CN102464331A - Melt flow index (MFI) structure titanium silicalite molecular sieve with small crystal particle and preparation method thereof - Google Patents
Melt flow index (MFI) structure titanium silicalite molecular sieve with small crystal particle and preparation method thereof Download PDFInfo
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- CN102464331A CN102464331A CN2010105520930A CN201010552093A CN102464331A CN 102464331 A CN102464331 A CN 102464331A CN 2010105520930 A CN2010105520930 A CN 2010105520930A CN 201010552093 A CN201010552093 A CN 201010552093A CN 102464331 A CN102464331 A CN 102464331A
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Abstract
The invention relates to a melt flow index (MFI) structure titanium silicalite molecular sieve with a small crystal particle and a preparation method thereof, which mainly solve the problem of big crystal particle of the MFI structure titanium silicalite molecular sieve in the prior art. The MFI structure titanium silicalite molecular sieve with the small crystal particle is prepared, wherein infrared spectrum data is provided with a corresponding organic silicon infrared absorption peak within the range of 1213-1278cm<-1>. The problem is better solved by the technical scheme of the preparation method. The preparation method can be used for preparing and producing the MFI structure titanium silicalite molecular sieve with the small crystal particle.
Description
Technical field
The present invention relates to a kind of little crystal grain MFI structure titanium silicon molecular sieve and preparation method thereof.
Background technology
USP 04410501 patent report Italy ENI (ENI) company has successfully synthesized MFI structure titanium silicon molecular sieve TS-1, and wherein titanium has got into the skeleton structure of molecular sieve, for new chapter has been opened up in the research in this field.As catalyst for catalytic oxidation, not only have very high catalytic activity and selectivity with TS-1, and reaction conditions is gentle, by product is water (H
2O
2Make oxygenant), environmental sound.With rare H
2O
2Be oxygenant, under mild conditions (normal temperature,＜60 ℃, normal pressure), the oxidation of hydroxylation, primary (second month in a season) alcohol of partially oxidation that can catalysis alkane, epoxidation, aromatic hydrocarbon and the phenol of alkene and the ammonia oxidation of ketone.We know that catalyst molecule sieve grain size is an important factor in order of reacting catalytic performance.The catalytic activity that the sieve catalyst of little crystal grain is compared big crystal grain sieve catalyst is higher; Therefore it is favourable to the raising of reacting catalytic performance to synthesize small crystal grain molecular sieve; We are the middle organic group of introducing in the process of synthesis of molecular sieve; The grain-size of molecular sieve can be reduced, the catalytic performance of catalyzer can be improved.
Summary of the invention
One of technical problem to be solved by this invention is to obtain the bigger problem of MFI structure titanium silicon molecular sieve crystal grain in the prior art, and a kind of new MFI structure titanium silicon molecular sieve is provided, and this molecular sieve has the little advantage of crystal grain.Two of technical problem to be solved by this invention provides preparation method a kind of and one of technical solution problem corresponding little crystal grain MFI structure titanium silicon molecular sieve.
For one of solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of little crystal grain MFI structure titanium silicon molecular sieve, in the ir data of molecular sieve at 1213～1278cm
-1Corresponding organosilyl infrared absorption peak is arranged.
For solve the problems of the technologies described above two; The technical scheme that the present invention adopts is following: a kind of preparation method of little crystal grain MFI structure titanium silicon molecular sieve may further comprise the steps: with the inorganic silicon source, and the organosilicon source; The titanium source; Organic formwork agent and water mix by stoichiometric ratio, and wherein each component mol ratio of raw material is: inorganic silicon source: organosilicon source: titanium source: organic formwork agent: alkali: water=1: 0.01～0.05: 0.01～0.03: 0.03～0.15: 0.4～2.0: 20～100.In 1～30 day time of 160 ℃～220 ℃ crystallization; Product is through filtering washing, drying; Obtain containing skeleton organic group MFI HTS; Wherein the inorganic silicon source is selected from least a in silicon sol, silicon ester or the solid oxidation silicon, and the organosilicon source is two (triethoxy is silica-based) methane, and the titanium source is selected from TiCl
4, TiCl
3, TiOCl
2, TiOSO
4Or general formula is (R
2O)
4At least a in the organic titanate of Ti, wherein R
2Alkyl for 1-4 carbon atom; Organic formwork agent is selected from least a in TPAOH, 4-propyl bromide, TBAH, Tetrabutyl amonium bromide, tetraethylammonium bromide or the tetraethyl ammonium hydroxide, and alkali is selected from least a in ammoniacal liquor, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, quadrol, tetramethylenediamine, hexanediamine, diethylamine, tripropyl amine, the Tributylamine.
In the technique scheme; Owing to used organosilicon source and inorganic silicon source simultaneously in synthetic; Therefore partly have the Si-CH-Si structure at the synthetic skeletal structure of compound, replaced the Si-O-Si structure in the conventional microvoid structure, therefore this material is littler than not containing organosilyl zeolite crystal size.Little crystal grain MFI structure titanium silicon molecular sieve of the present invention; 10 microns of its crystal grain length average out to; And do not contain 20 microns of organosilicon MFI structure titanium silicon molecular sieve crystal grain length average out to; It is thus clear that little crystal grain MFI structure titanium silicon molecular sieve grain size of the present invention is significantly less than and does not contain organosilyl MFI structure titanium silicon molecular sieve, has obtained better technical effect.
Description of drawings
Fig. 1 is the ir spectra of the MFI structure titanium silicon molecular sieve of embodiment 3.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
With silicon sol (40%, weight), two (triethoxy is silica-based) methane, TiCl
4, TPAOH, ammoniacal liquor and water mix by stoichiometric ratio, and wherein each component mol ratio of raw material is: 1: 0.01: 0.01: 0.03: 0.4: 20.In the 1 day time of 160 ℃ of crystallization, product is washed through filtering, and drying obtains containing skeleton organic group MFI HTS.Dried sample is through measuring, in its ir data at 1223cm
-1Corresponding organosilyl infrared absorption peak is arranged, 9 microns of crystal grain length average out to.
[embodiment 2]
With solid silica (2000 order), two (triethoxy is silica-based) methane, TiCl
3, 4-propyl bromide, ethamine and water mix by stoichiometric ratio, and wherein each component mol ratio of raw material is: 1: 0.05: 0.03: 0.15: 2.0: 100.In the 5 day time of 170 ℃ of crystallization, product is washed through filtering, and drying obtains containing skeleton organic group MFI HTS.Dried sample is through measuring, in its ir data at 1223cm
-1Corresponding organosilyl infrared absorption peak is arranged, 10 microns of crystal grain length average out to.
[embodiment 3]
With tetraethoxy, two (triethoxy is silica-based) methane, TiOCl
2, TBAH, Tri N-Propyl Amine and water mix by stoichiometric ratio, and wherein each component mol ratio of raw material is: 1: 0.03: 0.02: 0.09: 1.2: 60.In the 10 day time of 180 ℃ of crystallization, product is washed through filtering, and drying obtains containing skeleton organic group MFI HTS.Dried sample is through measuring, in its ir data at 1223cm
-1Corresponding organosilyl infrared absorption peak is arranged, 11 microns of crystal grain length average out to.
[embodiment 4]
With methyl silicate, two (triethoxy is silica-based) methane, tetrabutyl titanate, Tetrabutyl amonium bromide, n-Butyl Amine 99 and water mix by stoichiometric ratio, and wherein each component mol ratio of raw material is: 1: 0.02: 0.02: 0.06: 0.8: 40.In the 20 day time of 190 ℃ of crystallization, product is washed through filtering, and drying obtains containing skeleton organic group MFI HTS.Dried sample is through measuring, in its ir data at 1223cm
-1Corresponding organosilyl infrared absorption peak is arranged, 8 microns of crystal grain length average out to.
[embodiment 5]
With silicon sol (40%, weight), two (triethoxy is silica-based) methane, tetraethyl titanate, tetraethylammonium bromide, quadrol and water mix by stoichiometric ratio, and wherein each component mol ratio of raw material is: 1: 0.04: 0.02: 0.12: 1.6: 80.In the 30 day time of 200 ℃ of crystallization, product is washed through filtering, and drying obtains containing skeleton organic group MFI HTS.Dried sample is through measuring, in its ir data at 1223cm
-1Corresponding organosilyl infrared absorption peak is arranged, 9 microns of crystal grain length average out to.
[embodiment 6]
With silicon sol (40%, weight), the organosilicon source, tetrabutyl titanate, tetraethyl ammonium hydroxide, tetramethylenediamine and water mix by stoichiometric ratio, and wherein each component mol ratio of raw material is: 1: 0.01: 0.02: 0.07: 0.7: 50.In the 3 day time of 220 ℃ of crystallization, product is washed through filtering, and drying obtains containing skeleton organic group MFI HTS.Dried sample is through measuring, in its ir data at 1223cm
-1Corresponding organosilyl infrared absorption peak is arranged, 10 microns of crystal grain length average out to.
[comparative example 1]
With silicon sol (40%, weight), tetrabutyl titanate, tetraethyl ammonium hydroxide, tetramethylenediamine and water mix by stoichiometric ratio, and wherein each component mol ratio of raw material is: 1: 0.02: 0.07: 0.7: 50.In the 3 day time of 160 ℃ of crystallization, product is washed through filtering, and drying obtains the MFI HTS.Dried sample is through measuring 20 microns of crystal grain length average out to.
Claims (2)
1. one kind little crystal grain MFI structure titanium silicon molecular sieve is characterized in that in the ir data of molecular sieve at 1213～1278cm
-1Corresponding organosilyl infrared absorption peak is arranged.
2. the preparation method of the described little crystal grain MFI structure titanium silicon molecular sieve of claim 1 may further comprise the steps: with the inorganic silicon source, and the organosilicon source; The titanium source, organic formwork agent and water mix by stoichiometric ratio, and wherein each component mol ratio of raw material is: inorganic silicon source: organosilicon source: titanium source: organic formwork agent: alkali: water=1: 0.01～0.05: 0.01～0.03: 0.03～0.15: 0.4～2.0: 20～100; In 1～30 day time of 160 ℃～220 ℃ crystallization; Product is through filtering washing, drying; Obtain containing skeleton organic group MFI HTS; Wherein the inorganic silicon source is selected from least a in silicon sol, silicon ester or the solid oxidation silicon, and the organosilicon source is two (triethoxy is silica-based) methane, and the titanium source is selected from TiCl
4, TiCl
3, TiOCl
2, TiOSO
4Or general formula is (R
2O)
4At least a in the organic titanate of Ti, wherein R
2It is the alkyl of 1～4 carbon atom; Organic formwork agent is selected from least a in TPAOH, 4-propyl bromide, TBAH, Tetrabutyl amonium bromide, tetraethylammonium bromide or the tetraethyl ammonium hydroxide, and alkali is selected from least a in ammoniacal liquor, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, quadrol, tetramethylenediamine, hexanediamine, diethylamine, tripropyl amine or the Tributylamine.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104556113A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for synthesizing titanium silicate molecular sieve employing organic quaternary ammonium salt template agent |
| CN104556112A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Titanium-silicon micro-mesoporous molecular sieve composite material and synthetic method thereof |
| CN104556104A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for synthesizing titanium-silicalite molecular sieve employing organic quaternary ammonium salt template agent |
| CN104556114A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for synthesizing titanium-silicon micro-mesoporous composite material |
| CN104556111A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Ti-Si molecular sieve and synthesis method thereof |
| CN106145144A (en) * | 2015-04-17 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of micro-mesoporous composite material of hetero atom and synthetic method thereof |
| CN106145145A (en) * | 2015-04-17 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hetero-atom molecular-sieve and synthetic method thereof |
| TWI637912B (en) * | 2013-10-29 | 2018-10-11 | 中國石油化工科技開發有限公司 | Titanium bismuth molecular sieve and synthesis method thereof |
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| CN1275529A (en) * | 1999-05-28 | 2000-12-06 | 中国石油化工集团公司 | Process for preparation of titanium-silicon molecular sieve |
| CN101746775A (en) * | 2009-12-15 | 2010-06-23 | 上海师范大学 | Preparation method for organic functional ordered mesoporous titanium oxide silicon molecular sieve |
| CN102372280A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Titanium silicalite molecular sieve with mobil five (MFI) structure and preparation method thereof |
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2010
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| CN1275529A (en) * | 1999-05-28 | 2000-12-06 | 中国石油化工集团公司 | Process for preparation of titanium-silicon molecular sieve |
| CN101746775A (en) * | 2009-12-15 | 2010-06-23 | 上海师范大学 | Preparation method for organic functional ordered mesoporous titanium oxide silicon molecular sieve |
| CN102372280A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Titanium silicalite molecular sieve with mobil five (MFI) structure and preparation method thereof |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104556112B (en) * | 2013-10-29 | 2018-04-13 | 中国石油化工股份有限公司 | A kind of micro- mesoporous molecular sieve composite material of titanium silicon and its synthetic method |
| CN104556112A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Titanium-silicon micro-mesoporous molecular sieve composite material and synthetic method thereof |
| CN104556104A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for synthesizing titanium-silicalite molecular sieve employing organic quaternary ammonium salt template agent |
| CN104556114A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for synthesizing titanium-silicon micro-mesoporous composite material |
| CN104556111A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Ti-Si molecular sieve and synthesis method thereof |
| CN104556113B (en) * | 2013-10-29 | 2017-02-01 | 中国石油化工股份有限公司 | Method for synthesizing titanium silicate molecular sieve employing organic quaternary ammonium salt template agent |
| CN104556114B (en) * | 2013-10-29 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of method of the micro- mesoporous composite material of synthesis of titanium silicon |
| CN104556113A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for synthesizing titanium silicate molecular sieve employing organic quaternary ammonium salt template agent |
| TWI637912B (en) * | 2013-10-29 | 2018-10-11 | 中國石油化工科技開發有限公司 | Titanium bismuth molecular sieve and synthesis method thereof |
| CN106145144A (en) * | 2015-04-17 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of micro-mesoporous composite material of hetero atom and synthetic method thereof |
| CN106145145A (en) * | 2015-04-17 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hetero-atom molecular-sieve and synthetic method thereof |
| CN106145145B (en) * | 2015-04-17 | 2018-07-31 | 中国石油化工股份有限公司 | A kind of hetero-atom molecular-sieve and its synthetic method |
| CN106145144B (en) * | 2015-04-17 | 2019-09-24 | 中国石油化工股份有限公司 | A kind of micro- mesoporous composite material of hetero atom and its synthetic method |
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Application publication date: 20120523 |