CN1304871A - Dual-pore molecular sieve and its preparing process - Google Patents
Dual-pore molecular sieve and its preparing process Download PDFInfo
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- CN1304871A CN1304871A CN 00121011 CN00121011A CN1304871A CN 1304871 A CN1304871 A CN 1304871A CN 00121011 CN00121011 CN 00121011 CN 00121011 A CN00121011 A CN 00121011A CN 1304871 A CN1304871 A CN 1304871A
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Abstract
A dual-pore molecular sieve is prepared from organic siloxane and ethyl silicate, as well as biodegradable non-toxic non-ionic surfactant as templet agent through low-temp hydrolysis poly condensation in neutral condition. Obtained molecular sieve has specific surface area of 400-900 sq.m/g, pore volume of 0.4-2 cu.cm/g and the smaller pore diameter of 2-4 nm and the larger pore diameter of 16-90 nm. Its advantages are mild reaction condition, simple preparing process, and low cost of recoverable template agent.
Description
The invention belongs to a kind of molecular sieve and preparation method thereof, relate in particular to a kind of diplopore molecular sieve and preparation method thereof.
Adopt the preparation of new synthetic route to have property and the novel texture molecular sieve is the research focus in domestic and international material field.Since the appearance of M41S mesoporous molecular sieve in 1992, evoked the great interest of people by macromole assembling and the synthetic mesoporous molecular sieve of micella template, synthesized as MCM-41, HMS, MSU-x etc. have the mesoporous molecular sieve of different surfaces texture property.Are one of important branch of investigation of materials in recent years and Application Areas by regulating its preparation parameter and synthesis condition to the regulation and control that this molecular sieve analog carries out surface and texture character.The researchist is carrying out a large amount of significant explorations aspect the synthetic various types of mesoporous materials of design both at home and abroad.The wet gel that (J Chem.Soc., Chem Commun., 1998,1035) such as researchist PangWenqing etc. (J Chem.Soc., Chem.Commun., 1995,2367) and Wang Xiaozhong form by roasting tensio-active agent/silicate or utilize SiO
2Precursor and the polycondensation of surfactant micelle cohydrolysis obtain the pure silicon mesoporous material of two middle pore distributions respectively, and its process uses long-chain organic ammonium tensio-active agent to make the template synthetic in NaOH or aqueous ammonia medium.The small aperture of above-mentioned molecular sieve concentrates on 2-3nm, and macropore diameter concentrates on about 20nm.But this building-up process adopts highly basic medium, and the organic ammonium cats product is made template, is unfavorable for environmental requirement, and makes that template is difficult for removing in the synthetic product, causes caving in of molecular sieve structure easily.
Goal of the invention of the present invention provides that a kind of template is easily removed, constitutionally stable diplopore molecular sieve and preparation method thereof.
The object of the present invention is achieved like this, selects nontoxic, biodegradable nonionic surfactant to make template, and adopting organo-siloxane and tetraethoxy is presoma, the molecular sieve of the synthetic diplopore distribution of low temperature hydrolysis polycondensation under neutrallty condition.
The character of diplopore molecular sieve of the present invention is as follows:
Specific surface area: 400-900m
2/ g
Pore volume: 0.4-2cm
3/ g
Small aperture: 2-4nm
Macropore diameter: 16-90nm
Described diplopore molecular sieve has the MSU-x structure.
Described diplopore molecular sieve has Fig. 1 collection of illustrative plates, Fig. 2 collection of illustrative plates, the character of Fig. 3 collection of illustrative plates.
Fig. 1 is its XRD figure spectrum, has very strong diffraction unimodal about 1 degree of 2 θ angles, illustrates to have formed the orderly central hole structure of MSU-x under this synthesis condition.All molecular sieve XRD figure spectrums of synthetic are similar with it in this system, and just with the modulation of synthesis condition synthetic parameters, its d100 value changes slightly, at 6.0-9.5nm.
Fig. 2 is pure silicon MSU-x's (Si-MSU-x)
29SiCPMAS NMR spectrogram provides the vibration peak (Qn=Si (OSi) n (OH) 4-n n=2-4) of the Different Silicon environment of ingredient sieve skeleton frame, and wherein at-110PPM ,-101PPM is respectively Q
4(SiO
2) and Q
3(Si (OSi)
3(OH)) be the main silicon structural unit of synthesis of molecular sieve.
Fig. 3 be its typical synthetic sample by N
2The BJH diplopore distribution plan that absorption/desorption Qu Jing obtains.The molecular sieve diplopore distribution schematic diagram of Si-MSU-x and functional organic-MSU-x.Its pore size distribution size can be according to synthetic parameters, and synthesis condition changes and modulation.Be that less hole, molecular sieve diplopore of the present invention aperture can be at 2-4nm, modulation is carried out in bigger hole in two scopes of 16-90nm.Pore volume is at 0.4-2cm
3/ g.
Preparation method of the present invention comprises the steps:
(1) non-ionic surface active agent is added deionized water and form the solution I;
(2) ethyl orthosilicate (TEOS) and alkyl organic oxygen are mixed formation solution II;
(3) under agitation the solution I was added in the solution II after stirring reaction 60-120 minute, add KF2H2O continues to stir 12-16 hour, in 50 ℃ of ageing 3-4 days, obtains product;
(4) product after filtration, after the washing, drying, reflux with ethanolic solution and to remove alkyl organic Oxygen alkane, the drier functional organic dual-pure molecular sieve that obtains;
(5) functional organic dual-pure molecular sieve is carried out roasting under 550 ℃, obtain the pure silicon diplopore Molecular sieve;
The mol ratio of above-mentioned each component is:
Total SiO2: surfactant: H2O∶KF·2H
2O=1∶(0.05-0.11)∶(100-150)∶0.02
Total SiO2Molal quantity=TEOS molal quantity+alkylsiloxane molal quantity
Aforesaid nonionogenic tenside is alkyl polyoxyethylene (AEO
9), polyoxyethylene nonylphenol ether (Tx-15).The concrete nail ethyl triethoxy silicane of alkyl organic siloxane alkane (MTES), phenyl triethoxysilane (PTES), urea propyl group ethyl triethoxy silicane alkane (UPTES) and N-amine ethyl-amine propyl trimethoxy silicane (AE-APTMS), vinyltriethoxysilane (VTES), mercaptopropyltriethoxysilane (MPTES) etc.
Aforesaid organic polysiloxane precursor body is Union carbide A-162 (MTES), dimethyldiethoxysilane (DDS), urea propyl-triethoxysilicane (UPTES), phenyl triethoxysilane (PTES) and N-amine ethyl-amine propyl trimethoxy silicane (AE-APRMS), vinyltriethoxysilane (VTES), mercaptopropyltriethoxysilane (MPTES).
The present invention compared with prior art has following advantage:
(1) reaction conditions gentleness, preparation process is simple.
(2) employed template cheapness, nontoxic easy recycling helps the environmental friendliness development.
(3) made diplopore molecular sieve Stability Analysis of Structures, and its macropore is adjustable in a big way.
(4) diplopore molecular sieve that makes is of many uses.
Embodiments of the invention are as follows:
With 0.9814g AEO
9Adding the 40g deionized water and stirring makes its solution that fully dissolves formation solution 2.4690g TEOS and 0.74g PTES mix formation solution II, under agitation the solution II is added in the solution I then, continue reaction after 60 minutes, further add 0.0320g KF, continued stirring reaction 16 hours, then with reactant 323K ageing 72 hours, product after filtration, fully washing, drying, reflux with ethanolic soln at last and remove template, after the drying, synthetic sample is controlled roasting at 823K, obtain having the diplopore molecular sieve of MSU-x structure.Pure silicon-MSU-x mesopore molecular sieve that diplopore distributes
29Si CPMAS NMR spectrogram is seen Fig. 2.Synthetic diplopore distribution molecular sieve BET specific surface area: 402m
2/ g; Pore volume: 0.85cm
3/ g.Aperture size: 3.16nm, 69.5nm.
0.9778g Tx-15 is added the 40g deionized water and stirring makes it fully dissolve formation solution I, the solution of 3.1688g TEOS and 0.3g VTES is mixed formation solution II, under agitation the solution II is added in the solution I then, continue reaction after 120 minutes, further add 0.0320gKF, continue stirring at room reaction 16 hours, then with reactant 323K ageing 72 hours, product after filtration, fully washing, dry, reflux with ethanolic soln at last and remove template, obtain the molecular sieve of vinyl-functional after the drying, further sample after the drying is controlled roast at 823K, obtain pure silicon-MSU-x mesopore molecular sieve that diplopore distributes.The diplopore molecular sieve BET specific surface area of pure silicon: 688m
2/ g; Pore volume: 1.24cm
3/ g; Aperture size: 3.15nm, 40.15nm.
Embodiment 3
Adopt the preparation process of the foregoing description 1, under the same conditions, add 0.9752g AEO
9, the solution II is the mixing solutions of 2.1902g TEOS+0.4026MTES, the amount of KF is 0.0335g, the molecular sieve that the diplopore of pure silicon distributes.Pure silicon diplopore molecular sieve BET specific surface area is: 400m
2/ g; Pore volume: 1.24cm
3/ g; Aperture size: 2.80nm, 31.3nm.
Adopt the preparation process of the foregoing description 1, the solution II is the mixing solutions of 2.4698gTEOS+0.74PTES, and the amount of KF is 0.032g, obtains containing the mesopore molecular sieve that the pure silicon diplopore distributes.It is formed sign and sees embodiment 1 explanation.Its BET specific surface area: 627m
2/ g; Pore volume: 1.15cm
3/ g; Aperture size: 3.21nm, 46.67nm.
Embodiment 5
0.9667g AE09 is added the 40g deionized water and stirring makes it fully dissolve formation solution I.The methanol solution (containing UPTES 50%) of 2.4698g TEOS and 0.2g UPTES is mixed formation solution II.Under agitation the solution II is added in the solution I then, continue reaction after 90 minutes, further add 0.0334g KF, continued stirring reaction 14 hours, in 323K ageing 72 hours, product after filtration, fully washing, drying, reflux with ethanolic soln at last and remove template, obtain the functionalized molecular sieve of urea propyl group after the drying.The exsiccant sample is controlled roasting under 828K, obtain the molecular sieve of the pure silicon of diplopore distribution.Pure silicon diplopore molecular sieve BET specific surface area: 651m
2/ g; Pore volume: 0.8cm
3/ g; Aperture size: 3.3nm, 90nm.
Adopt the preparation process of the foregoing description 2, the solution II is 2.8240gTEOS+0.3500g AE-APTES under the same conditions, and the reaction times is 5 days, obtains the diplopore distribution mesopore molecular sieve of pure silicon.Its BET specific surface area: 651m
2/ g; Pore volume: 0.8cm
3/ g; Aperture size: 3.3nm, 25nm.
Embodiment 7
Adopt the preparation process of the foregoing description 2, the solution II is 2.467gTEOS+0.6025g VTES under the same conditions, reaction times is 4 days, obtains the diplopore distribution molecular sieve of vinyl-functional, and further calcination process obtains the molecular sieve that pure silicon-MSU-x diplopore distributes.Its BET specific surface area; 877m
2/ g; Pore volume: 1.97cm
3/ g aperture size 3.02nm, 19nm.
Adopt the preparation process of the foregoing description 3, the solution II is the mixing solutions of 2.4698gTEOS+0.7176g DDS under the same conditions, obtains the molecular sieve that the pure silicon diplopore distributes.Pure silicon diplopore molecular sieve BET specific surface area: 455m
2/ g; Pore volume: 1.45cm
3/ g, aperture size: 2.0nm, 16.2nm.
Claims (6)
1. diplopore molecular sieve is characterized in that:
Specific surface area: 400-900m
2/ g
Pore volume: 0.4-2cm
3/ g
Small aperture: 2-4nm
Macropore diameter: 16-90nm.
2. a kind of diplopore molecular sieve as claimed in claim 1 is characterized in that described diplopore molecular sieve has the MSU-x structure.
3. a kind of diplopore molecular sieve as claimed in claim 1 is characterized in that described diplopore molecular sieve has Fig. 1 collection of illustrative plates, Fig. 2 collection of illustrative plates, the character of Fig. 3 collection of illustrative plates.
4. the preparation method of a diplopore molecular sieve is characterized in that comprising the steps:
(1) nonionogenic tenside is added deionized water and form the solution I;
(2) tetraethoxy (TEOS) and alkyl organic oxygen are mixed formation solution II;
(3) under agitation the solution I was added in the solution II after stirring reaction 60-120 minute, add KF2H
2O continues to stir 12-16 hour, in 50 ℃ of ageing 3-4 days, obtains product;
(4) product after filtration, after the washing, drying, reflux with ethanolic soln and to remove alkyl organic siloxane, drying obtains functional organic dual-pure molecular sieve again;
(5) the hydridization diplopore molecular sieve is carried out roasting under 550 ℃, obtain the pure silicon diplopore molecular sieve;
The mol ratio of above-mentioned each component is:
Total SiO
2: tensio-active agent: H
2O: KF2H
2O=1: (0.05-0.11): (100-150): 0.02
Total SiO
2Mole number=TEOS mole number+alkylsiloxane mole number.
5. the preparation method of a kind of diplopore molecular sieve as claimed in claim 4 is characterized in that described nonionogenic tenside is alkyl polyoxyethylene (AEO
9), polyoxyethylene nonylphenol ether (Tx-15); The concrete nail ethyl triethoxy silicane of alkyl organic siloxane alkane (MTES), phenyl triethoxysilane (PTES), urea propyl group ethyl triethoxy silicane alkane (UPTES) and N-amine ethyl-amine propyl trimethoxy silicane (AE-APTMS), vinyltriethoxysilane (VTES), mercaptopropyltriethoxysilane (MPTES).
6. the preparation method of a kind of diplopore molecular sieve as claimed in claim 4 is characterized in that described organic polysiloxane precursor body is Union carbide A-162 (MTES), dimethyldiethoxysilane (DDS), urea propyl-triethoxysilicane (UPTES), phenyl triethoxysilane (PTES) and N-amine ethyl-amine propyl trimethoxy silicane (AE-APRMS), vinyltriethoxysilane (VTES), mercaptopropyltriethoxysilane (MPTES).
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| CN1298625C (en) * | 2005-01-10 | 2007-02-07 | 山西大学 | Double metaporous silicon dioxide material and its preparing method |
| CN1313371C (en) * | 2001-09-17 | 2007-05-02 | 皇家飞利浦电子股份有限公司 | Electronic device comprising a mesoporous silica layer and composition for preparing the mesoporous silica layer |
| WO2008019570A1 (en) * | 2006-08-11 | 2008-02-21 | China Petroleum & Chemical Corporation | A porous zeolite of organosilicon, a method for preparing the same and the use of the same |
| CN100460321C (en) * | 2005-05-31 | 2009-02-11 | 中国石油化工股份有限公司 | Diplopore silica gel material, and preparation method |
| CN102059118A (en) * | 2010-11-11 | 2011-05-18 | 中国科学院山西煤炭化学研究所 | Dual mesoporous cobalt-based catalyst as well as preparation method and application thereof |
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| CN104248980A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method |
| CN104248992A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method |
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2000
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| CN1313371C (en) * | 2001-09-17 | 2007-05-02 | 皇家飞利浦电子股份有限公司 | Electronic device comprising a mesoporous silica layer and composition for preparing the mesoporous silica layer |
| US8439047B2 (en) | 2003-12-22 | 2013-05-14 | Philip Morris Usa Inc. | Composite mesoporous/microporous materials and their use in smoking articles for removing certain gas phase constituents from tobacco smoke |
| CN1298625C (en) * | 2005-01-10 | 2007-02-07 | 山西大学 | Double metaporous silicon dioxide material and its preparing method |
| CN100460321C (en) * | 2005-05-31 | 2009-02-11 | 中国石油化工股份有限公司 | Diplopore silica gel material, and preparation method |
| WO2008019570A1 (en) * | 2006-08-11 | 2008-02-21 | China Petroleum & Chemical Corporation | A porous zeolite of organosilicon, a method for preparing the same and the use of the same |
| US8030508B2 (en) | 2006-08-11 | 2011-10-04 | China Petroleum & Chemical Corporation | Porous zeolite of organosilicon, a method for preparing the same and the use of the same |
| CN102059118A (en) * | 2010-11-11 | 2011-05-18 | 中国科学院山西煤炭化学研究所 | Dual mesoporous cobalt-based catalyst as well as preparation method and application thereof |
| CN102059118B (en) * | 2010-11-11 | 2012-11-14 | 中国科学院山西煤炭化学研究所 | Dual mesoporous cobalt-based catalyst as well as preparation method and application thereof |
| CN102676493A (en) * | 2011-03-31 | 2012-09-19 | 南京工业大学 | Mesoporous biomaterial containing porcine pancreatic lipase and preparation method of mesoporous biomaterial |
| CN104248993A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method |
| CN104248980A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method |
| CN104248992A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method |
| CN104248992B (en) * | 2013-06-28 | 2016-03-30 | 中国石油化工股份有限公司 | The preparation method of spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and ethyl acetate |
| CN104248980B (en) * | 2013-06-28 | 2016-04-27 | 中国石油化工股份有限公司 | The preparation method of spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and ethyl acetate |
| CN104261414A (en) * | 2014-09-25 | 2015-01-07 | 太原理工大学 | Synthesis method of bimodal mesoporous silicon dioxide |
| CN104261414B (en) * | 2014-09-25 | 2016-01-20 | 太原理工大学 | A kind of synthetic method of double-mesopore silicon dioxide |
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