CN101519214B - Method for synthesizing titanium-silicon materials with mesoporous and microporous structures - Google Patents
Method for synthesizing titanium-silicon materials with mesoporous and microporous structures Download PDFInfo
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Abstract
The invention provides a method for synthesizing titanium-silicon materials with mesoporous and microporous structures, which is characterized by comprising the following steps of: adding a titanium sThe invention provides a method for synthesizing titanium-silicon materials with mesoporous and microporous structures, which is characterized by comprising the following steps of: adding a titanium source and a silicon source to the water solution of organo-alkali compound respectively under the ultrasonic agitation to obtain two solutions after homogeneous mixing; and then mixing the two solutioource and a silicon source to the water solution of organo-alkali compound respectively under the ultrasonic agitation to obtain two solutions after homogeneous mixing; and then mixing the two solutions evenly under the ultrasonic agitation; mixing the mixture with the water solution of a surface active agent evenly under the ultrasonic agitation to obtain a mixture with the mole ratio of silicon ns evenly under the ultrasonic agitation; mixing the mixture with the water solution of a surface active agent evenly under the ultrasonic agitation to obtain a mixture with the mole ratio of silicon source: titanium source: organic base: surface active agent: water equals to 1: (0.001-0.5) : (0.05-0.8) : (0.05-0.5) : (5-200); putting the mixture into a sealed reaction kettle for hydrothermal cryssource: titanium source: organic base: surface active agent: water equals to 1: (0.001-0.5) : (0.05-0.8) : (0.05-0.5) : (5-200); putting the mixture into a sealed reaction kettle for hydrothermal crystallization; and then collecting the obtained titanium-silicon material. The titanium-silicon material synthesized by the method has good catalytic oxidation property and better effect on the oxidatiotallization; and then collecting the obtained titanium-silicon material. The titanium-silicon material synthesized by the method has good catalytic oxidation property and better effect on the oxidation reactions in the presence of large molecules. n reactions in the presence of large molecules.
Description
Technical field
The invention relates to a kind of synthetic method of inorganic materials, is the synthetic method that has the titanium silicalite material of mesoporous and microvoid structure about a kind of furtherly.
Background technology
HTS is the novel hetero-atom molecular-sieve that last century, early eighties began to develop.The Ti-ZSM-5 that MFI type structure is arranged that has synthesized at present is TS-1, the TS-2 of MEL type structure, and have than the TS-48 of macroporous structure etc.The TS-1 molecular sieve is that the transition metal titanium is introduced formed a kind of new titanium-silicone molecular sieve with good selective paraffin oxidation catalytic performance in the framework of molecular sieve with ZSM-5 structure, the TS-1 molecular sieve not only has the catalysed oxidn of titanium, but also has the shape effect selected and the advantages of excellent stability of ZSM-5 molecular sieve.But, the microvoid structure of about 0.55 nanometer of TS-1 molecular sieve, big organic molecule is difficult to spread therein and by catalyzed oxidation, make its good catalytic oxidation performance be difficult in more wide field, especially bring into play in biological and medicine macromole field, and then people think the more wide-aperture titanium-containing molecular sieve material of research and development.
The Mobil company of the U.S. in reported first in 1992 mesopore molecular sieve and the synthetic method thereof of M41S series, this series material has homogeneous granules degree and regular meso-hole structure, attracted the very big concern of relevant academia, for having brought hope in aspects such as macromolecular catalysis, separation.Representational in the M41S series is MCM-41, its meso-hole structure feature (Q.Huo etc., NATURE, 1994,368:317) be its X-ray diffraction spectrogram near 2 θ are 2.3 °, near 4.0 °, there is diffraction peak 4.6 ° of vicinity.But MCM-41 is the mesoporous SiO of pure silicon
2, must in its structure, introduce heteroatoms and just have catalytic activity.Corma (Corma etc., Chem.Commun., 1994,147-148) equal titanium to be incorporated in the structure of MCM-41 by synthesizing mean in 1994, success obtained titaniferous MCM-41, i.e. Ti-MCM-41 molecular sieve.
Because the homogeneous meso-hole structure of Ti-MCM-41 molecular sieve rule, people place high hopes at aspects such as macromole fine chemistry industry and medicine macromole are synthetic to it.But, this material is a non-crystalline state, hydrothermal stability and hydrophobic nature all are weaker than crystalline Ti-Si zeolite (TS-1), catalytic activity in the oxidizing reaction that with the aqueous hydrogen peroxide solution is oxygenant is lower, greatly limited its application (Microporous Materials, 1997,9:173 and Stud.Surf.Sci.Catal., 1995).
In order to overcome titaniferous micro porous molecular sieve TS-1 and titanium-containing meso-porous molecular sieve Ti-MCM-41 limitation separately, people try to explore synthetic titanium-containing meso-porous molecular sieve material with high catalytic activity.
CN1226187C has reported HTS matrix material and its preparation method with above-mentioned two kinds of structures, has certain catalytic activity, but the matrix material duct size that the subject matter of its existence is it to be mentioned single (in the X-ray diffraction spectrogram diffraction peak position restriction strict), and in its preparation method step comparatively numerous and diverse, environment and cost burden arranged.
Summary of the invention
The objective of the invention is deficiency, a kind of synthetic method with titanium silicalite material of mesoporous and micropore is provided at the synthetic aspect of existing mesoporous titanium-silicon material.
Synthetic method provided by the invention, it is characterized in that under ultrasonic agitation, respectively titanium source and silicon source are joined and mix the back in the aqueous solution of organo-alkali compound and form two kinds of solution, then with above-mentioned two kinds of solution mixing under ultrasonic agitation, the aqueous solution ultrasonic agitation of gained mixture and tensio-active agent is mixed, obtain mole and consist of the silicon source: titanium source: organic bases: tensio-active agent: water=1: (0.001-0.5): (0.05-0.8): (0.05-0.5): mixture (5-200), with mixture at the sealed reactor hydrothermal crystallizing, and reclaim and to obtain titanium silicalite material, said silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter.
The contriver finds that what be different from other pure silicon material or silica-alumina material is that it is preparation titanium silicalite material key of success that titanium silicalite material becomes the polymerization that prevents titanium in the glue process.This synthetic method makes the titanium of hydrolysis better combine with silicon and organic bases and tensio-active agent etc., eliminates the partial concn inequality, the TiO that makes the titanium source reunite and generate
2Few as far as possible, reduce the generation of extra-framework titanium, make the titanium-containing mesoporous material of preparing have good catalyzed oxidation function, better to the reaction effect of macromole participation especially.
Method provided by the invention is synthesized the titanium silicalite material that obtains, in its X-ray diffraction spectrogram near 2 θ are 2.3 °, near 4.0 °, there is diffraction peak 4.6 ° of vicinity, in its infrared spectrum, at wave number 550cm
-1And 960cm
-1Near have absorption band, near wavelength is 220nm, stronger absorption band is arranged in its ultraviolet-visible spectrum.
The synthetic titanium silicalite material that obtains of the inventive method, the feature that has similar mesoporous MCM-41 and part micropore Ti-ZSM-5 simultaneously, specifically in the X-ray diffraction spectrogram of this titanium silicalite material near 2 θ are 2.3 °, near 4.0 °, 4.6 ° of vicinity, generally diffraction peak is arranged at 2.3 ° ± 0.3 °, 4.0 ° ± 0.2 °, 4.6 ° ± 0.2 °, the X-ray diffraction of respectively corresponding [100], [110], [200] crystal face is the constitutional features of similar mesoporous MCM-41 molecular sieve; In its infrared spectra at wave number 550cm
-1Near and 960cm
-1There is absorption the vicinity, and wave number is at 550cm
-1Near absorption band add bright its have ZSM-5 feature (J.C.Jansen etc., Zeolite, 1984,4:369), and wave number is at 960cm
-1Near absorption band then is the feature of skeleton titanium, illustrates that Ti has entered skeleton; Near wavelength is 220nm, stronger absorption band is arranged in its ultraviolet-visible spectrum, illustrate that also Ti has entered skeleton.
In the method provided by the invention, said ultrasonic agitation mixing is meant and utilizes ultrasonic wave and mechanical stirring, promptly utilizes the technology that cavitation effect of ultrasonic waves and mechanical stirring merge mutually that mixture is mixed.
In the method provided by the invention, said silicon source can be organosilicon source or inorganic silicon source, is preferably the organosilicon source; Said inorganic silicon source can be silica gel, silicon sol, water glass or various forms of soft silica; Said organosilicon source preferred formula is R
1 4SiO
4The organosilicon acid esters, R wherein
1For having the alkyl of 1-4 carbon atom.
In the method provided by the invention, said titanium source can be inorganic ti sources or organic titanium source, is preferably the organic titanium source; Said inorganic ti sources is meant TiX
4, TiX
3, TiOX
2Or Ti (SO
4)
2Etc. various forms of metatitanic acid, alkali or the salt of containing, wherein X represents halogen, preferred chlorine; It is R that said organic titanium source is selected from general formula
2 4TiO
4Organic titanate, R wherein
2For having the alkyl of 1-6 carbon atom.
In the method provided by the invention, said tensio-active agent is meant cats product, and preferred formula is (R
3R
4NR
5R
6)
+X
-Quaternary ammonium salt surface active agent, wherein X represents halogen, R
3, R
4And R
5Be the alkyl that is less than 3 carbon atoms, R
3, R
4And R
5Carbonatoms can be identical or different, R
6For having the alkyl that is no less than 12 carbon atoms, preferred 12-22 carbon atom, preferred tensio-active agent is Tetradecyl Trimethyl Ammonium Bromide or cetyl trimethylammonium bromide.
In the method provided by the invention, said organo-alkali compound is selected from fat amine compound, alcamine compound or quaternary amine alkali compounds, or mixes the mixed amine compounds of forming mutually by them.Organic amine the more important thing is the effect of similar molecular sieve structure template except doing alkali source.
The general formula of said fat amine compound is R
7(NH
2)
n, R wherein
7Be alkyl or the alkylidene group with 1-6 carbon atom, n=1 or 2; Preferred fat amine compound is ethamine, n-Butyl Amine 99, butanediamine or hexanediamine.
The general formula of said alcamine compound is (HOR
8)
mNH
(3-m)R wherein
8For having the alkylidene group of 1-4 carbon atom, m=1-3; Preferred alcamine compound is monoethanolamine, diethanolamine or trolamine.
The general formula of said quaternary ammonium hydroxide compounds is (R
9)
4NOH, wherein R
9For having the alkyl of 1-4 carbon atom, preferred quaternary ammonium hydroxide compounds is a TPAOH.
In synthetic method provided by the invention, said hydrothermal crystallizing treating processes can be carried out under static state, also can carry out under dynamically.
The reaction conditions of said hydrothermal crystallizing be with mixture in sealed reactor under 20-190 ℃, preferred 80-180 ℃ and autogenous pressure hydrothermal crystallizing handled 2-360 hour, preferred 24-144 hour; Perhaps earlier 60-120 ℃ pre-crystallization 0.5-10 hour down, preferred 1-8 hour, and then, reclaim product more according to a conventional method 80-180 ℃ of following crystallization 1 hour to 10 days, preferred 1 hour-3 days.
In synthetic method provided by the invention, the process of the routine of said recovery product recovery product is meant the drying and the roasting process of crystallization product.Wherein said drying process can be carried out under the temperature between the room temperature to 200 ℃, said roasting can be between 300 to 800 ℃ be carried out in air atmosphere after 0.5-6 hour in nitrogen atmosphere earlier in 3-12 hour, can also remove organic substance in the material duct by means such as organic solvent extractions before the roasting.
Synthetic method provided by the invention has following advantage:
(1) silicon source hydrolyzed solution and titanium source hydrolyzed solution are proportionally mixed introduce tensio-active agent more earlier, guaranteed titanium in the mixed solution, the distribution of silicon homogeneous; Auxilliary ultrasonic agitation technology simple and easy to operate impel silicon source and titanium source with organic bases, tensio-active agent is better combines, make organic bases, tensio-active agent better play the effect of template and structure directing, reduced template agent, reduced synthetic cost, can eliminate simultaneously the partial concn inequality in the building-up process, the TiO2 that the reunion of titanium source is generated is few as far as possible, reduces the generation of extra-framework titanium.
(2) in the building-up process without other raw materials such as hydrochloric acid, Virahols, reduce cost and environmental pressure.
(3) utilize organic bases as alkali source, can provide alkaline environment for system on the one hand, can play the effect of similar micro porous molecular sieve stay in place form agent on the other hand, make the synthetic mesoporous material also have the part pore characteristics, in the oxidizing reaction that macromole participates in, embodied catalytic performance preferably.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of synthetic titanium silicalite material among the embodiment 1.
Fig. 2 is the infrared absorption spectrum spectrogram of synthetic titanium silicalite material among the embodiment 1.
Fig. 3 is the uv-visible absorption spectra spectrogram of synthetic titanium silicalite material among the embodiment 1.
Embodiment
Following embodiment will the present invention is further illustrated, but therefore do not limit content of the present invention.
The reagent that all are used among the embodiment is commercially available chemically pure reagent.
Used ultrasonic instrument is KQ-100DE type numerical control supersonic producer (220 volts of operating voltage, 50 hertz of the electric voltage frequency that Kunshan Ultrasonic Instruments Co., Ltd. produces; 40 kilo hertzs of operating frequencies; 100 watts of ultrasonic electric power).
The X-ray diffraction of sample (XRD) crystalline phase figure is determined on the Siemens D5005 type x-ray diffractometer and carries out, and gamma ray source is CuK α (λ=1.5418
), tube voltage 40kV, tube current 40mA, 0.25 °/min of sweep velocity, sweep limit 2 θ=1.5 °-15 °.
The fourier infrared of sample (FT-IR) spectrogram is measured on Nicolet 8210 type Fourier infrared spectrographs, adopts KBr compressing tablet (sample accounts for 1wt%), test specification 400-1400cm under the vacuum
-1
The solid ultraviolet-visible diffuse reflection spectrum (UV-Vis) of sample records test specification 200-850nm on Japanese SHIMADZU UV-3100 type ultraviolet-visual spectrometer.
Comparative Examples 1
According to document (J.C.Jansen etc., Zeolite, 1984,4:369) the synthetic Ti-ZSM-5 of method is TS-1.
The positive tetraethyl orthosilicate of 22.5 grams is mixed with 7.0 gram TPAOH, and add 59.8 the gram distilled water, mix the back in normal pressure and 60 ℃ of following hydrolysis 1.0 hours, obtain the hydrating solution of positive tetraethyl orthosilicate, under vigorous stirring, add the solution of forming by 1.1 gram tetrabutyl titanates and 5.0 gram anhydrous isopropyl alcohols lentamente, the gained mixture was stirred 3 hours down at 75 ℃, obtain the clear colloid.This colloid is put into the stainless steel sealed reactor, and constant temperature was placed 3 days under 170 ℃ temperature, obtained the mixture of crystallization product; This mixture is filtered, washes with water, and, obtain the former powder of TS-1 in 110 ℃ of dryings 60 minutes.With the former powder of this TS-1 in 550 ℃ of roasting temperatures 3 hours, the TS-1 molecular sieve.
Comparative Examples 2
According to document (Corma A. etc., J.Chem.Soc.Chem.Commun., 1994,147-148) the synthetic silicon titanium feed ratio of method is 50 Ti-MCM-41.
Comparative Examples 3
According to document (CN1226187C) embodiment 1 synthesizing titanium-containing meso-porous molecular sieve material.
Embodiment 1
Earlier positive tetraethyl orthosilicate of 30 grams and an amount of tetrabutyl titanate are joined respectively in the aqueous solution of TPAOH, make it to mix two kinds of solution of formation at normal pressure and 40 ℃ of following ultrasonic agitation, join after above-mentioned two kinds of solution are mixed and continue ultrasonic agitation in the aqueous solution of cetyl trimethylammonium bromide and make it to mix, the mol ratio of wherein positive tetraethyl orthosilicate, tetrabutyl titanate, TPAOH, cetyl trimethylammonium bromide and water is 1: 0.02: 0.4: 0.05: 25; Above-mentioned system is transferred in the stainless steel sealed reactor, first crystallization 5 hours under 100 ℃ temperature and autogenous pressure, crystallization 48 hours under 140 ℃ temperature and autogenous pressure again, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ of roasting temperatures 3 hours, obtain titanium silicalite material sample A then.
The XRD crystalline phase figure of sample A as shown in Figure 1, the fourier infrared spectrogram is as shown in Figure 2, and is visible-UV spectrum is as shown in Figure 3.
Among XRD crystalline phase Fig. 1 Small angle promptly 2 θ 2.3 °, 4.0 ° and 4.6 ° of vicinity diffraction peak is arranged, show that sample has the two-dimentional hexagonal mesoporous structure of similar MCM-41.
Sample is at 960cm in the fourier infrared spectrogram 2
-1The unexistent charateristic avsorption band of total silicon molecular sieve appears in the vicinity, is the feature of skeleton titanium, shows that titanium has entered the sample skeleton.
As seen-UV spectrum Fig. 3 in absorption about 220nm be the feature of four-coordination Ti, absorption band does not appear near 340nm, the Ti among the interpret sample A is nearly all on skeleton.
Earlier positive tetraethyl orthosilicate of 30 grams and an amount of metatitanic acid orthocarbonate are joined respectively in the aqueous solution of diethanolamine, make it to mix two kinds of solution of formation at normal pressure and 60 ℃ of following ultrasonic agitation, join after above-mentioned two kinds of solution are mixed and continue ultrasonic agitation in the aqueous solution of cetyl trimethylammonium bromide and make it to mix, the mol ratio of wherein positive tetraethyl orthosilicate, metatitanic acid orthocarbonate, diethanolamine, cetyl trimethylammonium bromide and water is 1: 0.08: 0.2: 0.2: 180.This mixed solution is put into the stainless steel sealed reactor, and crystallization is 48 hours under 120 ℃ temperature and autogenous pressure, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ of roasting temperatures 3 hours, obtains titanium silicalite material B then.This sample characterizes consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment 1 sample A through X-ray diffraction, Fourier infrared spectrum and visible-UV spectrum.
Earlier positive quanmethyl silicate of 30 grams and an amount of tetrabutyl titanate are joined respectively in the aqueous solution of TPAOH, ultrasonic agitation makes it to mix two kinds of solution of formation, join after above-mentioned two kinds of solution are mixed and continue ultrasonic agitation in the aqueous solution of Tetradecyl Trimethyl Ammonium Bromide and make it to mix, the mol ratio of wherein positive quanmethyl silicate, tetrabutyl titanate, TPAOH, Tetradecyl Trimethyl Ammonium Bromide and water is 1: 0.4: 0.1: 0.1: 130.This mixed solution is put into the stainless steel sealed reactor, first crystallization 5 hours under 80 ℃ temperature and autogenous pressure, crystallization 24 hours under 160 ℃ temperature and autogenous pressure again, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ of roasting temperatures 3 hours, obtain titanium silicalite material C then.This sample characterizes consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment 1 sample A through X-ray diffraction, Fourier infrared spectrum and visible-UV spectrum.
Earlier positive silicic acid orthocarbonate of 30 grams and an amount of tetrabutyl titanate are joined respectively in the aqueous solution of n-Butyl Amine 99, ultrasonic agitation makes it to mix two kinds of solution of formation, join after above-mentioned two kinds of solution are mixed and continue ultrasonic agitation in the aqueous solution of cetyl trimethylammonium bromide and make it to mix, the mol ratio of wherein positive silicic acid orthocarbonate, tetrabutyl titanate, n-Butyl Amine 99, cetyl trimethylammonium bromide and water is 1: 0.2: 0.45: 0.5: 90.This mixed solution is put into the stainless steel sealed reactor, first crystallization 5 hours under 100 ℃ temperature and autogenous pressure, crystallization 24 hours under 160 ℃ temperature and autogenous pressure again, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ of roasting temperatures 3 hours, obtain titanium silicalite material D then.This sample characterizes consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment 1 sample A through X-ray diffraction, Fourier infrared spectrum and visible-UV spectrum.
Earlier positive tetraethyl orthosilicate of 30 grams and an amount of tetrabutyl titanate are joined respectively in the aqueous solution of hexanediamine, ultrasonic agitation makes it to mix two kinds of solution of formation, join after above-mentioned two kinds of solution are mixed and continue ultrasonic agitation in the aqueous solution of cetyl trimethylammonium bromide and make it to mix, the mol ratio of wherein positive tetraethyl orthosilicate, tetrabutyl titanate, hexanediamine, cetyl trimethylammonium bromide and water is 1: 0.32: 0.75: 0.31: 60.This mixed solution is put into the stainless steel sealed reactor, and crystallization is 72 hours under 120 ℃ temperature and autogenous pressure, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ of roasting temperatures 3 hours, obtains titanium silicalite material E then.This sample characterizes consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment 1 sample A through X-ray diffraction, Fourier infrared spectrum and visible-UV spectrum.
The method gained sample of present embodiment explanation the inventive method and Comparative Examples is used for the effect of the catalytic oxidation of phenol hydroxylation.
The sample that the foregoing description and Comparative Examples is prepared is according to sample: phenol: the weight ratio of acetone=1: 25.0: 15.0 mixes in a there-necked flask that has a prolong, be warming up to 80 ℃, then under whipped state according to phenol: it is 27.5% hydrogen peroxide that the weight ratio of hydrogen peroxide=1: 0.35 adds mass percentage concentration, reaction is 6 hours under this temperature, products therefrom uses the 0V-101 capillary column on the Varian3400 chromatographic instrument (30m * 0.25mm) measure each product to distribute the results are shown in Table 1.
In table 1:
Table 1
| Title | Phenol conversion % | Product distribution % | ||
| Pyrocatechol | Resorcinol | Benzoquinones | ||
| Embodiment 1 | 18.86 | 48.12 | 44.53 | 7.35 |
| |
17.23 | 47.32 | 44.62 | 8.06 |
| |
16.14 | 46.59 | 45.04 | 8.37 |
| |
17.22 | 45.13 | 46.55 | 8.32 |
| |
16.95 | 45.75 | 45.98 | 8.27 |
| Comparative Examples 1 | 13.09 | 44.88 | 45.15 | 9.97 |
| Comparative Examples 2 | 7.42 | 38.30 | 50.39 | 11.31 |
| Comparative Examples 3 | 11.38 | 43.82 | 47.22 | 8.96 |
As can be seen from Table 1: titanium silicalite material provided by the invention, catalytic effect is significantly better than the molecular sieve of single structure.
The method gained sieve sample of present embodiment explanation the inventive method and Comparative Examples is used for 2,3, the effect of the catalytic oxidation of 6-pseudocuminol hydroxylation reaction.
2,3,6-pseudocuminol hydroxylation reaction is in carrying out in a volume is 30 milliliters the reactor that has circulator bath cover under 80 ℃, the catalyst sample consumption is 0.25 gram, 0.146 2,3 of mole, the 6-pseudocuminol is dissolved in 10 milliliters of acetonitriles, the dilute hydrogen peroxide that disposable adding is 0.055 mole, magnetic agitation reaction extract supernatant liquor and carry out result's test after centrifugal after 3 hours.Product Agilent GC-6890N type gas chromatograph and the HP-5 chromatogram column analysis that has thermal conductance and hydrogen flame dual-detector.The results are shown in Table 2.
In table 2:
Table 2
| Title | Phenol transformation efficiency % | Quinone selectivity % |
| Embodiment 1 | 20.6 | 84 |
| |
19.8 | 86 |
| |
19.3 | 85 |
| |
16.6 | 88 |
| |
15.1 | 83 |
| Comparative Examples 1 | 1.6 | 75 |
| Comparative Examples 2 | 3.4 | 77 |
| Comparative Examples 3 | 8.1 | 81 |
As can be seen from Table 2: the inventive method synthetic titanium silicalite material catalytic effect is significantly better than the molecular sieve of single structure, and under the slightly high situation of quinone selectivity, its transformation efficiency is improved largely.
Claims (16)
1. synthetic method with titanium silicalite material of mesoporous and microvoid structure, it is characterized in that under ultrasonic agitation, respectively titanium source and silicon source are joined and mix the back in the aqueous solution of organo-alkali compound and form two kinds of solution, then above-mentioned two kinds of solution are mixed under ultrasonic agitation, aqueous solution ultrasonic agitation with tensio-active agent mixes again, obtain mole and consist of the silicon source: titanium source: organo-alkali compound: tensio-active agent: water=1: (0.001-0.5): (0.05-0.8): (0.05-0.5): mixture (5-200), with mixture hydrothermal crystallizing in sealed reactor, and reclaim and to obtain titanium silicalite material, said silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, said titanium silicalite material, in its X-ray diffraction spectrogram near 2 θ are 2.3 °, near 4.0 °, there is diffraction peak 4.6 ° of vicinity, in its infrared spectrum, at wave number 550cm
-1And 960cm
-1Near have absorption band, near wavelength is 220nm, absorption band is arranged in its ultraviolet-visible spectrum.
2. according to the process of claim 1 wherein, said silicon source is selected from silica gel, silicon sol, water glass or soft silica; Perhaps being selected from general formula is R
1 4SiO
4The organosilicon acid esters, R
1For having the alkyl of 1-4 carbon atom.
3. according to the process of claim 1 wherein, said titanium source is selected from TiX
4, TiX
3, TiOX
2Or Ti (SO
4)
2, X represents halogen; Perhaps being selected from general formula is R
2 4TiO
4Organic titanate, R
2For having the alkyl of 1-6 carbon atom.
4. according to the method for claim 3, wherein, said halogen is a chlorine.
5. according to the method for claim 3, wherein, R
2For having the alkyl of 2-4 carbon atom.
6. according to the method for claim 1, it is characterized in that said silicon source is that organosilicon acid esters, titanium source are organic titanate.
7. according to the method for claim 1, it is characterized in that it is (R that said tensio-active agent is selected from general formula
3R
4NR
5R
6)
+X
-Quaternary ammonium salt surface active agent, wherein X represents halogen, R
3, R
4And R
5Be the alkyl that is less than 3 carbon atoms, R
3, R
4And R
5Carbonatoms identical or different, R
6For having the alkyl that is no less than 12 carbon atoms.
8. according to the method for claim 7, wherein, R
6For having the alkyl of 12-22 carbon atom.
9. according to the method for claim 7, wherein said quaternary ammonium salt surface active agent is Tetradecyl Trimethyl Ammonium Bromide or cetyl trimethylammonium bromide.
10. according to the method for claim 1, it is characterized in that the mixture that said organo-alkali compound is selected from quaternary ammonium hydroxide compounds, fat amine compound, alcamine compound or is made up of them.
11. according to the method for claim 10, wherein, the general formula of fat amine compound is R
7(NH
2)
n, R
7Be selected from alkyl or alkylidene group, n=1 or 2 with 1-6 carbon atom.
12. according to the method for claim 10, wherein, fat amine compound is selected from ethamine, n-Butyl Amine 99, butanediamine or hexanediamine.
13. according to the method for claim 10, wherein, the general formula of alcamine compound is (HOR
8)
mNH
(3-m), R
8Be selected from alkyl, m=1,2 or 3 with 1-4 carbon atom.
14. according to the method for claim 10, wherein, alcamine compound is selected from monoethanolamine, diethanolamine or trolamine.
15. according to the method for claim 10, wherein, the general formula of quaternary ammonium hydroxide compounds is (R
9)
4NOH, R
9For having the alkyl of 1-4 carbon atom.
16. according to the method for claim 10, wherein, said quaternary ammonium hydroxide compounds is a TPAOH.
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