CN101314136B - Titanium containing composite material with mesoporous and cellular structure, and preparation thereof - Google Patents
Titanium containing composite material with mesoporous and cellular structure, and preparation thereof Download PDFInfo
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- CN101314136B CN101314136B CN 200710099852 CN200710099852A CN101314136B CN 101314136 B CN101314136 B CN 101314136B CN 200710099852 CN200710099852 CN 200710099852 CN 200710099852 A CN200710099852 A CN 200710099852A CN 101314136 B CN101314136 B CN 101314136B
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Abstract
The invention discloses a titanium-containing composite material provided with mesopore and micropore structures, which is characterized in that: in an X-ray diffraction pattern of the composite material, the positions where 2theta is equal to 2.3 DEG+-0.1 DEG, 4.0 DEG+-0.2 DEG, and 4.6 DEG+-0.3 DEG are respectively provided with a diffraction peak, at least two diffraction peaks exist within the range of the 2theta being between 7.5 and 9.0 DEG, and three diffraction peaks exist within the range of the 2theta being between 23.0 and 25.0 DEG. The material has good catalytic oxidation function and better effect on reactions which giant molecules take part in.
Description
Technical field
The invention relates to a kind of titanium-containing materials and preparation method thereof, is about a kind of titanium containing composite material with mesoporous and microcellular structure and preparation method thereof furtherly.
Background technology
HTS is the novel hetero-atom molecular-sieve that early eighties begins 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 novel titanosilicate 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 good stability of ZSM-5 molecular sieve.Because the TS-1 molecular sieve is in organic oxidation reaction, can adopt free of contamination low concentration hydrogen peroxide as oxidant, avoided the problem of oxidizing process complex process and contaminated environment, has unrivaled energy-conservation, the advantage such as economy and environment is friendly of conventional oxidation system, and have good reaction selectivity, therefore good prospects for commercial application is arranged.
TS-1 is hydrophobic material, has very high catalytic oxidation activity, the good catalytic action of performance in a lot of organic oxidizing reactions, as its catalysis of phenol hydroxylating system adjacent (to) industrial applications all such as benzenediol and preparing cyclohexanone oxime by ammoximation of cyclohexanone.But TS-1 has micropore (aperture only have an appointment 0.55nm) structure, large organic molecule is difficult to spread therein and by catalytic oxidation, so that its good catalytic oxidation performance is difficult in more wide field especially biological and bring into play in the large molecule of medicine field, thereby 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 uniform granularity and regular meso-hole structure, attracted the very big concern of relevant academia, for having brought hope in the 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 °, the diffraction maximum of the 4.6 ° of vicinity X-ray diffraction of corresponding [100], [110], [200] crystal face respectively; The people such as Corma were incorporated into titanium in the structure of MCM-41 by synthesizing mean in 1994, the MCM-41 that has obtained titaniferous of success, 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 large molecule fine chemistry industry and the large molecule syntheses of medicine to it.But, this material is amorphous, hydrothermal stability and hydrophobicity all are weaker than the Ti-Si zeolite (TS-1) of crystallization, catalytic activity in the oxidation reaction take aqueous hydrogen peroxide solution as oxidant is lower, greatly limited its application (Micro.Mater., 1997,9:173 and Stud.Surf.Sci.Catal., 1995).
Has simple and mechanical mixing mesoporous and that composite molecular screen material micropore double-hole structure is not two kinds of single structure molecular sieves, because simple and mechanical mixing does not reach the advantage with the two, being about to that the high hydrothermal stability of TS-1 and hydrophobicity and the mesoporous characteristic of Ti-MCM-41 melt is purpose all over the body.In order to overcome titaniferous micro porous molecular sieve TS-1 and titanium-containing meso-porous molecular sieve Ti-MCM-41 deficiency separately, with the advantage combination of the two, being about to that the high hydrothermal stability of TS-1 and hydrophobicity and the mesoporous characteristic of Ti-MCM-41 melt is all over the body, people try to explore to synthesize to have mesoporous and composite molecular screen material micropore double-hole structure, in recent years, the research of this respect has become one of hot research problem.CN1226187C has reported the synthetic and preparation method of the HTS composite with the above-mentioned two kinds of structures of part, but the composite pore size that its Main Problems is it to be mentioned single (the diffraction maximum position limits strict in the X-ray diffraction spectrogram), and preparation process is comparatively numerous and diverse in its preparation method, also need use other unnecessary material when synthetic, relate to cost and environmental problem.The method of CN1162325C report also can be for the preparation of the HTS composite with the above-mentioned two kinds of structures of part, but preparation process is also comparatively numerous and diverse in its preparation method, also need use other unnecessary materials such as hydrochloric acid when synthetic, relate to cost and environmental problem.
Summary of the invention
The objective of the invention is for the deficiencies in the prior art, a kind of a kind of simple and feasible, environment amenable preparation method who has the titanium containing composite material of mesoporous and micropore double structure and this composite is provided is provided.
Provided by the invention have mesoporous and titanium containing composite material microcellular structure, it is characterized in that being 2.3 ° ± 0.1 °, 4.0 ° ± 0.2 °, 4.6 ° ± 0.3 ° at 2 θ in the X-ray diffraction spectrogram of this material locates respectively to have a diffraction maximum, in 2 θ are 7.5-9.0 ° of scope, have two diffraction maximums at least, in 2 θ are 23.0-25.0 ° of scope, have three diffraction maximums at least.
Simultaneously, in the infrared spectrum of this titanium containing composite material, at wave number 550cm
-1Near and 960cm
-1There is absorption band the vicinity; Near wavelength is 220nm, stronger absorption band is arranged in its ultraviolet-visible spectrum.
The titanium containing composite material of mesoporous and microcellular structure provided by the invention, its X-ray diffraction spectrogram near 2 θ are 2.3 °, near 4.0 °, the diffraction maximum of the 4.6 ° of vicinity X-ray diffraction of corresponding [100], [110], [200] crystal face respectively, be the architectural feature of similar mesoporous MCM-41 molecular sieve; The microcellular structure that contains similar MFI type in the stronger diffraction maximum explanation composite in 2 θ are 7.5-9.0 ° of scope and in 2 θ are 23.0-25.0 ° of scope.And in its infrared spectrum, wave number is at 550cm
-1Near absorption band add bright its have the MFI type the five-membered ring pore characteristics (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 its ultraviolet-visible spectrum, illustrate that also Ti has entered skeleton, exist with skeleton titanium form.
Composite provided by the invention, micropore size is distributed as 0.3-0.6nm, and mesoporous pore-size distribution is 2.0-6.0nm.
Titanium-silicone metapore-micropore molecular sieve composite material provided by the invention, the characteristics of mesoporous MCM-41 and two kinds of molecular sieves of micropore Ti-ZSM-5 are combined, have simultaneously the mesoporous characteristics of high hydrophobic and high catalytic activity and MCM-41, so that this composite has higher catalytic activity aspect the oxidation operation especially larger molecular organics oxidation, not two kinds of simple and mechanical physical mixed of molecular sieve of mesoporous MCM-41 and micropore Ti-ZSM-5.This titanium containing composite material has good catalytic oxidation function, and the reaction effect better (embodiment 11 and embodiment 12) that especially large molecule is participated in illustrates that also Ti has entered skeleton and embodied the characteristic of the reaction that the large molecule of mesoporous material catalysis participates in.
The present invention further also provides above-mentioned a kind of preparation method with titanium containing composite material of mesoporous and microcellular structure, and the method comprises step as described below:
(1) with the silicon source with join in the aqueous solution that is formed by organo-alkali compound and surfactant after mix in the titanium source, mixing and stirring obtains mixture, its mole consists of the silicon source: titanium source: organic base: surfactant: water=1:(0.0005-0.5): (0.05-1.0): (0.05-1.0): (5-150), wherein, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter;
(2) with step (1) gained mixture in sealed reactor first 60-120 ℃ lower pre-crystallization 0.5-36 hour, and then 100-180 ℃ of lower crystallization 1 hour to 10 days, reclaim according to a conventional method product.
Among the preparation method provided by the invention, the forming process of the said mixture of step (1) preferably is about to first titanium source and silicon source and is evenly mixed, and it is joined mixing in the aqueous solution that organo-alkali compound and surfactant form again.
Among the preparation method provided by the invention, wherein the mole proportion optimization of step (1) mixture is the silicon source: titanium source: organic base: surfactant: water=1:(0.005-0.2): (0.05-0.5): (0.01-0.5): (20-200).
The said silicon of step (1) source can be inorganic silicon source or organosilicon source, is preferably the organosilicon source.The inorganic silicon source can be silica gel or Ludox; It is R that the organosilicon source is selected from general formula
1 4SiO
4The organosilicon acid esters, R wherein
1For having the alkyl of 1-4 carbon atom.
The said titanium of step (1) source can be inorganic ti sources or organic titanium source, is preferably the organic titanium source.Inorganic ti sources refers to 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 titanium salt is TiCl
4, Ti (SO4)
2Or TiOCl
2It is R that the organic titanium source is selected from general formula
2 4TiO
4Organic titanate, R wherein
2For alkyl with 1-6 carbon atom, be preferably the alkyl with 2-4 carbon atom.
In the step (1) preferred simultaneously with organosilicon source and organic titanium source as raw material.
Among the preparation method provided by the invention, said surfactant refers to the surfactant of ordinary meaning in the step (1), comprise anion surfactant, cationic surfactant and non-ionic surface active agent, wherein be preferably cationic surfactant, more preferably general formula is (R
3R
4NR
5R
6)
+X
-Quaternary cationic surfactant, X represents halogen in the general formula, R
3, R
4And R
5Be the alkyl that is less than 3 carbon atoms, R
3, R
4And R
5Carbon number can be identical or different, R
6For having the alkyl that is no less than 12 carbon atoms, preferred 12-22 carbon atom.Among the preparation method provided by the invention, the example of preferred surfactant is TTAB or softex kw.
Among the preparation method provided by the invention, organic base the more important thing is the effect of molecular sieve structure template except doing alkali source.
Organic base is TPAOH, or the mixture that forms of TPAOH and fat amine compound, alcamine compound.
Its general formula of said fat amine compound is R
7(NH
2)
n, R wherein
7Be alkyl or the alkylidene with 1-4 carbon atom, n=1 or 2, wherein preferred fat amine compound is ethamine, n-butylamine, butanediamine or hexamethylene diamine.
Its general formula of said alcamine compound is (HOR
8)
mN; R wherein
8For having the alkylidene of 1-4 carbon atom; M=1-3; Wherein preferred alcamine compound is MEA, diethanol amine or triethanolamine.
In preparation method provided by the invention, in the step (2) said hydrothermal crystallizing condition be first 60-120 ℃ lower pre-crystallization 1-24 hour, and then 120-180 ℃ of lower crystallization 1 hour to 3 days.
The process of said conventional method recovery product refers to drying and the roasting process of crystallization product in the step (2).For example, dry run generally is to carry out between room temperature to 200 ℃, roasting generally can be between 300 to 800 ℃ be carried out in air atmosphere after 0.5-6 hour in nitrogen atmosphere first 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 characterised in that first silicon source and titanium source is evenly mixed, and utilizes the silicon source with the titanium source diluting on the one hand, without the materials such as other unnecessary solvent, Cost reduction and environmental pressure; On the other hand, first silicon source and titanium source mixing can be made hydrolysis after titanium, the silicon more homogeneous that distributes in the hydrolyzate that obtains, then it is joined mixing in the aqueous solution that is formed by organic alkali source and surfactant, again hydrothermal crystallizing and reclaim according to a conventional method product.The method is simple and feasible, environmentally friendly.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of the titanium containing composite material A of preparation among the embodiment 1.
Fig. 2 is the nitrogen adsorption isotherm figure of the titanium containing composite material A of preparation among the embodiment 1.
Fig. 3 is the pore distribution curve figure of the titanium containing composite material A of preparation among the embodiment 1.
Fig. 4 is the infrared absorption spectroscopy spectrogram of the titanium containing composite material A of preparation among the embodiment 1.
Fig. 5 is the uv-visible absorption spectra spectrogram of the titanium containing composite material A of preparation among the embodiment 1.
The specific embodiment
Following embodiment and Comparative Examples will be further described the present invention, but therefore not limit the present invention.
The reagent that all are used among the embodiment is commercially available chemically pure reagent.
X-ray diffraction (XRD) the crystalline phase figure that carries out sample at Siemens D5005 type x-ray diffractometer measures, and radiographic source is CuK α, tube voltage 40kV, tube current 40mA, 0.25 °/min of sweep speed, sweep limits 2 θ=1 °-40 °.
The adsorption isothermal curve of the low temperature nitrogen absorption of sample and pore size distribution curve are 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 at Nicolet8210 type Fourier infrared spectrograph, 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 200-1000nm at 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.
22.5 gram tetraethyl orthosilicates are mixed with 7.0 gram TPAOHs, and add 59.8 the gram distilled water, after mixing in the lower hydrolysis of normal pressure and 60 ℃ 1.0 hours, obtain the hydrating solution of tetraethyl orthosilicate, under vigorous stirring, add lentamente the solution that is formed by 1.1 gram butyl titanates and 5.0 gram anhydrous isopropyl alcohols, the gained mixture 75 ℃ of lower stirrings 3 hours, is obtained the clear colloid.This colloid is put into the stainless steel sealed reactor, and constant temperature was placed 3 days under 170 ℃ temperature, obtained the mixture of crystallization product; This mixture is filtered, washes with water, and in 110 ℃ of dryings 60 minutes, obtain the former powder of TS-1.The former powder of this TS-1 in 550 ℃ of roasting temperatures 3 hours, is got the TS-1 molecular sieve, numbering DB1.
Comparative Examples 2
According to document (Corma A. etc., J.Chem.Soc.Chem.Commun., 1994,147-148) the synthetic Ti-MCM-41 of method, numbering DB2.
Comparative Examples 3
With the Ti-MCM-41 of the TS-1 of Comparative Examples 1 and Comparative Examples 2 in mass ratio for the 1:1 mechanical mixture obtains molecular sieve mixture, numbering DB3.
Embodiment 1
First 50 gram tetraethyl orthosilicates and an amount of butyl titanate are mixed, then mixed liquor is joined in the aqueous solution that TPAOH and softex kw form, made it to mix in 8 hours at normal pressure and 40 ℃ of lower vigorous stirring, the mol ratio of tetraethyl orthosilicate, butyl titanate, TPAOH, softex kw and water is 1:0.05:0.25:0.05:125 in the system; Above-mentioned system is transferred in the stainless steel sealed reactor, first crystallization 5 hours under 100 ℃ temperature and self-generated pressure, crystallization 48 hours under 170 ℃ temperature and self-generated pressure again, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, then 550 ℃ of roasting temperatures 3 hours, obtain mesoporous-micropore molecular sieve composite material A.
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-ultraviolet spectra is as shown in Figure 5.
The XRD crystalline phase of sample A is that 2 θ have located diffraction maximum at 2.3 °, 4.0 ° and 4.6 ° at low-angle among Fig. 1, shows that composite sample has two dimension six side's central hole structures of similar MCM-41; Two diffraction maximums are arranged in 2 θ are 7.5-9.0 ° of scope, three diffraction maximums are arranged in 2 θ are 23.0-25.0 ° of scope, be the TS-1 characteristic diffraction peak, illustrate and contain the MFI construction unit in the composite.
The nitrogen adsorption isotherm of Fig. 2 and the pore distribution curve of Fig. 3 further specify the feature that sample A has similar Ti-MCM-41, p/p among Fig. 2
0Near 0.4 hop correspondence among Fig. 3 pore-size distribution very narrow about 2.4nm.Among Fig. 3 about 0.38nm very narrow pore-size distribution interpret sample have simultaneously the feature of similar micropore ZSM-5.
Sample A is at 960cm in the fourier infrared spectrum of Fig. 4
-1The unexistent characteristic absorption peak of silica zeolite appears in the vicinity, is the feature of skeleton titanium, shows that titanium has entered the sample skeleton.
Absorption in the visible ultraviolet spectra of Fig. 5 about 220nm is the feature of four-coordination Ti, does not occur absorption band near 340nm, illustrates that the Ti of A is nearly all on skeleton.
First 50 gram tetraethyl orthosilicates and an amount of butyl titanate are mixed, again the surfactant TTAB is joined in the aqueous solution of TPAOH and mix, then above-mentioned two kinds of mixed liquors are mixed, made it to mix in 6 hours at normal pressure and 35 ℃ of lower vigorous stirring, then being warmed up to 80 ℃ continues to stir 2 hours, moisturizing in the process guarantees that the mol ratio of tetraethyl orthosilicate, butyl titanate, TPAOH, surfactant and water is 1:0.15:0.15:0.40:185.Change this mixed liquor over to the stainless steel sealed reactor, first crystallization 4 hours under 120 ℃ temperature and self-generated pressure, crystallization 36 hours under 160 ℃ temperature and self-generated pressure again, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, then 550 ℃ of roasting temperatures 3 hours, obtain mesoporous-micropore molecular sieve composite material B, this sample characterizes consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment 1 sample A through X-ray diffraction, Fourier infrared spectrum and visible-ultraviolet spectra.
Embodiment 3
First 50 gram tetraethyl orthosilicates and an amount of metatitanic acid orthocarbonate are mixed, then mixed liquor is joined in the aqueous solution that TPAOH, n-butylamine and softex kw form, made it to mix in 5 hours at normal pressure and 60 ℃ of lower vigorous stirring, moisturizing in the process guarantees that the mol ratio of tetraethyl orthosilicate, metatitanic acid orthocarbonate, TPAOH, n-butylamine, surfactant and water is 1:0.025:0.05:0.05:0.02:40.This mixed liquor is put into the stainless steel sealed reactor, first crystallization 2 hours under 100 ℃ temperature and self-generated pressure, crystallization 72 hours under 150 ℃ temperature and self-generated pressure again, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, then 550 ℃ of roasting temperatures 3 hours, obtain mesoporous-micropore molecular sieve composite material C, this sample characterizes consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment 1 sample A through X-ray diffraction, Fourier infrared spectrum and visible-ultraviolet spectra.
First 50 gram tetraethyl orthosilicates and an amount of butyl titanate are mixed, again surfactant TTAB, diethanol amine are joined in the aqueous solution of TPAOH and mix, then above-mentioned two kinds of mixed liquors are mixed, vigorous stirring made it to mix in 12 hours at normal temperatures and pressures, moisturizing in the process guarantees that the mol ratio of tetraethyl orthosilicate, butyl titanate, TPAOH, diethanol amine, surfactant and water is 1:0.01:0.08:0.02:0.05:75.This mixed liquor is put into the stainless steel sealed reactor, first crystallization 18 hours under 80 ℃ temperature and self-generated pressure, crystallization 24 hours under 180 ℃ temperature and self-generated pressure again, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, then 550 ℃ of roasting temperatures 3 hours, obtain mesoporous-micropore molecular sieve composite material D, this sample characterizes consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment 1 sample A through X-ray diffraction, Fourier infrared spectrum and visible-ultraviolet spectra.
First 50 gram tetraethyl orthosilicates and an amount of tetraethyl titanate are mixed, then mixed liquor is joined that vigorous stirring makes it to mix in the aqueous solution that TPAOH, hexamethylene diamine and TTAB form, stirred 2 hours at normal pressure and 55 ℃ of lower continuation, then being warmed up to 90 ℃ continues to stir 2 hours, moisturizing in the process guarantees that the mol ratio of tetraethyl orthosilicate, tetraethyl titanate, TPAOH, hexamethylene diamine, surfactant and water is 1:0.08:0.25:0.25:0.1:100.This mixed liquor is put into the stainless steel sealed reactor, first crystallization 2 hours under 90 ℃ temperature and self-generated pressure, crystallization 8 hours under 170 ℃ temperature and self-generated pressure again, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, then 550 ℃ of roasting temperatures 3 hours, obtain mesoporous-micropore molecular sieve composite material E, this sample characterizes consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment 1 sample A through X-ray diffraction, Fourier infrared spectrum and visible-ultraviolet spectra.
First 50 gram tetraethyl orthosilicates and an amount of butyl titanate are mixed, then mixed liquor is joined that vigorous stirring makes it to mix in the aqueous solution that TPAOH, triethanolamine and TTAB form, stirred 6 hours at normal pressure and 65 ℃ of lower continuation, moisturizing in the process guarantees that the mol ratio of tetraethyl orthosilicate, butyl titanate, TPAOH, triethanolamine, surfactant and water is 1:0.04:0.05:0.15:0.01:30.This mixed liquor is put into the stainless steel sealed reactor, first crystallization 4 hours under 80 ℃ temperature and self-generated pressure, crystallization 48 hours under 180 ℃ temperature and self-generated pressure again, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, then 550 ℃ of roasting temperatures 3 hours, obtain mesoporous-micropore molecular sieve composite material F, this sample characterizes consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment 1 sample A through X-ray diffraction, Fourier infrared spectrum and visible-ultraviolet spectra.
Embodiment 7
First 50 gram tetraethyl orthosilicates and an amount of metatitanic acid orthocarbonate are mixed, then mixed liquor is joined in the aqueous solution that TPAOH, butanediamine and softex kw form, vigorous stirring makes it to mix, stirred 4 hours at normal pressure and 50 ℃ of lower continuation, then being warmed up to 90 ℃ continues to stir 3 hours, moisturizing in the process guarantees that the mol ratio of tetraethyl orthosilicate, metatitanic acid orthocarbonate, TPAOH, butanediamine, surfactant and water is 1:0.18:0.15:0.22:0.2:150.This mixed liquor is put into the stainless steel sealed reactor, first crystallization 2 hours under 120 ℃ temperature and self-generated pressure, crystallization 12 hours under 180 ℃ temperature and self-generated pressure again, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, then 550 ℃ of roasting temperatures 3 hours, obtain mesoporous-micropore molecular sieve composite material G, this sample characterizes consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment 1 sample A through X-ray diffraction, Fourier infrared spectrum and visible-ultraviolet spectra.
First 50 gram tetraethyl orthosilicates and an amount of butyl titanate are mixed, then mixed liquor is joined in the aqueous solution that TPAOH, MEA and TTAB form, the adularescent precipitation generates rapidly, vigorous stirring makes it to mix, stirred 6 hours at normal pressure and 30 ℃ of lower continuation, then being warmed up to 95 ℃ continues to stir 2 hours, moisturizing in the process guarantees that the mol ratio of tetraethyl orthosilicate, butyl titanate, TPAOH, MEA, surfactant and water is 1:0.05:0.15:0.10:0.15:160.This mixed liquor is put into the stainless steel sealed reactor, first crystallization 6 hours under 100 ℃ temperature and self-generated pressure, crystallization 48 hours under 150 ℃ temperature and self-generated pressure again, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, then 550 ℃ of roasting temperatures 3 hours, obtain mesoporous-micropore molecular sieve composite material H, this sample characterizes consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment 1 sample A through X-ray diffraction, Fourier infrared spectrum and visible-ultraviolet spectra.
Embodiment 9
First the positive silicic acid orthocarbonate of 50 grams and an amount of tetraethyl titanate are mixed, then mixed liquor is joined that vigorous stirring makes it to mix in the aqueous solution that TPAOH, ethamine and softex kw form, stirred 6 hours at normal pressure and 35 ℃ of lower continuation, then being warmed up to 80 ℃ continues to stir 4 hours, moisturizing in the process, the mol ratio that guarantees positive silicic acid orthocarbonate, tetraethyl titanate, TPAOH, ethamine, surfactant and water is 1:0.1:0.3:0.2:90.This mixed liquor is put into the stainless steel sealed reactor, first crystallization 7 hours under 80 ℃ temperature and self-generated pressure, crystallization 36 hours under 170 ℃ temperature and self-generated pressure again, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, then 550 ℃ of roasting temperatures 3 hours, obtain mesoporous-micropore molecular sieve composite material I, this sample characterizes consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment 1 sample A through X-ray diffraction, Fourier infrared spectrum and visible-ultraviolet spectra.
First 50 gram tetraethyl orthosilicates and an amount of butyl titanate are mixed, then mixed liquor is joined that vigorous stirring makes it to mix in the aqueous solution that TPAOH and TTAB form, stirred 6 hours at normal pressure and 35 ℃ of lower continuation, then being warmed up to 90 ℃ continues to stir 1 hour, moisturizing in the process guarantees that the mol ratio of tetraethyl orthosilicate, butyl titanate, TPAOH, surfactant and water is 1:0.1:0.4:0.3:120.This mixed liquor is put into the stainless steel sealed reactor, first crystallization 5 hours under 100 ℃ temperature and self-generated pressure, crystallization 48 hours under 140 ℃ temperature and self-generated pressure again, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, then 550 ℃ of roasting temperatures 3 hours, obtain mesoporous-micropore molecular sieve composite material J, this sample characterizes consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment 1 sample A through X-ray diffraction, Fourier infrared spectrum and visible-ultraviolet spectra.
Embodiment 11
The present embodiment illustrates that the sample of product provided by the invention and Comparative Examples is used for the effect of the catalytic oxidation of phenol hydroxylation.
The sample that above-described embodiment and Comparative Examples is prepared is according to sample: the weight ratio of phenol: acetone=1:25:15 mixes in a there-necked flask with condenser pipe, be warming up to 80 ℃, then under stirring according to phenol: it is 27.5% hydrogen peroxide that the mol ratio of hydrogen peroxide=1:0.34 adds mass fraction, reaction is 6 hours under this temperature, products therefrom uses the OV-101 capillary column at the Varian3400 chromatograph, and (30m * 0.25mm) measure each product to distribute the results are shown in Table 1.
In table 1:
Table 1
As can be seen from Table 1: the catalytic effect of composite A-J provided by the invention is better than the molecular sieve of single structure, and is better than the sample of mechanical mixture.In the situation that selective suitable, its conversion ratio is improved largely.Prove that composite provided by the invention is not the simple and mechanical mixing of two kinds of single structure molecular sieves, but organically be combined with each other.
Embodiment 12
The present embodiment illustrates that product provided by the invention and comparative sample gained are used for the catalytic oxidation effect of 2,6-DI-tert-butylphenol compounds oxidation reaction.
In being housed, the there-necked flask of reflux condenser adds 2 grams 2; 6-DI-tert-butylphenol compounds, 10 gram butanone, 3.5 gram mass marks are 27.5% aqueous hydrogen peroxide solution and 0.1 gram catalyst; 75 ℃ of lower reactions 2 hours under nitrogen protection; products therefrom uses the OV-101 capillary column at Agilent6890N type gas chromatograph, and (30m * 0.25mm) measure each product to distribute the results are shown in Table 2.
In table 2:
Table 2
| The composite numbering | Phenol conversion ratio % | The selective % of quinone |
| A | 64.5 | 97 |
| B | 62.9 | 98 |
| C | 60.4 | 98 |
| D | 58.6 | 96 |
| E | 59.8 | 97 |
| F | 57.4 | 97 |
| G | 54.3 | 98 |
| H | 56.1 | 97 |
| I | 58.7 | 96 |
| J | 57.6 | 97 |
| DB1 | 3.6 | 95 |
| DB2 | 18.1 | 97 |
| DB3 | 12.5 | 97 |
As can be seen from Table 2: the catalytic effect of composite A-J provided by the invention is significantly better than the molecular sieve of single structure, and is better than the sample of mechanical mixture.In the situation that selective suitable, its conversion ratio is improved largely.This illustrates that composite provided by the invention is not the simple and mechanical mixing of two kinds of single structure molecular sieves, but organically is combined with each other.
The result of embodiment 11 and embodiment 12 shows that titanium containing composite material provided by the invention has good catalytic oxidation function, and is better to the reaction effect of large molecule participation especially.
Claims (24)
1. one kind has mesoporous and titanium containing composite material microcellular structure, it is characterized in that in the X-ray diffraction spectrogram of this composite, it is 2.3 ° ± 0.1 ° at 2 θ, 4.0 ° ± 0.2 °, 4.6 ° ± 0.3 ° locate respectively to have a diffraction maximum, in being 7.5-9.0 ° of scope, 2 θ have two diffraction maximums at least, in being 23.0-25.0 ° of scope, 2 θ have three diffraction maximums at least, this molecular sieve is by the preparation of the method that comprises the following steps: (1) with the silicon source with join in the aqueous solution that is formed by organo-alkali compound and surfactant after mix in the titanium source, mixing and stirring obtains mixture, its mole consists of the silicon source: titanium source: organic base: surfactant: water=1: (0.0005-0.5): (0.05-1.0): (0.01-1.0): (5-250), wherein, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter; (2) with step (1) gained mixture in sealed reactor first 60-120 ℃ lower pre-crystallization 0.5-36 hour, and then 100-180 ℃ of lower crystallization 1 hour to 10 days, reclaim according to a conventional method product.
2. according to the titanium containing composite material of claim 1, it is characterized in that in the infrared spectrum of this material, at wave number 550cm
-1Near and 960cm
-1Near have absorption band.
3. according to the titanium containing composite material of claim 1, it is characterized in that near wavelength is 220nm, absorption band being arranged in the ultraviolet-visible spectrum of this material.
4. according to the titanium containing composite material of claim 1, it is characterized in that the micropore size of this material is distributed as 0.3-0.6nm, mesoporous pore-size distribution is 2.0-6.0nm.
5. according to the titanium containing composite material of claim 1, wherein the said silicon of step (1) source is selected from silica gel, Ludox or organosilicon acid esters.
6. according to the titanium containing composite material of claim 5, it is characterized in that said organosilicon acid esters general formula is R
1 4SiO
4, R wherein
1Be selected from the alkyl with 1-4 carbon atom.
7. according to the titanium containing composite material of claim 1, wherein the said titanium of step (1) source is inorganic titanium salt or organic titanate.
8. according to the titanium containing composite material of claim 7, wherein said inorganic titanium salt is selected from TiCl
4, Ti (SO
4)
2Or TiOCl
2
9. according to the titanium containing composite material of claim 7, it is characterized in that said organic titanate general formula is R
2 4TiO
4, R wherein
2Be selected from the alkyl with 1-6 carbon atom.
10. according to the titanium containing composite material of claim 9, R wherein
2Be selected from the alkyl with 2-4 carbon atom.
11. according to the titanium containing composite material of claim 1, wherein the said silicon of step (1) source is the organosilicon acid esters, the titanium source is organic titanate.
12. according to the titanium containing composite material of claim 1, wherein the said surfactant of step (1) is selected from one or more in anion surfactant, cationic surfactant and the non-ionic surface active agent.
13. according to the titanium containing composite material of claim 12, it is characterized in that said surfactant is cationic surfactant.
14. according to the titanium containing composite material of claim 13, it is characterized in that it is (R that said cationic surfactant is selected from general formula
3R
4NR
5R
6)
+X
-Quaternary ammonium salt surface active agent, wherein X represents halogen, R
3, R
4And R
5Be the alkyl that is less than 3 carbon atoms, R
3, R
4And R
5Carbon number identical or different, R
6For having the alkyl that is no less than 12 carbon atoms.
15. according to the titanium containing composite material of claim 14, it is characterized in that said R
6Be selected from the alkyl of 12-22 carbon atom.
16. according to the titanium containing composite material of claim 1, it is characterized in that said surfactant is TTAB or softex kw.
17. according to the titanium containing composite material of claim 1, wherein said organic base is TPAOH in the step (1), or the mixture that forms of TPAOH and fat amine compound, alcamine compound.
18. according to the titanium containing composite material of claim 17, wherein its general formula of said fat amine compound is R
7(NH
2)
n, R wherein
7Be selected from alkyl or alkylidene with 1-4 carbon atom, n=1 or 2.
19. according to the titanium containing composite material of claim 17 or 18, wherein said fat amine compound is ethamine, n-butylamine, butanediamine or hexamethylene diamine.
20. according to the titanium containing composite material of claim 17, wherein its general formula of said alcamine compound is (HOR
8)
mNH
(3-m)R wherein
8Be selected from the alkyl with 1-4 carbon atom, m=1,2 or 3.
21. according to the titanium containing composite material of claim 17 or 20, wherein said alcamine compound is MEA, diethanol amine or triethanolamine.
22. according to the titanium containing composite material of claim 1, wherein the mole proportioning of step (1) mixture is the silicon source: titanium source: organic base: surfactant: water=1: (0.005-0.2): (0.05-0.5): (0.01-0.5): (20-200).
23. according to the titanium containing composite material of claim 1, wherein in the step (2) said hydrothermal crystallizing condition be first 60-120 ℃ lower pre-crystallization 1-24 hour, and then 120-180 ℃ of lower crystallization 1 hour to 3 days.
24. according to the titanium containing composite material of claim 1, wherein the forming process of the said mixture of step (1) is to be about to first titanium source and silicon source evenly mix, and it is joined mixing in the aqueous solution that organo-alkali compound and surfactant form again.
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| CN110420134B (en) * | 2019-08-28 | 2022-04-15 | 广州骏朗生物科技有限公司 | Flaky silica/nano TiO2 composite material and preparation method thereof |
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| CN1393403A (en) * | 2001-06-29 | 2003-01-29 | 中国石油天然气股份有限公司 | Step crystallizing process for synthesizing composite mesaporous and microporous molecular sieve composition |
| CN1552626A (en) * | 2003-05-30 | 2004-12-08 | 中国石油化工股份有限公司 | Titanium silicon molecular sieve and synthetic method thereof |
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| CN1393403A (en) * | 2001-06-29 | 2003-01-29 | 中国石油天然气股份有限公司 | Step crystallizing process for synthesizing composite mesaporous and microporous molecular sieve composition |
| CN1552626A (en) * | 2003-05-30 | 2004-12-08 | 中国石油化工股份有限公司 | Titanium silicon molecular sieve and synthetic method thereof |
Non-Patent Citations (1)
| Title |
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| Arne Karlsson et al..Composites of micro- and mesoporous materials:simultaneous syntheses of MFI/MCM-41 like phases by a mixed template approach.《Microporous and Mesoporous Materials》.1999,第27卷第183页左栏第2段至第191页右栏最后1段. * |
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