CN1089274C - Process for preparing Ti-Si molecular sieve - Google Patents
Process for preparing Ti-Si molecular sieve Download PDFInfo
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- CN1089274C CN1089274C CN98102391A CN98102391A CN1089274C CN 1089274 C CN1089274 C CN 1089274C CN 98102391 A CN98102391 A CN 98102391A CN 98102391 A CN98102391 A CN 98102391A CN 1089274 C CN1089274 C CN 1089274C
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Abstract
The present invention provides a method for preparing a TS-1 molecular sieve, which comprises the following steps: uniformly agitating and mixing silicon source compounds and organic amine compounds with water in order to obtain hydrolyzing solution of silicon by a hydrolyzation reaction; uniformly agitating and mixing titanium source, isopropyl alcohol and organic base with water in order to obtain hydrolyzing solution of titanium; adding the obtained hydrolyzing solution of titanium in the obtained hydrolyzing solution of silicon, and mixing and agitating the mixture according to the molar ratio of silicon to titanium is 5 to 100 at 50 to 100 DEG C for reacting for 0.5 to 6 hours; obtaining titanium-silicon colloid; putting the obtained titanium-silicon colloid in a sealed stainless steel reaction kettle in order to crystallize with a conventional hydrothermal method; recovering product, wherein the organic amine compounds are fat amine compounds or amino alcohol compounds, or mixed amine compounds made by mixing the fat amine compounds and the amino alcohol compounds. The organic base is tetrapropylammonium hydroxide or a mixture made by mixing the tetrapropylammonium hydroxide and amino alcohol compounds. The activity of the obtained product can be improved by the method of the present invention, and simultaneously the dosage of the tetrapropylammonium hydroxide as a template agent can also be reduced.
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 (Zeolires 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, slowly adds the liquid mixture that the aqueous isopropanol of butyl titanate obtains clarifying then and (must slowly drip to prevent that tetrabutyl titanate hydrolysis is too fast and form white TiO under vigorous stirring
2Precipitation), stirs 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, get the TS-1 molecular sieve after the drying in 170 ℃ of following hydrothermal crystallizings 3～6 days.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.
The preparation cost of TS-1 molecular sieve is mainly reflected in the use amount of expensive TPAOH (TPAOH), the use amount of the method for above-mentioned prior art TPAOH in preparation is all bigger, make that the preparation cost of TS-1 is higher, and the reactivity of products obtained therefrom is lower, it is still less to illustrate that titanium enters the amount of framework of molecular sieve, has restricted the commercial Application of TS-1 molecular sieve.
The method that the purpose of this invention is to provide a kind of TS-1 of preparation molecular sieve improves the activity of products obtained therefrom, can also reduce the consumption of template agent TPAOH simultaneously.
Theme of the present invention is with comparatively cheap organic amine compound as organic base with the TPAOH of the instead of part costliness alkali source as hydrolysis, make TPAOH can be more effectively as template agent work.
The preparation method of TS-1 molecular sieve provided by the present invention is made up of the following step:
(1), with silicon source, organic amine compound and water according to 1: (0.05～2.0): (5～100), preferred 1: (0.10～0.35): the mol ratio of (10～35) mixes, and 0～40 ℃ of following hydrolysis 10～300 minutes, obtains the hydrating solution of silicon; Wherein said silicon source is silica gel, Ludox or organosilicon acid esters; Said organic amine compound is fatty amine or alcamine compound, or mixes the mixed amine compounds of forming mutually by them, wherein alcamine compound preferably;
(2), with titanium source, isopropyl alcohol, organic base and water according to 1: (0～60): (0.5～30): (10～100), preferred 1: (0～20): (0.8～5.5): the mol ratio of (10～40) mixes, in 0～40 ℃ of following hydrolysis 5～90 minutes, obtain the hydrating solution of titanium; Wherein said titanium source is inorganic titanium salt or organic titanate; Said organic base is a TPAOH, perhaps mixture for forming by TPAOH and alcamine compound, and should to make the mol ratio of TPAOH/titanium be 0.3～10 to its composition when being mixture, preferred 0.5～6;
(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 the titanium colloidal silica.
(4), with step (3) gained titanium colloidal silica hydrothermal crystallizing according to a conventional method in sealed reactor, reclaim product then.
Said its general formula of organosilicon acid esters of step in the method provided by the invention (1) is R
1 4SiO
4, R wherein
1For having the alkyl of 1～4 carbon atom.
Its general formula of the said fat amine compound of step in the method provided by the invention (1) 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, n-butylamine, butanediamine or hexamethylene diamine.
Its general formula of said alcamine compound is (HOR in step in the method provided by the invention (1) and (2)
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.Said alcamine compound can be identical or different in these two steps.
The said inorganic titanium salt of step in the method provided by the invention (2) can be TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2
Its general formula of the said organic titanate of step in the method provided by the invention (2) is Ti (OR
4)
4, R wherein
4For having the alkyl of 1～6 carbon atom, preferably has the alkyl of 2～4 carbon atoms.
Its condition of the said crystallization of step in the method provided by the invention (4) is 110～200 ℃ of following hydrothermal crystallizings 1～6 day, or descended pre-crystallization 0.2～5 hour at 110～145 ℃ earlier, acquisition contains the titanium silicon mixture of tiny crystal grains, and then 150～200 ℃ of following crystallization 1 hour to 3 days.
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 comparatively cheap organic alkali (alkyl amine or alcamines, its price only for the TPAOH price 1/30th～50) the silicon source is hydrolyzed, perhaps replace the part TPAOH that the titanium source is hydrolyzed with this organic alkali again, make TPAOH mainly play the template agent rather than work as the alkali source in the hydrolysis process more, effectively utilized TPAOH, make titanium can more effectively enter framework of molecular sieve, thereby improve the activity of product; And on the other hand, because TPAOH mainly plays the template agent rather than work as the alkali source more, thereby can reduce the consumption of TPAOH, to reduce the preparation cost of TS-1 molecular sieve.
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 1.25 moles of butanediamine, and add 25.5 moles distilled water,, obtain organosilyl hydrating solution in 30 ℃ of hydrolysis 50 minutes.
0.05 mole of metatitanic acid orthocarbonate is mixed with 1.25 moles of anhydrous isopropyl alcohols, 0.22 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 80 ℃, obtain the titanium colloidal silica.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, and pre-crystallization is 1.5 hours under 125 ℃, and the temperature to 165 that raises then ℃ continuation crystallization 15 hours obtains crystallization product.This crystallization product is filtered and is washed with water to pH=6～8, then in 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered T-1, its XRD crystalline phase figure as shown in Figure 1.
Embodiment 2
0.8 mole positive silicic acid orthocarbonate is mixed with 0.98 mole of diethanol amine, and add 10.5 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, 0.28 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 pre-crystallization is 30 minutes under 125 ℃, and the temperature to 165 that raises then ℃ continuation crystallization 10 hours obtains crystallization product.This crystallization product is filtered and is washed with water to pH=6～8, then in 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered T-2, the peak type of its XRD crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 3
1.2 moles positive silicic acid orthocarbonates are mixed with 2.32 moles of hexamethylene diamines, and add 35.5 moles distilled water,, obtain organosilyl hydrating solution in 30 ℃ of hydrolysis 50 minutes.
0.08 mole of metatitanic acid orthocarbonate is mixed with 1.25 moles of anhydrous isopropyl alcohols, 0.35 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 90 ℃, obtain the titanium colloidal silica.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, and pre-crystallization is 2.5 hours under 125 ℃, and the temperature to 165 that raises then ℃ continuation crystallization 20 hours obtains crystallization product.This crystallization product is filtered and is washed with water to pH=6～8, then in 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered T-3, the peak type of its XRD crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 4
0.8 mole positive silicic acid four butyl esters are mixed with 0.54 mole of triethanolamine, and add 12.5 moles distilled water,, obtain organosilyl hydrating solution in 15 ℃ of hydrolysis 35 minutes.
0.05 mole of tetraethyl titanate is mixed with 0.9 mole of anhydrous isopropyl alcohol, 0.25 mole of TPAOH and 0.74 mole 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, 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 pre-crystallization is 25 minutes under 115 ℃, and the temperature to 175 that raises then ℃ continuation crystallization 6 hours obtains crystallization product.This crystallization product is filtered and is washed with water to pH=6～8, then in 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered T-4, the peak type of its XRD crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 5
1.2 moles positive silicic acid four butyl esters are mixed with 0.32 mole of n-butylamine, and add 120 moles distilled water,, obtain organosilyl hydrating solution in 15 ℃ of hydrolysis 35 minutes.
0.05 mole of tetraethyl titanate is mixed with 2.8 moles of anhydrous isopropyl alcohols, 0.18 mole of TPAOH and 1.5 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, and the gained mixture was stirred 3 hours down in 90 ℃, obtain the titanium colloidal silica.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, and pre-crystallization is 25 minutes under 145 ℃, and the temperature to 175 that raises then ℃ continuation crystallization 18 hours obtains crystallization product.This crystallization product is filtered and is washed with water to pH=6～8, then in 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered T-5, the peak type of its XRD crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 6
0.8 mole positive tetraethyl orthosilicate is mixed with 0.1 mole of triethanolamine, and add 12.5 moles distilled water,, obtain organosilyl hydrating solution in 15 ℃ of hydrolysis 35 minutes.
0.03 mole of butyl titanate is mixed with 0.9 mole of anhydrous isopropyl alcohol, 0.20 mole of TPAOH and 0.74 mole of distilled water,, obtain the hydrating solution of butyl titanate in 22 ℃ of hydrolysis 12 minutes.
Under agitation lentamente the hydrating solution of butyl titanate is joined in the organosilyl hydrating solution, and the gained mixture was stirred 2 hours down in 70 ℃, obtain the titanium colloidal silica.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, and pre-crystallization is 12 minutes under 120 ℃, and the temperature to 170 that raises then ℃ continuation crystallization 12 hours obtains crystallization product.This crystallization product is filtered and is washed with water to pH=6～8, then in 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered T-6, the peak type of its XRD crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 7
1.0 moles positive tetraethyl orthosilicates are mixed with 0.54 mole of triethanolamine, and add 35.5 moles distilled water,, obtain organosilyl hydrating solution in 15 ℃ of hydrolysis 35 minutes.
0.05 mole of butyl titanate is mixed with 1.2 moles of anhydrous isopropyl alcohols, 0.14 mole of TPAOH and 0.95 mole of distilled water,, obtain the hydrating solution of butyl titanate in 22 ℃ of hydrolysis 12 minutes.
Under agitation lentamente the hydrating solution of butyl titanate 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 pre-crystallization is 1.5 hours under 125 ℃, and the temperature to 170 that raises then ℃ continuation crystallization 16 hours obtains crystallization product.This crystallization product is filtered and is washed with water to pH=6～8, then in 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered T-7, the peak type of its XRD crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 8
1.2 moles positive tetraethyl orthosilicates are mixed with 1.5 mole of triethanolamine, and add 20.5 moles distilled water,, obtain organosilyl hydrating solution in 15 ℃ of hydrolysis 35 minutes.
0.09 mole of butyl titanate is mixed with 3.8 moles of anhydrous isopropyl alcohols, 0.11 mole of TPAOH and 1.5 moles of distilled water,, obtain the hydrating solution of butyl titanate in 22 ℃ of hydrolysis 12 minutes.
Under agitation lentamente the hydrating solution of butyl titanate is joined in the organosilyl hydrating solution, and the gained mixture was stirred 2 hours down in 95 ℃, obtain the titanium colloidal silica.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, and pre-crystallization is 2.5 hours under 130 ℃, and the temperature to 170 that raises then ℃ continuation crystallization 24 hours obtains crystallization product.This crystallization product is filtered and is washed with water to pH=6～8, then in 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered T-8, the peak type of its XRD crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 9
In the mixed amine of forming by 0.1 mole triethanolamine, 0.05 mole hexamethylene diamine, add 0.8 mole of SiO
2Glue (white carbon black, Qingdao silica gel manufacturer industry product), and add 25.5 moles distilled water, in room temperature (22 ℃) hydrolysis 4 hours, obtain the hydrating solution of silicon.
0.04 mole of butyl titanate is mixed with 0.8 mole of anhydrous isopropyl alcohol, to wherein adding by 0.05 mole of triethanolamine, 0.03 mole of hexamethylene diamine and 0.104 mole of mixed amine that TPAOH is formed, adding 0.85 mole of distilled water again mixes, in 28 ℃ of hydrolysis 60 minutes, obtain the hydrating solution of titanium.
Under agitation lentamente the hydrating solution of titanium is joined in the hydrating solution of silicon, and the gained mixture was stirred 4 hours down in 90 ℃, obtain the titanium colloidal silica.
Gained titanium colloidal silica is put into the stainless steel sealed reactor,, obtain crystallization product 170 ℃ of crystallization 5 days.This crystallization product is filtered and is washed with water to pH=6～8, then in 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered T-9, the peak type of its XRD crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 10
In the mixed amine of forming by 0.1 mole triethanolamine, 0.05 mole hexamethylene diamine, add 1.0 moles positive tetraethyl orthosilicate, and add 25.5 moles distilled water,, obtain the hydrating solution of silicon in 8 ℃ of following hydrolysis 4 hours.
In the mixed amine of forming by 0.05 mole of triethanolamine, 0.03 mole of hexamethylene diamine and 0.12 mole of TPAOH, add 2.5 moles of distilled water and make solution, again to wherein slowly adding 0.06 mole of TiCl
4, in 15 ℃ of following hydrolysis 60 minutes, the hydrating solution of the titanium that obtains clarifying.
Under agitation lentamente the hydrating solution of titanium is joined in the hydrating solution of silicon, and the gained mixture was stirred 4 hours down in 90 ℃, obtain the titanium colloidal silica.
Gained titanium colloidal silica is put into the stainless steel sealed reactor,, obtain crystallization product 190 ℃ of crystallization 4 days.This crystallization product is filtered and is washed with water to pH=6～8, then in 110 ℃ of dryings 60 minutes, again 550 ℃ of following roastings 3 hours, the TS-1 molecular sieve, it is numbered T-10, the peak type of its XRD crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 11
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 aqueous hydrogen peroxide solution 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:
Table 1
From table 1 data as can be seen, the inventive method products obtained therefrom molecular sieve compares its reactivity with Comparative Examples 1 products obtained therefrom molecular sieve and selectivity improves greatly, illustrate that the inventive method can improve the utilization rate of TPAOH effectively, make titanium can more effectively enter framework of molecular sieve, thereby improve product activity.
| Numbering | Phenol conversion % | Benzenediol selectivity % | Product distribution % | ||
| Catechol | Hydroquinones | Benzoquinones | |||
| T-1 | 15.32 | 96.55 | 52.19 | 44.36 | 3.45 |
| T-2 | 16.43 | 95.79 | 50.18 | 45.61 | 4.21 |
| T-3 | 17.35 | 96.89 | 47.23 | 49.66 | 3.11 |
| T-4 | 19.45 | 97.51 | 53.49 | 44.02 | 2.49 |
| T-5 | 14.66 | 93.77 | 46.33 | 47.44 | 6.23 |
| T-6 | 15.64 | 95.33 | 47.69 | 47.64 | 4.67 |
| T-7 | 14.78 | 95.63 | 51.34 | 44.29 | 4.37 |
| T-8 | 13.21 | 92.79 | 46.13 | 46.66 | 7.21 |
| T-9 | 11.37 | 91.36 | 45.32 | 46.04 | 8.64 |
| T-10 | 10.83 | 90.32 | 45.18 | 45.14 | 9.68 |
| DB-1 | 8.65 | 88.87 | 68.13 | 20.74 | 11.13 |
Claims (10)
1. preparation method with HTS (TS-1) of MFI structure, it is characterized in that this method is made up of the following step: (1), with silicon source, organic amine compound and water according to 1: (0.05～2.0): (5～100), and, obtain the hydrating solution of silicon 0～40 ℃ of following hydrolysis 10～300 minutes; Wherein said silicon source is silica gel, Ludox or organosilicon acid esters; Said organic amine compound is fatty amine or alcamine compound, or mixes the mixed amine compounds of forming mutually by them; (2), with titanium source, isopropyl alcohol, organic base and water according to 1: (0～60): (0.5～30): the mol ratio of (10～100) mixes, and in 0～40 ℃ of following hydrolysis 5～90 minutes, obtains the hydrating solution of titanium; Wherein said titanium source is inorganic titanium salt or organic titanate; Said organic base is a TPAOH, perhaps mixture for forming by TPAOH and alcamine compound, and should to make the mol ratio of TPAOH/titanium be 0.3～10 to its composition when being mixture; (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 the titanium colloidal silica; (4), with step (3) gained titanium colloidal silica in sealed reactor 110～200 ℃ of following hydrothermal crystallizings 1～6 day, perhaps earlier 110～145 ℃ of pre-crystallization 0.2～5 hour down, and then, reclaim product then 150～200 ℃ of following crystallization 1 hour to 3 days.
2. according to the process of claim 1 wherein that the said silicon of step (1) source is the organosilicon acid esters, its general formula is R
1 4SiO
4, R wherein
1For having the alkyl of 1～4 carbon atom.
3. according to the process of claim 1 wherein that the said organic amine compound of step (1) is an alcamine compound.
4. according to the process of claim 1 wherein that its general formula of the said fat amine compound of step (1) is R
2(NH
2)
n, R wherein
2For having the alkyl of 1～4 carbon atom, n=1 or 2.
5. according to the method for claim 4, fat amine compound wherein is ethamine, n-butylamine, butanediamine or hexamethylene diamine.
6. according to the method for claim 1 or 3, wherein its general formula of said alcamine compound is (HOR in step (1) and (2)
3)
mN; R wherein
3For having the alkyl of 1～4 carbon atom, m=1～3.
7. according to the method for claim 6, alcamine compound wherein is MEA, diethanol amine or triethanolamine.
8. according to the process of claim 1 wherein that the said titanium of step (2) source is an organic titanate, its general formula is Ti (OR
4)
4, R wherein
4For having the alkyl of 2～4 carbon atoms.
9. according to the process of claim 1 wherein that the said inorganic titanium salt of step (2) is TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2
10. 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, organic amine compound and water according to 1: (0.10～0.35): the mol ratio of (10～35) mixes, and, obtain the hydrating solution of silicon 0～40 ℃ of following hydrolysis 10～120 minutes; Wherein said silicon source is silica gel, Ludox or organosilicon acid esters; Said organic amine compound is an alcamine compound; (2), with titanium source, isopropyl alcohol, organic base and water according to 1: (2～20): (0.8～5.5): the mol ratio of (10～40) mixes, and in 0～40 ℃ of following hydrolysis 10～60 minutes, obtains the hydrating solution of titanium; Wherein said titanium source is an organic titanate; Said organic base is a TPAOH, perhaps mixture for forming by TPAOH and alcamine compound, and should to make the mol ratio of TPAOH/titanium be 0.5～6 to its composition when being mixture; (3), the hydrating solution of step (2) gained titanium mixed under 60～90 ℃ according to the mol ratio of silicon/titanium=5～50 with the hydrating solution of step (1) gained silicon and stirring reaction 1～4 hour, obtain the titanium colloidal silica; (4), with step (3) gained titanium colloidal silica hydrothermal crystallizing according to a conventional method in sealed reactor, reclaim product then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102391A CN1089274C (en) | 1998-06-12 | 1998-06-12 | Process for preparing Ti-Si molecular sieve |
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| CN98102391A CN1089274C (en) | 1998-06-12 | 1998-06-12 | Process for preparing Ti-Si molecular sieve |
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| CN1239016A CN1239016A (en) | 1999-12-22 |
| CN1089274C true CN1089274C (en) | 2002-08-21 |
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| CN98102391A Expired - Lifetime CN1089274C (en) | 1998-06-12 | 1998-06-12 | Process for preparing Ti-Si molecular sieve |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100386262C (en) * | 2003-12-28 | 2008-05-07 | 福州大学 | Process for preparing Si-Ti molecular sieve |
| CN100384733C (en) * | 2005-08-15 | 2008-04-30 | 中国石油化工股份有限公司 | Method for preparing sieve of containing titanium MCM-41 |
| CN101434400B (en) * | 2007-11-15 | 2011-06-15 | 中国石油化工股份有限公司 | Method for synthesizing TS-1 molecular sieve |
| CN102442683A (en) * | 2011-09-27 | 2012-05-09 | 华东理工大学 | Solvent volatilization method for preparing titanium-containing zeolite with multilevel porous channels |
| CN102502690A (en) | 2011-10-31 | 2012-06-20 | 大连理工大学 | Method for modifying TS (Titanium silicalite)-1 based on mixed liquor of quaternary ammonium salt and inorganic base |
| CN104556114B (en) * | 2013-10-29 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of method of the micro- mesoporous composite material of synthesis of titanium silicon |
| CN105540943B (en) | 2015-10-30 | 2018-03-20 | 中国石油化工股份有限公司 | The processing method of silicon-containing wastewater and the Application way of silicon-containing wastewater and molecular sieve preparation method |
| CN106006665B (en) * | 2016-05-13 | 2018-08-21 | 浙江师范大学 | A kind of preparation method of titanium-silicon molecular sieve TS-1 |
| 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 |
| CN114950543A (en) * | 2022-06-30 | 2022-08-30 | 格润科技(大连)有限责任公司 | Preparation method and application of titanium silicalite molecular sieve catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0311983A2 (en) * | 1987-10-12 | 1989-04-19 | Enichem Anic S.r.l. | Method for the preparation of titanium-silicalites |
| CN1167082A (en) * | 1996-06-05 | 1997-12-10 | 中国石油化工总公司 | Method for preparing titanium-silicon molecular sieve (TS-1) |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0311983A2 (en) * | 1987-10-12 | 1989-04-19 | Enichem Anic S.r.l. | Method for the preparation of titanium-silicalites |
| CN1167082A (en) * | 1996-06-05 | 1997-12-10 | 中国石油化工总公司 | Method for preparing titanium-silicon molecular sieve (TS-1) |
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| CN1239016A (en) | 1999-12-22 |
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