CN1102442C - Preparation method for Ti-Si molecular sieve - Google Patents
Preparation method for Ti-Si molecular sieve Download PDFInfo
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- CN1102442C CN1102442C CN98101357A CN98101357A CN1102442C CN 1102442 C CN1102442 C CN 1102442C CN 98101357 A CN98101357 A CN 98101357A CN 98101357 A CN98101357 A CN 98101357A CN 1102442 C CN1102442 C CN 1102442C
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Abstract
The present invention provides a method for preparing Ti-Si molecular sieves (TS-1) with an MFI structure. The present invention is characterized in that the method comprises the following steps: uniformly mixing hydrolyzation solution of titanium with a TS-1 molecular sieve synthesized already according to the proportion that the ratio of the molecular sieve to Ti is (200 to 1500)g to 1 mol; leading the obtained mixture to react at 120 to 200 DEG C for 1 to 8 days in a reaction kettle; obtaining the TS-1 molecular sieve synthesized by adding Ti by filtering, washing and drying. Because the Ti amount in skeletons of the obtained TS-1 molecular sieve is improved by the method of the present invention, compared with the prior art, the catalytic oxidation activity and selectivity are obviously improved. Simultaneously, the TS-1 molecular sieve has preferable catalytic activity and stability.
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.
The TS-1 molecular sieve is that the transition metal titanium is introduced formed a kind of new titanium-silicone molecular sieve with good selective paraffin oxidation catalytic performance in the framework of molecular sieve with ZSM-5 structure.TS-1 not only has the catalysed oxidn of titanium, but also has the shape effect selected and the advantages of excellent stability of ZSM-5 molecular sieve.Because the TS-1 molecular sieve is in organic oxidation reaction, can adopt free of contamination low concentration hydrogen peroxide as oxidant, oxidizing process complex process and problem of environment pollution caused have been avoided, have unrivaled energy-conservation, economy of conventional oxidation system and advantages of environment protection, and have good reaction selectivity, therefore favorable industrial application prospect is arranged.
The synthetic method of TS-1 disclosed (GB2071071A, USP 4,410,501) first by people such as gondola Marco Taramasso in 1981.This method is to prepare a kind of silicon source, titanium source, organic base (RN of containing earlier
+) and/or basic anhydride (Men/
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 (OC2H
5)
4, the preferred TPAOH of the organic base wherein mole compositing range of reactant mixture is:
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 said method synthesizes effective Ti content seldom, so they disclose a kind of method (Zeolites that can effectively increase the synthetic TS-1 molecular sieve of skeleton Ti content in 1992,1992, Vol.12, 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: 0.36 TPAOH: 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 subject matter that exists in the prior art of above-mentioned synthetic TS-1 molecular sieve is: the effective Ti content that enters framework of molecular sieve on the one hand is less, be difficult on the other hand stably obtaining to have the TS-1 molecular sieve of good catalytic oxidation activity, the activity stability of gained TS-1 molecular sieve is relatively poor, has therefore restricted the commercial Application of TS-1 molecular sieve.
The objective of the invention is to overcome the shortcoming of prior art, the method for the HTS (TS-1) that a kind of preparation has the MFI structure is provided, make gained TS-1 molecular sieve have better catalytic oxidation activity and activity stability preferably.
The method for preparing HTS (TS-1) provided by the present invention comprises:
(1). the method by prior art synthesizes the TS-1 molecular sieve;
(2). with titanium-containing compound, isopropyl alcohol, organic amine and water according to 1: (0.0～50): (0.3～10): the mol ratio of (120～450), be preferably 1: (0.0～20): (0.8～4.5): the mixed in molar ratio of (220～350) is even, and allow its hydrolysis, obtain the hydrating solution of titanium;
(3). with the hydrating solution of (1) said molecular sieve and (2) said titanium according to molecular sieve (gram): Ti (mole)=(200～1500): 1 ratio, preferably (300～650): 1 ratio mixes, the gained mixture is put into reactor, under 120～200 ℃ temperature, place 1～8 day time, preferably under 150～180 ℃ temperature, placed 1～4 day, products therefrom is filtered, washs and drying, obtain the synthetic TS-1 molecular sieve of titanium that adds of the present invention.
Can also comprise the described process of repetition one or many step (3) in the method provided by the present invention, thereby improve its catalytic oxidation activity with the titaniferous amount in the further raising framework of molecular sieve.
The said TS-1 molecular sieve of step in the method provided by the present invention (1) can be the TS-1 molecular sieve that synthesizes according to the whole bag of tricks of the prior art, and it can pass through or without calcination process, promptly can contain or not contain organic formwork agent.
The said titanium-containing compound of step in the method provided by the present invention (2) can be inorganic titanium-containing compound such as TiCl
4, TiOCl
2, Ti (SO
4)
2Deng, also can be organic titanium-containing compound titanate esters Ti (OR)
4, wherein R is the alkyl with 2～5 carbon atoms, preferably butyl.
The said organic amine of step in the method provided by the present invention (2) is fatty amine, alcamines or quaternary ammonium base compounds, wherein quaternary ammonium base compounds preferably.
Its general formula of said fat amine compound is R (NH
2)
n, wherein R is the alkyl with 1～4 carbon atom, n=1～2, and wherein preferred fat amine compound is ethamine, n-butylamine, butanediamine or hexamethylene diamine.
Its general formula of said alcamine compound is (HOR ')
mN, wherein R ' is the alkyl with 1～4 carbon atom, m=1～3, wherein preferred alcamine compound is MEA, diethanol amine or triethanolamine.
Said its general formula of quaternary ammonium base compounds is R "
3NOH, wherein R are " for having the alkyl of 1～4 carbon atom, preferably propyl group.
The time of said hydrolysis is 2～90 minutes in the step in the method provided by the present invention (2), and preferred 5～30 minutes, the temperature during hydrolysis had no particular limits, and is generally room temperature.
Fig. 1 is X-ray diffraction (XRD) the crystalline phase figure of embodiment 1 gained sample.
The present invention is because employing adds the synthetic method of titanium, the skeleton titaniferous amount of gained TS-1 molecular sieve is improved, thereby make its catalytic oxidation activity and selectivity compared with prior art obviously improve (seeing embodiment 10), have stability of catalytic activity (seeing embodiment 11) preferably simultaneously.
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 all the other reagent are commercially available chemically pure reagent.
Comparative Examples 1
The effect of TS-1 molecular sieve is not synthesized in the explanation of this Comparative Examples according to the method for of the present invention, prior art (Zeolites, 1992, Vol.12, the 943rd～950 page).
The positive tetraethyl orthosilicate of 22.5 grams is mixed with 7.0 gram TPAOHs, and add 59.8 the gram distilled water, mix the back in normal pressure and 60 ℃ of following hydrolysis 1.0 hours, obtain the hydrating solution of positive tetraethyl orthosilicate, under vigorous stirring, add 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 stainless steel cauldron, 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 former powder of TS-1.With the former powder of this TS-1 in 550 ℃ of roasting temperatures 3 hours, the TS-1 molecular sieve, its XRD crystalline phase figure and Fig. 1 are similar.
Embodiment 1
With butyl titanate, anhydrous isopropyl alcohol, TPAOH and distilled water according to 1: 8.76: 1.24: 185.56 mixed in molar ratio is even, in normal pressure and 25 ℃ of following hydrolysis 25 minutes, obtains the hydrating solution of butyl titanate.The TS-1 molecular sieve of getting Comparative Examples 1 gained mixes according to molecular sieve (gram): Ti (mole)=358.53: 1 the ratio and the hydrating solution of above-mentioned butyl titanate, in normal pressure and 70 ℃ of following dispersed with stirring 4 hours, obtains uniform dispersion.This dispersion is put into stainless steel cauldron, and constant temperature is placed 1 day time under 170 ℃ of temperature, obtains containing the mixture of liquid and solid.This mixture is filtered, is washed with water to pH value=6～8, and, obtain the synthetic TS-1 molecular sieve of titanium that adds of the present invention in 110 ℃ of oven dry 50 minutes.Its XRD crystalline phase figure sees Fig. 1, is indicated as the MFI structure.
Embodiment 2
With butyl titanate, anhydrous isopropyl alcohol, TPAOH and distilled water according to 1: 13.78: 1.58: 333.46 mixed in molar ratio is even, in normal pressure and 30 ℃ of following hydrolysis 15 minutes, obtains the hydrating solution of butyl titanate.The TS-1 molecular sieve of getting Comparative Examples 1 gained mixes according to molecular sieve (gram): Ti (mole)=583.73: 1 the ratio and the hydrating solution of above-mentioned butyl titanate, in normal pressure and 75 ℃ of dispersed with stirring 3 hours, obtains uniform dispersion.This dispersion is put into stainless steel cauldron, and constant temperature is placed 2 day time under 160 ℃ temperature, obtains containing the mixture of liquid and solid.This mixture is filtered, is washed with water to pH is 6～8, and in 110 ℃ of oven dry 50 minutes, obtains the synthetic TS-1 molecular sieve of titanium that adds of the present invention.Its XRD crystalline phase figure and Fig. 1 are similar.
Embodiment 3
With butyl titanate, anhydrous isopropyl alcohol, TPAOH and distilled water according to 1: 32.42: 5.78: 423.56 mixed in molar ratio is even, in normal pressure and 35 ℃ of hydrolysis 10 minutes, obtains the hydrating solution of butyl titanate.The TS-1 molecular sieve of getting Comparative Examples 1 gained mixes according to molecular sieve (gram): Ti (mole)=634.42: 1 the ratio and the hydrating solution of above-mentioned butyl titanate, in normal pressure and 65 ℃ of dispersed with stirring 2.5 hours, obtains uniform dispersion.This dispersion is put into stainless steel cauldron, and constant temperature is placed 3 day time under 155 ℃ temperature, obtains containing the mixture of liquid and solid.This mixture is filtered, is washed with water to pH is 6～8, and in 110 ℃ of oven dry 50 minutes, obtains the synthetic TS-1 molecular sieve of titanium that adds of the present invention.Its XRD crystalline phase figure and Fig. 1 are similar.
Embodiment 4
With tetraethyl titanate, anhydrous isopropyl alcohol, triethanolamine and distilled water according to 1: 8.34: 3.42: 270.54 mixed in molar ratio is even, in normal pressure and 25 ℃ of following hydrolysis 25 minutes, obtains the hydrating solution of tetraethyl titanate.The former powder of the TS-1 that does not pass through roasting of getting Comparative Examples 1 gained mixes according to TS-1 (gram): Ti (mole)=634.35: 1 the ratio and the hydrating solution of above-mentioned tetraethyl titanate, in normal pressure and 90 ℃ of dispersed with stirring 4.5 hours, obtains uniform dispersion.This dispersion is put into stainless steel cauldron, and constant temperature is placed 2.5 day time under 180 ℃ temperature, obtains containing the mixture of liquid and solid.This mixture is filtered, is washed with water to pH is 6～8, and in 110 ℃ of oven dry 60 minutes, then 550 ℃ of roastings 3 hours, obtains the synthetic TS-1 molecular sieve of titanium that adds of the present invention.Its XRD crystalline phase figure and Fig. 1 are similar.
Embodiment 5
With butyl titanate, anhydrous isopropyl alcohol, tetraethyl ammonium hydroxide and distilled water according to 1: 45.35: 67.53: 430.47 mixed in molar ratio is even, in normal pressure and 35 ℃ of following hydrolysis 8 minutes, obtains the hydrating solution of butyl titanate.The TS-1 molecular sieve of getting Comparative Examples 1 gained mixes according to molecular sieve (gram): Ti (mole)=228.46: 1 the ratio and the hydrating solution of above-mentioned butyl titanate, in normal pressure and 85 ℃ of dispersed with stirring 2 hours, obtains uniform dispersion.This dispersion is put into stainless steel cauldron, and constant temperature is placed 3.5 day time under 155 ℃ temperature, obtains containing the mixture of liquid and solid.This mixture is filtered, is washed with water to pH is 6～8, and in 115 ℃ of oven dry 45 minutes, obtains the synthetic TS-1 molecular sieve of titanium that adds of the present invention.Its XRD crystalline phase figure and Fig. 1 are similar.
Embodiment 6
With butyl titanate, anhydrous isopropyl alcohol, tetraethyl ammonium hydroxide and distilled water according to 1: 10.55: 4.55: 435.32 mixed in molar ratio is even, in normal pressure and 25 ℃ of following hydrolysis 25 minutes, obtains the hydrating solution of butyl titanate.The TS-1 molecular sieve of getting Comparative Examples 1 gained mixes according to molecular sieve (gram): Ti (mole)=463.36: 1 the ratio and the hydrating solution of above-mentioned butyl titanate, in normal pressure and 95 ℃ of dispersed with stirring 5.5 hours, obtains uniform dispersion.This dispersion is put into stainless steel cauldron, and constant temperature is placed 3 day time under 175 ℃ temperature, obtains containing the mixture of liquid and solid.This mixture is filtered, is washed with water to pH is 6～8, and in 120 ℃ of oven dry 40 minutes, obtains the synthetic TS-1 molecular sieve of titanium that adds of the present invention.Its XRD crystalline phase figure and Fig. 1 are similar.
Embodiment 7
Titanium tetrachloride, hexamethylene diamine and distilled water is even according to 1: 1.34: 296.64 mixed in molar ratio, in normal pressure and 32 ℃ of following hydrolysis 20 minutes, obtain the hydrating solution of titanium.The TS-1 molecular sieve of getting Comparative Examples 1 gained mixes according to molecular sieve (gram): Ti (mole)=331.28: 1 the ratio and the hydrating solution of above-mentioned titanium, in normal pressure and 85 ℃ of dispersed with stirring 3 hours, obtains uniform dispersion.This dispersion is put into stainless steel cauldron, and constant temperature is placed 3 day time under 150 ℃ temperature, obtains containing the mixture of liquid and solid.This mixture is filtered, is washed with water to pH is 6～8, and in 105 ℃ of oven dry 60 minutes, obtains the synthetic TS-1 molecular sieve of titanium that adds of the present invention.Its XRD crystalline phase figure and Fig. 1 are similar.
Embodiment 8
With Ti (SO
4)
2, anhydrous isopropyl alcohol, tetraethyl ammonium hydroxide and distilled water is according to 1: 0: 4.28: 135.40 mixed in molar ratio is even, in normal pressure and 28 ℃ of following hydrolysis 15 minutes, obtains Ti (SO
4)
2Hydrating solution.The TS-1 molecular sieve of getting Comparative Examples 1 gained is according to ratio and the above-mentioned Ti (SO of molecular sieve (gram): Ti (mole)=648.45: 1
4)
2Hydrating solution mix, in normal pressure and 80 ℃ of dispersed with stirring 2.5 hours, obtain uniform dispersion.This dispersion is put into stainless steel cauldron, and constant temperature is placed 2 day time under 160 ℃ temperature, obtains containing the mixture of liquid and solid.This mixture is filtered, is washed with water to pH is 6～8, and in 120 ℃ of oven dry 30 minutes, obtains the synthetic TS-1 molecular sieve of titanium that adds of the present invention.Its XRD crystalline phase figure and Fig. 1 are similar.
Embodiment 9
Repeat embodiment 8 described steps one time, the TS-1 molecular sieve that different is uses the method by embodiment 8 to obtain replaces the TS-1 molecular sieve of wherein said Comparative Examples 1 gained, promptly obtains according to the synthetic TS-1 molecular sieve of titanium that adds once more of the present invention.Its XRD crystalline phase figure and Fig. 1 are similar.
Embodiment 10
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 (product does not contain resorcinol) to distribute the results are shown in Table 1.In table 1:
Table 1
| Molecular sieve | Phenol conversion % | Benzenediol selectivity % | Product distribution % | ||
| Catechol | Hydroquinones | Benzoquinones | |||
| Embodiment 1 | 21.70 | 100.00 | 59.13 | 40.87 | 0.00 |
| Embodiment 2 | 21.38 | 100.00 | 56.92 | 43.08 | 0.00 |
| Embodiment 3 | 21.57 | 100.00 | 58.14 | 41.86 | 0.00 |
| Embodiment 4 | 20.52 | 100.00 | 53.73 | 46.27 | 0.00 |
| Embodiment 5 | 21.26 | 100.00 | 50.94 | 49.06 | 0.00 |
| Embodiment 6 | 21.16 | 100.00 | 56.52 | 43.48 | 0.00 |
| Embodiment 7 | 18.71 | 100.00 | 48.50 | 51.50 | 0.00 |
| Embodiment 8 | 19.43 | 100.00 | 51.26 | 48.74 | 0.00 |
| Embodiment 9 | 22.31 | 100.00 | 50.32 | 49.68 | 0.00 |
| Comparative Examples 1 | 5.30 | 88.87 | 38.30 | 50.57 | 11.13 |
From table 1 data as can be seen, method gained TS-1 molecular sieve provided by the invention is compared with the Comparative Examples molecular sieve, and not only reactivity improves greatly in the oxidation of phenol reaction, and does not have the benzoquinones accessory substance
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 ammoxidation of cyclohexanone.
With the TS-1 molecular sieve of gained among the embodiment 2 according to TS-1: the tert-butyl alcohol: the weight ratio of 25 heavy % ammoniacal liquor=1: 7.5: 7.5 mixes in slurry bed, be warming up to 80 ℃, then in this temperature and under stirring, add the mixture (volume ratio of water and hydrogen peroxide is 10: 9) of the hydrogen peroxide of entry and 30 heavy % with 5.7 milliliters/hour speed, the mixture (volume ratio of the cyclohexanone and the tert-butyl alcohol is 1: 2.5) that adds the cyclohexanone and the tert-butyl alcohol with 10.5 milliliters/hour speed, add 25 heavy % ammoniacal liquor with 5.7 milliliters/hour speed, above-mentioned three bursts of material flow are for adding simultaneously, simultaneously with the continuous discharging of corresponding speed, every 2 hours product sampling is analyzed with chromatogram after the stable reaction, the production rate of cyclohexanone oxime is defined as follows, and gained the results are shown in Table 2.
Table 2
| First day average | Second day average | The 3rd day average | The 4th day average | The 5th day average | |
| The production rate % of cyclohexanone oxime | 89.83 | 73.25 | 95.11 | 92.61 | 95.00 |
The TS-1 molecular sieve through roasting of Comparative Examples 1 gained is carried out the ammoxidation of cyclohexanone reaction evaluating by above-mentioned identical method, every 1 hour product is carried out sample analysis, the results are shown in Table 3 for gained.
The result of table 2 and table 3 shows that the inventive method gained TS-1 molecular sieve has activity stability preferably.
Table 3
| The 3rd hour | The 8th hour | The 10th hour | |
| The production rate % of cyclohexanone oxime | 52.34 | 37.21 | 32.15 |
Claims (18)
1. method for preparing the HTS (TS-1) with MFI structure is characterized in that this method comprises:
(1). the method by prior art synthesizes the TS-1 molecular sieve;
(2). with titanium-containing compound, isopropyl alcohol, organic amine and water according to 1: (0.0～50): (0.3～10): the mixed in molar ratio of (120～450) is even, and allows its hydrolysis, obtains the hydrating solution of titanium;
(3). with the hydrating solution of (1) said molecular sieve and (2) said titanium according to molecular sieve (gram): Ti (mole)=(200～1500): 1 ratio mixes, the gained mixture was reacted under 120～200 ℃ temperature 1～8 day in reactor, products therefrom is filtered, washs and drying.
2. according to the method for claim 1, it is characterized in that this method also comprises the described process of repetition one or many step (3).
3. according to the process of claim 1 wherein that the said TS-1 molecular sieve of step (1) is the TS-1 molecular sieve that synthesizes according to the whole bag of tricks of the prior art, it can pass through or without calcination process, promptly can contain or not contain organic formwork agent.
4. according to the process of claim 1 wherein that the said titanium-containing compound of step (2) is for comprising TiCl
4, TiOCl
2And Ti (SO
4)
2At interior inorganic titanium-containing compound.
5. according to the process of claim 1 wherein that the said titanium-containing compound of step (2) is organic titanium-containing compound titanate esters Ti (OR)
4, wherein R is the alkyl with 2～5 carbon atoms.
6. according to the method for claim 5, wherein R is a butyl.
7. according to the process of claim 1 wherein that the said organic amine of step (2) is fatty amine, alcamines or quaternary ammonium base compounds.
8. according to the method for claim 7, wherein said organic amine is the quaternary ammonium base compounds.
9. according to the method for claim 7, wherein said its general formula of fat amine compound is R (NH
2)
n, wherein R is the alkyl with 1～4 carbon atom, n=1～2.
10. according to the method for claim 9, wherein said fat amine compound is ethamine, n-butylamine, butanediamine or hexamethylene diamine.
11. according to the method for claim 7, wherein said its general formula of alcamine compound is (HOR ')
mN, wherein R ' is for having the alkyl of 1～4 carbon atom, m=1～3.
12. according to the method for claim 11, wherein said alcamine compound is MEA, diethanol amine or triethanolamine.
13. according to the method for claim 7 or 8, wherein said its general formula of quaternary ammonium base compounds is R "
3NOH, wherein R are " for having the alkyl of 1～4 carbon atom.
14. according to the method for claim 13, wherein R " is propyl group.
15. according to the process of claim 1 wherein that the mol ratio of the said titanium-containing compound of step (2), isopropyl alcohol, organic amine and water is 1: (0.0～20): (0.8～4.5): (220～350).
16. according to the process of claim 1 wherein that the time of said hydrolysis is 2～90 minutes in the step (2).
17. according to the process of claim 1 wherein middle molecular sieve (gram): Ti (mole)=(300～650) of step (3): 1.
18. according to the process of claim 1 wherein that said reaction is to react 1～4 day in the step (3) under 150～180 ℃ temperature.
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|---|---|---|---|---|
| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| CN1113454A (en) * | 1993-12-23 | 1995-12-20 | 阿克奥化学技术有限公司 | Epoxidation process and catalyst therefore |
| 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) |
-
1998
- 1998-04-10 CN CN98101357A patent/CN1102442C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| CN1113454A (en) * | 1993-12-23 | 1995-12-20 | 阿克奥化学技术有限公司 | Epoxidation process and catalyst therefore |
| 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) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102259022A (en) * | 2010-05-27 | 2011-11-30 | 中国石油化工股份有限公司 | Titanium-containing molecular sieve composite material and preparation method thereof |
| CN102259022B (en) * | 2010-05-27 | 2013-07-31 | 中国石油化工股份有限公司 | Titanium-containing molecular sieve composite material and preparation method thereof |
| DE102014222042A1 (en) | 2013-10-29 | 2015-04-30 | China Petroleum And Chemical Corporation | Titanium silicalite molecular sieve and its synthesis |
| US9896343B2 (en) | 2013-10-29 | 2018-02-20 | China Petroleum & Chemical Corporation | Titanium silicalite molecular sieve and its synthesis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1260241A (en) | 2000-07-19 |
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