CN1247771A - Synthesis of titania-silica molecular sieve - Google Patents
Synthesis of titania-silica molecular sieve Download PDFInfo
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- CN1247771A CN1247771A CN 98119915 CN98119915A CN1247771A CN 1247771 A CN1247771 A CN 1247771A CN 98119915 CN98119915 CN 98119915 CN 98119915 A CN98119915 A CN 98119915A CN 1247771 A CN1247771 A CN 1247771A
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Abstract
The synthesis process features that the waste liquid is used as part of raw material for organosilicon to hydrolyze and part of fatty amine compound or alcohol amine is used to substitute tetrapropylammonium hydroxide as part of alkali source for hydrolyzing silicon and titanium compound. Utilizing the waste material eliminates the environmental pollution during the synthesis of titania-silica molecular sieve and reduces the preparation cost of the titani-silica molecular sieve TS-1.
Description
The present invention relates to a kind of synthetic method of 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 the reactant mixture of basic anhydride (Men/2O), 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, 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 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, P943～950), 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.
Technology (GB2,071,071A at the existing preparation HTS, USP 4,410, and 501, and Zeolites, 1992, Vol.12, P943～950) in, organosilyl utilization rate is about 75～95%, and template agent utilization rate is about 50～95%, having the template agent of 5～25% organosilicon and 5～50% to be retained in the synthetic waste liquid does not so obtain utilizing, if as sewage discharge, not only cause very big waste, and can pollute environment.
Propose to utilize the mother liquor of synthetic Y zeolite or modenite to synthesize the X zeolite among the prior art DD227416A; SU975573A proposes the NaY mother liquor is made silicon (aluminium) glue, and then synthesizes the raw material of NaY zeolite with the conduct of this silicon (aluminium) glue.Known to the inventor, do not see in the prior art that the synthetic waste liquid of useful HTS prepares the method report with MFI structure titanium silicon molecular sieve (TS-1).
The purpose of this invention is to provide a kind of synthetic waste liquid of HTS that utilizes as organosilyl partial hydrolysis raw material, the method for preparing TS-1 molecular sieve with MFI structure, make refuse obtain utilizing, get rid of in the HTS building-up process pollution, and reduce the preparation cost of TS-1 molecular sieve environment.
The preparation method of TS-1 molecular sieve provided by the present invention specifically utilizes the synthetic waste liquid of HTS as organosilyl partial hydrolysis raw material, add the titanium source of mixing then and prepare the TS-1 molecular sieve with organic amine, and replace the part alkali source of TPAOH as hydrolysis silicon and titanium with part fat amine compound or alcamine compound, so both avoided the pollution of the waste liquid that produces in the TS-1 building-up process, reduced the preparation cost of TS-1 again environment.
The preparation method of TS-1 molecular sieve provided by the present invention comprises:
(1). the synthetic waste liquid of a kind of silicon source, organo-alkali compound, water and HTS is mixed and make the hydrolysis of silicon source, obtain the hydrating solution of silicon, its mole consists of SiO
2: organic base: water=1: (0.05～0.80): (5～100) are preferably 1: (0.05～0.50): (5～60) comprise contained silicon and organic base in the synthetic waste liquid of said HTS, wherein contained SiO in the waste liquid in this composition
2Account for total SiO in the mixture
21～20% of amount;
(2). with titanium source, isopropyl alcohol, organic base and water according to 1: (0～60): (0～30): (10～100), preferred 1: (0～20): (0～5.5): the mol ratio of (10～40) 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 mixed in molar ratio and 50～100 ℃ of following stirring reactions 0.5～6 hour, obtain the titanium colloidal silica, TPAOH/SiO in this colloid
2Mol ratio be (0.02～0.5): 1, preferred (0.05～0.4): 1;
(4), with step (3) gained titanium colloidal silica hydrothermal crystallizing according to a conventional method in sealed reactor, reclaim product then.
Wherein, said organic base can be identical or different in step (1) and the step (2), this organic base is fat amine compound, alcamine compound, TPAOH or the mixture be made up of them, and in step (1) and the step (2) in the said organic base content of TPAOH (effect of lifting plate agent) be not zero simultaneously.
The said silicon of step in the method provided by the invention (1) source is silica gel, Ludox or organosilicon acid esters; Said its general formula of organosilicon acid esters is R
1 4SiO
4, R wherein
1For having the alkyl of 1～4 carbon atom, preferably ethyl; Organosilicon acid esters preferably in the said silicon source.
The synthetic waste liquid (crystallization mother liquor) that is produced behind the hydrothermal crystallizing when the synthetic waste liquid of the said HTS of step in the method provided by the invention (1) is synthesis of titanium silicon molecular sieve, wherein the concentration of silicon and organic base is not really definite, they generally contain the SiO of 0.01～5 heavy % with synthetic and the filtration washing condition is relevant
2The organic base of source and 0.001～0.05 heavy %.
The said titanium of step in the method provided by the invention (2) source is inorganic titanium salt or organic titanate; Said inorganic titanium salt can be TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2Its general formula of said organic titanate is Ti (OR
2)
4, R wherein
2For having the alkyl of 1～6 carbon atom, preferably has the alkyl of 2～4 carbon atoms; Organic titanate preferably in the said titanium source.
Its general formula of said fat amine compound is R in the method provided by the invention
3(NH
2)
n, R wherein
3For 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 the method provided by the invention
4)
mN; R wherein
4For 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.
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.
Method provided by the invention is owing to utilize the synthetic waste liquid of HTS as organosilyl partial hydrolysis raw material, thereby saved raw material, make refuse obtain utilizing, got rid of in the HTS building-up process pollution to environment, and owing to replace the part alkali source of TPAOH as hydrolysis silicon and titanium with part fat amine compound or alcamine compound, reduce the consumption of expensive TPAOH, thereby further reduced the preparation cost of TS-1 molecular sieve.
Fig. 1 is X-ray diffraction (XRD) the crystalline phase figure of the TS-1 sieve sample of pressing prior art (Zeolites, 1992, Vol.12, the 943rd～950 page) preparation of Comparative Examples 1.
Fig. 2 is X-ray diffraction (XRD) the crystalline phase figure of embodiment 1 gained sample.
(a) is commercially available total silicon ZSM-5 molecular sieve (Silicalite-1 among Fig. 3, dying of Shanghai seven manufacturers industry product) fourier infrared spectrogram, (b), (c) among Fig. 3, (d), (e) and (f) be respectively fourier infrared (FT-IR) spectrogram of the TS-1 sieve sample of embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5 preparations, among Fig. 3 (g) be Comparative Examples 1 by prior art (Zeolites, 1992, Vol.12, the 943rd～950 page) fourier infrared (FT-IR) spectrogram of preparation gained TS-1 sieve sample.
Following embodiment will the present invention is further illustrated.
In each embodiment, relative crystallinity be with gained sample and standard specimen separately the ratio of the peak height sum of five diffraction maximums (be commonly called as Five Fingers Peak) of 2-Theta angle between 22.5～25.0 of X-ray diffraction (XRD) represent, standard specimen herein (degree of crystallinity is decided to be 100%) is for adopting prior art (Zeolites, 1992, Vol.12, the 943rd～950 page) the TS-1 sieve sample of preparation.The BET surface area of sample adopts the GB/T5816-1995 standard method to measure.
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
This Comparative Examples is for by prior art Zeolites, 1992, Vol.12, the TS-1 sieve sample of the method preparation described in the 943rd～950 page, its XRD crystalline phase figure as shown in Figure 1, the fourier infrared spectrogram is shown in (g) among Fig. 3.
Embodiment 1
With 1.0 moles positive tetraethyl orthosilicates and 1000 gram titanium silicon waste liquids (the crystallization waste liquid of gained, wherein SiO when synthesizing the TS-1 molecular sieve for the laboratory
2Content is 4.2 heavy %, and TPAOH content is 0.75 heavy %, TiO
2Content less than 0.05 heavy %, down with) mix, hydrolysis is 45 minutes under normal pressure and 85 ℃ of temperature, obtains the hydrating solution of positive tetraethyl orthosilicate.
With butyl titanate, anhydrous isopropyl alcohol, TPAOH and water with mol ratio: 0.035: 0.55: 0.045: 0.95 ratio mixed, and hydrolysis is 25 minutes under normal pressure and 35 ℃ of temperature, obtains tetrabutyl titanate hydrolysis solution.
With the hydrating solution of gained titanium, with the organosilicon hydrolyzation solution of titanium silicon waste liquid hydrolysis organosilicon gained, mix by weight 1: 15 ratio, under normal pressure and 85 ℃ of temperature, stirring reaction 3.5 hours obtains the titanium Ludox.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, under 120 ℃ temperature and self-generated pressure, stirred pre-crystallization 0.5 hour, the temperature to 175 that raises then ℃ continues to stir crystallization 12 hours, and the gained crystallization product is filtered, is washed with water to pH value=6～8, and in 110 ℃ of oven dry 60 minutes, 550 ℃ of roasting temperatures 3 hours, obtain the TS-1 molecular sieve then, its XRD crystalline phase figure as shown in Figure 2, relative crystallinity is 98.5%, and the BET surface area is 438m
2/ g, fourier infrared spectrogram the unexistent 967cm of total silicon molecular sieve occurs in infrared spectrum shown in (b) among Fig. 3
-1Absworption peak, show that titanium has entered framework of molecular sieve.
Embodiment 2
With positive silicic acid four butyl esters, tetrapropyl aqua ammonia, water and titanium silicon waste liquid with 1.0 (moles): 0.10 (mole): 5.0 (moles): the ratio of 800 (grams) mixes, hydrolysis is 20 minutes under normal pressure and 40 ℃ of temperature, obtains the hydrating solution of positive silicic acid four butyl esters.
With tetraethyl titanate, anhydrous isopropyl alcohol, tetraethyl ammonium hydroxide and water with mol ratio: 0.075: 4.50: 0.15: 5.5 ratio mixed, and hydrolysis is 65 minutes under normal pressure and 10 ℃ of temperature, obtains the tetraethyl titanate hydrating solution.
With the hydrating solution of gained titanium, with the organosilicon hydrolyzation solution of titanium silicon waste liquid hydrolysis organosilicon gained, mix by weight 1: 3.5 ratio, under normal pressure and 65 ℃ of temperature, stirring reaction 6.0 hours obtains the titanium Ludox.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, under 110 ℃ temperature and self-generated pressure, stirred pre-crystallization 2.5 hours, the temperature to 170 that raises then ℃ continues to stir crystallization 24 hours, and the gained crystallization product is filtered, is washed with water to pH value=6～8, and in 110 ℃ of oven dry 60 minutes, 550 ℃ of roasting temperatures 3 hours, obtain the TS-1 molecular sieve then, its XRD crystalline phase figure and Fig. 2 are similar, relative crystallinity is 92.8%, and the BET surface area is 414m
2/ g, fourier infrared spectrogram the unexistent 967cm of total silicon molecular sieve occurs in infrared spectrum shown in (c) among Fig. 3
-1Absworption peak, show that titanium has entered framework of molecular sieve.
Embodiment 3
With positive silicic acid orthocarbonate, n-butylamine, water and titanium silicon waste liquid with 1.0 (moles): 0.08 (mole): 1.5 (moles): the ratio of 1800 (grams) mixes, and hydrolysis is 35 minutes under normal pressure and 60 ℃ of temperature, obtains the hydrating solution of positive silicic acid orthocarbonate.
With metatitanic acid tetramethyl ester, anhydrous isopropyl alcohol, TPAOH and water with mol ratio: 0.055: 1.50: 0.25: 3.5 ratio mixed, and hydrolysis is 40 minutes under normal pressure and 25 ℃ of temperature, obtains metatitanic acid tetramethyl ester hydrating solution.
With the hydrating solution of gained titanium, with the organosilicon hydrolyzation solution of titanium silicon waste liquid hydrolysis organosilicon gained, mix by weight 1: 10 ratio, under normal pressure and 75 ℃ of temperature, stirring reaction 4.0 hours obtains the titanium Ludox.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, under 115 ℃ temperature and self-generated pressure, stirred pre-crystallization 3.0 hours, the temperature to 180 that raises then ℃ continues to stir crystallization 2.5 hours, and the gained crystallization product is filtered, is washed with water to pH value=6～8, and in 110 ℃ of oven dry 60 minutes, 550 ℃ of roasting temperatures 3 hours, obtain the TS-1 molecular sieve then, its XRD crystalline phase figure and Fig. 2 are similar, relative crystallinity is 93.7%, and the BET surface area is 415m
2/ g, fourier infrared spectrogram the unexistent 967cm of total silicon molecular sieve occurs in infrared spectrum shown in (d) among Fig. 3
-1Absworption peak, show that titanium has entered framework of molecular sieve.
Embodiment 4
(commodity are called white carbon with solid silicone, Qingdao silica gel manufacturer industry product), triethanolamine, water and titanium silicon waste liquid are with 1.0 (moles): 0.75 (mole): 18 (moles): the ratio of 50 (grams) mixes, hydrolysis is 10 minutes under normal pressure and 5 ℃ of temperature, obtains the hydrating solution of positive quanmethyl silicate.
With butyl titanate, anhydrous isopropyl alcohol, TPAOH and water with mol ratio: 0.10: 6.50: 0.55: 10.0 ratio mixed, and hydrolysis is 5 minutes under normal pressure and 5 ℃ of temperature, obtains tetrabutyl titanate hydrolysis solution.
With the hydrating solution of gained titanium, with the organosilicon hydrolyzation solution of titanium silicon waste liquid hydrolysis organosilicon gained, mix by weight 1: 25 ratio, under normal pressure and 55 ℃ of temperature, stirring reaction 1.0 hours obtains the titanium Ludox.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, under 135 ℃ temperature and self-generated pressure, stirred pre-crystallization 0.2 hour, the temperature to 165 that raises then ℃ continues to stir crystallization 72 hours, and the gained crystallization product is filtered, is washed with water to pH value=6～8, and in 110 ℃ of oven dry 60 minutes, 550 ℃ of roasting temperatures 3 hours, obtain the TS-1 molecular sieve then, its XRD crystalline phase figure and Fig. 2 are similar, relative crystallinity is 96.8%, and the BET surface area is 435m
2/ g, fourier infrared spectrogram the unexistent 967cm of total silicon molecular sieve occurs in infrared spectrum shown in (e) among Fig. 3
-1Absworption peak, show that titanium has entered framework of molecular sieve.
Embodiment 5
With 0.5 mole of positive tetraethyl orthosilicate, 0.35 mole of butanediamine, 10.0 mole of water and contain 0.05 mole of SiO
2Mix with the titanium silicon waste liquid of 0.03 mole of organic base, hydrolysis is 15 minutes under normal pressure and 15 ℃ of temperature, obtains the hydrating solution of positive tetraethyl orthosilicate.
With TPAOH and triethanolamine in molar ratio: ratio mixed in 1: 0.6, formed mixed amine.
With titanium tetrachloride, mixed amine and water with mol ratio: 0.1: 0.025: 8.5 ratio mixes, and hydrolysis is 85 minutes under normal pressure and 40 ℃ of temperature, obtains the hydrating solution of titanium.
With the hydrating solution of gained titanium, evenly mix with the hydrating solution that contains silicate, under normal pressure and 90 ℃ of temperature, stirring reaction 2.5 hours obtains the titanium Ludox.
Gained titanium colloidal silica is put into the stainless steel sealed reactor, under 175 ℃ temperature and self-generated pressure, stirred crystallization 5 days, the gained crystallization product is filtered, is washed with water to pH value=6～8, and in 110 ℃ of oven dry 60 minutes, 550 ℃ of roasting temperatures 3 hours, obtain the TS-1 molecular sieve then, its XRD crystalline phase figure and Fig. 2 are similar, relative crystallinity is 94.6%, and the BET surface area is 422m
2/ g, fourier infrared spectrogram the unexistent 967cm of total silicon molecular sieve occurs in infrared spectrum shown in (f) among Fig. 3
-1Absworption peak, show that titanium has entered framework of molecular sieve.
Claims (17)
1. the preparation method of a TS-1 molecular sieve, it is characterized in that this method comprises the following steps: (1). the synthetic waste liquid of a kind of silicon source, organo-alkali compound, water and HTS is mixed and makes the hydrolysis of silicon source, obtain the hydrating solution of silicon, its mole consists of SiO
2: organic base: water=1: (0.05～0.80): (5～100) comprise contained silicon and organic base in the synthetic waste liquid of said HTS, wherein contained SiO in the waste liquid in this composition
2Account for total SiO in the mixture
21～20% of amount; (2). with a kind of titanium source, isopropyl alcohol, organo-alkali compound and water according to 1: (0～60): (0～30): the mol ratio of (10～100) 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 the mixed in molar ratio of silicon/titanium=5～100 and 50～100 ℃ of following stirring reactions 0.5～6 hour, obtain the titanium colloidal silica, TPAOH/SiO in this colloid
2Mol ratio be (0.02～0.5): 1; (4), with step (3) gained titanium colloidal silica hydrothermal crystallizing according to a conventional method in sealed reactor, reclaim product then.Wherein, said organic base can be identical or different in step (1) and the step (2), this organic base is fat amine compound, alcamine compound, TPAOH or the mixture be made up of them, and in step (1) and the step (2) in the said organic base content of TPAOH be not zero simultaneously.
2. according to the process of claim 1 wherein that the said silicon of step (1) source is silica gel, Ludox or organosilicon acid esters; Said its general formula of organosilicon acid esters is R
1 4SiO
4, R wherein
1For having the alkyl of 1～4 carbon atom.
3. according to the method for claim 2, wherein the said silicon of step (1) source is the organosilicon acid esters.
4. according to the process of claim 1 wherein that the mole of hydrating solution of the said silicon of step (1) consists of SiO
2: organic base: water=1: (0.05～0.50): (5～60).
5. according to the process of claim 1 wherein that the said titanium of step (2) source is inorganic titanium salt or organic titanate.
6. according to the method for claim 5, wherein said inorganic titanium salt is TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2
7. according to the method for claim 5, wherein said its general formula of organic titanate is Ti (OR
2)
4, R wherein
2For having the alkyl of 1～6 carbon atom.
8. according to the method for claim 7, R wherein
2For having the alkyl of 2～4 carbon atoms.
9. according to the method for claim 1 or 5, wherein the said titanium of step (2) source is an organic titanate.
10. according to the process of claim 1 wherein that the mole proportioning of each raw material of step (2) is the titanium source: isopropyl alcohol: organic base: water=1: (0～20): (0.5～5.5): (10～40).
11. according to the process of claim 1 wherein that its general formula of said fat amine compound is R
3(NH
2)
n, R wherein
3For having the alkyl of 1～4 carbon atom, n=1 or 2.
12. according to the method for claim 1 or 11, wherein said fat amine compound is ethamine, n-butylamine, butanediamine or hexamethylene diamine.
13. according to the process of claim 1 wherein that its general formula of said alcamine compound is (HOR
4)
mN; R wherein
4For having the alkyl of 1～4 carbon atom; M=1～3.
14. according to the method for claim 1 or 13, wherein said alcamine compound is MEA, diethanol amine or triethanolamine.
15. according to the process of claim 1 wherein TPAOH/SiO in the said colloid of step (3)
2Mol ratio be (0.05～0.4): 1.
16. according to the process of claim 1 wherein that its condition of the said crystallization of step (4) is 110～200 ℃ of following hydrothermal crystallizings 1～6 day.
17. according to the process of claim 1 wherein that its condition of the said crystallization of step (4) is earlier 110～145 ℃ of pre-crystallization 0.2～5 hour down, and then 150～200 ℃ of following crystallization 1 hour to 3 days.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134575B (en) * | 2006-08-31 | 2010-12-22 | 中国石油化工股份有限公司 | Method for preparing TS-1 molecular sieve |
| CN101190793B (en) * | 2006-11-30 | 2011-01-19 | 中国石油化工股份有限公司石油化工科学研究院 | Method for synthesizing TS-1 molecular screen |
| CN101428814B (en) * | 2007-11-07 | 2011-04-27 | 中国石油化工股份有限公司 | Synthesis of titanium-silicon molecular sieve TS-1 |
| CN102205974A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Method for preparing titanium silicon 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8329973D0 (en) * | 1983-11-10 | 1983-12-14 | Exxon Research Engineering Co | Recycled zeolite l preparation |
| US4853202A (en) * | 1987-09-08 | 1989-08-01 | Engelhard Corporation | Large-pored crystalline titanium molecular sieve zeolites |
| CN1048228C (en) * | 1995-12-22 | 2000-01-12 | 吉林大学 | titanium silicate zeolite molecular sieve crystal and preparation method thereof |
| US5637287A (en) * | 1996-02-02 | 1997-06-10 | Exxon Research & Engineering Company | Synthesis process for faujasite family zeolites using mother liquor recycle |
-
1998
- 1998-09-17 CN CN98119915A patent/CN1089279C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134575B (en) * | 2006-08-31 | 2010-12-22 | 中国石油化工股份有限公司 | Method for preparing TS-1 molecular sieve |
| CN101190793B (en) * | 2006-11-30 | 2011-01-19 | 中国石油化工股份有限公司石油化工科学研究院 | Method for synthesizing TS-1 molecular screen |
| CN101428814B (en) * | 2007-11-07 | 2011-04-27 | 中国石油化工股份有限公司 | Synthesis of titanium-silicon molecular sieve TS-1 |
| CN102205974A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Method for preparing titanium silicon molecular sieve |
| CN102205974B (en) * | 2010-03-31 | 2012-12-12 | 中国石油化工股份有限公司 | Method for preparing titanium silicon 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 |
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