CN1321062C - Process for synthesizing microporous titanium silicon fluorite ETS-10 - Google Patents
Process for synthesizing microporous titanium silicon fluorite ETS-10 Download PDFInfo
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- CN1321062C CN1321062C CNB2005100270745A CN200510027074A CN1321062C CN 1321062 C CN1321062 C CN 1321062C CN B2005100270745 A CNB2005100270745 A CN B2005100270745A CN 200510027074 A CN200510027074 A CN 200510027074A CN 1321062 C CN1321062 C CN 1321062C
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Abstract
The present invention relates to a synthetic method of a microporous titanium-silicon zeolite ETS-10. Under the conditions that an organic template agent, or a fluorine ion or a seed crystal is not added, the microporous titanium-silicon zeolite ETS-10 is synthesized in alkaline water solution in hydrothermal synthesis method with an inorganic titanium source and an inorganic silicon source as raw materials. By the synthetic method, the microporous titanium-silicon zeolite ETS-10 with high purity and high degree of crystallinity can be obtained simply and conveniently in direct synthesis with the utilization of the raw materials with low price, and the microporous titanium-silicon zeolite ETS-10 has wide application foreground in the technical fields of catalysis, ion exchange, etc.
Description
Technical field
The invention belongs to inorganic molecule sieve technical field, be specifically related to the synthetic method of a kind of microporous titanium silicon fluorite ETS-10.
Background technology
ETS-10 is a kind of Ti-Si zeolite with unique microvoid structure, and molecular formula is (NaK)
2Si
5TiO
13Kuznicki in reported first in 1989 synthetic (the US patent 4853202) of this Ti-Si zeolite.Studies show that, have the mutually perpendicular two group one-dimensional long chains of titanium-oxygen octahedra by the shared composition in summit during this is zeolite structured, this long-chain is wrapped in the middle of the pore passage structure of silicon-oxygen tetrahedron composition.The skeleton of ETS-10 has ternary, five yuan, seven yuan and twelve-ring, and wherein the micropore size that is made of twelve-ring is about 7.6 * 4.9 (Nature, 1994,367,347).Therefore, the structure of ETS-10 can be regarded as the titanium dioxide long-chain with semiconductor property and is inclusive in the middle of the silicon dioxide skeleton structure, and this makes ETS-10 have the character of a lot of uniquenesses.The ETS-10 skeleton is negativity, and there are sodium, potassium counter cation in the surface, can introduce other metallic cation (US patent 4994191) by ion-exchange.The most noticeable then is that ETS-10 is very fast relatively greater than the organic molecule degraded of its microvoid structure to size, then want slowly for little organic molecule degradation speed, thereby show the selective photocatalysis characteristic, therefore can effectively realize selective photocatalysis (Chem.Commun. to different size size organic molecule, 2001,20,2130), become a class novel photocatalysis material that is getting more and more people's extensive concerning in recent years.
The synthesis step more complicated of ETS-10, synthetic organic formwork agent (Zeolites, 1994,14,697 such as use quaternary ammonium salt, aliphatic amide of needing of ETS-10 in the report greatly; J.Chem.Soc.Chem.Commun., 1994,261; Micopor.Mater., 1996,5,401; Micropor.Mater., 1995,4,195; Micopor.Mesopor.Mater., 2002,56,89; Micropor.Mesopor.Mater., 2004,71,77; Stud.Surf.Sci.Catal., 1997,105,221; Stud.Surf.Sci.Catal., 2004,154,334.).Also there are some research work not report having also can synthesize under the condition of organic formwork agent and obtain ETS-10, but need in the presence of a large amount of fluorions, use TiO
2, TiCl
3, TiCl
4, TiF
4, Ti
2(SO
4)
3As titanium source (US Patent 4853202; US Patent 4938939; Chem.Commun., 1996,10,1105; Chem.Commun., 1996,12,1435; Micropor.Mesopor.Mater., 2001,46,1; Micropor.Mesopor.Mater., 2001,47,285; Micropor.Mesopor.Mater., 2002,56,227; Micropor.Mesopor.Mater., 2000,41,79; Micropor.Mesopor.Mater., 2005,80,263; Langmuir, 2003,19,1977; J.Radioanal.Nucl.Chem., 2003,258,243; J.Catal., 2004,224,107.),, except fluorion, in some reports, also add a certain amount of crystal seed (Naure, 1994,367,347 in order to obtain the ETS-10 of high purity, high-crystallinity; Micropor.Mater., 1995,4,195; Micropor.Mesopor.Mater., 1998,23,253; Micopor.Mesopor.Mater., 2005,79,13; USPatent 5453263.).Also there is research to report under the condition that does not add fluorion, organic formwork agent and crystal seed and uses Ti
2(SO
4)
3, TiCl
3, TiO
2As the synthetic preparation in titanium source ETS-10, but contain titanium dioxide impurity (Micropor.Mesopor.Mater., 2004,67,181 in the product with this understanding; Micopor.Mesopor.Mater., 2004,76,113; Stud.Surf.Sci.Catal., 2004,154,770.).Therefore, people are still continuing the simple and effective ETS-10 synthetic method of research exploration.
Summary of the invention
The object of the present invention is to provide a kind of in the system that does not add organic formwork agent, fluorion and crystal seed the synthetic method of microporous titanium silicon fluorite ETS-10.
The present invention proposes the synthetic method of a kind of micropore titanium-silicon zeolite ETS-10, and it is a raw material with inorganic ti sources, inorganic silicon source and mineral alkali under the condition of not using organic formwork agent, fluorion and crystal seed, and is synthetic under hydrothermal condition.Concrete synthesis step is: at first with sodium hydroxide and potassium hydroxide mineral alkali, inorganic silicon source, inorganic ti sources, hydromassage you than 4.0-5.0: 5.0-6.0: 1.0: 100-150 mixes, and the pH value is adjusted to 10.3-10.6; The reactor of packing into then, 200-230 ° of C hydrothermal treatment consists 24-36 hour; The pressed powder that obtains after filtration, after the washing, drying, oven dry obtains having the Ti-Si zeolite ETS-10 of microvoid structure.
Inorganic ti sources such as titanium tetrachloride, titanous chloride, titanium dioxide etc. in the above-mentioned system, inorganic silicon source such as water glass, oxyethyl group silicon etc., alkaline aqueous solution is the mixing solutions of sodium hydroxide and potassium hydroxide.
In the inventive method, good conditions is:
Under 95-105 ℃, dried after the pressed powder drying that obtains after the hydrothermal treatment consists through 10-13 hour.
The mol ratio of synthetic system sodium hydroxide and potassium hydroxide is 2-2.4.
The silicon source of using is sodium silicate aqueous solution, and the titanium source is a titanium tetrachloride.
The microporous titanium silicon fluorite ETS-10 that synthetic method of the present invention obtains is widely used in the synthetic field of catalysis.
Synthetic product nitrogen absorption of the present invention,
29Si solid state nmr and X-ray powder diffraction characterize, and illustrate that the synthetic micro porous molecular sieve that obtains has the feature structure of ETS-10 and do not have other impurity phase.The about 350m of specific surface
2/ g, pore volume are 0.17cm
3/ g.
The advantage of the inventive method is: (1) synthetic system is in the middle of alkaline aqueous solution, obtains by collosol and gel approach hydro-thermal, and method is simple; (2) the synthetic raw material that uses is an industrial chemicals cheap and easy to get; (3) do not need in the building-up process to use organic formwork agent, fluorion and crystal seed, synthetic system is simple and direct, has reduced cost, thereby uses the directly synthetic microporous titanium silicon fluorite ETS-10 that obtains high purity, high-crystallinity of cheap raw material simply and easily.
Description of drawings
Fig. 1 is inorganic silicon source and TiCl in the building-up process
4The different XRD spectra that add than following synthetic microporous titanium silicon fluorite ETS-10; Fig. 1 (a), (b), (c) mesosilicic acid sodium and TiCl
4Molar ratio is respectively 5.2/1,5.5/1, and 5.8/1.
Fig. 2 is embodiment 1 microporous titanium silicon fluorite ETS-10's
29Si solid-state nuclear magnetic resonance spectrogram.
Fig. 3 is embodiment 2 microporous titanium silicon fluorite ETS-10's
29Si solid-state nuclear magnetic resonance spectrogram.
Fig. 4 is embodiment 3 microporous titanium silicon fluorite ETS-10's
29Si solid-state nuclear magnetic resonance spectrogram.
Embodiment
Embodiment 1:
6.00 gram NaOH and 3.90 gram KOH are dissolved in 8.0mL distilled water, then the solution that obtains are slowly added in the 30.28 gram sodium silicate solutions (service water glass), obtain settled solution A; Under vigorous stirring, with 4.75 gram TiCl
4Slowly add in the 10.0mL distilled water, be anti-TiCl in the adition process
4Hydrolysis is too fast, must keep solution temperature to be lower than 10 ℃ with ice-water bath, obtains faint yellow settled solution B.Under the vigorous stirring, solution B is dropwise added solution A, add back pH value of solution value and be about 11.5, with concentrated hydrochloric acid the pH value is transferred to 10.4-10.5 then, the colloid that obtains is transferred in the water heating kettle of teflon lined, 230 ℃ of crystallization 36 hours, naturally cooling, with the products therefrom suction filtration, distilled water wash, 100 ℃ of oven dry.BET measuring result product specific surface 347.6m
2/ g, pore volume are 0.171cm
3/ g.
Embodiment 2:
6.40 gram NaOH and 4.20 gram KOH are dissolved in 10.0mL distilled water, then the solution that obtains are slowly added in the 32.03 gram sodium silicate solutions (water glass), obtain settled solution A; Under vigorous stirring, with 4.75 gram TiCl
4Slowly add in the 8.0mL distilled water, keep solution temperature to be lower than 10 ℃ with ice-water bath in the adition process, obtain faint yellow settled solution B.Under the vigorous stirring, solution B is dropwise added solution A, add back pH value of solution value and be about 11.5, with concentrated hydrochloric acid the pH value is transferred to 10.4-10.5 then, the colloid that obtains is transferred in the water heating kettle of teflon lined, 200 ℃ of crystallization 24h, naturally cooling, with the products therefrom suction filtration, distilled water wash, 100 ℃ of oven dry.BET measuring result product specific surface 357.1m
2/ g, pore volume are 0.172cm
3/ g.
Embodiment 3:
6.40 gram NaOH and 4.20 gram KOH are dissolved in 10.0mL distilled water, then the solution that obtains are slowly added in the 33.78 gram sodium silicate solutions (water glass), obtain settled solution A; Under vigorous stirring, with 4.75 gram TiCl
4Slowly add in the 10.0mL distilled water, keep solution temperature to be lower than 10 ℃ with ice-water bath in the adition process, obtain faint yellow settled solution B.Under the vigorous stirring, solution B is dropwise added solution A, add back pH value of solution value and be about 11.5, with concentrated hydrochloric acid the pH value is transferred to 10.4-10.5 then, the colloid that obtains is transferred in the water heating kettle of teflon lined, 230 ℃ of crystallization 36h, naturally cooling, with the products therefrom suction filtration, distilled water wash, 100 ℃ of oven dry.BET measuring result product specific surface 364.8m
2/ g, pore volume are 0.180cm
3/ g.
Claims (4)
1. the synthetic method of a microporous titanium silicon fluorite ETS-10, it is characterized in that under the condition of not using organic formwork agent, fluorion and crystal seed, with inorganic ti sources, inorganic silicon source and mineral alkali is raw material, synthetic under hydrothermal condition, concrete synthesis step is: at first with mineral alkali sodium hydroxide and potassium hydroxide, inorganic silicon source, inorganic ti sources, hydromassage you than 4.0-5.0: 5.0-6.0: 1.0: 100-150 mixes, and the pH value is adjusted to 10.3-10.6; The reactor of packing into then, 200-230 ℃ hydrothermal treatment consists 24-36 hour; The pressed powder that obtains after filtration, after the washing, drying, oven dry obtains having the Ti-Si zeolite ETS-10 of microvoid structure.
2. microporous titanium silicon fluorite ETS-10 synthetic method according to claim 1 was dried through 10-13 hour under 95-105 ℃ after the pressed powder drying that it is characterized in that obtaining after the hydrothermal treatment consists.
3. microporous titanium silicon fluorite ETS-10 synthetic method according to claim 1, the mol ratio that it is characterized in that synthetic system sodium hydroxide and potassium hydroxide is 2-2.4.
4. the titanium silicon molecular sieve ETS-4 of microvoid structure according to claim 1-10 synthetic method is characterized in that the silicon source of using is sodium silicate aqueous solution, and the titanium source is a titanium tetrachloride.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935052B (en) * | 2009-06-30 | 2012-05-30 | 中国石油化工股份有限公司 | Method for synthesizing titanium silicon zeolite material |
| CN103159225B (en) | 2011-12-13 | 2015-01-21 | 中国石油天然气集团公司 | Synthetic method of ETS-10 titanium silicalite molecular sieve |
| CN103073021A (en) * | 2013-01-11 | 2013-05-01 | 东北大学 | Method for preparing titanium silicalite ETS-10 with high-silicon industrial raw material |
| CN104229819B (en) * | 2014-08-15 | 2016-02-24 | 温州大学 | The synthetic method of the mesoporous ETS-10 zeolite molecular sieve of a kind of strong basicity |
| CN104725280B (en) * | 2015-03-04 | 2017-04-12 | 温州大学 | Synthesis method of diarylurea compounds |
| CN112320816A (en) * | 2020-12-09 | 2021-02-05 | 成都理工大学 | Low-temperature green synthesis method of NaY molecular sieve with small crystal grains and large specific surface area |
| CN114350182A (en) * | 2021-12-17 | 2022-04-15 | 沈阳市津浩科技有限公司 | Preparation method of modified zeolite for environment-friendly high-performance interior wall coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1426962A (en) * | 2001-12-21 | 2003-07-02 | 清华大学 | Nano grade titanium silicon molecular sieve and its synthesis technology |
| CN1552626A (en) * | 2003-05-30 | 2004-12-08 | 中国石油化工股份有限公司 | Titanium silicon molecular sieve and synthetic method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1426962A (en) * | 2001-12-21 | 2003-07-02 | 清华大学 | Nano grade titanium silicon molecular sieve and its synthesis technology |
| CN1552626A (en) * | 2003-05-30 | 2004-12-08 | 中国石油化工股份有限公司 | Titanium silicon molecular sieve and synthetic method thereof |
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