CN101497450B - Method for preparing titanium-containing mesoporous material - Google Patents
Method for preparing titanium-containing mesoporous material Download PDFInfo
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- CN101497450B CN101497450B CN 200810057265 CN200810057265A CN101497450B CN 101497450 B CN101497450 B CN 101497450B CN 200810057265 CN200810057265 CN 200810057265 CN 200810057265 A CN200810057265 A CN 200810057265A CN 101497450 B CN101497450 B CN 101497450B
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Abstract
The invention discloses a method for preparing a mesoporous material containing titanium, which is characterized in that a silicon source and a titanium source are mixed evenly and then are added into a water solution consisting of an organo-alkali compound and a surfactant, and the mixture is subjected to ultrasonic stirring to ensure that the mixture is mixed evenly; and the obtained mixture is treated under hydrothermal crystallization conditions, and a product is recovered. The mesoporous material containing the titanium prepared by the method has good catalytic oxidation function, and particularly has better effect on reactions that macromolecules take part in.
Description
Technical field
The invention relates to a kind of method for preparing titanium-containing materials, is the method for preparing titanium-containing mesoporous material about a kind of furtherly.
Background technology
HTS is the novel hetero-atom molecular-sieve that last century, early eighties began to develop, and the Ti-ZSM-5 that has synthesized at present the MFI structure is TS-1, the TS-2 of MEL 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.TS-1 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 Ti-ZSM-5 has micropore (about 0.55 nanometer) structure, and big organic molecule is difficult to spread therein and by catalyzed oxidation, makes its good catalytic oxidation performance be difficult in more wide field especially biological and bring into play in medicine macromole field.
The Mobil company reported first of the U.S. meso-porous molecular sieve material and the synthetic method thereof of M41S series, the M41S series material has homogeneous granules degree and regular meso-hole structure, attracted the very big concern of relevant academia, this material is that hope has been brought in aspects such as macromolecular catalysis, separation.Wherein representational 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) titanium was 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, and hydrothermal stability and hydrophobic nature all are weaker than crystalline HTS (TS-1).Be in the oxidizing reaction of oxygenant with the aqueous hydrogen peroxide solution, the catalytic activity of Ti-MCM-41 is lower, has greatly limited its application (MicroporousMaterials, 1997,9:173 and Stud.Surf.Sci.Catal., 1995).
CN1552626A has reported HTS matrix material with above-mentioned two kinds of structures and preparation method thereof, though matrix material has certain catalytic activity, but the subject matter that exists is that the duct size is single, preparation process is comparatively numerous and diverse, and environment and cost burden are arranged.
Summary of the invention
The objective of the invention is deficiency, a kind of method for preparing titanium-containing mesoporous material is provided at existing preparation titanium-containing mesoporous material method.This preparation 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, and catalytic oxidation activity can increase substantially.
Titanium-containing mesoporous material is different from other pure silicon molecular screen material or Si-Al molecular sieve material, and the titanium source easily generates TiO in the preparation process from reuniting
2, produce extra-framework titanium, therefore becoming the polymerization that prevents titanium in the glue process is that titanium-containing meso-porous molecular sieve material prepares key of success.
Therefore, the method for preparing titanium-containing mesoporous material provided by the invention, it is characterized in that earlier silicon source and titanium source being mixed, join then that ultrasonic agitation makes it to mix in the aqueous solution that organo-alkali compound and tensio-active agent form, the gained mixture is handled under the hydrothermal crystallizing condition, and recovery product, the mixture mole consists of the silicon source: titanium source: organic bases: tensio-active agent: water=1: (0.0005-0.5): (0.05-0.2): (0.005-0.2): (5-200), said silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter.
The resulting titanium-containing meso-porous molecular sieve material of preparation method provided by the invention, the feature that has similar mesoporous MCM-41 and part micropore Ti-ZSM-5 simultaneously, specifically in the X-ray diffraction spectrogram of this 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 illustrate its have the feature of ZSM-5 (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 to make it mixing, promptly utilizes the synthetic technology that ultransonic cavatition and mechanical stirring merge mutually to make it mixing.
Among the preparation method provided by the invention, said mixture is in mole, the silicon source: titanium source: organic bases: tensio-active agent: water is preferably 1: (0.001-0.2): (0.05-0.2): (0.01-0.1): (5-200), more preferably 1: (0.005-0.2): (0.05-0.1): (0.01-0.1): (20-150), wherein said silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter.
Among the preparation method provided by the present 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 other various forms of amorphous silicas; 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 present 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, and preferred chlorine is as TiCl
4, TiCl
3, TiOCl
2Deng; It is R that said organic titanium source is selected from general formula
2 4TiO
4Organic titanate, R wherein
2For having the alkyl of 1-4 carbon atom.
In the method provided by the invention, said tensio-active agent is meant cats product.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, more preferably 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.
Wherein said its general formula of fat amine compound is R
7(NH
2)
n, R wherein
7Be alkyl or alkylidene group with 1-6 carbon atom, n=1 or 2, wherein preferred fat amine compound is ethamine, n-Butyl Amine 99, butanediamine or hexanediamine.
Its general formula of said alcamine compound is (HOR
8)
mH
(3-m)R wherein
8For having the alkylidene group of 1-4 carbon atom; M=1-3; Wherein preferred alcamine compound is monoethanolamine, diethanolamine or trolamine.
Said its general formula of quaternary ammonium hydroxide compounds is (R
9)
4NOH, wherein R
9For having the alkyl of 1-4 carbon atom, preferred propyl group.
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.The process of said 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.
Preparation method provided by the invention is earlier silicon source and titanium source proportionally to be mixed, and utilizes the silicon source with the titanium source diluting on the one hand, without materials such as other unnecessary solvents such as hydrochloric acid, Virahol, reduces cost and environmental pressure; On the other hand, earlier with silicon source and titanium source mixing, can make in the hydrolyzed solution that obtains after the hydrolysis titanium, the silicon more homogeneous that distributes.Method provided by the invention is also with the partial concn inequality in the ultrasonic agitation technology elimination building-up process, the TiO that makes the titanium source reunite and generate
2Few as far as possible, reduce the generation of extra-framework titanium.Since ultrasonic agitation impel silicon source and titanium source with organic bases, tensio-active agent is better combines, and makes organic bases, tensio-active agent better play the effect of template and structure directing, has reduced organic bases, template agent, has reduced synthetic cost.
The titanium-containing mesoporous material of method preparation provided by the invention has good catalyzed oxidation function, and is better to the reaction effect of macromole participation especially, illustrates that also Ti has entered skeleton and embodied the reaction properties that mesoporous catalysis macromole participates in.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of the titanium-containing mesoporous material of preparation among the embodiment 1.
Fig. 2 is the nitrogen adsorption isotherm figure of the titanium-containing mesoporous material of preparation among the embodiment 1.
Fig. 3 is the pore distribution curve figure of the titanium-containing mesoporous material of preparation among the embodiment 1.
Fig. 4 is the infrared absorption spectrum spectrogram of the titanium-containing mesoporous material of preparation among the embodiment 1.
Fig. 5 is the uv-visible absorption spectra spectrogram of the titanium-containing mesoporous material of preparation among the embodiment 1.
Embodiment
Following embodiment will the present invention is further illustrated, but therefore do not limit the present invention.
The reagent that all are used among the embodiment is commercially available chemically pure reagent.
Used ultrasonoscope is KQ-100DE type numerical control supersonic cleanser (220 volts of working powers, 50 hertz that Kunshan Ultrasonic Instruments Co., Ltd. produces among the embodiment; 40 kilo hertzs of operating frequencies; 100 watts of ultrasonic electric power).
The X-ray diffraction of embodiment 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 °-6 °.
The adsorption-desorption isothermal curve of the low temperature nitrogen absorption of sample is to measure according to ASTM D4222-98 standard method on the static n2 absorption apparatus of the ASAP2405 of U.S. Micromeritics company.
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 400-1600cm 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 J.C.Jansen etc., Zeolite, 1984, the synthetic Ti-ZSM-5 of 4:369 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, placed 3 days, obtain the mixture of crystallization product at 170 ℃ of following constant temperature; This mixture is filtered, washes with water, and, obtain the former powder of TS-1 in 110 ℃ of dryings 60 minutes.The former powder of this TS-1 in 550 ℃ of roastings 3 hours, is got 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 CN1552626A embodiment 1 synthesizing titanium-containing meso-porous molecular sieve material.
Earlier 26 positive tetraethyl orthosilicates of gram and tetrabutyl titanate are mixed, then mixed solution is joined in the aqueous solution that TPAOH and cetyl trimethylammonium bromide form, make it to mix at normal pressure and 40 ℃ of following ultrasonic agitation, the mol ratio of wherein positive tetraethyl orthosilicate, tetrabutyl titanate, TPAOH, cetyl trimethylammonium bromide and water is 1: 0.02: 0.05: 0.05: 25; Above-mentioned system is transferred in the stainless steel sealed reactor, first crystallization 5 hours under 100 ℃ and autogenous pressure, crystallization 48 hours under 140 ℃ and autogenous pressure again, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ of following roastings 3 hours, obtain titanium-containing mesoporous material sample A then.
The XRD crystalline phase figure of sample A as shown in Figure 1, nitrogen adsorption isotherm as shown in Figure 2, pore distribution curve as shown in Figure 3, the fourier infrared spectrogram is as shown in Figure 4, and is visible-UV spectrum is as shown in Figure 5.
In Fig. 1 XRD crystalline phase Small angle promptly 2 θ 2.3 °, 4.0 ° and 4.6 ° of vicinity diffraction peak is arranged, show that this sample has the two-dimentional hexagonal mesoporous structure of similar MCM-41.
Fig. 2 nitrogen adsorption isotherm and Fig. 3 pore distribution curve further specify the feature that sample A has similar Ti-MCM-41, p/p among Fig. 2
0Value is that near the hop correspondence 0.4 pore size distribution about 2.4nm among Fig. 3, among Fig. 3 about 0.37nm narrower pore size distribution interpret sample have the feature of similar micropore ZSM-5 simultaneously.
Sample is at 960cm in Fig. 4 fourier infrared spectrum
-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.
Fig. 5 is visible-UV spectrum 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 26 positive tetraethyl orthosilicates of gram and metatitanic acid orthocarbonate are mixed, again mixed solution is joined in the mixed aqueous solution of tensio-active agent by cetyl trimethylammonium bromide, TPAOH and butanediamine, make it to mix at normal pressure and 50 ℃ of following ultrasonic agitation, the mol ratio of wherein positive tetraethyl orthosilicate, metatitanic acid orthocarbonate, TPAOH, butanediamine, tensio-active agent and water is 1: 0.08: 0.04: 0.04: 0.1: 45.This mixed solution is put into the stainless steel sealed reactor, and crystallization is 48 hours under 120 ℃ and autogenous pressure, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, then 550 ℃ of roastings 3 hours, obtain titanium-containing mesoporous material sample B.
Sample B is through X-ray diffraction, Fourier infrared spectrum and visible-signs such as UV spectrum are consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment 1 sample A.
Earlier with 26 positive quanmethyl silicate of gram and TiCl
4Mix, then mixed solution is joined in the aqueous solution that TPAOH and cetyl trimethylammonium bromide form, make it to mix, wherein positive quanmethyl silicate, TiCl at normal pressure and 40 ℃ of following ultrasonic agitation
4, TPAOH, tensio-active agent and water mol ratio be 1: 0.08: 0.06: 0.01: 125.This mixed solution is put into the stainless steel sealed reactor, first crystallization 5 hours under 100 ℃ and autogenous pressure, crystallization 24 hours under 160 ℃ and autogenous pressure again, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ of roastings 3 hours, obtain titanium-containing mesoporous material sample C then.
Sample C is through X-ray diffraction, Fourier infrared spectrum and visible-signs such as UV spectrum are consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment 1 sample A.
Embodiment 4
Earlier with 26 positive tetraethyl orthosilicate of gram and TiOCl
2Mix, then mixed solution is joined in the aqueous solution that TPAOH, diethanolamine and cetyl trimethylammonium bromide form, make it to mix, wherein positive tetraethyl orthosilicate, TiOCl at normal pressure and 60 ℃ of following ultrasonic agitation
2, TPAOH, diethanolamine, tensio-active agent and water mol ratio be 1: 0.18: 0.03: 0.01: 0.1: 85.This mixed solution is put into the stainless steel sealed reactor, first crystallization 5 hours under 120 ℃ and autogenous pressure, crystallization 24 hours under 180 ℃ and autogenous pressure again, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ of roastings 3 hours, obtain titanium-containing mesoporous material sample D then.
Sample D is through X-ray diffraction, Fourier infrared spectrum and visible-signs such as UV spectrum are consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment 1 sample A.
Embodiment 5
Earlier 26 positive tetraethyl orthosilicates of gram and tetrabutyl titanate are mixed, then mixed solution is joined in the aqueous solution that TPAOH and cetyl trimethylammonium bromide form, make it to mix at normal pressure and 40 ℃ of following ultrasonic agitation, the mol ratio of wherein positive tetraethyl orthosilicate, tetrabutyl titanate, TPAOH, tensio-active agent and water is 1: 0.12: 0.05: 0.01: 100.This mixed solution is put into the stainless steel sealed reactor, and crystallization is 24 hours under 160 ℃ and autogenous pressure, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, then 550 ℃ of roastings 3 hours, obtain titanium-containing mesoporous material sample E.
Sample E is through X-ray diffraction, Fourier infrared spectrum and visible-signs such as UV spectrum are consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment 1 sample A.
Comparative Examples 4
The sample of the method preparation of this Comparative Examples explanation Comparative Examples 1-3 is used for the effect of phenol hydroxylation reaction.
The comparative sample that above-mentioned Comparative Examples 1-3 is prepared is according to sample: phenol: the weight ratio of acetone=1: 25: 15 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, and products therefrom uses 0V-101 capillary column (30m * 0.25mm) measure each product to distribute on the Varian3400 chromatographic instrument.
The results are shown in Table 1.
In table 1:
The sample A-E of present embodiment explanation the inventive method preparation is used for the effect of phenol hydroxylation reaction.Reaction process the results are shown in Table 1 with Comparative Examples 4.
Table 1
| Numbering | Phenol conversion % | Product distribution % | ||
| Pyrocatechol | | Benzoquinones | ||
| Embodiment | ||||
| 1 | 19.5 | 46.3 | 45.5 | 8.2 |
| |
17.7 | 46.1 | 45.4 | 8.5 |
| |
17.8 | 46.0 | 45.4 | 8.6 |
| Embodiment 4 | 17.1 | 45.4 | 46.3 | 8.3 |
| Embodiment 5 | 18.2 | 46.7 | 45.2 | 8.1 |
| Comparative Examples 1 | 13.1 | 44.9 | 45.2 | 9.9 |
| Comparative Examples 2 | 7.4 | 38.3 | 50.4 | 11.3 |
| Comparative Examples 3 | 11.4 | 43.8 | 47.3 | 8.9 |
Comparative Examples 5
The method gained sieve sample of this Comparative Examples explanation Comparative Examples 1-3 is used for the effect of 2,6 di t butyl phenol oxidizing reaction.
In being housed, the there-necked flask of reflux exchanger adds 2.0 grams 2; 6-DI-tert-butylphenol compounds, 10.0 gram solvent acetonitriles, 3.50 gram mass marks are 27.5% aqueous hydrogen peroxide solution and 0.05 gram catalyzer; 75 ℃ were reacted 2 hours down under nitrogen protection, and products therefrom uses 0V-101 capillary column (30m * 0.25mm) measure each product to distribute on Agilent6890N type gas chromatograph.
The results are shown in Table 2.In table 2:
Embodiment 7
Present embodiment explanation the inventive method gained sieve sample A-E is used for the effect of 2,6 di t butyl phenol oxidizing reaction.
Reaction method is with Comparative Examples 5.The results are shown in Table 2.
Table 2
| Numbering | Phenol transformation efficiency % | Quinone |
| Embodiment | ||
| 1 | 87.7 | 94 |
| |
74.8 | 92 |
| |
63.2 | 87 |
| Embodiment 4 | 74.3 | 86 |
| Embodiment 5 | 83.7 | 95 |
| Comparative Examples 1 | 3.8 | 73 |
| Comparative Examples 2 | 17.1 | 71 |
| Comparative Examples 3 | 19.4 | 80 |
As can be seen from Table 2: matrix material catalytic effect provided by the invention is significantly better than the molecular sieve of single structure, and under the suitable situation of selectivity, its transformation efficiency is improved largely.
Claims (17)
1. method for preparing titanium-containing mesoporous material, it is characterized in that earlier silicon source and titanium source being mixed, join then that ultrasonic agitation makes it to mix in the aqueous solution that organo-alkali compound and tensio-active agent form, the gained mixture is handled under the hydrothermal crystallizing condition, and recovery product, the mixture mole consists of the silicon source: titanium source: organic bases: tensio-active agent: water=1: (0.0005-0.5): (0.05-0.2): (0.005-0.2): (5-200), said silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, in its X-ray diffraction spectrogram of said product 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.
2. according to the process of claim 1 wherein that the mixture mole consists of the silicon source: titanium source: organo-alkali compound: tensio-active agent: water=1: (0.001-0.2): (0.05-0.2): (0.01-0.1): (5-200).
3. according to the process of claim 1 wherein that the mixture mole consists of the silicon source: titanium source: organo-alkali compound: tensio-active agent: water=1: (0.005-0.2): (0.05-0.1): (0.01-0.1): (20-150).
4. according to the process of claim 1 wherein that said silicon source is silica gel, silicon sol or organosilicon acid esters, said its general formula of organosilicon acid esters is R
1 4SiO
4, R wherein
1Be selected from alkyl with 1-4 carbon atom.
5. according to the process of claim 1 wherein that said titanium source is inorganic ti sources or organic titanate, said inorganic ti sources is TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2, its general formula of said organic titanate is R
2 4TiO
4, R wherein
2Be selected from alkyl with 1-6 carbon atom.
6. according to the method for claim 5, R wherein
2Be selected from alkyl with 2-4 carbon atom.
7. according to the process of claim 1 wherein that said tensio-active agent is a cats product.
8. according to the method for claim 7, said cats product is that general 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 identical or different, R
6For having the alkyl that is no less than 12 carbon atoms.
9. according to the method for claim 8, said R
6Alkyl for 12-22 carbon atom.
10. according to the method for claim 8, said cats product is Tetradecyl Trimethyl Ammonium Bromide or cetyl trimethylammonium bromide.
11. according to the process of claim 1 wherein that said organo-alkali compound is TPAOH, fat amine compound, alcamine compound or the mixture be made up of them.
12. according to the method for claim 11, its general formula of said fat amine compound is R
7(NH
2)
n, R wherein
7Be selected from alkyl or alkylidene group, n=1 or 2 with 1-6 carbon atom.
13. according to the method for claim 11, said fat amine compound is ethamine, n-Butyl Amine 99, butanediamine or hexanediamine.
14. according to the method for claim 11, its general formula of said alcamine compound is (HOR
8)
mNH
(3-m), R wherein
8Be selected from alkylidene group, m=1,2 or 3 with 1-4 carbon atom.
15. according to the method for claim 11, said alcamine compound is monoethanolamine, diethanolamine or trolamine.
16. according to the method for claim 1, said hydrothermal crystallizing is to handle 2-360 hour under the autogenous pressure in 20-190 ℃ of encloses container.
17. according to the method for claim 1, said hydrothermal crystallizing be earlier 60-120 ℃ pre-crystallization 0.5-10 hour down, and then 80-180 ℃ of following crystallization 1 hour to 10 days.
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| CN104418355B (en) * | 2013-09-09 | 2016-06-22 | 中国石油化工股份有限公司 | A kind of mesoporous titanium-silicon material and synthetic method thereof |
| CN104418344B (en) * | 2013-09-09 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of synthetic method of total silicon mesoporous material |
| CN105084382B (en) * | 2014-05-08 | 2017-09-26 | 中国石油化工股份有限公司 | A kind of mesoporous titanium-silicon material and its synthetic method |
| CN104495867B (en) * | 2014-11-28 | 2017-10-20 | 巨化集团技术中心 | The preparation method of big particle diameter HTS |
| CN104495868B (en) * | 2014-11-28 | 2017-12-22 | 巨化集团技术中心 | A kind of preparation method of big particle diameter HTS |
| CN115363049A (en) * | 2022-06-17 | 2022-11-22 | 苏州京程材料有限公司 | Preparation method of nano composite material and product thereof |
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| CN1428296A (en) * | 2001-12-28 | 2003-07-09 | 中国科学院大连化学物理研究所 | Method for synthesizing new titanium-silicone metapore molecular sieve |
| CN1751993A (en) * | 2005-07-28 | 2006-03-29 | 复旦大学 | Titanium bearing mesohole molecular sieve and its preparation method |
| CN101012063A (en) * | 2007-02-07 | 2007-08-08 | 中国日用化学工业研究院 | Method for preparing titanium-containing molecular sieve |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1428296A (en) * | 2001-12-28 | 2003-07-09 | 中国科学院大连化学物理研究所 | Method for synthesizing new titanium-silicone metapore molecular sieve |
| CN1751993A (en) * | 2005-07-28 | 2006-03-29 | 复旦大学 | Titanium bearing mesohole molecular sieve and its preparation method |
| CN101012063A (en) * | 2007-02-07 | 2007-08-08 | 中国日用化学工业研究院 | Method for preparing titanium-containing molecular sieve |
Non-Patent Citations (1)
| Title |
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| 史春风等.超声辅助合成钛硅分子筛.《分子催化》.2007,第21卷第MC157-MC158页. * |
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