CN1428296A - Method for synthesizing new titanium-silicone metapore molecular sieve - Google Patents

Method for synthesizing new titanium-silicone metapore molecular sieve Download PDF

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CN1428296A
CN1428296A CN 01138950 CN01138950A CN1428296A CN 1428296 A CN1428296 A CN 1428296A CN 01138950 CN01138950 CN 01138950 CN 01138950 A CN01138950 A CN 01138950A CN 1428296 A CN1428296 A CN 1428296A
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titanium
synthetic method
molecular sieve
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CN1235799C (en
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李�灿
张文华
应品良
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Dalian Institute of Chemical Physics of CAS
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Abstract

The synthesis method of titanium-silicon metaporous molecular sieve uses non-ionic surfactant P123 as template agent, uses F(-1) as catalyst and utilizes silicon source and titanium source to make synthesis under the acid condition, and its preparation process includes the following steps: (1). using template agent and making it into acid solution, stirring for 5-24 hr, at 35-80 deg.c; (2). adding fluoride and stirring for above 5 hr.; (3) mixing silicon source and titanium source, adding them and continuously stirring for 12-48 hr, and obtaining primary gel product; (4) crystallizing said product for above 12 hr. at 40-100 deg.c and (5) precipitation, separation, washing, drying and roasting for above 5 hr. at 450-800 deg.C so as to obtain the invented product.

Description

A kind of synthetic method of new titanium-silicone metapore molecular sieve
Technical field
The present invention relates to heteroatom mesopore molecular sieve, specifically a kind of synthetic method of new titanium-silicone metapore molecular sieve.
Background technology
Titanium-silicone metapore molecular sieve is widely used in the selective oxidation of large volume organic compound and produces in the fine chemicals, its active centre is commonly referred to be the titanium of the tetrahedral coordination of that part of isolated existence of isomorphous substitution silicon in the skeleton, and irrelevant with the outer titanium species that exists of skeleton.Up to now, titaniferous mesopore molecular sieve, as Ti-MCM-41, Ti-MCM-48, Ti-HMS and Ti-MSU etc. successfully synthesize.And for one in the mesopore molecular sieve very important member SBA-15, because need be synthetic through hydrothermal treatment consists under strong acidic condition, considerably less to the report that its element replaces.This pure silica SAB-15 material generally all is synthetic in the HCl of 1.6M solution, and through 100 ℃ of hydrothermal treatment consists, though Al can enter in the SAB-15 material skeleton, but there is (document 1:Yue.Y.et al. in the Al species that a large amount of non-skeletons is arranged simultaneously, Chem., Commun., 1999,1967).Ti-SBA-15 only can be synthesized out under the situation of microwave heating, and its weak point is: its application is restricted, and structurally ordered property good inadequately (document 2:Newalkar, B.L, et al., Chem., Mater., 2001,13,552).Also do not utilize at present synthesis of molecular sieve universal method--hydrothermal synthesis method prepares the report of Ti-SBA-15 material.
Summary of the invention
The hydrothermal synthesis method that the purpose of this invention is to provide the good new titanium-silicone metapore molecular sieve of a kind of structurally ordered property.This mesoporous molecular sieve framework is made up of silicon-oxy tetrahedron and titanyl tetrahedron, and its Si/Ti=20～1000, aperture are 5～30nm, and are adjustable in this scope, and pore wall thickness is 2.5～6nm.
Synthetic method of the present invention to achieve these goals is a template with nonionic surface active agent P123, with F -Be catalyzer, silicon source and titanium source are synthetic under acidic conditions, and concrete preparation process is as follows:
(1) in proportion template is mixed with acidic solution, stirred 5～24 hours at 35～80 ℃;
(2) in proportion fluorochemical is joined in the above-mentioned solution, and stir more than 5 hours;
(3) silicon source and titanium source are mixed, under vigorous stirring, they are joined in the above-mentioned solution fast, and continue to stir 12～48 hours, obtain initial jel product;
(4) with top products therefrom in 40～100 ℃ of following crystallization more than 12 hours;
(5) the white solid precipitation is separated with mother liquor, after washing and drying, obtain the former powder of titaniferous mesopore molecular sieve, more than 5 hours, obtain titanium-silicone metapore molecular sieve 450～800 ℃ of roastings.
Wherein said preparation of raw material mol ratio is: SiO 2/ P123=9.5～95, SiO 2/ H +=0.27～27, SiO 2/ TiO 2=20～1000, SiO 2/ H 2O=0.005～0.05, SiO 2/ F -=20～100.
Wherein said crystallization can be carried out in baking oven; Described roasting can be carried out under air or oxygen atmosphere in muffle furnace, then can remove the tensio-active agent on the mesopore molecular sieve; Described fluorochemical is NaF or NH 4Capacitive fluorochemicals such as F are as hydrolytic accelerating agent, with F -Promote the hydrolysis of silicon source material for catalyzer; Wherein said silicon source is the organo-silicon ester compound, and described organo-silicon ester can be methyl silicate or tetraethoxy etc.; Wherein said titanium source is organic titanium ester or inorganic titanium compound; Described organic titanium ester or inorganic titanium compound can be butyl (tetra) titanate, the different third titanium ester of metatitanic acid, titanium sulfate or titanous chloride etc.; Wherein said acid is strong acid, as HCl, and H 2SO 4Or HNO 3Deng; Wherein said crystallization optimum temps is 50～80 ℃; Wherein said crystallization time is preferably 24～144h, and best crystallization time is 48～84h; In the wherein said crystallization process, crystallization pressure is autogenous pressure or nitrogen, air or the rare gas element that charges into 0.01～0.1Mpa;
Titanium is coordinated in the framework of molecular sieve in the tetrahedron mode in the titanium-silicone metapore molecular sieve of the present invention's preparation, also can otherwise be present in outside the skeleton, but not have TiO 2Crystalline phase generates;
Wherein said P123 is triblock copolymer nonionic surface active agent EO 20PO 70EO 20Abbreviation, be used as template (being called the structure indicator again).
The present invention utilizes conventional hydrothermal synthesis method, greatly reducing on the tart basis of solution,, promoting the hydrolysis of silicon source material by adding soluble fluoride, and the polymerization that improves silicate ion, thereby under lower temperature, synthesize high-quality Ti-SAB-15 meso-porous molecular sieve material.
The present invention has following advantage:
(1) the present invention utilizes conventional hydrothermal synthesis method directly to prepare the mesopore molecular sieve Ti-SAB-15 material that contains Ti first, and method is simple, the reaction conditions gentleness.
(2) the present invention does hydrolytic accelerating agent with the solubility villiaumite, and synthetic under acidic conditions uses the solubility villiaumite to promote the hydrolysis of silicon source material greatly in the building-up process, can reduce even avoid TiO 2Sedimentary generation effectively enters in the skeleton of molecular sieve Ti, and the product structure order that is obtained is good.
(3) the present invention uses biodegradable nonionogenic tenside P123 to do template, and is environmentally friendly.
(4) use the price of nonionogenic tenside P123 more cheap than the template cetyl trimethylammonium bromide of synthetic MCM-41 system mesopore molecular sieve, cost is lower.
(5) in building-up process, can not add alcohol and can stop and avoid TiO 2The generation of dephasign, easy to operation.
Description of drawings
Fig. 1 is the XRD diffracting spectrum of sample 1#.
Fig. 2 is that the UV-vis of sample 1# absorbs collection of illustrative plates.
Fig. 3 is the XRD diffracting spectrum of sample 2#.
Fig. 4 is that the UV-vis of sample 2# absorbs collection of illustrative plates.
Fig. 5 is the XRD diffracting spectrum of sample 3#.
Fig. 6 is that the UV-vis of sample 3# absorbs collection of illustrative plates.
Fig. 7 is the XRD diffracting spectrum of sample 4#.
Fig. 8 is that the UV-vis of sample 4# absorbs collection of illustrative plates.
Fig. 9 is the XRD diffracting spectrum of sample 5#.
Figure 10 is that the UV-vis of sample 5# absorbs collection of illustrative plates.
Figure 11 is the XRD diffracting spectrum of sample 6#.
Figure 12 is that the UV-vis of sample 6# absorbs collection of illustrative plates.
Embodiment
Example 1
With 2 gram P123 (EO 20PO 70EO 20) surfactant dissolves in the HCl of the pH1.0 of 75ml solution, add mol ratio SiO at 35～45 ℃ after down stirring 5 hours 2/ F -Be 35 NH 4F adds 7 gram methyl silicate and TiO under vigorous stirring 2/ SiO 2Mol ratio is 1% the different third titanium mixture, continues high-speed stirring after 15 hours, the gained gel is transferred in 60 ℃ the baking oven, is incubated at least 24 hours.The white crystalline solid product is separated with mother liquor, to neutral, and after under the air atmosphere below 100 ℃ dry 10 hours,, then obtain titanium content and be 1.0% Ti-SBA-15 meso-porous molecular sieve material at last through 500 ℃ of sintering 10 hours with deionized water wash.Wherein titanium content be 1.0% sample 1# XRD crystalline phase collection of illustrative plates as shown in Figure 1, uv-visible absorption spectra (UV-vis) is seen Fig. 2; As seen from the figure, three diffraction peaks of XRD figure spectrum in the low angle scope reflect that gained sample 1# is the SBA-15 structure type material of high-sequential; And a strong absorption band only arranged near 210nm in Fig. 2, it is that titanium has entered the sign in the skeleton of mesoporous material; The crystalline state titanium oxide has strong absorption band to exist near 330nm, and does not demonstrate this absorption among Fig. 2, does not promptly have crystalline state TiO 2Generate,, exist with the state of high degree of isolation so most titaniums have entered in the skeleton of mesoporous material in the experiment.
Example 2
The HCl solution of pH1.0 in the example 1 is changed into the solution of pH2.0, and other conditions and process are constant, also can obtain titaniferous-SBA-15 meso-porous molecular sieve material.Wherein titanium content be 1.0% sample 2# XRD crystalline phase collection of illustrative plates as shown in Figure 3, UV-vis absorbs collection of illustrative plates and sees Fig. 4; Though sample still has three low angle diffraction peaks, show that the gained sample is that high quality gets the SBA-15 structured material, in the UV-vis collection of illustrative plates, can find that sample 2# is very serious at the conditions of streaking of the absorption band at 210nm place, this explanation not only has part Ti 4+Entered in the skeleton of sample, the non-skeleton TiO of a quantity has been arranged simultaneously 2Exist.
Example 3
The HCl solution of pH1.0 in the example 1 is changed into the HCl solution of 1M concentration, and other conditions and process are constant, also can obtain titaniferous Ti-SBA-15 meso-porous molecular sieve material.Wherein titanium content be 1.0% sample 3# XRD crystalline phase collection of illustrative plates as shown in Figure 3, as seen from Figure 3, the gained material is high-quality SBA-15 structure, simultaneously, from UV-vis collection of illustrative plates Fig. 4 as can be known, do not find the existence of extra-framework titanium species among the sample 3#, most titaniums should exist with the form of skeleton titanium.
Example 4
The crystallization temperature of mother liquor in the example 1 is changed into 80 ℃, and other conditions and process are constant, also can obtain titaniferous Ti-SBA-15 meso-porous molecular sieve material.Wherein titanium content is the XRD crystalline phase collection of illustrative plates of 1.0% sample 4#, as shown in Figure 7; The UV-vis collection of illustrative plates as shown in Figure 8, as seen from the figure, gained sample 4# is high-quality SBA-15 material, and the Ti atom overwhelming majority has entered in the skeleton of mesoporous material.
Example 5
The different third titanium ester of metatitanic acid in the example 1 is changed into titanous chloride, and other conditions and process are constant, also can obtain titaniferous Ti-SBA-15 meso-porous molecular sieve material.Wherein titanium content be 1.0% sample 5# XRD crystalline phase collection of illustrative plates as shown in Figure 9; The UV-vis collection of illustrative plates is seen shown in Figure 10, show that gained sample 5# still is high-quality SBA-15 material, and skeleton is not found TiO outward 2Exist.
Example 6
Methyl silicate in the example 1 is changed into tetraethoxy, and other conditions and process are constant, also can obtain titaniferous Ti-SBA-15 meso-porous molecular sieve material.Wherein titanium content be 1.0% sample 6# XRD crystalline phase collection of illustrative plates as shown in figure 11; UV-vis spectrum as shown in figure 12, the UV-vis spectrum experiment shows, gets skeleton although titanium has entered mesoporous material, yet has a large amount of extra-framework titanium to exist simultaneously.

Claims (10)

1. the synthetic method of a new titanium-silicone metapore molecular sieve, it is characterized in that: with nonionic surface active agent P123 is template, with F -Be catalyzer, silicon source and titanium source are synthetic under acidic conditions, and concrete preparation process is as follows:
(1) in proportion template is mixed with acidic solution, stirred 5～24 hours at 35～80 ℃;
(2) in proportion fluorochemical is joined in the above-mentioned solution, and stir more than 5 hours;
(3) silicon source and titanium source are mixed, under vigorous stirring, they are joined in the above-mentioned solution fast, and continue to stir 12～48 hours, obtain initial jel product;
(4) with top products therefrom in 40～100 ℃ of following crystallization more than 12 hours;
(5) the white solid precipitation is separated with mother liquor, after washing and drying, obtain the former powder of titaniferous mesopore molecular sieve, more than 5 hours, obtain titanium-silicone metapore molecular sieve 450～800 ℃ of roastings.
2. according to the described synthetic method of claim 1, it is characterized in that: wherein said preparation of raw material mol ratio is: SiO 2/ P123=9.5～95, SiO 2/ H +=0.27～27, SiO 2/ TiO 2=20～1000, SiO 2/ H 2O=0.005～0.05, SiO 2/ F -=20～100.
3. according to the described synthetic method of claim 1, it is characterized in that: wherein said fluorochemical is capacitive fluorochemical NaF or NH 4F.
4. according to the described synthetic method of claim 1, it is characterized in that: wherein said silicon source is methyl silicate or a tetraethoxy in the organo-silicon ester compound.
5. according to the described synthetic method of claim 1, it is characterized in that: wherein said titanium source is butyl (tetra) titanate or the different third titanium ester of metatitanic acid in the organic titanium ester, or titanium sulfate or titanous chloride in the inorganic titanium compound.
6. according to the described synthetic method of claim 1, it is characterized in that: wherein said crystallization temperature is 40～100 ℃.
7. according to the described synthetic method of claim 1, it is characterized in that: wherein said crystallization time is 24～144h.
8. according to the described synthetic method of claim 1, it is characterized in that: wherein said crystallization time is 48～84h.
9. according to the described synthetic method of claim 1, it is characterized in that: in the wherein said crystallization process, crystallization pressure is autogenous pressure or nitrogen, air or the rare gas element that charges into 0.01～0.1Mpa.
10. according to the described synthetic method of claim 1, it is characterized in that: wherein said acid is HCl in the strong acid, H 2SO 4Or HNO 3
CN 01138950 2001-12-28 2001-12-28 Method for synthesizing new titanium-silicone metapore molecular sieve Expired - Fee Related CN1235799C (en)

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Cited By (15)

* Cited by examiner, † Cited by third party
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CN100453167C (en) * 2007-06-07 2009-01-21 云南大学 Method for preparing mesoporous titanium dioxide optical catalyst using plant peels and films
CN101497451B (en) * 2008-01-31 2011-07-20 中国石油化工股份有限公司 Method for preparing mesoporous titanium-silicon material
CN101497450B (en) * 2008-01-31 2011-11-02 中国石油化工股份有限公司 Method for preparing titanium-containing mesoporous material
CN102344150A (en) * 2010-07-29 2012-02-08 中国石油化工股份有限公司 Synthetic method for mesopore titanium-silicon molecular sieve
CN102614857A (en) * 2012-03-15 2012-08-01 华东师范大学 Preparation method of metal ion dosed monodisperse mesoporous silicon dioxide spherical nanoparticles
CN102774848A (en) * 2011-05-13 2012-11-14 中国石油化工股份有限公司 Method for preparing Ti-SBA-15 molecular sieve
CN103395798A (en) * 2013-06-24 2013-11-20 山西大同大学 Synthesis method of Ti-Beta molecular sieve
CN104445257A (en) * 2014-11-25 2015-03-25 河北美邦工程科技有限公司 Preparation method for high-stable-activity titanium silicalite molecular sieve catalyst
CN106185958A (en) * 2016-07-23 2016-12-07 安阳华森纸业有限责任公司 The preparation method of hydrophobic mesoporous silicon and the application in preparing waterproof color coating thereof
CN106517227A (en) * 2016-11-08 2017-03-22 上海纳米技术及应用国家工程研究中心有限公司 Microwave method for rapidly preparing short-rod-like SBA-15
CN106554029A (en) * 2016-11-14 2017-04-05 南开大学 The compound FAU types molecular sieve of package metals chromic compound and its synthetic method
CN106587101A (en) * 2016-12-14 2017-04-26 上海卓悦化工科技有限公司 Method for synthesizing nano-sized zeolite molecular sieve suitable for VOCs adsorption
CN113683097A (en) * 2021-09-23 2021-11-23 深圳科冠华太新材料技术有限公司 Preparation method of TS-1 molecular sieve rich in framework four-coordinate titanium
CN113788745A (en) * 2021-09-16 2021-12-14 万华化学集团股份有限公司 Preparation method of lilial
CN114367304A (en) * 2021-12-28 2022-04-19 中国科学技术大学 Composite molecular sieve, preparation method and application thereof

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100453167C (en) * 2007-06-07 2009-01-21 云南大学 Method for preparing mesoporous titanium dioxide optical catalyst using plant peels and films
CN101497451B (en) * 2008-01-31 2011-07-20 中国石油化工股份有限公司 Method for preparing mesoporous titanium-silicon material
CN101497450B (en) * 2008-01-31 2011-11-02 中国石油化工股份有限公司 Method for preparing titanium-containing mesoporous material
CN102344150A (en) * 2010-07-29 2012-02-08 中国石油化工股份有限公司 Synthetic method for mesopore titanium-silicon molecular sieve
CN102774848B (en) * 2011-05-13 2014-08-27 中国石油化工股份有限公司 Method for preparing Ti-SBA-15 molecular sieve
CN102774848A (en) * 2011-05-13 2012-11-14 中国石油化工股份有限公司 Method for preparing Ti-SBA-15 molecular sieve
CN102614857A (en) * 2012-03-15 2012-08-01 华东师范大学 Preparation method of metal ion dosed monodisperse mesoporous silicon dioxide spherical nanoparticles
CN102614857B (en) * 2012-03-15 2013-10-30 华东师范大学 Preparation method of metal ion dosed monodisperse mesoporous silicon dioxide spherical nanoparticles
CN103395798A (en) * 2013-06-24 2013-11-20 山西大同大学 Synthesis method of Ti-Beta molecular sieve
CN104445257A (en) * 2014-11-25 2015-03-25 河北美邦工程科技有限公司 Preparation method for high-stable-activity titanium silicalite molecular sieve catalyst
CN106185958A (en) * 2016-07-23 2016-12-07 安阳华森纸业有限责任公司 The preparation method of hydrophobic mesoporous silicon and the application in preparing waterproof color coating thereof
CN106185958B (en) * 2016-07-23 2018-02-23 安阳华森纸业有限责任公司 The preparation method of hydrophobic mesoporous silicon and its application in waterproof color coating is prepared
CN106517227A (en) * 2016-11-08 2017-03-22 上海纳米技术及应用国家工程研究中心有限公司 Microwave method for rapidly preparing short-rod-like SBA-15
CN106517227B (en) * 2016-11-08 2018-11-16 上海纳米技术及应用国家工程研究中心有限公司 A kind of method that microwave method quickly prepares the SBA-15 of corynebacterium
CN106554029A (en) * 2016-11-14 2017-04-05 南开大学 The compound FAU types molecular sieve of package metals chromic compound and its synthetic method
CN106587101A (en) * 2016-12-14 2017-04-26 上海卓悦化工科技有限公司 Method for synthesizing nano-sized zeolite molecular sieve suitable for VOCs adsorption
CN113788745A (en) * 2021-09-16 2021-12-14 万华化学集团股份有限公司 Preparation method of lilial
CN113683097A (en) * 2021-09-23 2021-11-23 深圳科冠华太新材料技术有限公司 Preparation method of TS-1 molecular sieve rich in framework four-coordinate titanium
CN114367304A (en) * 2021-12-28 2022-04-19 中国科学技术大学 Composite molecular sieve, preparation method and application thereof

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