CN100383043C - Process for synthesizing mesic porous molecular sieve SBA-15 - Google Patents
Process for synthesizing mesic porous molecular sieve SBA-15 Download PDFInfo
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- CN100383043C CN100383043C CNB2005100500910A CN200510050091A CN100383043C CN 100383043 C CN100383043 C CN 100383043C CN B2005100500910 A CNB2005100500910 A CN B2005100500910A CN 200510050091 A CN200510050091 A CN 200510050091A CN 100383043 C CN100383043 C CN 100383043C
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Abstract
The present invention belongs to the technical field of inorganic nanometer materials, particularly relates to a a preparation method of a mesoporous molecular sieve by using heteropoly acid and tri-block high molecular polymer. Tri-block high molecular surfactant of polyepoxyethene-polyepoxypropane-polyepoxyethene is used as a template agent, and a small amount of heteropoly acid is added in the process of preparation; as a pH regulator, the consumption of acid as corrosive liquid can be considerably reduced by the heteropoly acid, and the heteropoly acid can serve as an accelerator for accelerating the forming speed of the mesoporous material. The material can be used as a catalyst, a catalyst carrier, adsorbent, an organic-inorganic composite material, a sensor, a template agent for synthesizing other nanometer materials, etc., and the material can be used for the separation of biomacromolecules.
Description
Technical field
The present invention relates to a kind of synthetic method of eco-friendly, efficient mesoporous molecular sieve SBA-15, belong to technical field of inorganic nanometer material.
Background technology
A new generation wide aperture (1-30 nanometer), mesopore molecular sieve all are with a wide range of applications in fields such as macromole conversion, absorption, biomacromolecule separation and electromagnetism, transmitter, photoelectrons.The most representative mesopore molecular sieve is MCM-41 and SBA-15 at present.MCM-41 is that the long-chain organic quaternary ammonium salt cats product by costliness is the template synthetic, because its aperture is little, hydrothermal stability is poor.SBA-15 then is to be the template synthetic with the block macromolecular multipolymer, has aperture homogeneous, degree of order height, an advantage such as the aperture is big and hydro-thermal is functional, has obtained extensive studies and concern in recent years.Separation, recovery and the proteinic controlled release that can be used for heavy metal after modifying through organosilane on the SBA-15 skeleton with separate etc.; People find that also SBA-15 can still be the isolating superior adsorbent of light oil in a kind of crude oil recently.Simultaneously, Chinese scholars are template with the SBA-15 molecular sieve, have successfully prepared nano wire, nanometer ball of carbon and metal etc.
The SBA-15 synthesis technique all carries out in strong liquid acid (as concentrated hydrochloric acid) medium, synthetic every gram SBA-15 consumes concentrated hydrochloric acid (36wt%) 10-11 gram (Science, 1998,279,548), this causes not only that building-up process is very dangerous, corrodibility is serious, also can generate a large amount of environmental pollutant in last handling processes such as drying, roasting; And generated time long (crystallization time is more than 24 hours).
Therefore develop an environmental friendliness, the mesopore molecular sieve synthetic route has important Practical significance to industrialization and the scale operation that realizes mesopore molecular sieve early fast.
Summary of the invention
The objective of the invention is to use three block macromoleculars to gather oxyethylene-poly-epoxy third rare-poly-oxyethylene as template, by adding a small amount of heteropolyacid or reclaiming heteropolyacid (phospho-molybdic acid, phospho-wolframic acid, silicotungstic acid), synthesize the mesopore molecular sieve that the aperture is big, the degree of order is high.
The present invention proposes to add the method for a small amount of heteropolyacid as pH regulator agent and the synthesising mesoporous molecular sieve of promotor, can fall the consumption of the hydrochloric acid that few environmental pollution is serious, corrodibility is extremely strong significantly and shorten generated time.Main technique step of the present invention is as follows:
1, (three block macromoleculars gather oxyethylene-poly-epoxy third rare-poly-oxyethylene high molecular polymer, EO with template
20PO
70EO
20, be called for short P123) add in the middle of the deionized water, stir under the room temperature and make its dissolving, the mol ratio of control template agent and water is 1: 7000-17000;
2, add a small amount of heteropolyacid in the solution of step 1, continue at room temperature to stir heteropolyacid is dissolved fully, the mol ratio of control heteropolyacid and water is 1: 10000-40000;
3, in the solution of step 2, add silicon source and concentrated hydrochloric acid, the control heteropolyacid and mol ratio be 1: 60-280, the weight ratio in concentrated hydrochloric acid and silicon source is 7.48: 100, and this solution is placed water-bath hydrolysis silicon source 20 hours between 40-80 ℃;
4, the mixture that step 3 is obtained is transferred in the hydrothermal reaction kettle of tetrafluoroethylene, leaves standstill crystallization 6-24 hour at 90-96 ℃;
5, the mixture that step 4 is obtained at room temperature cools off, filter then, wash, with the solid collected 40-50 ℃ of drying 48 hours, roasting is 8 hours in 550 ℃ of air atmospheres, obtains mesoporous molecular sieve SBA-15 of the present invention.
The present invention will recycle in the above-mentioned method for preparing medium pore molecular sieve and to filter and the heteropolyacid of washings, and as mesopore molecular sieve synthetic promotor and acid regulator, as the another kind of method of synthesising mesoporous molecular sieve SBA-15, processing step is as follows:
1, heteropolyacid in filtration in the above-mentioned synthesising mesoporous molecular sieve method steps 5 and the washings is reclaimed, with filter and washings at 55 ℃ of-65 ℃ of unnecessary water of evaporation under reduced pressure removed, make its simmer down to 110mL;
2, then to wherein adding a small amount of template (P123), and at room temperature constantly stir template is dissolved fully, the mol ratio of control P123 and water is 1: 7000-17000;
3, in the solution of step 2, add tetraethoxy and concentrated hydrochloric acid, control heteropolyacid and tetraethoxy mol ratio are 1: 60-280, the weight ratio of concentrated hydrochloric acid and tetraethoxy is 7.48: 100, and this solution is placed water-bath hydrolysis tetraethoxy 20 hours between 40-80 ℃;
4, the mixture that step 2 is obtained is transferred in the hydrothermal reaction kettle of tetrafluoroethylene, leaves standstill crystallization 6-24 hour at 90-96 ℃;
5, the mixture that step 3 is obtained at room temperature cools off, filter then, wash, with the solid collected 40-50 ℃ of drying 48 hours, at last with the roasting 8 hours in 550 ℃ of air atmospheres of gained solid sample.
The heteropolyacid that is adopted among the present invention can be phospho-molybdic acid (H
3PO
412MoO
324H
2O), phospho-wolframic acid (H
2PO
412WO
324H
2O) and silicotungstic acid (H
2SiO
412WO
324H
2O) a kind of in.
The silicon source of being adopted among the present invention is the kind in methyl silicate, tetraethoxy, positive silicic acid propyl ester and the butyl silicate.
The present invention proposes to utilize the method for heteropolyacid as pH regulator agent and the synthesising mesoporous molecular sieve of promotor, can fall the consumption of the hydrochloric acid that few environmental pollution is serious, corrodibility is extremely strong significantly and shorten generated time, heteropolyacid can be recycled, and reduces synthetic cost, is mainly reflected in:
1, the consumption of liquid acid reduces significantly: be example with hydrochloric acid, hydrochloric acid content required for the present invention has only 3.8% of traditional method.
2, shorten crystallization time: the crystallization time that the mesoporous molecular sieve SBA-15 of the synthesising mesoporous molecular sieve of this method forms is 6 hours, is 1/4th of traditional technology.
3, heteropolyacid can be reused in the middle of the present invention.
Embodiment
Embodiment 1
4 gram template P123 are joined in the middle of the 110 gram deionized waters, at room temperature stirred 3 hours, in the middle of solution, add 0.65 gram phospho-molybdic acid (H again
3PO
412MoO
324H
2O), and continue to be stirred to P123 and phospho-molybdic acid dissolves fully, then add 8.55 gram tetraethoxys and 0.64 gram concentrated hydrochloric acid in the solution upward, then, put it in 40 ℃ the water-bath hydrolysis 20 hours, next, hydrolysate is transferred in the hydrothermal reaction kettle of tetrafluoroethylene, left standstill crystallization 24 hours at 96 ℃, afterwards, the resulting product of crystallization is filtered, and with a large amount of deionized water wash.With solid dry 48 h under 45 ℃ condition that collect, last, under air atmosphere, slowly be warmed up to 550 ℃, and this roasting temperature 8 hours.Learn that through sign this material is to have the mesoporous SBA-15 that two-dimentional hexagonal structure is arranged, product yield and characterization result (d
100, specific surface, pore volume, average pore diameter and wall thickness) see Table one.
Embodiment 2
Filtration in the middle of the embodiment 1 and washing liq are reclaimed, and under 55 ℃ condition, wherein unnecessary water is removed in underpressure distillation, making solution concentration is 110mL.Then to wherein adding 1 gram template (P123), and at room temperature stirred 3 hours, then, add 8.55 gram tetraethoxys and 0.64 gram concentrated hydrochloric acid, and put it in 40 ℃ the water-bath hydrolysis 20 hours, next, hydrolysate is transferred in the hydrothermal reaction kettle of tetrafluoroethylene, left standstill crystallization 6 hours at 96 ℃, afterwards, the resulting product of crystallization is filtered, and with a large amount of deionized water wash.With the solid dry 48h under 45 ℃ condition that collects, last, under air atmosphere, slowly be warmed up to 550 ℃, and this roasting temperature 8 hours.Learn that through sign this material is to have the mesoporous SBA-15 that two-dimentional hexagonal structure is arranged, product yield and characterization result (d
100, specific surface, pore volume, average pore diameter and wall thickness) see Table one.
Embodiment 3
4 gram template P123 are joined in the middle of the 110 gram deionized waters, at room temperature stirred 3 hours, in the middle of solution, add 0.99 gram phospho-molybdic acid (H again
3PO
412MoO
324H
2O), and continue to be stirred to P123 and phospho-molybdic acid dissolves fully, then add 8.55 gram methyl silicates and 0.64 gram concentrated hydrochloric acid in the solution upward, then, put it in 40 ℃ the water-bath hydrolysis 20 hours, next, hydrolysate is transferred in the hydrothermal reaction kettle of tetrafluoroethylene, left standstill crystallization 6 hours at 96 ℃, afterwards, the resulting product of crystallization is filtered, and with a large amount of deionized water wash.With solid dry 48 h under 45 ℃ condition that collect, last, under air atmosphere, slowly be warmed up to 550 ℃, and this roasting temperature 8 hours.Learn that through sign this material is to have the mesoporous SBA-15 that two-dimentional hexagonal structure is arranged, product yield and characterization result (d
100, specific surface, pore volume, average pore diameter and wall thickness) see Table one.
Embodiment 4
4 gram template P123 are joined in the middle of the 110 gram deionized waters, at room temperature stirred 3 hours, in the middle of solution, add 1.29 gram phospho-molybdic acid (H again
3PO
412MoO
324H
2O), and continue to be stirred to P123 and phospho-molybdic acid dissolves fully, then add 8.55 positive silicic acid propyl ester of gram and 0.64 gram concentrated hydrochloric acid in the solution upward, then, put it in 40 ℃ the water-bath hydrolysis 20 hours, next, hydrolysate is transferred in the hydrothermal reaction kettle of tetrafluoroethylene, left standstill crystallization 6 hours at 96 ℃, afterwards, the resulting product of crystallization is filtered, and with a large amount of deionized water wash.With the solid dry 48h under 45 ℃ condition that collects, last, under air atmosphere, slowly be warmed up to 550 ℃, and this roasting temperature 8 hours.Learn that through sign this material is to have the mesoporous SBA-15 that two-dimentional hexagonal structure is arranged, product yield and characterization result (d
100, specific surface, pore volume, average pore diameter and wall thickness) see Table one.
Embodiment 5
4 gram template P123 are joined in the middle of the 110 gram deionized waters, at room temperature stirred 3 hours, in the middle of solution, add 0.99 gram phospho-wolframic acid (H again
3PO
412WO
324H
2O), and continue to be stirred to P123 and phospho-wolframic acid dissolves fully, then add 8.55 gram butyl silicates and 0.64 gram concentrated hydrochloric acid in the solution upward, then, put it in 40 ℃ the water-bath hydrolysis 20 hours, next, hydrolysate is transferred in the hydrothermal reaction kettle of tetrafluoroethylene, left standstill crystallization 24 hours at 96 ℃, afterwards, the resulting product of crystallization is filtered, and with a large amount of deionized water wash.With the solid dry 48h under 45 ℃ condition that collects, last, under air atmosphere, slowly be warmed up to 550 ℃, and this roasting temperature 8 hours.Learn that through sign this material is to have the mesoporous SBA-15 that two-dimentional hexagonal structure is arranged, product yield and characterization result (d
100, specific surface, pore volume, average pore diameter and wall thickness) see Table one.
Embodiment 6
4 gram template P123 are joined in the middle of the 110 gram deionized waters, at room temperature stirred 3 hours, in the middle of solution, add 1.13 gram silicotungstic acid (H again
2SiO
412WO
324H
2O), and continue to be stirred to P123 and silicotungstic acid dissolves fully, then add 8.55 gram tetraethoxys and 0.64 gram concentrated hydrochloric acid in the solution upward, then, put it in 40 ℃ the water-bath hydrolysis 20 hours, next, hydrolysate is transferred in the hydrothermal reaction kettle of tetrafluoroethylene, left standstill crystallization 24 hours at 96 ℃, afterwards, the resulting product of crystallization is filtered, and with a large amount of deionized water wash.With the solid dry 48h under 45 ℃ condition that collects, last, under air atmosphere, slowly be warmed up to 550 ℃, and this roasting temperature 8 hours.Learn that through sign this material is to have the mesoporous SBA-15 that two-dimentional hexagonal structure is arranged, product yield and characterization result (d
100, specific surface, pore volume, average pore diameter and wall thickness) see Table one.
The yield of reaction product, structure and physicochemical characteristic
Claims (4)
1. the synthetic method of a mesoporous molecular sieve SBA-15 adopts the poly-oxyethylene one poly-epoxy third rare one poly-oxyethylene of three block macromoleculars as template, adds heteropolyacid as promotor and acid regulator, synthesising mesoporous molecular sieve, and its step is as follows:
1) will gather oxyethylene one poly-propylene oxide one poly-oxyethylene three block macromolecular tensio-active agents and dissolve in the deionized water as template, at room temperature constantly stirring is dissolved template fully, and the mol ratio of control template agent and water is 1: 7000-17000;
2) add heteropolyacid in the middle of the solution of step (1) preparation, and at room temperature stirring makes it to form clear solution, the mol ratio of control heteropolyacid and water is 1: 10000-40000;
3) add silicon source and concentrated hydrochloric acid in the solution of step (2) preparation, the mol ratio in control heteropolyacid and silicon source is 1: 60-280, and the weight ratio in concentrated hydrochloric acid and silicon source is 7.48: 100, and places the water-bath hydrolysis 20 hours between 40-80 ℃;
4) mixture that step (3) is obtained is transferred in the hydrothermal reaction kettle of tetrafluoroethylene, leaves standstill crystallization 6-24 hour at 90-96 ℃;
5) the resulting product of step (4) is filtered, and use deionized water wash, filtration gained solid product is 40-50 ℃ of drying 48 hours, and roasting 8 hours in 550 ℃ of air atmospheres, promptly gets mesoporous SBA-15 molecular sieve.
2. according to the described mesoporous molecular sieve SBA-15 synthetic method of claim 1, it is characterized in that: the heteropolyacid of filtration and washings in the described method for preparing medium pore molecular sieve of recycling claim 1, as mesopore molecular sieve synthetic promotor and acid regulator, synthesising mesoporous molecular sieve SBA-15, its step is as follows:
1) filtered liquid that step in the claim 1 (5) is produced and washings reclaim, and at 55 ℃ of-65 ℃ of unnecessary water of evaporation under reduced pressure removed, it are concentrated;
2) then to wherein adding template, and at room temperature constantly stir the template of adding is dissolved fully, the mol ratio of controlling initiate template and water is 1: 7000-17000;
3) in the solution of step (2) preparation, add tetraethoxy and concentrated hydrochloric acid, the mol ratio of control heteropolyacid and tetraethoxy is 1: 60-280, the weight ratio of concentrated hydrochloric acid and tetraethoxy is 7.48: 100, and places the water-bath hydrolysis 20 hours between 40-80 ℃;
4) mixture that step (3) is obtained is transferred in the hydrothermal reaction kettle of tetrafluoroethylene, leaves standstill crystallization 6-24 hour at 90-96 ℃;
5) the resulting product of step (4) is filtered, and with a large amount of deionized water wash, 40-50 ℃ of drying of gained solid product 48 hours, and roasting 8 hours in 550 ℃ of air atmospheres promptly get mesoporous SBA-15 molecular sieve.
3. the preparation method of mesopore molecular sieve according to claim 1 and 2 is characterized in that the heteropolyacid that is adopted is a kind of in phospho-molybdic acid, phospho-wolframic acid and the silicotungstic acid.
4. the preparation method of mesopore molecular sieve according to claim 1 is characterized in that the silicon source of being adopted is a kind of in methyl silicate, tetraethoxy, positive silicic acid propyl ester and the butyl silicate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100450609C (en) * | 2006-11-01 | 2009-01-14 | 南京师范大学 | Hybridization materials of polymetallic salts of oxygen and acid / mesoporous molecular sieve, and preparation method |
| CN100446857C (en) * | 2006-11-02 | 2008-12-31 | 武汉理工大学 | Method for preparing heteropoly acid/ordered mesic porous silicon oxide catalyst, and its application |
| CN101190867B (en) * | 2006-11-21 | 2010-10-06 | 中国石油化工股份有限公司 | Method for preparing propylene by olefin dismutation reaction |
| RU2012120435A (en) * | 2009-10-16 | 2013-11-27 | Асахи Гласс Компани, Лимитед | METHOD FOR PRODUCING WATER POLYTETRAFLUORETHYLENE DISPERSION FOR THE COAGULATION PROCESS AND WATER POLYTETRAFLUORETHYRENE DISPERSION FOR THE COAGULATION PROCESS |
| JP2014533653A (en) * | 2011-11-23 | 2014-12-15 | ダウ グローバル テクノロジーズ エルエルシー | An environmentally friendly method of preparing mesoporous silica structures |
| CN107970901A (en) * | 2017-10-30 | 2018-05-01 | 上海泰坦科技股份有限公司 | A kind of synthetic method of SBA-15 mesoporous materials |
| CN110496647A (en) * | 2018-05-18 | 2019-11-26 | 天津工业大学 | A kind of synthesis of BV catalysts --- the mesoporous catalyst preparation method of containing transition metal molybdenum ion |
| CN110614100A (en) * | 2018-06-20 | 2019-12-27 | 天津工业大学 | Preparation of caprolactone by mesoporous silicon catalyst green oxygen-sharing doped with iron-molybdenum transition metal |
| CN111498862B (en) * | 2020-04-03 | 2022-07-01 | 三峡大学 | Preparation method and application of spherical SBA-15 mesoporous molecular sieve |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341553A (en) * | 2001-08-14 | 2002-03-27 | 复旦大学 | Preparation method of mesonic pore molecular sieve carrier material |
| CN1613764A (en) * | 2004-12-01 | 2005-05-11 | 长春理工大学 | Preparation for SBA-15 molecular sieve |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341553A (en) * | 2001-08-14 | 2002-03-27 | 复旦大学 | Preparation method of mesonic pore molecular sieve carrier material |
| CN1613764A (en) * | 2004-12-01 | 2005-05-11 | 长春理工大学 | Preparation for SBA-15 molecular sieve |
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