CN101519213B - Synthetic method of titanium-containing mesoporous materials - Google Patents
Synthetic method of titanium-containing mesoporous materials Download PDFInfo
- Publication number
- CN101519213B CN101519213B CN 200810101123 CN200810101123A CN101519213B CN 101519213 B CN101519213 B CN 101519213B CN 200810101123 CN200810101123 CN 200810101123 CN 200810101123 A CN200810101123 A CN 200810101123A CN 101519213 B CN101519213 B CN 101519213B
- Authority
- CN
- China
- Prior art keywords
- titanium
- mixture
- active agent
- source
- alkyl
- 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.)
- Active
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 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 anorgano-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 miorgano-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)xture 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-contain:(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.ing 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 compound method of inorganic materials, further say so about a kind of compound 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 compound 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 characteristic (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 through 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 macromole fine chemistry industry and aspects such as the medicine macromole synthesizes to it.But; This material is a non-crystalline state, and hydrothermal stability and hydrophobic nature all are weaker than crystalline Ti-Si zeolite (TS-1), and the 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 compound method of titanium-containing mesoporous material is provided to existing synthesizing titanium-containing mesoporous material aspect.This compound method makes the titanium of hydrolysis better combine with silicon and organic bases and tensio-active agent etc., and it is uneven to eliminate partial concn, 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, compound method provided by the invention 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, treat that hydrolysis fully after, the 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); Mixture at the sealed reactor hydrothermal crystallizing, and is reclaimed and to obtain mesoporous titanium-containing materials, and 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 characteristic 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 at 2.3 ° ± 0.3 °, 4.0 ° ± 0.2 °, 4.6 ° ± 0.2 ° diffraction peak is arranged, 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 ir spectra at wave number 550cm
-1Near and 960cm
-1There is absorption the vicinity, add bright its have ZSM-5 characteristic (J.C.Jansen etc., Zeolite, 1984,4:369), wave number is at 960cm
-1Near absorption band then is the characteristic of skeleton titanium, explains that Ti has got into skeleton.Near wavelength is 220nm, stronger absorption band is arranged in the ultraviolet-visible spectrum, explain that also Ti has got into skeleton.
In compound method provided by the invention, said ultrasonic agitation mixing is meant and utilizes UW and mechanical stirring, promptly utilizes the synthetic technology that ultransonic cavatition and mechanical stirring merge mutually to make the mixed technology uniformly of raw material.
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 ℃ preparatory crystallization 0.5-10 hour down, preferred 1-8 hour, and then, reclaim product by ordinary method again 80-180 ℃ of following crystallization 1 hour to 10 days, preferred 1 hour-3 days.
In the compound 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 TTAB 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 each other 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, tetramethylenediamine 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, diethylolamine 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 the organic substance in the material duct through means such as organic solvent extractions before the roasting.
Compound method provided by the invention has following advantage:
1,, again with hydrolysis titanium source hydrolysis faster, helps silicon, and, make the more even of silicon and titanium species distribution at silicon source and the hydrolysis of titanium source back introducing tensio-active agent fully with titanium better combines earlier with the hydrolysis of silicon source.
2, ultrasonic agitation impels silicon source and titanium source better to combine with organic bases, tensio-active agent, 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 partial concn that the ultrasonic agitation technology is eliminated in the building-up process is uneven, 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, explain that also Ti has got into skeleton and embodied the reaction properties that mesoporous catalysis macromole is participated 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 be further described the present invention, but therefore not limit content of the present invention.
The reagent that all are used among the embodiment is commercially available chemically pure reagent, and used UW is KQ-100DE type numerical control supersonic producer (220 volts of WVs, 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 (λ=1.5418
), 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 Nicolet 8210 type Fourier infrared spectrographs, 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.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 TPAOHs; And add 59.8 the gram zero(ppm) 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 lentamente by 1.1 gram tetrabutyl titanates and restrain the solution that anhydrous isopropyl alcohols are formed with 5.0; 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, uses water washing, 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; Earlier 100 ℃ with autogenous pressure under crystallization 5 hours; Again 120 ℃ with autogenous pressure under crystallization 48 hours, with the gained crystallization product filter, washing, 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 is as shown in Figure 1, and nitrogen adsorption isotherm is as shown in Figure 2, and pore distribution curve is as shown in Figure 3, and the fourier infrared spectrogram is as shown in Figure 4, visible-UV spectrum is as shown in Figure 5.
Among XRD crystalline phase Fig. 1 maller 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 characteristic of skeleton titanium, shows that titanium has got into the sample skeleton.
It is thus clear that the absorption among-UV spectrum Fig. 3 about 220nm is the characteristic of four-coordination Ti, absorption band does not appear near 340nm, and 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 TTAB, 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; 100 ℃ with autogenous pressure under crystallization 72 hours; With the gained crystallization product filter, washing, 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; Earlier 100 ℃ with autogenous pressure under crystallization 5 hours, again 160 ℃ with autogenous pressure under crystallization 24 hours, the gained crystallization product is filtered, uses water washing; 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; Earlier 100 ℃ with autogenous pressure under crystallization 5 hours, again 140 ℃ with autogenous pressure under crystallization 48 hours, the gained crystallization product is filtered, uses water washing; 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 tetramethylenediamine; 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, tetramethylenediamine, 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; 160 ℃ with autogenous pressure under crystallization 36 hours; The gained crystallization product is filtered, use water washing, and dried 120 minutes in 110 ℃, 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: 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 OV-101 capillary column on the Varian3400 chromatographic instrument (30m * 0.25mm) measure each product to distribute, the result sees 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 t butyl phenol oxidizing reaction.
, the there-necked flask of reflux exchanger adds 3.0 grams 2 in being housed; 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 result sees table 2.
In table 2:
Table 2
Can be found out by table 1 and table 2: material catalytic effect provided by the invention obviously is better than the molecular sieve of single structure, and under the suitable situation of selectivity, its transformation efficiency is improved largely.
Claims (15)
1. the compound 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 the titanium-containing mesoporous material of the characteristic had similar mesoporous MCM-41 and part micropore Ti-ZSM-5 simultaneously, said silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter; The said titanium-containing mesoporous material that has the characteristic of similar mesoporous MCM-41 and part micropore Ti-ZSM-5 simultaneously; 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.
2. 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).
3. 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.
4. 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.
5. according to the method for claim 4, wherein, R
2For having the alkyl of 2-4 carbon atom.
6. 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.
7. according to the method for claim 6, wherein, R
6Alkyl for 12-22 carbon atom.
8. according to the method for claim 6, wherein, tensio-active agent is TTAB or cetyl trimethylammonium bromide.
9. according to the process of claim 1 wherein, organo-alkali compound is selected from fat amine compound, alcamine compound or quaternary ammonium hydroxide compounds, the mixture of perhaps being made up of them.
10. according to the method for claim 9, wherein, the general formula of fat amine compound is R
7(NH
2)
n, R
7Be alkyl or the alkylidene group with 1-6 carbon atom, n=1 or 2.
11. according to the method for claim 9, wherein, fat amine compound is ethamine, n-Butyl Amine 99, tetramethylenediamine or hexanediamine.
12. according to the method for claim 9, wherein, alcamine compound is monoethanolamine, diethylolamine or trolamine.
13. according to the method for claim 9, the general formula of said quaternary ammonium hydroxide compounds is (R
9)
4NOH, R
9For having the alkyl of 1-4 carbon atom.
14. according to the method for claim 9, said quaternary ammonium hydroxide compounds is a TPAOH.
15. according to the method for claim 1, said hydrothermal crystallizing, its condition is in 20-190 ℃ of encloses container, to handle 2-360 hour under the autogenous pressure; Or earlier 60-120 ℃ preparatory 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 CN101519213A (en) | 2009-09-02 |
| CN101519213B true 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) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104556220B (en) * | 2013-10-29 | 2016-06-15 | 中国石油化工股份有限公司 | One prepares nano-TiO2Method |
| CN104556219B (en) * | 2013-10-29 | 2016-06-01 | 中国石油化工股份有限公司 | One prepares nano-TiO2Method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299777A (en) * | 1999-12-15 | 2001-06-20 | 中国科学院大连化学物理研究所 | Titanium-silicon molecular sieve and its synthesis and application |
| CN1475441A (en) * | 2002-08-15 | 2004-02-18 | 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
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299777A (en) * | 1999-12-15 | 2001-06-20 | 中国科学院大连化学物理研究所 | Titanium-silicon molecular sieve and its synthesis and application |
| CN1475441A (en) * | 2002-08-15 | 2004-02-18 | 中国石油化工股份有限公司 | Preparation method of high titanium content mesoppore molecular sieve |
Non-Patent Citations (1)
| Title |
|---|
| XiangHai Tang et al.Novel Synthesis of Ordered MCM-41 Titanosilicates with Very High Titanium Content via Ultrasound Radiation.《Israel Journal of Chemistry》.2004,第44卷(第1-3期),235-241. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101519213A (en) | 2009-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101190794B (en) | Method for synthesizing mesoporous titanium-silicon molecular screen material | |
| CN104556111B (en) | A kind of Titanium Sieve Molecular Sieve and its synthetic method | |
| CN101190792B (en) | Method for synthesizing titanium-silicon molecular screen | |
| CN100586566C (en) | Method for preparing oxidation catalyst of cyclopropene | |
| CN101190793B (en) | Method for synthesizing TS-1 molecular screen | |
| 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 | |
| CN105271294B (en) | Tin-silicon molecular sieve and synthetic method and application thereof, and phenol hydroxylation method | |
| CN101497450B (en) | Method for preparing titanium-containing mesoporous material | |
| CN106276944B (en) | A kind of HTS and its synthetic method and application and a kind of method for hydroxylation of phenol | |
| CN104512904B (en) | A kind of method preparing mesoporous titanium-silicon material | |
| CN101519213B (en) | Synthetic method of titanium-containing mesoporous materials | |
| CN106904632B (en) | A kind of HTS and its synthetic method and application and a kind of method for hydroxylation of phenol | |
| CN104556113A (en) | Method for synthesizing titanium silicate molecular sieve employing organic quaternary ammonium salt template agent | |
| CN103395798A (en) | Synthesis method of Ti-Beta molecular sieve | |
| CN101205075B (en) | Method for synthesizing titanium-containing molecular sieve 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 | |
| CN101497451B (en) | Method for preparing mesoporous titanium-silicon material | |
| Tang et al. | Regulation of framework titanium siting in MWW-type titanosilicates by boron and aluminum incorporation and its effect on the catalytic performance | |
| CN101314136B (en) | Titanium containing composite material with mesoporous and cellular structure, and preparation thereof | |
| CN104340988B (en) | The forming method of HTS and the shaping HTS obtained by the method and application | |
| CN102311128B (en) | Method for treating titanium-silicon molecular sieve | |
| CN101519214B (en) | Method for synthesizing titanium-silicon materials with mesoporous and microporous structures | |
| CN103896301B (en) | A kind of method of synthesis of titanium silicon molecular sieve | |
| CN101205074A (en) | Method for preparing titanium-containing meso-porous molecular sieve material |
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 |