CN1167010A - Process of synthesizing titanium-silicon molecular sieve TS-1 using silica gel as raw material - Google Patents
Process of synthesizing titanium-silicon molecular sieve TS-1 using silica gel as raw material Download PDFInfo
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- CN1167010A CN1167010A CN 97104636 CN97104636A CN1167010A CN 1167010 A CN1167010 A CN 1167010A CN 97104636 CN97104636 CN 97104636 CN 97104636 A CN97104636 A CN 97104636A CN 1167010 A CN1167010 A CN 1167010A
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Abstract
The present invention uses the silica gel and titanate as raw material, and the mixture of tetraethyl ammonium hydroxide (TEAOH) and tetrabutyl ammonium hydroxide (TBAOH) as formwork agent to prepare Ti-Si molecular sieve TS-1. The finished product is obtained by adopting static method or dynamic method to crystalize for 4-6 days under 170-180 deg.C and through the process of separating, washing, drying and roasting. Said invention features easy available raw material, simple technological process. When TS-1 molecular sieve is used in the hydroxylating reaction of phenol, the selective oxidisability is high, the utilicing factor of H2O2 is increased greatly.
Description
The present invention relates to the preparation of titanium-silicon molecular sieve TS-1.
At present, active day by day to the research of HTS both at home and abroad.Synthetic and the application of silicalite TS-1 etc. makes the zeolite catalysis field step into a new stage, and HTS is for H is arranged
2O
2The selective oxidation reaction that participates in has excellent catalytic performance, and this discovery is considered to the milestone of the eighties zeolite catalysis.
Synthesizing titanium-silicon molecular sieve TS-1 normally uses silicate class as silicon source (A.Tuel and Y.Ben Taarit Zeslites, 1994, Vo1.14, Feb, 130), as the titanium source, is that template agent (U.S.Patent 4,410 with TPAOH (TPAOH) with titanate ester, 501) synthesize, yet this synthetic method craft step complexity, used expensive raw material price obtains with being difficult to, and is unfavorable for the promotion and application of TS-1 molecular sieve.
The purpose of this invention is to provide a kind of is the process of feedstock production titanium-silicon molecular sieve TS-1 with silica gel.Raw material of the present invention is easy to get, and processing step is simple, when resulting product is used for the phenol hydroxylation catalyst for reaction, and the catalytic activity height of its selective oxidation.
The present invention with silica white or Ludox as the silicon source, with butyl titanate or isopropyl titanate as the titanium source, with organic amine (RN
+) for example TEAOH (tetraethyl ammonium hydroxide) and TBAOH (TBAH) synthesize for the template agent.
Concrete processing step is:
1. in autoclave, add silica gel, template agent RN
+And an amount of distilled water, strong agitation under the normal temperature makes it dissolving;
2. in above-mentioned system, add titanate ester, stir into glue;
3. adopt static method or dynamic method under 170-180 ℃ of temperature crystallization 4-6 days;
4. synthetic molecular sieve is separated from system, washed to PH=6-7,120 ℃ dry down, and the template agent is driven away in 500 ℃-650 ℃ following roastings, and unimpeded duct promptly obtains the TS-1 molecular sieve.
The mol ratio of each material of the present invention is: silica gel is (with SiO
2Meter)/titanate esters is (with TiO
2Meter)=20～60, RN
+/ SiO
2=0.02～0.5, H
2O/SiO
2=8～120.Wherein can select following mole proportioning for use:
SiO
2/TiO
2 30～40
RN
+/SiO
2 0.05～0.3
H
2O/SiO
2 10～60
The organic amine template agent RN that the present invention selects for use
+, R is an alkyl, uses the mixture of TEAOH and TBAOH can reach extraordinary effect, the mole proportioning of the two is: 0.2～4.0: 1, preferably 0.5～2.0: 1.
Fig. 1 is the XRD spectra of the TS-1 molecular sieve that synthesizes; Fig. 2 is the IR spectrogram of synthetic TS-1 molecular sieve.
Adopt synthesizing titanium-silicon molecular sieve TS-1 of the present invention to have many advantages: 1. employed silica white or Ludox are compared with esters of silicon acis, and be cheap; 2. use silica white or Ludox to synthesize the TS-1 molecular sieve, in ageing process, can heat and drive away the alcohols material that produces because of the esters of silicon acis hydrolysis, this process is carried out at normal temperatures; 3. the used template TPAOH (TPAOH) of synthetic TS-1 is difficult to obtain owing to not yet popularizing at home to produce usually, and adopts TEAOH and TBAOH mixture to replace, and raw material is easy to get and is effective.
Outstanding substantive distinguishing features of the present invention and beneficial effect can obtain embodying from following embodiment, but are not that the present invention is imposed any restrictions.
Embodiment 1
In having the teflon-lined autoclave, 80ml adds commercially available silica white 10g and 26ml distilled water, 10%TEAOH 10.47ml and 10%TBAOH 13.10ml, strong agitation is 6 hours at normal temperatures, make it to dissolve fully, adding butyl titanate 1.93ml then continues to stir 2 hours, leave standstill crystallization after 6 days 175 ℃ of static state, synthetic molecular sieve is separated from system, be washed with distilled water to PH=6, dried 4 hours down at 120 ℃, in 200 ℃, 400 ℃, clean template agent is caught up with in 550 ℃ of staged roastings, continues at 550 ℃ of activation 6 hours, and product is a white powder, material phase analysis adopts the analysis of Japanese D/MAX-III type X-ray diffractometer of science, sample confirms that this sub-sieve has the MFI structure, adopts FI-IR-50X infrared spectrometer analytic sample, and the spectrogram that obtains is at 960cm
-1There is an absworption peak at the place, confirms that titanium enters framework of molecular sieve.
Embodiment 2
With putting into acetone 20ml as solvent in the glass reactor of jacket type water-bath, add 10g phenol and make it dissolving, add TS-1 molecular sieve 1g that embodiment 1 synthesizes then as catalyst.Temperature of reaction system kept being constant at 80 ℃, in stirring, dropwise add 30% H
2O
24ml is reflected in the stirring and continues 6 hours, after the cooling catalyst is leached from reaction system, uses the gas chromatographic analysis product, and reaction result is: phenol conversion 7.73%; H
2O
2Utilization rate 23.21%; Benzenediol yield 17.85%; Product distributes: hydroquinones 56.81%, catechol 19.88%.
Embodiment 3
Press the material proportion synthesis of molecular sieve TS-1 of example 1, after 4 days, use the method roasting of embodiment 1 regulation and characterize molecular sieve 175 ℃ of dynamic agitation crystallization.Carry out the phenol hydroxylation reaction with the method for embodiment 2 then, and carry out product analysis, reaction result is: phenol conversion 12.18%; H
2O
2Utilization rate 36.54%; Benzenediol yield 30.31%; Product distributes: hydroquinones 52.13%, catechol 30.70%.
Embodiment 4
In the autoclave of embodiment 1, add commercially available silica white and the 26.43ml distilled water of 13.3g, 10%TEAOH10.47ml and 10%TBAOH 13.10ml be strong agitation 6 hours at normal temperatures, make it to dissolve fully, add butyl titanate 1.93ml then, continue to stir 2 hours, adopt the dynamic agitation crystallization after 4 days at 175 ℃, synthetic molecular sieve is pressed method processing, roasting and the sign of embodiment 1 regulation.Carry out the phenol hydroxylation reaction with the method for embodiment 2 then, and carry out product analysis, the result of reaction is: phenol conversion 5.70%; H
2O
2Utilization rate 17.10%; Benzenediol yield 10.28; Product distributes: hydroquinones 51.37%, catechol 31.63%.
Embodiment 5
In the autoclave of embodiment 1, add commercially available silica white of 10g and 4.4ml distilled water, 25% TEAOH 10.91ml and 10% TBAOH 32.76ml, strong agitation is 6 hours at normal temperatures, make it to dissolve fully, add butyl titanate 1.93ml then, continue to stir 2 hours, and left standstill crystallization after 6 days, characterize with the method processing of embodiment 1 regulation, molecular sieve that roasting synthesizes and by the method for embodiment 1 175 ℃ of static state.The method of stipulating with embodiment 2 is carried out the phenol hydroxylation reaction and product is analyzed then, and the result of reaction is: phenol conversion 12.83%; H
2O
2Utilization rate 38.40%; Benzenediol yield 34.56%; Product distributes: hydroquinones 56.60%, catechol 33.14%.
Press the material proportion synthesis of molecular sieve TS-1 of embodiment 5.175 ℃ of dynamic agitation crystallization after 4 days, with the method for embodiment 1 handle, roasting characterizes the molecular sieve that synthesizes.Carry out phenol hydroxylation reaction and analytical reactions product with the method for embodiment 2 regulations then, the result of reaction is: phenol conversion 13.10%; H
2O
2Utilization rate 39.30%; Benzenediol yield 36.56%; Product distributes: hydroquinones 54.16%, catechol 33.47%.
Embodiment 7
Press the synthetic TS-1 molecular sieve of material proportion of embodiment 1, replace butyl titanate with isopropyl titanate in the material, its consumption is constant, 175 ℃ of dynamic agitation crystallization after 4 days, with method processing, roasting and the sign molecular sieve of embodiment 1 regulation, then, carry out the phenol hydroxylation reaction by the method for embodiment 2, and the analytical reactions product, reaction result is: phenol conversion 15.96%; H
2O
2Utilization rate 47.90%; Benzenediol yield 41.64%; Product distributes: hydroquinones 48.37%, catechol 38.48%.
In the autoclave of embodiment 1, add commercially available silica white and the 30.54ml distilled water of 10g, 10%TEAOH5.06ml, 10%TBAOH 12.47ml is strong agitation 6 hours at normal temperatures, make it to dissolve fully, add butyl titanate 1.93ml then, continue to stir 2 hours, 175 ℃ of dynamic agitation crystallization after 4 days, press method processing, roasting and the sign molecular sieve of embodiment 1, carry out phenol hydroxylation reaction and analytical reactions product by the method for embodiment 2 then, reaction result is: phenol conversion 9.30%; H
2O
2Utilization rate 27.90%; Benzenediol yield 24.01%; Product distributes: hydroquinones 50.86%, catechol 39.09%.
Embodiment 9
In the autoclave of embodiment 1, add commercially available silica gel of 5.67g and 30.40ml distilled water, 10%TEAOH 3.97ml and 10%TBAOH 14.56ml be strong agitation 6 hours at normal temperatures, make it to dissolve fully, add butyl titanate 1.07ml then, continue to stir 2 hours, 175 ℃ of dynamic agitation crystallization after 4 days, press the method for embodiment 1 and handle roasting and characterize molecular sieve, carry out phenol hydroxylation reaction, 30%H in the reaction mass by the method for embodiment 2 then
2O
2Consumption is 2ml, and reaction result is: phenol conversion 13.30%; H
2O
2Utilization rate 80.40%; Benzenediol yield 63.64%; Product distributes: hydroquinones 40.45%, catechol 39.02%.
In the autoclave of embodiment 1, feed intake by following method:
Adding concentration earlier is 25.37% commercially available Ludox 16.75ml, and add 10%TEAOH 11.90ml and 10%TBAOH 21.84ml strong agitation 6 hours under normal temperature, fully mix, add butyl titanate 0.8ml then, continue to stir 2 hours, after 4 days, press method processing, roasting and the sign molecular sieve of embodiment 1 175 ℃ of dynamic agitation crystallization, carry out the phenol hydroxylation reaction by the method for embodiment 2, and the analytical reactions product.Reaction result is: phenol conversion 11.29%; H
2O
2Utilization rate 33.88%; Benzenediol yield 33.23%; Product distributes: hydroquinones 61.30%, catechol 36.75%.
Claims (6)
1. the process of a synthesizing titanium-silicon molecular sieve TS-1 is characterized in that it is is that raw material comprises the steps: with silica gel
(1) in autoclave, adds silica gel, the template agent RN that measures
+And water, strong agitation under the normal temperature makes it dissolving;
(2) add metering titanate ester, stir into glue;
(3) adopt static state or dynamic method under 170-180 ℃ of temperature crystallization 4-6 days;
(4) isolate synthetic molecular sieve after, be washed with water to PH=6-7;
(5) dry under 120 ℃, promptly got the TS-1 molecular sieve then in 500-650 ℃ of roasting temperature 4-6 hour;
The mol ratio of each material is:
SiO
2/TiO
2： 20～60
RN
+/SiO
2：?0.02～0.5
H
2O/SiO
2： 8～120
2. according to the process of the described synthesizing titanium-silicon molecular sieve TS-1 of claim 1, it is characterized in that described silica gel is silica white or Ludox.
3. according to the process of the described synthesizing titanium-silicon molecular sieve TS-1 of claim 1, it is characterized in that described titanate ester is butyl titanate or isopropyl titanate.
4. according to the process of the described synthesizing titanium-silicon molecular sieve TS-1 of claim 1, it is characterized in that described RN
+The template agent is the mixture of TEAOH and TBAOH, and the mole proportioning is 0.2～4.0: 1.
5. according to the process of the described synthesizing titanium-silicon molecular sieve TS-1 of claim 1, it is characterized in that the mole proportioning of described each material is:
SiO
2/TiO
2： 30～40
RN
+/SiO
2：?0.05～0.3
H
2O/SiO
2： 10～60
6. according to the process of the described synthesizing titanium-silicon molecular sieve TS-1 of claim 1, it is characterized in that TEAOH/TBAOH is 0.5-2.0 in the described template agent: 1.
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| CN1060411C CN1060411C (en) | 2001-01-10 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864093A (en) * | 2014-02-18 | 2014-06-18 | 太原大成环能化工技术有限公司 | Stepped-type crystallization preparation method of titanium-containing molecular sieve |
| CN104556116A (en) * | 2015-01-13 | 2015-04-29 | 大连理工齐旺达化工科技有限公司 | Method for assisted synthesis of TS-1 molecular sieve by using aerosol |
| 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 |
| CN106082262A (en) * | 2016-06-15 | 2016-11-09 | 山东齐鲁华信高科有限公司 | The preparation method of Hydrogen ZSM 11 molecular sieve |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103846A (en) * | 1984-04-26 | 1986-11-05 | 联合碳化公司 | Titanium-silicate compositions |
| IT1222868B (en) * | 1987-10-12 | 1990-09-12 | Montedipe Spa | METHOD FOR THE PREPARATION OF TITANIUM SILICALITES |
| RU2140819C1 (en) * | 1993-12-23 | 1999-11-10 | Арко Кемикал Текнолоджи, Л.П. | TITANIUM-CONTAINING ZEOLITE, METHOD OF ITS PRODUCTION (Versions), METHOD OF EPOXIDATION OF OLEFINS AND DIQUATERNARY AMMONIUM COMPOUND FOR PRODUCTION OF TITANIUM-CONTAINING ZEOLITE |
| CN1049610C (en) * | 1995-06-02 | 2000-02-23 | 复旦大学 | Preparation of non-aluminum Ti(Zr, V)-Si five-membered ring zeolite catalyst |
| 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) |
-
1997
- 1997-04-16 CN CN97104636A patent/CN1060411C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103864093A (en) * | 2014-02-18 | 2014-06-18 | 太原大成环能化工技术有限公司 | Stepped-type crystallization preparation method of titanium-containing molecular sieve |
| CN104556116A (en) * | 2015-01-13 | 2015-04-29 | 大连理工齐旺达化工科技有限公司 | Method for assisted synthesis of TS-1 molecular sieve by using aerosol |
| CN104556116B (en) * | 2015-01-13 | 2016-08-17 | 大连理工齐旺达化工科技有限公司 | A kind of method of aerosol auxiliary synthesis TS-1 molecular sieve |
| CN106082262A (en) * | 2016-06-15 | 2016-11-09 | 山东齐鲁华信高科有限公司 | The preparation method of Hydrogen ZSM 11 molecular sieve |
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