catalysis, sensing and as the every field such as template of synthetic other material.This family of inorganic porous material comprises following main member: poromerics, mesoporous material, large pore material and multilevel hole material.At preparation inorganic hole material, when especially having the hole material of orderly pore passage structure, all need use organic structure directed agents, i.e. organic formwork agent under most of conditions.For the micro porous molecular sieve material, the structure directing agent that is adopted when synthetic mostly is the small molecule amine of short chain; For mesopore molecular sieve, the structure directing agent that people adopt is amphipathic tensio-active agent, comprises cationic surfactant, aniorfic surfactant, nonionogenic tenside and two surfacant.In reaction process, obtain having only its organic formwork agent that contains being removed, the pore space structure that just can obtain having open bore after the composite organic-inorganic material of inorganic species arrangement around organic formwork agent.
Up to now, in the world for two kinds of methods of the many uses of the removal of organic formwork agent: direct roasting method, ion exchange method and solvent extration.The direct roasting method is meant the synthetic composite organic-inorganic material that obtains directly in calcination in air or oxygen atmosphere under the specific temperature, makes organic formwork agent be oxidized to gas molecules and removes from system; Ion exchange method is meant uses certain ion that the structure directing agent in the duct is cemented out; Solvent extration is meant organic-inorganic composition is placed certain solvent (as the mixing solutions of ethanol, methyl alcohol or they and hydrochloric acid), utilize solvent that the high solubleness of organic formwork agent is extracted it from the duct of mixture, thereby obtain open pore space structure.But this several method all exists certain shortcoming.For the direct roasting method, the porous material of formation is compared with original matrix material, and skeleton has bigger contraction, makes the aperture diminish; And because the journey of correcting one's mistakes is carried out under higher temperature, the surface group of material (as hydroxyl etc.) can be subjected to destruction to a certain degree, has influenced the property of material itself greatly.In addition, roasting method is inapplicable for the relatively poor material of thermostability, has bigger limitation.For ion exchange method and solvent extration, though the material that obtains is at last compared with matrix material, skeleton does not have tangible shrinkage phenomenon, but operate more time-consuming, and organic formwork agent (structure directing agent) can not all be removed, the duct does not reach 100% and opens, and material duct, hole internal surface also can not come out effectively.
Summary of the invention
The objective of the invention is to propose a kind of method that can remove the contained organic formwork agent of organic and inorganic composite porous material quick, easy, effectively.Thereby make the hole material of last gained keep more surface hydroxyl, have lower skeleton shrinking percentage and high specific surface area, pore volume, structurally ordered degree and big aperture, and the clearance of organic species can reach 100%, to satisfy the needs of scientific research and industrial application.
The removal methods of the organic and inorganic composite porous material organic formwork agent that the present invention proposes is to adopt microwave heating to clear up system, is solvent in conjunction with oxidisability mineral acid and hydrogen peroxide with cheapness, utilizes pressure spontaneous in the system, removes organic formwork agent.
The removal methods of the organic and inorganic composite porous material organic formwork agent that the present invention proposes, its specific operation process is as described below: at first the organic and inorganic composite porous material is placed the micro-wave digestion jar, add oxidizing acid and hydrogen peroxide, screw and clear up cover and be placed in the microwave cavity; Pressure and digestion time are cleared up in selection; Clear up and make the system cooling after finishing, remove by filter digestion solution immediately, and use distilled water wash; The mass ratio of oxidizing acid, hydrogen peroxide and composite porous material is 4-10: 1-20: 1; Clearing up pressure is 5-20 normal atmosphere; Digestion condition is 120-200 ℃; Digestion time is 1-20 minute.
In the above-mentioned removal methods, used oxidizing acid can be a concentrated nitric acid when removing organic formwork agent, also can be the vitriol oil or perchloric acid etc.
In the above-mentioned removal methods, used hydrogen peroxide can be the commodity hydrogen peroxide when removing organic formwork agent, also can be to be formed by superoxide such as Potassium peroxide, sodium peroxide and nitric acid reaction.
In the above-mentioned removal methods, organic formwork agent adopts high-pressure sealed micro-wave digestion system when removing, and clearing up pressure is 5-20 normal atmosphere.
The organic and inorganic composite porous material that the removal methods of above-mentioned organic formwork agent is suitable for, comprise that micro porous molecular sieve material (as ZSM-5 etc.), meso-porous molecular sieve material are (as MCM-41, MCM-48, SBA-2, SBA-12, SBA-15, SBA-16, MSU-X, HMS etc.), large pore material, foramen magnum-mesoporous multilevel hole material and mesoporous-micropore multilevel hole material.
Adopt the more general material that obtains through methods such as direct roasting or solvent extractions of material of aforesaid method gained that higher specific surface area, pore volume and structurally ordered degree are arranged, bigger aperture, more surface silanol group and lower skeleton shrinking percentage, the clearance of organic species can reach 100%.The hole material that this class has a premium properties is in catalysis, absorption and as the special effect of aspects such as hard template performance of nano materials.
Embodiment
Embodiment 1:
Removing of micro porous molecular sieve ZSM-5 organic amine template.The ZSM-5 powder that 0.5g is contained organic amine adds in the tetrafluoroethylene high-pressure digestion jar, adds the dense hydrogen peroxide of the 3-5g vitriol oil and 1-2g more respectively.Behind the sealed digestion jar, be placed in the MK-II type optical fiber pressure automatic control microwave oven, it is 10 normal atmosphere that pressure is set.Program is cleared up in unlatching, clears up 10 minutes under 10 normal atmosphere, and digestion condition is 180 ℃.Clear up the back system cooling 10 minutes that finishes, remove by filter digestion solution immediately, and get final product with distilled water wash.
Embodiment 2:
Removing of mesoporous molecular sieve SBA-15 high polymer templates.The SBA-15 powder of 0.5g pbz polymer (P123) is added in the tetrafluoroethylene high-pressure digestion jar, add the dense hydrogen peroxide of the 3-5g vitriol oil and 0.5-2g more respectively.Behind the sealed digestion jar, be placed in the MK-II type optical fiber pressure automatic control microwave oven, it is 5 normal atmosphere that pressure is set.Program is cleared up in unlatching, clears up 4 minutes under 5 normal atmosphere, and digestion condition is 120 ℃.Clear up the back system cooling number minute of finishing, remove by filter digestion solution immediately, and get final product with distilled water wash.
Embodiment 3:
Removing of mesopore molecular sieve film high polymer templates.The mesopore molecular sieve film of 0.5g pbz polymer (F127) is added in the tetrafluoroethylene high-pressure digestion jar, add the dense hydrogen peroxide of 2-4g concentrated nitric acid and 5-8g more respectively.Behind the sealed digestion jar, be placed in the MK-II type optical fiber pressure automatic control microwave oven, it is 20 normal atmosphere that pressure is set.Program is cleared up in unlatching, clears up 3 minutes under 20 normal atmosphere, and digestion condition is 200 ℃, clears up the back system cooling number minute of finishing, and removes by filter digestion solution immediately, and gets final product with distilled water wash.
Embodiment 4:
Removing of large pore material high polymer templates.The large pore material of 0.4g pbz polymer (polystyrene) is added in the tetrafluoroethylene high-pressure digestion jar, add the dense hydrogen peroxide of 3-4g perchloric acid and 1-2g more respectively.Behind the sealed digestion jar, be placed in the MK-II type optical fiber pressure automatic control microwave oven, it is 10 normal atmosphere that pressure is set.Program is cleared up in unlatching, clears up 20 minutes under 10 normal atmosphere, and digestion condition is 180 ℃.Clear up the back system cooling number minute of finishing, remove by filter digestion solution immediately, and get final product with distilled water wash.
Embodiment 5:
Removing of macropore one mesoporous multilevel hole material high polymer templates.The foramen magnum-mesoporous multilevel hole material of 0.2g pbz polymer (polystyrene and P123) is added in the tetrafluoroethylene high-pressure digestion jar, add the dense hydrogen peroxide of 0.8-1g concentrated nitric acid and 3-4g more respectively.Behind the sealed digestion jar, be placed in the MK-II type optical fiber pressure automatic control microwave oven, it is 5 normal atmosphere that pressure is set.Program is cleared up in unlatching, clears up 5 minutes under 5 normal atmosphere, and digestion condition is 120 ℃.Clear up the back system cooling number minute of finishing, remove by filter digestion solution immediately, and get final product with distilled water wash.
By the organic and inorganic composite porous material that the foregoing description obtains, the clearance of its organic formwork agent all reaches 100%, and material property is good.
Claims (3)
1, a kind of removal methods of organic and inorganic composite porous material organic formwork agent, it is characterized in that concrete steps are as follows: at first the organic and inorganic composite porous material is placed the micro-wave digestion jar, add oxidizing acid and hydrogen peroxide, screw and clear up cover and be placed in the microwave cavity; It is 5-20 normal atmosphere that pressure is cleared up in selection, and digestion condition is 120-200 ℃, and digestion time is 1-20 minute; Clear up finish after with system cooling, remove by filter digestion solution immediately, and use distilled water wash; The mass ratio of oxidizing acid, hydrogen peroxide and composite porous material is 4-10: 1-20: 1.
2, the removal methods of a kind of organic and inorganic composite porous material organic formwork agent according to claim 1 is characterized in that used oxidizing acid is a concentrated nitric acid, or the vitriol oil, or perchloric acid.
3, the removal methods of a kind of organic and inorganic composite porous material organic formwork agent according to claim 1, it is characterized in that the organic and inorganic composite porous material is antacid material, comprise various micro porous molecular sieve materials, various meso-porous molecular sieve material, large pore material, foramen magnum-mesoporous multilevel hole material and macropore-micropore multilevel hole material.
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| CN 03150611 CN1219701C (en) | 2003-08-26 | 2003-08-26 | Method for removing organic-inorganic composite porous material organic template agent |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307097C (en) * | 2005-10-20 | 2007-03-28 | 浙江大学 | Method of removing organic template agent from molecular sieve |
| WO2007091828A1 (en) * | 2006-02-07 | 2007-08-16 | Korea Research Institute Of Chemical Technology | A preparation method of porous hybrid inorganic-organic materials |
| CN102180479A (en) * | 2011-03-21 | 2011-09-14 | 复旦大学 | Method for digesting organic template agent of nano zeolite in situ with assistance of microwave |
| CN102583529A (en) * | 2012-02-28 | 2012-07-18 | 南京大学 | Method for preparing mesoporous titanium dioxide by template method and application of mesoporous titanium dioxide to preparation of dye-sensitized solar cells |
| CN104556100A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Method for removing organic amine template in borosilicate beta molecular sieve |
| CN105271284A (en) * | 2015-06-09 | 2016-01-27 | 浙江师范大学 | Method for removing organic template agent in porous material through wet method |
| CN106745026A (en) * | 2016-12-16 | 2017-05-31 | 南京工业大学 | A kind of preparation method of zero defect DDR molecular screen membranes |
| CN109731579A (en) * | 2018-12-25 | 2019-05-10 | 天津大学 | A kind of mesoporous lanthanum oxide catalyst of nickel load and preparation method thereof |
| CN113912109A (en) * | 2021-11-23 | 2022-01-11 | 成都先进金属材料产业技术研究院股份有限公司 | Preparation method of nano titanium dioxide porous material |
-
2003
- 2003-08-26 CN CN 03150611 patent/CN1219701C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307097C (en) * | 2005-10-20 | 2007-03-28 | 浙江大学 | Method of removing organic template agent from molecular sieve |
| WO2007091828A1 (en) * | 2006-02-07 | 2007-08-16 | Korea Research Institute Of Chemical Technology | A preparation method of porous hybrid inorganic-organic materials |
| US7855299B2 (en) | 2006-02-07 | 2010-12-21 | Korea Research Institute Of Chemical Technology | Preparation method of porous organic inorganic hybrid materials |
| CN102180479A (en) * | 2011-03-21 | 2011-09-14 | 复旦大学 | Method for digesting organic template agent of nano zeolite in situ with assistance of microwave |
| CN102583529A (en) * | 2012-02-28 | 2012-07-18 | 南京大学 | Method for preparing mesoporous titanium dioxide by template method and application of mesoporous titanium dioxide to preparation of dye-sensitized solar cells |
| CN102583529B (en) * | 2012-02-28 | 2014-12-10 | 南京大学 | Method for preparing mesoporous titanium dioxide by template method and application of mesoporous titanium dioxide to preparation of dye-sensitized solar cells |
| CN104556100A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Method for removing organic amine template in borosilicate beta molecular sieve |
| CN105271284A (en) * | 2015-06-09 | 2016-01-27 | 浙江师范大学 | Method for removing organic template agent in porous material through wet method |
| CN106745026A (en) * | 2016-12-16 | 2017-05-31 | 南京工业大学 | A kind of preparation method of zero defect DDR molecular screen membranes |
| CN106745026B (en) * | 2016-12-16 | 2019-01-11 | 南京工业大学 | A kind of preparation method of zero defect DDR molecular screen membrane |
| CN109731579A (en) * | 2018-12-25 | 2019-05-10 | 天津大学 | A kind of mesoporous lanthanum oxide catalyst of nickel load and preparation method thereof |
| CN113912109A (en) * | 2021-11-23 | 2022-01-11 | 成都先进金属材料产业技术研究院股份有限公司 | Preparation method of nano titanium dioxide porous material |
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| CN1219701C (en) | 2005-09-21 |
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