CN1239015A - Process for synthesizing Ti-Si molecular sieve - Google Patents
Process for synthesizing Ti-Si molecular sieve Download PDFInfo
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- CN1239015A CN1239015A CN 98102390 CN98102390A CN1239015A CN 1239015 A CN1239015 A CN 1239015A CN 98102390 CN98102390 CN 98102390 CN 98102390 A CN98102390 A CN 98102390A CN 1239015 A CN1239015 A CN 1239015A
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Abstract
A process for synthesizing Ti-Si molecular sieve (TS-1) includes preparing a reaction mixture used to synthesize molecular sieve TS-1, pre-crystallizing at 110-145 deg.C for 0.1-5 hr in sealed reactor, heating to 150-200deg.C, and continuous crystallizing for one hr-3 days. Its advantages include greatly decreased crystallization period, high day output and high catalytic oxidizing activity and selectivity of molecular sieve.
Description
The present invention relates to a kind of preparation method of HTS, more particularly relate to a kind of preparation method of five-membered ring HTS (TS-1) of the MFI of having structure.
HTS is the novel hetero-atom molecular-sieve that early eighties begins to develop.The TS-1 that MFI type structure is arranged that has synthesized at present, the TS-2 of MEL type structure, and have than the TS-48 of macroporous structure etc.This molecular sieve analog is to many organic oxidizing reactions, for example the reactions such as oxidation of the epoxidation of alkene, aromatic hydrocarbons hydroxylating, cyclohexanone oximate, alcohol have excellent catalytic activity and selective paraffin oxidation performance, and they have a good application prospect as redox (redox) type molecular sieve catalyst.
TS-1 introduces the framework of molecular sieve with ZSM-5 structure, formed a kind of new titanium-silicone molecular sieve with good selective paraffin oxidation catalytic performance with transition metals Ti.TS-1 not only has the titanium catalysed oxidn good to organic compound, but also has the shape effect selected and the advantages of excellent stability of ZSM-5 molecular sieve.Because the TS-1 molecular sieve in organic oxidation reaction, can adopt the low concentration hydrogen peroxide as oxidant, and have good reaction selectivity, can avoid problem such as complex process and environmental pollution in the oxidizing process.Therefore, have unrivaled energy-conservation, economy of conventional oxidation system and advantages of environment protection, favorable industrial application prospect is arranged.
The preparation method of TS-1 that people such as gondola Marco Taramasso disclose (GB2,071,071A, USP4,410,501) first in 1981.This method is to prepare a kind of silicon source, titanium source, organic base (RN of containing earlier
+) and/or basic anhydride (Me
N/2O) reactant mixture, with this reactant mixture in autoclave in 130～200 ℃ of hydrothermal crystallizings 6～30 days, separate then, wash, dry, roasting and product.Silicon source wherein can be tetraalkyl esters of silicon acis, colloidal state SiO
2Or alkali silicate, the titanium source can be hydrolyzable titanium compound, preferred Ti (OC
2H
5)
4, the preferred TPAOH of organic base (TPAOH), wherein the mole compositing range of reactant mixture is:
The general range preferable range
SiO
2/TiO
2:??5～200????????35～65
OH-/SiO
2:????0.1～1.0??????0.3～0.6
H
2O/SiO
2:???20～200???????60～100
Me/SiO
2:?????0～0.5??????????0
RN
+/SiO
2:???0.1～2.0??????0.4～1.0
People such as Thangaraj think enter skeleton in the TS-1 molecular sieve that method for preparing goes out effective Ti content seldom, so they disclose a kind of method (Zeolites for preparing the TS-1 molecular sieve that can effectively increase the skeleton Ti content in 1992,1992, the 12nd volume, the 943rd～950 page), it is said that the Si/Ti of the method gained molecular sieve that people such as Taramasso can be proposed is than dropping to 20 from 39.This method is that an amount of TPAOH (TPAOH) aqueous solution is joined stirring and dissolving certain hour in the ethyl silicate solution, under vigorous stirring, slowly add the liquid mixture that the aqueous isopropanol of butyl titanate obtains clarifying (must slowly drip form white TiO2 precipitate) then to prevent that tetrabutyl titanate hydrolysis is too fast, stir after 15 minutes, slowly add an amount of TPAOH aqueous solution again, catch up with alcohol to be transferred to after 3～6 hours in the autoclave in 75～80 ℃ reactant mixture then in 170 ℃ of following hydrothermal crystallizings 3～6 days, after the drying the TS-1 molecular sieve.Wherein the mole of reactant mixture consists of: SiO
2: (0.01～0.10) TiO
2: 0.36TPAOH:35H
2O.
Du Hongwei etc. have proposed a kind of preparation method of TS-1 molecular sieve in CN1167082A, this method is that the titanium source is dissolved in TPAOH (TPAOH) aqueous solution, and mix with the solid silicone bead and to obtain reactant mixture, with this reactant mixture in autoclave in 130～200 ℃ of hydrothermal crystallizings 1～6 day, filter according to a conventional method then, wash, drying and roasting; Experiment show when crystallization time during less than two days the crystallization effect bad.
The method of above-mentioned prior art crystallization time in preparation is all very long, generally all more than 3 days, even reach more than 6 days, make that the preparation cost of TS-1 is higher, and the reactivity of products obtained therefrom is lower, prepared its quality of every batch of product is difficult for repeating, and has restricted the commercial Application of TS-1 molecular sieve.
The synthetic method that the purpose of this invention is to provide a kind of TS-1 molecular sieve with the shortening crystallization time, and improves the activity of products obtained therefrom.
The synthetic method of TS-1 molecular sieve provided by the present invention is to prepare a kind of reactant mixture that is used for synthetic TS-1 molecular sieve according to the method for prior art earlier; With this reactant mixture in sealed reactor in 110～145 ℃ of pre-crystallization 0.1～5 hour, preferably in 120～130 ℃ of pre-crystallization 0.5～3 hour, obtain to contain the titanium silicon mixture of tiny crystal grains; Temperature to the 150～200 ℃ continuation crystallization that raises then 1 hour～3 days preferably continued crystallization 5 hours～1 day at 150～180 ℃.
Said reactant mixture can prepare according to the method for prior art in the synthetic method of TS-1 molecular sieve provided by the present invention, and for example the method for people's propositions such as the method for people's propositions such as the method that proposes according to people such as foregoing Taramasso, Thangaraj and Du Hongwei prepares.
The synthetic method of TS-1 molecular sieve provided by the present invention can be made up of the following step:
(1). with silicon source, organo-alkali compound and water according to 1: (0.05～2.00): (5～100), preferred 1: (0.10～0.35): the mol ratio of (10～60) mixes and makes the hydrolysis of silicon source, obtains the hydrating solution of silicon;
(2). with titanium source, isopropyl alcohol, tetrapropyl aqua ammonia and water according to 1: (0～60): (0.3～30): (10～100), preferred 1: (0～20): (0.8～5.5): the mol ratio of (10～60) mixes and makes the hydrolysis of titanium source, obtains the hydrating solution of titanium.
(3), with the hydrating solution of the hydrating solution of step (2) gained titanium and step (1) gained silicon according to silicon/titanium=5～100, preferred 5～50 mol ratio is mixed down and stirring reaction 0.5～6 hour at 50～100 ℃, obtains said reactant mixture.
(4). step (3) gained reactant mixture is put into sealed reactor,,, obtain to contain the titanium silicon mixture of tiny crystal grains preferably in 120～140 ℃ of pre-crystallization 0.5～3 hour in 110～145 ℃ of pre-crystallization 0.1～5 hour; Temperature to the 150～200 ℃ continuation crystallization that raises then 1 hour～3 days preferably continued crystallization 5 hours～1 day at 150～180 ℃.
Wherein the said silicon of step (1) source is silica gel such as white carbon black, Ludox or tetraalkyl esters of silicon acis, wherein tetraalkyl esters of silicon acis preferably; Said its general formula of tetraalkyl esters of silicon acis is R
1 4SiO
4, R wherein
1For having the alkyl of 1～4 carbon atom.
Wherein the said organo-alkali compound of step (1) is fat amine compound, alcamine compound or quaternary amine alkali compounds, or mix the mixed amine compounds of forming mutually by them, wherein preferably alcamine compound or quaternary amine alkali compounds are more preferably the quaternary amine alkali compounds; Said quaternary amine alkali compounds is the quaternary amine alkali compounds that contains the alkyl with 1～4 carbon atom, wherein preferably tetraethyl aqua ammonia or tetrapropyl aqua ammonia.
Its general formula of said fat amine compound is R
2(NH
2)
n, R wherein
2For having the alkyl of 1～4 carbon atom, n=1 or 2, wherein preferred fat amine compound is ethamine, ethylenediamine, n-butylamine, butanediamine or hexamethylene diamine.
Its general formula of said alcamine compound is (HOR
3)
mN; R wherein
3For having the alkyl of 1～4 carbon atom; M=1～3; Wherein preferred alcamine compound is MEA, diethanol amine or triethanolamine.
Wherein said hydrolysis time is 10～300 minutes in the step (1), is preferably 10～120 minutes, and hydrolysising reacting temperature is 0～45 ℃, is preferably 0～20 ℃.
Wherein the said titanium of step (2) source is inorganic titanium salt such as TiCl
4, Ti (SO
4)
2Perhaps organic titanate Ti (OR
4)
4, R wherein
4For having 1～6, the alkyl of preferred 2～4 carbon atoms; Wherein preferred titanium source is an organic titanate.
Wherein the said hydrolysis time of step (2) is 5～90 minutes, is preferably 10～60 minutes, and hydrolysis temperature need not strict control, is generally 0～45 ℃.
Fig. 1 is X-ray diffraction (XRD) the crystalline phase figure of embodiment 1 gained sample.
Compared with prior art, the present invention is owing to adopt first at a lower temperature pre-crystallization, and the technique of crystallization under higher temperature again is so that crystallization time shortens greatly. By several days of prior art, shorten to several hours, thereby can improve the daily output of HTS, reduce cost, and the catalytic oxidation activity of the inventive method gained HTS and selectively high than Comparative Examples, illustrate that the inventive method is also beneficial to the activity and selectivity that improves HTS.
Following embodiment will the present invention is further illustrated.In each of the embodiments described below, used TPAOH is that the Tokyo changes into product, and white carbon black is a Qingdao silica gel factory product, and all the other reagent are commercially available chemically pure reagent.
Comparative Examples 1
The effect of the synthetic TS-1 molecular sieve of the method that the explanation of this Comparative Examples proposes according to people such as Thangaraj (Zeolites, 1992, the 12 volumes, the 943rd～950 page).
The positive tetraethyl orthosilicate of 22.5 grams is mixed with 7.0 gram (0.034 mole) TPAOHs, and add 59.8 the gram distilled water, mix the back in 60 ℃ of following hydrolysis 1.0 hours, obtain the hydrating solution of positive tetraethyl orthosilicate, under vigorous stirring, in above-mentioned solution, add the solution of forming by 1.1 gram butyl titanates and 5.0 gram anhydrous isopropyl alcohols lentamente, the gained mixture was stirred 3 hours down at 75 ℃, obtain the clear colloid.This colloid is put into the stainless steel sealed reactor, and constant temperature was placed 3 days under 170 ℃ temperature, obtained the mixture of crystallization product; This mixture is filtered, is washed with water to pH is 6～8, and in 110 ℃ of dryings 60 minutes, obtains the TS-1 molecular screen primary powder.The former powder of this TS-1 in 550 ℃ of following roastings 3 hours, is got the TS-1 molecular sieve, it is numbered DB-1, the peak type of its XRD crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 1
1.0 moles positive silicic acid orthocarbonates are mixed with 0.25 mole of tetrapropyl aqua ammonia, and add 25.5 moles distilled water,, obtain organosilyl hydrating solution in 30 ℃ of hydrolysis 50 minutes.
0.03 mole of metatitanic acid orthocarbonate is mixed with 1.25 moles of anhydrous isopropyl alcohols, 0.15 mole of TPAOH and 2.85 moles of distilled water,, obtain the hydrating solution of metatitanic acid orthocarbonate in 35 ℃ of hydrolysis 30 minutes.
Under agitation lentamente the hydrating solution of metatitanic acid orthocarbonate is joined in the organosilyl hydrating solution, and the gained mixture was stirred 3 hours down in 50 ℃, obtain the titanium colloidal silica.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, and 125 ℃ of following pre-crystallization 2 hours, the temperature to 160 that raises then ℃ continued crystallization 10 hours, obtained crystallization product.This crystallization product is filtered and is washed with water to pH=6～8, then 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered A-1.Its XRD crystalline phase figure as shown in Figure 1.
Embodiment 2
1.0 moles positive silicic acid orthocarbonates are mixed with 0.25 mole of tetrapropyl aqua ammonia, and add 25.5 moles distilled water,, obtain organosilyl hydrating solution in 30 ℃ of hydrolysis 50 minutes.
0.03 mole of metatitanic acid orthocarbonate is mixed with 1.25 moles of anhydrous isopropyl alcohols, 0.25 mole of TPAOH and 2.85 moles of distilled water,, obtain the hydrating solution of metatitanic acid orthocarbonate in 35 ℃ of hydrolysis 30 minutes.
Under agitation lentamente the hydrating solution of metatitanic acid orthocarbonate is joined in the organosilyl hydrating solution, and the gained mixture was stirred 3 hours down in 75 ℃, obtain the titanium colloidal silica.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, and 125 ℃ of following pre-crystallization 20 minutes, the temperature to 160 that raises then ℃ continued crystallization 1.5 hours, obtained crystallization product.This crystallization product is filtered and is washed with water to pH=6～8, then 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered A-2.The peak type of its XRD crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 3
1.0 moles positive silicic acid orthocarbonates are mixed with 0.25 mole of tetrapropyl aqua ammonia, and add 25.5 moles distilled water,, obtain organosilyl hydrating solution in 30 ℃ of hydrolysis 50 minutes.
0.03 mole of metatitanic acid orthocarbonate is mixed with 1.25 moles of anhydrous isopropyl alcohols, 0.05 mole of TPAOH and 2.85 moles of distilled water,, obtain the hydrating solution of metatitanic acid orthocarbonate in 35 ℃ of hydrolysis 30 minutes.
Under agitation lentamente the hydrating solution of metatitanic acid orthocarbonate is joined in the organosilyl hydrating solution, and the gained mixture was stirred 2 hours down in 85 ℃, obtain the titanium colloidal silica.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, and 125 ℃ of following pre-crystallization 2 hours, the temperature to 155 that raises then ℃ continued crystallization 5 hours, obtained crystallization product.This crystallization product is filtered and is washed with water to pH=6～8, then 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered A-3.The peak type of its XRD crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 4
1.0 moles positive silicic acid four butyl esters are mixed with 0.12 mole of tetraethyl ammonium hydroxide, and add 12.0 moles distilled water,, obtain organosilyl hydrating solution in 15 ℃ of hydrolysis 35 minutes.
0.05 mole of tetraethyl titanate is mixed with 1.0 moles of anhydrous isopropyl alcohols, 0.15 mole of TPAOH and 1.0 moles of distilled water,, obtain the hydrating solution of tetraethyl titanate in 15 ℃ of hydrolysis 8 minutes.
Under agitation lentamente the hydrating solution of tetraethyl titanate is joined in the organosilyl hydrating solution, the gained mixture was stirred 4 hours in 65 ℃, obtain the titanium colloidal silica.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, and 115 ℃ of following pre-crystallization 4.5 hours, the temperature to 175 that raises then ℃ continued crystallization 6 hours, obtained crystallization product.This crystallization product is filtered and is washed with water to pH=6～8, then 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered A-4.The peak type of its XRD crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 5
1.0 moles positive silicic acid four butyl esters are mixed with 0.12 mole of tetraethyl ammonium hydroxide, and add 12.0 moles distilled water,, obtain organosilyl hydrating solution in 15 ℃ of hydrolysis 35 minutes.
0.05 mole of tetraethyl titanate is mixed with 1.0 moles of anhydrous isopropyl alcohols, 0.55 mole of TPAOH and 1.0 moles of distilled water,, obtain the hydrating solution of tetraethyl titanate in 15 ℃ of hydrolysis 8 minutes.
Under agitation lentamente the hydrating solution of tetraethyl titanate is joined in the organosilyl hydrating solution, the gained mixture was stirred 4 hours in 80 ℃, obtain the titanium colloidal silica.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, and 135 ℃ of following pre-crystallization 3 hours, the temperature to 175 that raises then ℃ continued crystallization 10 hours, obtained crystallization product.This crystallization product is filtered and is washed with water to pH=6～8, then 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered A-5.The peak type of its XRD crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 6
1.0 moles positive silicic acid four butyl esters are mixed with 0.12 mole of tetraethyl ammonium hydroxide, and add 12.0 moles distilled water,, obtain organosilyl hydrating solution in 15 ℃ of hydrolysis 35 minutes.
0.05 mole of tetraethyl titanate is mixed with 1.0 moles of anhydrous isopropyl alcohols, 0.35 mole of TPAOH and 1.0 moles of distilled water,, obtain the hydrating solution of tetraethyl titanate in 15 ℃ of hydrolysis 8 minutes.
Under agitation lentamente the hydrating solution of tetraethyl titanate is joined in the organosilyl hydrating solution, the gained mixture was stirred 2 hours in 90 ℃, obtain the titanium colloidal silica.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, and 145 ℃ of following pre-crystallization 0.5 hour, the temperature to 175 that raises then ℃ continued crystallization 18 hours, obtained crystallization product.This crystallization product is filtered and is washed with water to pH=6～8, then 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered A-6.The peak type of its XRD crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 7
With 0.85 mole (with SiO
2Meter) white carbon black mixes with the mixed amine of being made up of 0.1 mole of triethanolamine and 0.1 mole of TPAOH, to the distilled water that wherein adds 38.5 moles, stirs hydrolysis 45 minutes down in normal pressure and 10 ℃, obtains siliceous mixed liquor.
0.08 mole of butyl titanate is mixed with 2.6 moles of anhydrous isopropyl alcohols, 0.2 mole of TPAOH and 0.54 mole of distilled water, under normal pressure,, obtain the hydrating solution of titanium in 24 ℃ of hydrolysis 16 minutes.
Under agitation lentamente the hydrating solution of titanium is joined in the siliceous mixed liquor, and the gained mixture was stirred 3.5 hours down in 50 ℃, obtain the titanium colloidal silica.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, and 120 ℃ of pre-crystallization 3.5 hours, the temperature to 185 that raises then ℃ continued crystallization 0.8 hour, obtained crystallization product.This crystallization product is filtered and is washed with water to pH=6～8, then 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered A-7.The peak type of its XRD crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 8
1.0 moles positive tetraethyl orthosilicates and the mixed amine of being made up of 0.1 mole of triethanolamine and 0.1 mole of TPAOH are mixed, to the distilled water that wherein adds 38.5 moles, stir hydrolysis 45 minutes down in normal pressure and 10 ℃, obtain the hydrating solution of silicon.
Under 24 ℃ with 0.1 mole of TiCl
4Be added dropwise in the solution that contains 0.2 mole of TPAOH and 3.1 moles of distilled water, again 24 ℃ of following hydrolysis 30 minutes, obtain the hydrating solution of titanium after dripping.
Under agitation lentamente the hydrating solution of titanium is joined in the hydrating solution of silicon, and the gained mixture was stirred 2.5 hours down in 70 ℃, obtain the titanium colloidal silica.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, and 125 ℃ of pre-crystallization 1 hour, the temperature to 170 that raises then ℃ continued crystallization 2 hours, obtained crystallization product.This crystallization product is filtered and is washed with water to pH=6～8, then 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered A-8.The peak type of its XRD crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 9
The method gained TS-1 molecular sieve of present embodiment explanation the inventive method and Comparative Examples is used for the effect of the catalytic oxidation of phenol hydroxylation.
The TS-1 molecular sieve that the foregoing description and Comparative Examples is prepared is according to TS-1: phenol: the weight ratio of acetone=1: 20.0: 16.0 mixes in a there-necked flask that has a condenser pipe, be warming up to 80 ℃, then under stirring according to phenol: the weight ratio of hydrogen peroxide=1: 0.39 adds the hydrogen peroxide that concentration is 30 heavy %, reaction is 6 hours under this temperature, products therefrom uses the OV-101 capillary column on the Varian3400 chromatograph (30m * 0.25mm) measure each product to distribute the results are shown in Table 1.In table 1:
From table 1 data as can be seen, the inventive method products obtained therefrom molecular sieve is compared its reactivity with Comparative Examples 1 products obtained therefrom molecular sieve and selectivity improves a lot.Illustrate that the inventive method not only can shorten crystallization time, but also can improve the catalytic oxidation activity and the selectivity of product.
Table 1
| Title | Phenol conversion % | Benzenediol selectivity % | Product distribution % | ||
| Catechol | Hydroquinones | Benzoquinones | |||
| A-1 | 20.54 | 97.46 | 49.59 | 47.87 | 2.54 |
| A-2 | 19.87 | 95.64 | 51.45 | 44.19 | 4.36 |
| A-3 | 18.67 | 98.15 | 51.67 | 46.48 | 1.85 |
| A-4 | 21.68 | 96.26 | 52.41 | 43.85 | 3.74 |
| A-5 | 18.61 | 98.26 | 53.17 | 45.09 | 1.74 |
| A-6 | 17.37 | 98.16 | 50.49 | 47.67 | 1.84 |
| A-7 | 11.84 | 92.49 | 57.84 | 34.65 | 7.51 |
| A-8 | 14.12 | 94.78 | 58.16 | 36.62 | 5.22 |
| DB-1 | 8.65 | 88.87 | 68.13 | 20.74 | 11.13 |
Claims (15)
1. preparation method with HTS (TS-1) of MFI structure, it is characterized in that this method is to prepare a kind of reactant mixture that is used for synthetic TS-1 molecular sieve according to the method for prior art earlier, with this reactant mixture in sealed reactor in 110～145 ℃ of pre-crystallization 0.1～5 hour, temperature to the 150～200 ℃ continuation crystallization that raises then 1 hour～3 days reclaims product then.
2. according to the method for claim 1, it is characterized in that this method is to prepare a kind of reactant mixture that is used for synthetic TS-1 molecular sieve according to the method for prior art earlier, with this reactant mixture in sealed reactor in 120～140 ℃ of pre-crystallization 0.5～3 hour, temperature to the 150～180 ℃ continuation crystallization that raises then 5 hours～1 day reclaims product then.
3. according to the method for claim 1, it is characterized in that this method is made up of the following step:
(1). with silicon source, organo-alkali compound and water according to 1: (0.05～2.00): the mol ratio of (5～100) mixes and makes the hydrolysis of silicon source, obtains the hydrating solution of silicon;
(2). with titanium source, isopropyl alcohol, tetrapropyl aqua ammonia and water according to 1: (0～60): (0.3～30): the mol ratio of (10～100) mixes and makes the hydrolysis of titanium source, obtains the hydrating solution of titanium.
(3), the hydrating solution of step (2) gained titanium mixed under 50～100 ℃ according to the mol ratio of silicon/titanium=5～100 with the hydrating solution of step (1) gained silicon and stirring reaction 0.5～6 hour, obtain said reactant mixture.
(4). step (3) gained reactant mixture is put into sealed reactor, and in 110～145 ℃ of pre-crystallization 0.1～5 hour, crystallization ℃ was continued 1 hour～3 days in temperature to 150～200 that raise then, reclaimed product then.
4. according to the method for claim 3, it is characterized in that this method is made up of the following step:
(1). with silicon source, organo-alkali compound and water according to 1: (0.10～0.35): the mol ratio of (10～60) mixes and makes the hydrolysis of silicon source, obtains the hydrating solution of silicon;
(2). with titanium source, isopropyl alcohol, tetrapropyl aqua ammonia and water according to 1: (0～20): (0.8～5.5): the mol ratio of (10～60) mixes and makes the hydrolysis of titanium source, obtains the hydrating solution of titanium.
(3), the hydrating solution of step (2) gained titanium mixed under 50～100 ℃ according to the mol ratio of silicon/titanium=5～50 with the hydrating solution of step (1) gained silicon and stirring reaction 0.5～6 hour, obtain said reactant mixture.
(4). step (3) gained reactant mixture is put into sealed reactor, and in 110～145 ℃ of pre-crystallization 0.1～5 hour, crystallization ℃ was continued 5 hours～1 day in temperature to 150～180 that raise then, reclaimed product then.
5. according to the method for claim 3, wherein the said silicon of step (1) source is silica gel, Ludox or tetraalkyl esters of silicon acis; Said its general formula of tetraalkyl esters of silicon acis is R
1 4SiO
4, R wherein
1For having the alkyl of 1～4 carbon atom.
6. according to the method for claim 5, wherein said silicon source is the tetraalkyl esters of silicon acis.
7. according to the method for claim 3, wherein the said organo-alkali compound of step (1) is fat amine compound, alcamine compound or quaternary amine alkali compounds, or mixes the mixed amine compounds of forming mutually by them; Its general formula of said fat amine compound is R
2(NH
2)
n, R wherein
2For having the alkyl of 1～4 carbon atom, n=1 or 2; Its general formula of said alcamine compound is (HOR
3)
mN; R wherein
3For having the alkyl of 1～4 carbon atom; M=1～3; Said quaternary amine alkali compounds is the quaternary amine alkali compounds that contains the alkyl with 1～4 carbon atom.
8. according to the method for claim 7, wherein said organo-alkali compound is ethamine, ethylenediamine, n-butylamine, butanediamine or hexamethylene diamine.
9. according to the method for claim 7, wherein said organo-alkali compound is MEA, diethanol amine or triethanolamine.
10. according to the method for claim 7, wherein said organo-alkali compound is tetraethyl aqua ammonia or tetrapropyl aqua ammonia.
11. according to the method for claim 3, wherein said hydrolysis time is 10～300 minutes in the step (1), hydrolysising reacting temperature is 0～45 ℃.
12. according to the method for claim 3, wherein the said titanium of step (2) source is inorganic titanium salt or organic titanate Ti (OR
4)
4, R wherein
4For having the alkyl of 1～6 carbon atom.
13. according to the method for claim 12, wherein said titanium source is an organic titanate.
14. according to the method for claim 13, wherein R
4For having the alkyl of 2～4 carbon atoms.
15. according to the method for claim 3, wherein the said hydrolysis time of step (2) is 5～90 minutes, hydrolysising reacting temperature is 0～45 ℃.
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| CN102153104A (en) * | 2010-02-12 | 2011-08-17 | 中国石油化学工业开发股份有限公司 | Method for preparing titanium-silicon molecular sieve and method for preparing cyclohexane oxime by using molecular sieve |
| CN101905891B (en) * | 2009-06-05 | 2012-10-24 | 复旦大学 | Method for synthesizing ordered mesoporous titanium oxide silicon molecular sieve |
| CN102745712A (en) * | 2011-04-19 | 2012-10-24 | 中国石油化学工业开发股份有限公司 | Method for preparing titanium-silicon molecular sieve and method for preparing cyclohexanone oxime by using molecular sieve |
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| CN106006665A (en) * | 2016-05-13 | 2016-10-12 | 浙江师范大学 | Method for preparing titanium silicalite molecular sieve TS-1 |
| US9486790B2 (en) | 2011-10-31 | 2016-11-08 | Dalian University Of Technology | Modification method of titanium-silicalite zeolite based on the mixture of quaternary ammonium salt and inorganic alkali |
| CN107539999A (en) * | 2016-06-27 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of HTS and its preparation method and application and a kind of method of cyclic ketones oxidation |
| CN109019627A (en) * | 2017-06-12 | 2018-12-18 | 中国石油化工股份有限公司 | The preparation method of Titanium Sieve Molecular Sieve and preparation method thereof and propylene glycol |
| CN110314699A (en) * | 2018-03-30 | 2019-10-11 | 中国石油化工股份有限公司 | The preparation method of titanium-silicon molecular sieve catalyst |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1222868B (en) * | 1987-10-12 | 1990-09-12 | Montedipe Spa | METHOD FOR THE PREPARATION OF TITANIUM SILICALITES |
| CN1050584C (en) * | 1996-06-05 | 2000-03-22 | 中国石油化工总公司 | Method for preparing titanium-silicon molecular sieve (TS-1) |
| CN1084294C (en) * | 1996-07-10 | 2002-05-08 | 中国科学院兰州化学物理研究所 | Synthesis of selective oxidation catalyst Ti-Si molecular sieves |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101905891B (en) * | 2009-06-05 | 2012-10-24 | 复旦大学 | Method for synthesizing ordered mesoporous titanium oxide silicon molecular sieve |
| CN102153104A (en) * | 2010-02-12 | 2011-08-17 | 中国石油化学工业开发股份有限公司 | Method for preparing titanium-silicon molecular sieve and method for preparing cyclohexane oxime by using molecular sieve |
| CN102745712A (en) * | 2011-04-19 | 2012-10-24 | 中国石油化学工业开发股份有限公司 | Method for preparing titanium-silicon molecular sieve and method for preparing cyclohexanone oxime by using molecular sieve |
| US9486790B2 (en) | 2011-10-31 | 2016-11-08 | Dalian University Of Technology | Modification method of titanium-silicalite zeolite based on the mixture of quaternary ammonium salt and inorganic alkali |
| CN103214000A (en) * | 2013-04-22 | 2013-07-24 | 江苏怡达化学股份有限公司 | Synthesis method of titanium-silicon molecular sieve TS-1 |
| CN103818921A (en) * | 2014-02-26 | 2014-05-28 | 中国天辰工程有限公司 | Method for preparing TS-1 molecular sieve by using composite template |
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| CN104528761A (en) * | 2014-12-25 | 2015-04-22 | 中国天辰工程有限公司 | Synthesis method of titanium-silicon molecular sieve with high content of framework titanium |
| US11161746B2 (en) | 2015-10-30 | 2021-11-02 | China Petroleum & Chemical Corporation | Preparation of molecular sieve and treatment of silicon-containing wastewater therefrom |
| CN106006665A (en) * | 2016-05-13 | 2016-10-12 | 浙江师范大学 | Method for preparing titanium silicalite molecular sieve TS-1 |
| CN107539999A (en) * | 2016-06-27 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of HTS and its preparation method and application and a kind of method of cyclic ketones oxidation |
| CN107539999B (en) * | 2016-06-27 | 2020-01-10 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve, preparation method and application thereof, and cyclic ketone oxidation method |
| CN109019627A (en) * | 2017-06-12 | 2018-12-18 | 中国石油化工股份有限公司 | The preparation method of Titanium Sieve Molecular Sieve and preparation method thereof and propylene glycol |
| CN109019627B (en) * | 2017-06-12 | 2020-12-04 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve, preparation method thereof and preparation method of propylene glycol ether |
| CN110314699A (en) * | 2018-03-30 | 2019-10-11 | 中国石油化工股份有限公司 | The preparation method of titanium-silicon molecular sieve catalyst |
| CN110314699B (en) * | 2018-03-30 | 2021-11-16 | 中国石油化工股份有限公司 | Preparation method of titanium silicalite molecular sieve catalyst |
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