CN102344150A - Synthetic method for mesopore titanium-silicon molecular sieve - Google Patents
Synthetic method for mesopore titanium-silicon molecular sieve Download PDFInfo
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- CN102344150A CN102344150A CN2010102400034A CN201010240003A CN102344150A CN 102344150 A CN102344150 A CN 102344150A CN 2010102400034 A CN2010102400034 A CN 2010102400034A CN 201010240003 A CN201010240003 A CN 201010240003A CN 102344150 A CN102344150 A CN 102344150A
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Abstract
The invention belongs to the mesopore material preparation field, concretely relates to a synthetic method for a mesopore titanium-silicon molecular sieve. The method is characterized in that a low temperature rapid crystallization method is used, an inorganic silicon source and an inorganic titanium source are taken as the raw materials, a quaternary ammonium cationic surfactant is taken as a template agent, a Ti-MCM-41 molecular sieve with an ordered mesoporous structure and high specific surface area can be obtained through product recovery. Compared with the preparation method of the traditional Ti-MCM-41 molecular sieve, the method uses the inorganic silicon source and the titanium source as the raw materials, simultaneously the auxiliary template agent is avoided to use, so that the generation of TiO2 outside of a framework is reduced, the synthetic process is simplified and the synthesis cost is reduced; The method of the invention uses the low temperature rapid crystallization method and avoids a hydrothermal synthesis method, and has the advantages of simple operation, easy repetition, short synthesis time, low equipment requirement, easy process control and the like.
Description
Technical field
The invention belongs to the mesoporous material preparing technical field, be specifically related to a kind of synthesis method of mesoporous titanium-silicon molecular screen.
Background technology
HTS is one type of new catalytic material (US4410501) that the eighties of last century the eighties occurs.Because transition metals Ti has variable valent state; Therefore the introducing of titanium gives HTS unique catalyzed oxidation function, in the oxidizing reaction of alkene epoxidation, aromatic hydrocarbons hydroxylation, ketone ammonia oxidation and alcohols, alkane and sulfide, all shows excellent catalytic performance.But the aperture of Ti-Si zeolite molecular sieve catalyst less (＜0.7nm), can't satisfy the oxidizing reaction needs that macromole is participated in.
1992; It is the M41S series mesoporous silica molecular sieve (Nature of representative that the researchist of Mobil company successfully synthesizes with MCM-41; 1992; 359 (6397): 710-712), this type material have broad duct (＞2.0nm), uniformly pore size distribution and bigger specific surface area (700～1600m
2/ g).The successful preparation that appears as mesoporous titanium-silicon molecular screen of pure silicon mesoporous material provides good opportunity.1994; People such as Corma adopt the Direct Water thermal synthesis method to prepare Ti-MCM-41 molecular sieve (Chem.Commun., 1994, (2): 147-148); And find that it shows good catalytic performance in the oxidizing reaction of macromole alkene, this is the reported first of relevant mesoporous titanium-silicon molecular screen.Subsequently ten surplus year in, a series of mesoporous titanium-silicon molecular screens such as Ti-MCM-48, Ti-HMS, Ti-MSU, Ti-SBA-15 etc. are born in succession, these materials have been brought into play important effect in the macromolecular oxidizing reaction in meticulous and petrochemical complex.
As first mesoporous titanium-silicon molecular screen that emerges, the study on the synthesis of Ti-MCM-41 has received extensive concern.Most of choose organo-silicon esters or aerosol are the silicon source, and the organic titanium ester is the titanium source, use template and auxiliary template agent simultaneously, adopt hydrothermal synthesis method to prepare Ti-MCM-41.For example, in the US Patent No. 5783167, with amorphous Si O
2Do the silicon source, tetraethyl titanate is done the titanium source, and the quaternary ammonium cation tensio-active agent is made template, and Tetramethylammonium hydroxide is the auxiliary template agent, has synthesized the Ti-MCM-41 molecular sieve through hydrothermal method.In synthetic, because the hydrolysis rate of titanium ester, can cause the outer TiO of skeleton faster than the hydrolysis rate of estersil
2The generation of species, even when titanium content is higher, can destroy the formation of meso-hole structure.In order to reduce the outer TiO of skeleton
2The generation of species, Chinese patent CN 101190794A utilizes the ultrasonic agitation technology, is raw material with estersil and titanium ester, and cetyl trimethylammonium bromide is a template, and tetra-alkyl ammonium hydroxide is the auxiliary template agent, adopts hydrothermal method to synthesize Ti-MCM-41.People such as Luan are dissolved in the ethanol butyl (tetra) titanate to suppress its hydrolysis (J.Phys.Chem.; 1995,99 (26): 10590-10593), but before hydrothermal crystallizing; The alcohol that adds must be evaporated, otherwise can have influence on the degree of crystallinity of molecular sieve and the order of structure.Obviously, all are in order to reduce TiO
2The preparation condition that carries out from reunion is regulated all can increase synthesis step, makes process more complicated.In addition, compare with inorganic raw material, the costing an arm and a leg of organosilicon source and titanium source, thus limited its industrial application.Use inorganic silicon source and inorganic ti sources to prepare Ti-MCM-41 and not only can solve estersil, the unmatched problem of titanium ester hydrolysis rate, can also reduce synthetic cost.Chinese patent CN1299777A has reported and has used inorganic silicon source (silica gel) and inorganic ti sources (TiCl simultaneously
3), be template with the cetyl trimethylammonium bromide, tetra-alkyl ammonium hydroxide is the auxiliary template agent, prepares Ti-MCM-41 through hydrothermal synthesis method.Up to now, in the patent about the Ti-MCM-41 preparation, all use the auxiliary template agent and adopt hydrothermal synthesis method.Use the auxiliary template agent not only to make building-up process become complicated, also improved synthetic cost; Adopt hydrothermal synthesis method not only to need comparatively high temps, and consuming time longer, also require to use high pressure resistant synthesis reactor.The above shortcoming all can increase industrial difficulty.
Because the employed organic raw material of synthesising mesoporous HTS Ti-MCM-41 and organic auxiliary template agent cost an arm and a leg, the complicated harshness of synthesis condition, synthesis cycle is longer, has limited the scale operation and the industrial application of Ti-MCM-41 molecular screen material.
Summary of the invention
The technical problem that the present invention will solve:
The objective of the invention is deficiency,, shorten generated time, save synthetic cost, a kind of preparation method of easy mesoporous titanium-silicon molecular screen is provided in order to simplify the preparation process to the synthetic aspect of existing mesoporous titanium-silicon molecular screen Ti-MCM-41.This method adopts low temperature rapid crystallization method, uses inorganic silicon source and inorganic ti sources to be raw material, does not use the auxiliary template agent.The mesoporous titanium-silicon molecular screen that is obtained has orderly meso-hole structure, high-specific surface area, and titanium silicon adjustable ratio, the titanium active sites is dispersed in the framework of molecular sieve.This material is expected to become the effective catalyst of macromolecular organic substrates oxidizing reaction.
Technical scheme of the present invention may further comprise the steps: at ambient temperature; With water glass or Starso is the silicon source; Inorganic titanium salt is the titanium source; Quaternary ammonium cation is a template; Water is solvent, above-mentioned raw materials is mixed, with sour regulation system pH value to 7～12; Crystallization is 1～24 hour under 0～50 ℃ of stirring, and product obtains mesoporous titanium-silicon molecular screen material through separation, washing, drying, roasting.Wherein the feed molar proportioning is:
SiO
2: quaternary ammonium cation=1～20: 1
SiO
2∶TiO
2＝10～1000∶1
SiO
2∶H
2O＝0.001～0.05∶1
Specifically, technical scheme of the present invention may further comprise the steps:
1, at ambient temperature, the quaternary ammonium cation template is dissolved in deionized water, forms colourless transparent solution, stirred 10～120 minutes.
2, at ambient temperature, the silicon source is mixed with deionized water, obtain water white transparency or translucent solution; In the template aqueous solution, add the silicon source aqueous solution, form gel mixture.In the adition process, siliceous ionic concn gathers way and is no more than 5.0mol/L/h in the system, and vigorous stirring is to avoid local siliceous ionic concn too high simultaneously.
3, at ambient temperature, the titanium source is mixed with deionized water, obtain the aqueous solution; In the gel mixture in template and silicon source, add the titanium source aqueous solution, contain titanium ion concentration in the system and gather way and be no more than 5.0mol/L/h, vigorous stirring is too high to avoid the part to contain titanium ion concentration simultaneously.
In the above step, the ratio of water and raw material is not strict with, as long as under the laboratory temperature condition, raw material can be dissolved in the water fully gets final product.
4, with sour regulation system pH value to 7～12, crystallization is 1～24 hour under 0～50 ℃ of stirring.
5, solid product is separated with mother liquor, to neutral, obtained the former powder of titanium-containing meso-porous molecular sieve in 3～10 hours at 70～120 ℃ air dryings with deionized water wash.At last in retort furnace, 400～600 ℃ of roastings 2～16 hours obtain mesoporous titanium-silicon molecular screen material of the present invention.
Among the present invention, the silicon source is at least a in following: water glass and Starso.
Among the present invention, the titanium source is inorganic titanium-containing compound, at least a in for example following: TiCl
3, TiCl
4, TiOCl
2, Ti (NO
3)
4Or Ti (SO
4)
2
Among the present invention, the general formula of quaternary ammonium ion template is [NR
1R
2R
3R
4]
+, R wherein
1Represent C
12～C
30The straight or branched alkyl, R
2, R
3And R
4Be C
1～C
4The straight or branched alkyl, R
2, R
3And R
4Can be identical or different, preferably identical.
Among the present invention, the acid that is used for regulation system pH value is organic acid or mineral acid, preferred mineral acid, at least a in for example following: hydrochloric acid, sulfuric acid and nitric acid.
In Ti-MCM-41 synthetic prior art, crystallization process all carries out under static or dynamic hydrothermal condition.Adopt hydrothermal synthesis method not only to need comparatively high temps, and consuming time longer, major part also requires to use synthesis reactor, brings certain difficulty to large-scale commercial production.Synthesis method provided by the invention can be accomplished crystallization process at ambient temperature fast, has successfully solved energy dissipation and time loss problem that the hydrothermal crystallizing step is brought.
Can obtain a kind of mesoporous titanium-silicon molecular screen material according to synthesis method provided by the present invention, this material is made up of silicon-oxy tetrahedron and titanyl tetrahedron, has the adjustable cavernous structure of 3.0～8.0nm, 1000～1600m
2The high-specific surface area of/g.This material has the characteristic of MCM-41, and titanium has got into framework of molecular sieve.In its ultraviolet-visible spectrum, wavelength has very strong absorption band between 210～230nm, corresponding to the skeleton titanium species of four-coordination, proves that the Ti species have entered into framework of molecular sieve.The absorption band of non-skeleton titanium dioxide is near 340nm, and on this sample, the extra-framework titanium species content is few.
The invention has the beneficial effects as follows:
(1) uses inorganic silicon source and inorganic ti sources, under the weak base condition, get final product abundant hydrolysis, can solve estersil, the unmatched problem of titanium ester hydrolysis rate, avoid the generation of non-skeleton titanium dioxide.Even in the higher sample of titanium content, titanium atom still can enter into framework of molecular sieve, extra-framework titanium content is lower.In addition, the relative low price of inorganic raw material can reduce synthetic cost.
(2) do not use auxiliary template agent (being mostly tetra-alkyl ammonium hydroxide), further reduce synthetic cost, and simplify synthesis technique, reduce operation easier.
(3) do not adopt hydrothermal synthesis method and adopt low temperature rapid crystallization method; Avoided the requirement of crystallization process fully to temperature, pressure and time; Make synthetic can under room temperature and condition of normal pressure, the completion; Not only shortened synthetic consuming time greatly; Also reduced requirement, be more conducive to industrial production synthesis device.
(4) because this method steps is simple, condition is easy to control, so it is good to repeat preparation property.
(5) use raw material simple in the building-up process, can reduce environmental pressure.
Description of drawings
Fig. 1 is embodiment 1,2, the X-ray diffractogram of 3,4 and 5 synthetic mesoporous titanium-silicon molecular screens.
Fig. 2 is the ultraviolet-visible light spectrogram of 1 synthetic mesoporous titanium-silicon molecular screen of embodiment.
Fig. 3 is the X-ray diffractogram of embodiment 6,7 and 8 synthetic mesoporous titanium-silicon molecular screens.
Fig. 4 is the ultraviolet-visible light spectrogram of embodiment 6,7 and 8 synthetic mesoporous titanium-silicon molecular screens.
Fig. 5 is the X-ray diffractogram of embodiment 9,10 and 11 synthetic mesoporous titanium-silicon molecular screens.
Fig. 6 is the ultraviolet-visible light spectrogram of embodiment 9,10 and 11 synthetic mesoporous titanium-silicon molecular screens.
Embodiment
The 18.3g cetyl trimethylammonium bromide is dissolved in the 250ml deionized water, at room temperature stirred 30 minutes; With 42.6g water glass (SiO
2Content is 28.26wt%) mix with the 150ml deionized water, in the cetyl trimethylammonium bromide aqueous solution, slowly drip, simultaneously vigorous stirring; With 9.1g 17.0wt%TiCl
3The aqueous solution mixes with the 100ml deionized water, in above-mentioned mixing solutions, slowly drips, simultaneously vigorous stirring; Wherein the mol ratio of silicon source, titanium source, template is 1: 0.05: 0.25.With dilute hydrochloric acid solution system pH is adjusted to 9.5; Continue to stir crystallization 5 hours at 20 ℃.Solid product is separated with mother liquor, with deionized water wash to neutral, 110 ℃ air dryings 5 hours; 550 ℃ of roastings 6 hours, obtain the Ti-MCM-41 mesopore molecular sieve at last.Its specific surface area is 1067m
2/ g; Its X-ray diffraction spectrogram (XRD) as shown in Figure 1,110 spacing d
110Be 3.14nm; Its ultraviolet-visible light spectrogram as shown in Figure 2.
The 18.3g cetyl trimethylammonium bromide is dissolved in the 250ml deionized water, at room temperature stirred 30 minutes; With 42.6g water glass (SiO
2Content is 28.26wt%) mix with the 150ml deionized water, in the cetyl trimethylammonium bromide aqueous solution, slowly drip, simultaneously vigorous stirring; With 9.1g 17.0wt%TiCl
3The aqueous solution mixes with the 100ml deionized water, in above-mentioned mixing solutions, slowly drips, simultaneously vigorous stirring; Wherein the mol ratio of silicon source, titanium source, template is 1: 0.05: 0.25.With dilute hydrochloric acid solution system pH is adjusted to 8.0; Continue to stir crystallization 5 hours at 20 ℃.Solid product is separated with mother liquor, with deionized water wash to neutral, 110 ℃ air dryings 5 hours; 550 ℃ of roastings 6 hours, obtain the Ti-MCM-41 mesopore molecular sieve at last.Its specific surface area is 1062m
2/ g; Its X-ray diffraction spectrogram (XRD) as shown in Figure 1,110 spacing d
110Be 3.35nm; Its ultraviolet-visible spectrum is consistent with the SPECTROSCOPIC CHARACTERIZATION of sample among the embodiment 1.
The 18.3g cetyl trimethylammonium bromide is dissolved in the 250ml deionized water, at room temperature stirred 30 minutes; With 42.6g water glass (SiO
2Content is 28.26wt%) mix with the 150ml deionized water, in the cetyl trimethylammonium bromide aqueous solution, slowly drip, simultaneously vigorous stirring; With 9.1g 17.0wt%TiCl
3The aqueous solution mixes with the 100ml deionized water, in above-mentioned mixing solutions, slowly drips, simultaneously vigorous stirring; Wherein the mol ratio of silicon source, titanium source, template is 1: 0.05: 0.25.With dilute hydrochloric acid solution system pH is adjusted to 9.0; Continue to stir crystallization 5 hours at 20 ℃.Solid product is separated with mother liquor, with deionized water wash to neutral, 110 ℃ air dryings 5 hours; 550 ℃ of roastings 6 hours, obtain the Ti-MCM-41 mesopore molecular sieve at last.Its specific surface area is 1079m
2/ g; Its X-ray diffraction spectrogram (XRD) as shown in Figure 1,110 spacing d
110Be 3.20nm; Its ultraviolet-visible spectrum is consistent with the SPECTROSCOPIC CHARACTERIZATION of sample among the embodiment 1.
The 18.3g cetyl trimethylammonium bromide is dissolved in the 250ml deionized water, at room temperature stirred 30 minutes; With 42.6g water glass (SiO
2Content is 28.26wt%) mix with the 150ml deionized water, in the cetyl trimethylammonium bromide aqueous solution, slowly drip, simultaneously vigorous stirring; With 9.1g 17.0wt%TiCl
3The aqueous solution mixes with the 100ml deionized water, in above-mentioned mixing solutions, slowly drips, simultaneously vigorous stirring; Wherein the mol ratio of silicon source, titanium source, template is 1: 0.05: 0.25.With dilute hydrochloric acid solution system pH is adjusted to 10.0; Continue to stir crystallization 5 hours at 20 ℃.Solid product is separated with mother liquor, with deionized water wash to neutral, 110 ℃ air dryings 5 hours; 550 ℃ of roastings 6 hours, obtain the Ti-MCM-41 mesopore molecular sieve at last.Its specific surface area is 1084m
2/ g; Its X-ray diffraction spectrogram (XRD) as shown in Figure 1,110 spacing d
110Be 3.18nm; Its ultraviolet-visible spectrum is consistent with the SPECTROSCOPIC CHARACTERIZATION of sample among the embodiment 1.
The 18.3g cetyl trimethylammonium bromide is dissolved in the 250ml deionized water, at room temperature stirred 30 minutes; With 42.6g water glass (SiO
2Content is 28.26wt%) mix with the 150ml deionized water, in the cetyl trimethylammonium bromide aqueous solution, slowly drip, simultaneously vigorous stirring; With 9.1g 17.0wt%TiCl
3The aqueous solution mixes with the 100ml deionized water, in above-mentioned mixing solutions, slowly drips, simultaneously vigorous stirring; Wherein the mol ratio of silicon source, titanium source, template is 1: 0.05: 0.25.With dilute hydrochloric acid solution system pH is adjusted to 11.0; Continue to stir crystallization 5 hours at 20 ℃.Solid product is separated with mother liquor, with deionized water wash to neutral, 110 ℃ air dryings 5 hours; 550 ℃ of roastings 6 hours, obtain the Ti-MCM-41 mesopore molecular sieve at last.Its specific surface area is 1109m
2/ g; Its X-ray diffraction spectrogram (XRD) as shown in Figure 1,110 spacing d
110Be 3.06nm; Its ultraviolet-visible spectrum is consistent with the SPECTROSCOPIC CHARACTERIZATION of sample among the embodiment 1.
The 18.3g cetyl trimethylammonium bromide is dissolved in the 250ml deionized water, at room temperature stirred 30 minutes; With 57.0g Na
2SiO
39H
2O is dissolved in the 150ml deionized water, in the cetyl trimethylammonium bromide aqueous solution, slowly drips, simultaneously vigorous stirring; With 9.1g 17.0wt%TiCl
3The aqueous solution mixes with the 100ml deionized water, in above-mentioned mixing solutions, slowly drips, simultaneously vigorous stirring; Wherein the mol ratio of silicon source, titanium source, template is 1: 0.05: 0.25.With dilute hydrochloric acid solution system pH is adjusted to 9.5; Continue to stir crystallization 3 hours at 30 ℃.Solid product is separated with mother liquor, with deionized water wash to neutral, 110 ℃ air dryings 5 hours; 550 ℃ of roastings 6 hours, obtain the Ti-MCM-41 mesopore molecular sieve at last.Its specific surface area is 1093m
2/ g; Its X-ray diffraction spectrogram (XRD) as shown in Figure 3,110 spacing d
110Be 3.34nm; Its ultraviolet-visible light spectrogram as shown in Figure 4.
The 18.3g cetyl trimethylammonium bromide is dissolved in the 250ml deionized water, at room temperature stirred 30 minutes; With 57.0g Na
2SiO
39H
2O is dissolved in the 150ml deionized water, in the cetyl trimethylammonium bromide aqueous solution, slowly drips, simultaneously vigorous stirring; With 5.5g 17.0wt%TiCl
3The aqueous solution mixes with the 100ml deionized water, in above-mentioned mixing solutions, slowly drips, simultaneously vigorous stirring; Wherein the mol ratio of silicon source, titanium source, template is 1: 0.03: 0.25.With dilute hydrochloric acid solution system pH is adjusted to 9.5; Continue to stir crystallization 5 hours at 20 ℃.Solid product is separated with mother liquor, with deionized water wash to neutral, 110 ℃ air dryings 5 hours; 550 ℃ of roastings 6 hours, obtain the Ti-MCM-41 mesopore molecular sieve at last.Its specific surface area is 1136m
2Its X-ray diffraction spectrogram (XRD) of/g as shown in Figure 3,110 spacing d
110Be 3.43nm; Its ultraviolet-visible light spectrogram as shown in Figure 4.
The 18.3g cetyl trimethylammonium bromide is dissolved in the 250ml deionized water, at room temperature stirred 30 minutes; With 42.6g water glass (SiO
2Content is 28.26wt%) mix with the 150ml deionized water, in the cetyl trimethylammonium bromide aqueous solution, slowly drip, simultaneously vigorous stirring; With 3.6g 17.0wt%TiCl
3The aqueous solution mixes with the 100ml deionized water, in above-mentioned mixing solutions, slowly drips, simultaneously vigorous stirring; Wherein the mol ratio of silicon source, titanium source, template is 1: 0.02: 0.25.With dilute hydrochloric acid solution system pH is adjusted to 9.5; Continue to stir crystallization 5 hours at 10 ℃.Solid product is separated with mother liquor, with deionized water wash to neutral, 110 ℃ air dryings 5 hours; 550 ℃ of roastings 6 hours, obtain the Ti-MCM-41 mesopore molecular sieve at last.Its specific surface area is 1189m
2/ g; Its X-ray diffraction spectrogram (XRD) as shown in Figure 3,110 interplanar d
110Be 3.44nm; Its ultraviolet-visible light spectrogram as shown in Figure 4.
The 18.3g cetyl trimethylammonium bromide is dissolved in the 250ml deionized water, at room temperature stirred 30 minutes; With 42.6g water glass (SiO
2Content is 28.26wt%) mix with the 150ml deionized water, in the cetyl trimethylammonium bromide aqueous solution, slowly drip, simultaneously vigorous stirring; The 2.4g titanium sulfate is dissolved in the 100ml dilute sulphuric acid, in above-mentioned mixing solutions, slowly drips, simultaneously vigorous stirring; Wherein the mol ratio of silicon source, titanium source, template is 1: 0.05: 0.25.With dilution heat of sulfuric acid system pH is adjusted to 9.5; Continue to stir crystallization 5 hours at 20 ℃.Solid product is separated with mother liquor, with deionized water wash to neutral, 110 ℃ air dryings 5 hours; 550 ℃ of roastings 6 hours, obtain the Ti-MCM-41 mesopore molecular sieve at last.Its specific surface area is 1169m
2/ g; Its X-ray diffraction spectrogram (XRD) as shown in Figure 5,110 interplanar d
110Be 3.61nm; Its ultraviolet-visible light spectrogram as shown in Figure 6.
The 18.3g cetyl trimethylammonium bromide is dissolved in the 250ml deionized water, at room temperature stirred 30 minutes; With 57.0g Na
2SiO
39H
2O is dissolved in the 150ml deionized water, in the cetyl trimethylammonium bromide aqueous solution, slowly drips, simultaneously vigorous stirring; The 1.2g titanium sulfate is dissolved in the 100ml dilute sulphuric acid, in above-mentioned mixing solutions, slowly drips, simultaneously vigorous stirring; Wherein the mol ratio of silicon source, titanium source, template is 1: 0.025: 0.25.With dilution heat of sulfuric acid system pH is adjusted to 9.5; Continue to stir crystallization 5 hours at 10 ℃.Solid product is separated with mother liquor, with deionized water wash to neutral, 110 ℃ air dryings 5 hours; 550 ℃ of roastings 6 hours, obtain the Ti-MCM-41 mesopore molecular sieve at last.Its specific surface area is 1254m
2/ g; Its X-ray diffraction spectrogram (XRD) as shown in Figure 5,110 spacing d
110Be 3.52nm; Its ultraviolet-visible light spectrogram as shown in Figure 6.
Embodiment 11
The 18.3g cetyl trimethylammonium bromide is dissolved in the 250ml deionized water, at room temperature stirred 30 minutes; With 42.6g water glass (SiO
2Content is 28.26wt%) mix with the 150ml deionized water, in the cetyl trimethylammonium bromide aqueous solution, slowly drip, simultaneously vigorous stirring; The 0.9g titanium sulfate is dissolved in the 100ml dilute sulphuric acid, in above-mentioned mixing solutions, slowly drips, simultaneously vigorous stirring; Wherein the mol ratio of silicon source, titanium source, template is 1: 0.018: 0.25.With dilution heat of sulfuric acid system pH is adjusted to 9.5; Continue to stir crystallization 5 hours at 10 ℃.Solid product is separated with mother liquor, with deionized water wash to neutral, 110 ℃ air dryings 5 hours; 550 ℃ of roastings 6 hours, obtain the Ti-MCM-41 mesopore molecular sieve at last.Its specific surface area is 1307m
2/ g; Its X-ray diffraction spectrogram (XRD) as shown in Figure 5,110 spacing d
110Be 3.54nm; Its ultraviolet-visible light spectrogram as shown in Figure 6.
Claims (5)
1. the synthesis method of a mesoporous titanium-silicon molecular screen material; Comprise the steps: at ambient temperature; With water glass or Starso is the silicon source; Inorganic titanium salt is the titanium source, and quaternary ammonium cation is a template, and water is solvent; Above-mentioned raw materials is mixed; With sour regulation system pH value to 7～12, crystallization is 1～24 hour under 0～50 ℃ of stirring, and product obtains mesoporous titanium-silicon molecular screen material through separation, washing, drying, roasting;
Wherein the feed molar proportioning is:
SiO
2: quaternary ammonium cation=1～20: 1
SiO
2∶TiO
2＝10～1000∶1
SiO
2∶H
2O＝0.001～0.05∶1。
2. according to the synthesis method of the said mesoporous titanium-silicon molecular screen material of claim 1, it is characterized in that inorganic ti sources adopts TiCl
3, TiCl
4, TiOCl
2, Ti (NO
3)
4Or Ti (SO
4)
2
3. according to the synthesis method of the said mesoporous titanium-silicon molecular screen material of claim 1, the general formula that it is characterized in that the quaternary ammonium cation template is [NR
1R
2R
3R
4]
+, R wherein
1Represent C
12～C
30The straight or branched alkyl, R
2, R
3And R
4Be C
1～C
4The straight or branched alkyl, R
2, R
3And R
4Can be identical or different, preferably identical.
4. according to the synthesis method of the said mesoporous titanium-silicon molecular screen material of claim 1, the acid that it is characterized in that regulation system pH value is organic acid or mineral acid, preferred mineral acid, at least a in for example following: hydrochloric acid, sulfuric acid and nitric acid.
5. according to the synthesis method of the said mesoporous titanium-silicon molecular screen material of claim 1, comprise the steps:
(1) at ambient temperature, the quaternary ammonium cation template is dissolved in deionized water, forms colourless transparent solution, stirred 10～120 minutes
(2) at ambient temperature, the silicon source is mixed with deionized water, obtain water white transparency or translucent solution; In the template aqueous solution, add the silicon source aqueous solution, form gel mixture.In the adition process, siliceous ionic concn gathers way and is no more than 5.0mol/L/h in the system, simultaneously vigorous stirring;
(3) at ambient temperature, the titanium source is mixed with deionized water, obtain the aqueous solution; In the gel mixture in template and silicon source, add the titanium source aqueous solution, contain titanium ion concentration in the system and gather way and be no more than 5.0mol/L/h, simultaneously vigorous stirring;
(4) with sour regulation system pH value to 7～12, crystallization is 1～24 hour under 0～50 ℃ of stirring;
(5) solid product is separated with mother liquor, to neutral, 3～10 hour obtain titanium-containing meso-porous molecular sieve former powder at 70～120 ℃ air dryings with deionized water wash, 400～600 ℃ of roastings 2～16 hours obtain mesoporous titanium-silicon molecular screen material.
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| CN103861574A (en) * | 2014-02-28 | 2014-06-18 | 中国海洋石油总公司 | Method for preparing titanium-silicon composite oxide |
| CN104418343A (en) * | 2013-08-20 | 2015-03-18 | 大连多相触媒有限公司 | TS-1 titanium silicon molecular sieve, preparation method and application thereof |
| CN104556104A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for synthesizing titanium-silicalite molecular sieve employing organic quaternary ammonium salt template agent |
| CN104556111A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Ti-Si molecular sieve and synthesis method thereof |
| CN106145145A (en) * | 2015-04-17 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hetero-atom molecular-sieve and synthetic method thereof |
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| CN112429747A (en) * | 2020-11-30 | 2021-03-02 | 大连理工大学 | Preparation method for rapidly synthesizing titanium silicalite TS-1 with high titanium content under normal pressure by circularly using crystallization mother liquor |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1428296A (en) * | 2001-12-28 | 2003-07-09 | 中国科学院大连化学物理研究所 | Method for synthesizing new titanium-silicone metapore molecular sieve |
| CN1513760A (en) * | 2002-12-31 | 2004-07-21 | 中国石油化工股份有限公司 | Method of synthesizing titanium silicon molecular sieve |
| CN101012063A (en) * | 2007-02-07 | 2007-08-08 | 中国日用化学工业研究院 | Method for preparing titanium-containing molecular sieve |
| CN101456562A (en) * | 2009-01-06 | 2009-06-17 | 北京科技大学 | Method for preparing mesoporous titanium silicate molecular sieve |
-
2010
- 2010-07-29 CN CN2010102400034A patent/CN102344150A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1428296A (en) * | 2001-12-28 | 2003-07-09 | 中国科学院大连化学物理研究所 | Method for synthesizing new titanium-silicone metapore molecular sieve |
| CN1513760A (en) * | 2002-12-31 | 2004-07-21 | 中国石油化工股份有限公司 | Method of synthesizing titanium silicon molecular sieve |
| CN101012063A (en) * | 2007-02-07 | 2007-08-08 | 中国日用化学工业研究院 | Method for preparing titanium-containing molecular sieve |
| CN101456562A (en) * | 2009-01-06 | 2009-06-17 | 北京科技大学 | Method for preparing mesoporous titanium silicate molecular sieve |
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| CN104556111B (en) * | 2013-10-29 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of Titanium Sieve Molecular Sieve and its synthetic method |
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| CN104556111A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Ti-Si molecular sieve and synthesis method thereof |
| CN103818923A (en) * | 2014-01-17 | 2014-05-28 | 温州大学 | Mesoporous TS-1 zeolite and application thereof |
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| CN106145145B (en) * | 2015-04-17 | 2018-07-31 | 中国石油化工股份有限公司 | A kind of hetero-atom molecular-sieve and its synthetic method |
| CN106145144B (en) * | 2015-04-17 | 2019-09-24 | 中国石油化工股份有限公司 | A kind of micro- mesoporous composite material of hetero atom and its synthetic method |
| CN108529643A (en) * | 2018-06-14 | 2018-09-14 | 辽宁科技大学 | A method of preparing titanium doped mesopore molecular sieve |
| CN108529643B (en) * | 2018-06-14 | 2020-01-03 | 辽宁科技大学 | Method for preparing titanium-doped mesoporous molecular sieve |
| CN112010321A (en) * | 2019-05-31 | 2020-12-01 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve, preparation method thereof and method for producing ketoxime by macromolecular ketone ammoximation reaction |
| CN112010321B (en) * | 2019-05-31 | 2022-06-24 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve, preparation method thereof and method for producing ketoxime by macromolecular ketone ammoximation reaction |
| CN112429747A (en) * | 2020-11-30 | 2021-03-02 | 大连理工大学 | Preparation method for rapidly synthesizing titanium silicalite TS-1 with high titanium content under normal pressure by circularly using crystallization mother liquor |
| CN112624144A (en) * | 2020-12-25 | 2021-04-09 | 南开大学 | Preparation method of heteroatom MFI molecular sieve nanosheet |
| CN112624144B (en) * | 2020-12-25 | 2024-03-12 | 南开大学 | Preparation method of heteroatom MFI molecular sieve nanosheets |
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