CN101519213A - Synthetic method of titanium-containing mesoporous materials - Google Patents
Synthetic method of titanium-containing mesoporous materials Download PDFInfo
- Publication number
- CN101519213A CN101519213A CN 200810101123 CN200810101123A CN101519213A CN 101519213 A CN101519213 A CN 101519213A CN 200810101123 CN200810101123 CN 200810101123 CN 200810101123 A CN200810101123 A CN 200810101123A CN 101519213 A CN101519213 A CN 101519213A
- Authority
- CN
- China
- Prior art keywords
- titanium
- alkyl
- active agent
- mixture
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a synthetic method of titanium-containing mesoporous materials, which is characterized by comprising the following steps of: adding a silicon source to the water solution of an organo-alkali compound in a dropping manner under the ultrasonic agitation; after homogeneous mixing, adding a titanium source to the mixture; after the hydrolysis is completed, mixing the obtained mixture with the water solution of a surface active agent to obtain a mixture with the mole ratio of silicon source: titanium source: organic base: surface active agent: water=1:(0.001-0.5) :(0.05-0.8) :(0.01-0.5) :(5-250); putting the mixture into a sealed reaction kettle for hydrothermal crystallization; and then collecting the obtained titanium-containing mesoporous material. The titanium-containing mesoporous material synthesized by the method has good catalytic oxidation function and better effect on the reactions in the presence of large molecules.
Description
Technical field
The invention relates to a kind of synthetic method of inorganic materials, further say so about a kind of synthetic method of titanium-containing mesoporous material.
Background technology
HTS is the novel molecular sieve that contains the heteroatoms titanium 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.Wherein 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 only has micropore (about 0.55 nanometer) structure, 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 biological and bring into play in medicine macromole field, and then impel people to research and develop the more wide-aperture titanium-containing molecular sieve material of preparation.
The Mobil company reported first of the U.S. 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.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) 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.In recent years, the research of this respect has become one of hot research problem.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 preparation process 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 of titanium-containing mesoporous material is provided at existing synthesizing titanium-containing mesoporous material aspect.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 that synthesizes have good catalyzed oxidation function, better to the reaction effect of macromole participation especially.
Therefore, synthetic method provided by the invention, it is characterized in that under ultrasonic agitation, the silicon source is added drop-wise to mix in the aqueous solution of organo-alkali compound after, add the titanium source again, after treating hydrolysis fully, aqueous solution with tensio-active agent is even again, 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): (0.01-0.5): mixture (5-250), with mixture at the sealed reactor hydrothermal crystallizing, and reclaim and to obtain mesoporous titanium-containing materials, said silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, in its X-ray diffraction spectrogram of said mesoporous titanium-silicon material 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 resulting titanium-containing mesoporous material of the inventive method, it is characterized in that having simultaneously the feature of similar mesoporous MCM-41 and part micropore Ti-ZSM-5, 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, add bright its have ZSM-5 feature (J.C.Jansen etc., Zeolite, 1984,4:369), 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 the ultraviolet-visible spectrum, illustrate that also Ti has entered skeleton.
In synthetic method provided by the invention, said ultrasonic agitation mixing is meant and utilizes ultrasonic wave and mechanical stirring, promptly utilizes the synthetic technology that ultransonic cavatition and mechanical stirring merge mutually to make raw material mix uniform technology.
In the method provided by the invention, said mixture is in mole, silicon source: titanium source: organic bases: tensio-active agent: water=1:(0.001-0.5): (0.05-0.8): (0.01-0.5): (5-200), preferred 1:(0.005-0.5): (0.05-0.5): (0.05-0.5): (20-180), wherein said silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter.
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 the synthetic 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; The preferred organic silicon ester in said organosilicon source, general formula is R
1 4SiO
4, R
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, preferred chlorine; It is R that said organic titanium source is selected from general formula
2 4TiO
4Organic titanate, R
2For having the alkyl of 1-4 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 quaternary ammonium salt surface 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 ammonium hydroxide 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.
Its general formula of said 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, preferred fat amine compound is ethamine, n-Butyl Amine 99, butanediamine or hexanediamine.
Its 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.
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 quaternary ammonium hydroxide compounds is a TPAOH.
In method provided by the invention, the process of said recovery product is meant the washing of crystallization product, drying and roasting process.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, earlier with the hydrolysis of silicon source, with hydrolysis titanium source hydrolysis faster, helps the better combination of silicon and titanium again, and introduce tensio-active agent in the back fully, make the more even of silicon and titanium species distribution in silicon source and the hydrolysis of titanium source.
2, 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 template agent, has reduced synthetic cost; Simultaneously, the ultrasonic agitation technology is eliminated the partial concn inequality in the 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.
3, in the building-up process without other raw materials such as hydrochloric acid, Virahols, reduce cost and environmental pressure.
4, synthesize titanium-containing materials have good catalyzed oxidation function, its catalytic oxidation activity and selectivity compared with prior art obviously improve, better to the reaction effect of macromole participation especially, illustrate 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 synthetic titanium-containing mesoporous material among the embodiment 1.
Fig. 2 is the infrared absorption spectrum spectrogram of synthetic titanium-containing mesoporous material among the embodiment 1.
Fig. 3 is the uv-visible absorption spectra spectrogram of synthetic titanium-containing mesoporous 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, and used ultrasonic wave 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 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
, tube voltage 40kV, tube current 40mA, 0.25 °/min of sweep velocity, sweep limit 2 θ=1.5 °-10 °; Fourier infrared (FT-IR) spectrogram is measured on Nicolet8210 type Fourier infrared spectrograph, adopts KBr compressing tablet (sample accounts for 1wt%), test specification 400-1800cm under the vacuum
-1Solid ultraviolet-visible diffuse reflection spectrum (UV-Vis) records test specification 200-500nm on Japanese SHIMADZU UV-3100 type ultraviolet-visual spectrometer.
Comparative Examples 1
According to document (J.C.Jan sen etc., Zeoli te, 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, 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.With the former powder of this TS-1 in 550 ℃ roasting temperature 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 the positive tetraethyl orthosilicate of 50 grams is joined that ultrasonic agitation makes it to mix in the aqueous solution of TPAOH, under the normal temperature and pressure ultrasonic agitation, drip then an amount of tetrabutyl titanate with wherein, mixed solution is joined that ultrasonic agitation makes it to mix in the aqueous solution of cetyl trimethylammonium bromide, the mol ratio of wherein positive tetraethyl orthosilicate, tetrabutyl titanate, TPAOH, cetyl trimethylammonium bromide and water is 1:0.02:0.45:0.15:85 again; Above-mentioned system is transferred in the stainless steel sealed reactor, first crystallization 5 hours under 100 ℃ and autogenous pressure, crystallization 48 hours under 120 ℃ and autogenous pressure again, the gained crystallization product is filtered, washs, and in 110 ℃ of dryings 120 minutes, 550 ℃ roasting temperature 3 hours, obtain titanium-containing mesoporous material A then.
The XRD crystalline phase figure of 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.
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 composite sample has two dimension six side's central hole structures 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 that A is described is nearly all on skeleton.
Earlier the positive quanmethyl silicate of 50 grams is joined that ultrasonic agitation makes it to mix in the aqueous solution of TPAOH, under the normal temperature and pressure ultrasonic agitation, slowly drip then an amount of tetraethyl titanate with wherein, mixed solution is joined that ultrasonic agitation makes it to mix in the aqueous solution of tensio-active agent Tetradecyl Trimethyl Ammonium Bromide, the mol ratio of wherein positive quanmethyl silicate, tetraethyl titanate, TPAOH, tensio-active agent and water is 1:0.008:0.15:0.05:25 again.This mixed solution is put into the stainless steel sealed reactor, crystallization is 72 hours under 100 ℃ and autogenous pressure, the gained crystallization product is filtered, washs, and in 110 ℃ of oven dry 120 minutes, then 550 ℃ roasting temperature 3 hours, obtain titanium-containing mesoporous material B, 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 the positive tetraethyl orthosilicate of 50 grams is joined that ultrasonic agitation makes it to mix in the aqueous solution of ethamine, under the normal temperature and pressure ultrasonic agitation, slowly drip then an amount of tetrabutyl titanate with wherein, mixed solution is joined that ultrasonic agitation makes it to mix in the aqueous solution of cetyl trimethylammonium bromide, the mol ratio of wherein positive tetraethyl orthosilicate, tetrabutyl titanate, ethamine, tensio-active agent and water is 1:0.4:0.35:0.25:150 again.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 ℃ roasting temperature 3 hours, obtain titanium-containing mesoporous 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 the positive tetraethyl orthosilicate of 50 grams is joined that ultrasonic agitation makes it to mix in the aqueous solution of trolamine, under the normal temperature and pressure ultrasonic agitation, slowly drip then an amount of metatitanic acid orthocarbonate with wherein, mixed solution is joined that ultrasonic agitation makes it to mix in the aqueous solution of cetyl trimethylammonium bromide, the mol ratio of wherein positive tetraethyl orthosilicate, metatitanic acid orthocarbonate, trolamine, tensio-active agent and water is 1:0.2:0.05:0.35:60 again.This mixed solution is put into 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 ℃ roasting temperature 3 hours, obtain titanium-containing mesoporous 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 the positive silicic acid orthocarbonate of 50 grams is joined that ultrasonic agitation makes it to mix in the aqueous solution of butanediamine, under the normal temperature and pressure ultrasonic agitation, slowly drip then an amount of tetrabutyl titanate with wherein, mixed solution is joined that ultrasonic agitation makes it to mix in the aqueous solution of cetyl trimethylammonium bromide, the mol ratio of wherein positive silicic acid orthocarbonate, tetrabutyl titanate, butanediamine, tensio-active agent and water is 1:0.12:0.25:0.45:120 again.This mixed solution is put into the stainless steel sealed reactor, crystallization is 36 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 ℃ roasting temperature 3 hours, obtain titanium-containing mesoporous material E, 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: the weight ratio of phenol: 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 OV-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
The method gained sieve sample of present embodiment explanation the inventive method and Comparative Examples is used for the effect of the catalytic oxidation of 2,6-DI-tert-butylphenol compounds oxidizing reaction.
In being housed, the there-necked flask of reflux exchanger adds 3.0 grams 2; 6-DI-tert-butylphenol compounds, 10.0 gram butanone, 4.5 gram mass marks are 27.5% aqueous hydrogen peroxide solution and 0.10 gram catalyzer; 75 ℃ were reacted 1.5 hours down under nitrogen protection; products therefrom uses the OV-101 capillary column on Agilent 6890N type gas chromatograph (30m * 0.25mm) measure each product to distribute the results are shown in Table 2.
In table 2:
Table 2
| Title | Phenol transformation efficiency % | Quinone selectivity % |
| Embodiment 1 | 57.2 | 97 |
| |
45.3 | 95 |
| |
53.6 | 97 |
| |
51.3 | 96 |
| |
42.8 | 97 |
| Comparative Examples 1 | 3.3 | 95 |
| Comparative Examples 2 | 12.1 | 97 |
| Comparative Examples 3 | 26.4 | 95 |
By table 1 and table 2 as can be seen: 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. the synthetic method of a titanium-containing mesoporous material, it is characterized in that under ultrasonic agitation, the silicon source is added drop-wise to mix in the aqueous solution of organo-alkali compound after, add the titanium source again, after treating hydrolysis fully, the aqueous solution of gained mixture and tensio-active agent is even, 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): (0.01-0.5): mixture (5-250), with mixture at the sealed reactor hydrothermal crystallizing, and reclaim and to obtain titanium-containing mesoporous material, said silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter.
2. according to the process of claim 1 wherein, in its X-ray diffraction spectrogram of said titanium-containing mesoporous material 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.
3. according to the process of claim 1 wherein the silicon source that consists of of mixture: titanium source: organo-alkali compound: tensio-active agent: water=1:(0.005-0.5): (0.05-0.5): (0.05-0.5): (20-180).
4. according to the process of claim 1 wherein, the silicon source is selected from silica gel, silicon sol, water glass or soft silica, and perhaps being selected from general formula is R
1 4SiO
4The organosilicon acid esters, R
1For having the alkyl of 1-4 carbon atom.
5. according to the process of claim 1 wherein, the titanium source is selected from TiCl
4, Ti (SO
4)
2Or TiOCl
2, perhaps
Being selected from general formula is R
2 4OTi
4Organic titanate, R
2For having the alkyl of 1-6 carbon atom.
6. according to the method for claim 5, wherein, R
2For having the alkyl of 2-4 carbon atom.
7. according to the process of claim 1 wherein, it is (R that tensio-active agent is selected from general formula
3R
4NR
5R
6)
+X
-Quaternary ammonium salt surface active agent, X represents halogen in the formula, 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
6Alkyl for 12-22 carbon atom.
9. according to the method for claim 7, wherein, tensio-active agent is Tetradecyl Trimethyl Ammonium Bromide or cetyl trimethylammonium bromide.
10. according to the process of claim 1 wherein, organo-alkali compound is selected from fat amine compound, alcamine compound or quaternary amine alkali compounds, the perhaps mixture of being 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
7For
Alkyl or alkylidene group with 1-6 carbon atom, n=1 or 2.
12. according to the method for claim 10, wherein, fat amine compound is 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
8For having the alkyl of 1-4 carbon atom, m=1,2 or 3.
14. according to the method for claim 10, wherein, alcamine compound is monoethanolamine, diethanolamine or trolamine.
15. according to the method for claim 10, the general formula of said 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, said quaternary ammonium hydroxide compounds is a TPAOH.
17. according to the method for claim 1, said hydrothermal crystallizing, its condition is to handle 2-360 hour under the autogenous pressure in 20-190 ℃ of encloses container; Or earlier 60-120 ℃ pre-crystallization 0.5-10 hour down, and then 80-180 ℃ of following crystallization 1 hour to 10 days.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810101123 CN101519213B (en) | 2008-02-28 | 2008-02-28 | Synthetic method of titanium-containing mesoporous materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810101123 CN101519213B (en) | 2008-02-28 | 2008-02-28 | Synthetic method of titanium-containing mesoporous materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101519213A true CN101519213A (en) | 2009-09-02 |
| CN101519213B CN101519213B (en) | 2012-12-12 |
Family
ID=41080038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810101123 Active CN101519213B (en) | 2008-02-28 | 2008-02-28 | Synthetic method of titanium-containing mesoporous materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101519213B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102826566A (en) * | 2012-09-25 | 2012-12-19 | 宁夏兴平精细化工股份有限公司 | Synthetic method of mesoporous molecular sieve used for thioether oxidization |
| CN104556219A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing nano-TiO2 |
| CN104556220A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing nano-TiO2 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113813C (en) * | 1999-12-15 | 2003-07-09 | 中国科学院大连化学物理研究所 | Titanium-silicon molecular sieve and its synthesis and application |
| CN1246224C (en) * | 2002-08-15 | 2006-03-22 | 中国石油化工股份有限公司 | Preparation method of high titanium content mesoppore molecular sieve |
-
2008
- 2008-02-28 CN CN 200810101123 patent/CN101519213B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102826566A (en) * | 2012-09-25 | 2012-12-19 | 宁夏兴平精细化工股份有限公司 | Synthetic method of mesoporous molecular sieve used for thioether oxidization |
| CN104556219A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing nano-TiO2 |
| CN104556220A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing nano-TiO2 |
| CN104556219B (en) * | 2013-10-29 | 2016-06-01 | 中国石油化工股份有限公司 | One prepares nano-TiO2Method |
| CN104556220B (en) * | 2013-10-29 | 2016-06-15 | 中国石油化工股份有限公司 | One prepares nano-TiO2Method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101519213B (en) | 2012-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101190794B (en) | Method for synthesizing mesoporous titanium-silicon molecular screen material | |
| CN101190792B (en) | Method for synthesizing titanium-silicon molecular screen | |
| CN104556111B (en) | A kind of Titanium Sieve Molecular Sieve and its synthetic method | |
| CN101190793B (en) | Method for synthesizing TS-1 molecular screen | |
| CN105271294B (en) | Tin-silicon molecular sieve and synthetic method and application thereof, and phenol hydroxylation method | |
| CN104556114B (en) | A kind of method of the micro- mesoporous composite material of synthesis of titanium silicon | |
| CN110180586A (en) | The alkali metal ion modifying titanium-silicon molecular sieve TS-1 and preparation method thereof reacted for propylene and hydrogen peroxide gas-phase epoxidation | |
| CN101497450B (en) | Method for preparing titanium-containing mesoporous material | |
| CN101850986A (en) | Method for modifying titanium-silicalite | |
| CN106276944B (en) | A kind of HTS and its synthetic method and application and a kind of method for hydroxylation of phenol | |
| CN101519213B (en) | Synthetic method of titanium-containing mesoporous materials | |
| CN104557479B (en) | A kind of method preparing propylene glycol monomethyl ether | |
| CN103395798B (en) | Synthesis method of Ti-Beta molecular sieve | |
| CN106904632B (en) | A kind of HTS and its synthetic method and application and a kind of method for hydroxylation of phenol | |
| CN104512904A (en) | Mesoporous titanium-silicon material preparation method | |
| CN101205075B (en) | Method for synthesizing titanium-containing molecular sieve material | |
| CN104556109B (en) | Method for preparing titanosilicate molecular sieve and phenol oxidation method | |
| CN101497451B (en) | Method for preparing mesoporous titanium-silicon material | |
| CN105217650B (en) | Mesoporous titanium silicate molecular sieve, synthetic method therefor and application thereof as well as method for oxidizing 2,6-di-tert-butylphenol | |
| CN104418338B (en) | A kind of silica zeolite and synthetic method thereof and a kind of method preparing caprolactam | |
| CN101314136B (en) | Titanium containing composite material with mesoporous and cellular structure, and preparation thereof | |
| Tang et al. | Regulation of framework titanium siting in MWW-type titanosilicates by boron and aluminum incorporation and its effect on the catalytic performance | |
| CN102311128B (en) | Method for treating titanium-silicon molecular sieve | |
| CN104340988B (en) | The forming method of HTS and the shaping HTS obtained by the method and application | |
| CN103896301B (en) | A kind of method of synthesis of titanium silicon molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |