CN1101267C - Synthesis method of titanium silicon molecular sieve - Google Patents
Synthesis method of titanium silicon molecular sieve Download PDFInfo
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- CN1101267C CN1101267C CN99113569A CN99113569A CN1101267C CN 1101267 C CN1101267 C CN 1101267C CN 99113569 A CN99113569 A CN 99113569A CN 99113569 A CN99113569 A CN 99113569A CN 1101267 C CN1101267 C CN 1101267C
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- hts
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- sio
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- tbah
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Abstract
The present invention relates to a method for synthesizing a titanium-silicon molecular sieve (TS-2). The the prior art mainly has the disadvantages of large dosage of template agents, high cost of used raw material and high synthesis cost. The present invention reduces the synthesis cost by a method for adopting silica sol as a silicon source, adopting tetrabutyl titanate as a titanium source, adopting tetrabutylammonium hydroxide as a template agent and adding inorganic ammonia (ammonium hydroxide) in the synthesis process. At the same time, a method for circularly using the template agent tetrabutylammonium hydroxide is adopted, so the synthesis cost is further reduced, and the present invention can be used in industrial production.
Description
The present invention relates to the synthetic method of HTS, particularly about the synthetic method of TS-2 HTS.
HTS is a kind of active catalytic material of good catalytic selective oxidation that has.In reactions such as benzene oxidation system phenol, oxidation of phenol preparing benzenediol, oxidation of alkanes system ketone and alcohol, ammoxidation of cyclohexanone preparing cyclohexanone oxime, olefin oxidation system epoxide, pure oxidation system carbonyl compound, HTS has excellent catalytic activity and selectivity as catalyzer.U.S. Pat 4410501 reported first be the silicon source with the tetraethyl orthosilicate, tetrabutyl titanate is the titanium source, TPAOH is a template synthetic TS-1 HTS, document Journal of Catalysis 130 afterwards, introduced a kind of synthetic, feature of TS-2 HTS and the MEL structure that has among the 440-446 (1991).Document Applied Catalysis has introduced the composite character and the catalytic characteristics of TS-2 HTS among 58 (1990) L1-L4.Above-mentioned two documents all use conventional methods, and are the silicon source with the tetraethyl orthosilicate promptly, are that template is synthesized the TS-2 HTS with the TBAH.Because tetraethyl orthosilicate and TBAH cost of material are all expensive, have limited HTS in industrial further application.
The objective of the invention is in order to overcome the shortcoming of synthetic TS-2 HTS raw materials cost costliness in the past, a kind of synthetic method of new TS-2 HTS is provided, it is inexpensive that this synthetic method has raw material, and synthetic cost is low, and the big characteristics of synthetic TS-2 HTS specific surface.
The objective of the invention is to realize: a kind of synthetic method of TS-2 HTS by following technical scheme, it is to be the titanium source with the tetrabutyl titanate, silicon sol is the silicon source, TBAH is a template, as additive, the mol ratio of reaction mixture was before molecular sieve was synthetic: SiO with inorganic ammonia
2/ TiO
2Be 20～200, TBAH/SiO
2Be 0.05～0.45, H
2O/SiO
2Be 60～100, NH
3/ SiO
2Be 0.01～3.00, reaction mass is under 140～180 ℃ of conditions of crystallization temperature, and crystallization 24～240 hours makes the TS-2 HTS with crystallization gained mixture through separation, washing, drying and roasting then.
The consumption preferable range of inorganic ammonia is with molar ratio computing NH in the technique scheme
3/ SiO
2Be 0.3～1.65.Because template is excessive in reaction process, therefore part or all of template TBAH can reclaim crystalline mother solution from TS-2 HTS synthetic, and its preferable range accounts for 60～80% of the total template dosage of building-up process for each amount from template TBAH in the TS-2 HTS synthetic recovery crystalline mother solution.
General tetrabutyl titanate uses with isopropanol in the building-up process of TS-2 HTS of the present invention, and after the crystallization building-up process, the molecular sieve drying temperature is 100～140 ℃, and maturing temperature is 450～600 ℃.
The present invention greatly reduces synthetic cost owing to use silicon sol cheap and easy to get to replace tetraethyl orthosilicate as the silicon source.On the basis of the above the template TBAH is recycled, further reduced synthetic cost.In the reaction system with inorganic ammonia as additive, synthetic TS-2 HTS particle is diminished, increased the specific surface area of HTS, thereby catalytic activity and selectivity of product can obviously improve the TS-2 HTS time as catalyzer.By using inorganic ammonia (ammoniacal liquor) as additive, synthetic TS-2 HTS is used for the reaction of hydrogen peroxide and phenol, 70 ℃ of temperature of reaction, with molar ratio computing phenol/hydrogen peroxide is 3.0, water/hydrogen peroxide is under 45 the condition, the transformation efficiency that makes phenol is from 16.7% promotion to 24.7%, and the dihydroxy-benzene selectivity also rises to 88% from 65% simultaneously, has obtained effect preferably.
The present invention is further elaborated below by embodiment.[embodiment 1]
At 60 gram (SiO
2Weight percentage be 17%) silicon sol in add the TBAH (TBAOH) of 20 ml waters, 20 milliliters of Virahols, 0.0017 mole of ammoniacal liquor and 105 milliliter of 0.4 mol concentration, induction stirring 0.5 hour, 28 milliliters of the tetrabutyl titanates (the tetrabutyl titanate weight percent concentration is 5%) that slowly added then with isopropanol, vigorous stirring 0.5 hour gets transparent uniform mixture.Consist of with molar ratio computing in the mixture: SiO
2/ TiO
2=40, TBAOH/SiO
2=0.25, H
2O/SiO
2=80, NH
3/ SiO
2=0.01.Slowly be warmed up to 60 ℃ then, be warming up to again after 1 hour and remove alcohol more than 80 ℃.Stir after 2 hours in 170 ℃ of static crystallizations 48 hours.After crystallization is finished, isolate crystallized product and wash with water.After 120 ℃ of oven dry, 550 ℃ of roastings 6 hours, TS-2 HTS A.
With the above-mentioned TS-2 HTS A that obtains, under following condition, carry out catalytic performance test.The examination condition is: hydrogen peroxide (H
2O
2) be the disposable sample introduction of oxygenant, temperature of reaction is 70 ℃, reaction pressure is a normal pressure, phenol/TS-2 HTS=10 (gram/gram), with molar ratio computing phenol/hydrogen peroxide=3.0, water/hydrogen peroxide=45, appraisal result is listed in table 1.[embodiment 2～4]
According to each operation steps of embodiment 1, just change the consumption of inorganic ammonia, successively with molar ratio computing NH
3/ SiO
2Be 0.30,1.60 and 3.00, make TS-2 HTS B, C, D respectively, wherein the grain diameter of TS-2 HTS C is 1 * 2 micron.Check and rate with the examination condition of embodiment 1 then, appraisal result is listed in table 1.[embodiment 5]
Synthetic and the evaluation TS-2 HTS according to each step of embodiment 1, just the template in the building-up process is used the circulation crystalline mother solution that reclaims in the building-up process first time, add the TBAH of 21 milliliter of 0.4 mol concentration in addition, get TS-2 HTS E at last, its evaluation result is listed in table 1.[embodiment 6]
Synthetic and the evaluation TS-2 HTS according to each step of embodiment 1, just the template in the building-up process is used the circulation crystalline mother solution that reclaims in the building-up process second time, add the TBAH of 42 milliliter of 0.4 mol concentration in addition, get TS-2 HTS F at last, its evaluation result is listed in table 1.[embodiment 7]
Synthetic and the evaluation TS-2 HTS according to each step of embodiment 1, just the template in the building-up process is used the circulation crystalline mother solution that reclaims in the building-up process for the third time, add the TBAH of 31.5 milliliter of 0.4 mol concentration in addition, get TS-2 HTS G at last, its evaluation result is listed in table 1.[comparative example 1]
Synthetic and evaluation TS-2 HTS is not just added the additive inorganic ammonia in the building-up process according to each step of embodiment 1, gets TS-2 HTS H at last, and its grain diameter is 5 * 6 microns, and its evaluation result is listed in table 1.[embodiment 8]
Embodiment 1～6 and comparative example 1 synthetic TS-2 HTS A, B, C, D, E, F, H are measured the SiO of molecular sieve
2/ TiO
2Mol ratio, it the results are shown in table 2.[embodiment 9]
Embodiment 3 and comparative example 1 synthetic TS-2 HTS C, H are measured the specific surface area and the pore volume of molecular sieve, and it the results are shown in table 3.
The performance evaluation data of table 1 synthetic TS-2 HTS in the phenol hydroxylation reaction
| The molecule screen size | A B C D E F G H |
| Phenol conversion % | 18.2 21.2 24.7 23.3 22.2 23.5 23.1 16.7 |
| Dihydroxy-benzene selectivity % | 73 82 88 89 88 86 86 65 |
The silicon titanium mol ratio of table 2 synthetic TS-2 HTS
| The molecule screen size | SiO 2/TiO 2(moles/mole) |
| The synthetic back of collosol intermixture molecular sieve | |
| A B C D E F H | 40 75.3 40 65.9 40 39.9 40 41.2 40 45.8 40 49.2 40 80.4 |
The physical data of table 3 synthetic TS-2 HTS
| The molecule screen size | Inorganic ammonia | Specific surface area (rice 2/ gram) pore volume (milliliter/gram) |
| C | Add | 503.5 0.292 |
| H | Do not add | 455.7 0.224 |
As shown in Table 1, add small amounts of inorganic ammonia (ammoniacal liquor) in the TS-2 HTS building-up process and can obviously improve activity of such catalysts and selectivity.This is because the interpolation of inorganic ammonia (ammoniacal liquor) can effectively improve the relative content (as table 2) of titanium in the crystallized product; Add inorganic ammonia (ammoniacal liquor) simultaneously the crystallized product particle is diminished, reduce to 1 * 2 micron (embodiment 3) by 5 * 6 microns (comparative examples 1), the specific surface area and the pore volume of product TS-2 HTS also increase (as table 3) simultaneously.Template recycle in the mother liquor as known from Table 1 in addition, institute's synthetic TS-2 HTS has excellent catalytic performance equally.
Claims (4)
1, a kind of synthetic method of TS-2 HTS, it is to be the titanium source with the tetrabutyl titanate, and silicon sol is the silicon source, and TBAH is a template, and as additive, the mol ratio of reaction mixture was before molecular sieve was synthetic: SiO with inorganic ammonia
2/ TiO
2Be 20～200, TBAH/SiO
2Be 0.05～0.45, H
2O/SiO
2Be 60～100, NH
3/ SiO
2Be 0.01～3.00, reaction mass is under 140～180 ℃ of conditions of crystallization temperature, and crystallization 24～240 hours makes the TS-2 HTS with crystallization gained mixture through separation, washing, drying and roasting then.
2, according to the synthetic method of the described TS-2 HTS of claim 1, the consumption that it is characterized in that inorganic ammonia is with molar ratio computing NH
3/ SiO
2Be 0.3～1.65.
3, according to the synthetic method of the described TS-2 HTS of claim 1, part or all that it is characterized in that the template TBAH reclaims crystalline mother solution from TS-2 HTS synthetic.
4,, it is characterized in that each amount from template TBAH in the TS-2 HTS synthetic recovery crystalline mother solution accounts for 60～80% of the total template dosage of building-up process according to the synthetic method of the described TS-2 HTS of claim 3.
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| CN99113569A CN1101267C (en) | 1999-03-30 | 1999-03-30 | Synthesis method of titanium silicon molecular sieve |
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| CN99113569A CN1101267C (en) | 1999-03-30 | 1999-03-30 | Synthesis method of titanium silicon molecular sieve |
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|---|---|---|---|---|
| CN103043678B (en) * | 2013-01-11 | 2015-01-28 | 东北大学 | Method for preparing titanium silicalite molecular sieve ETS-4 from high-silicon industrial raw materials |
| CN103657715B (en) * | 2013-12-04 | 2015-08-19 | 中国科学院山西煤炭化学研究所 | The catalyst of methyl alcohol or the acetic acid synthesized methyl esters of Dimethyl ether carbonylation and method for making and application |
| CN108554444B (en) * | 2018-05-08 | 2019-07-30 | 哈尔滨工业大学 | A kind of preparation method of multi-stage porous Ti-ZSM-5 molecular sieve auto-exhaust catalyst |
Citations (2)
| 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 |
| CN1180587A (en) * | 1996-10-22 | 1998-05-06 | 中国石油化工总公司上海石油化工研究院 | Synthetic method for titaniam silicon molecular sieve |
-
1999
- 1999-03-30 CN CN99113569A patent/CN1101267C/en not_active Expired - Fee Related
Patent Citations (2)
| 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 |
| CN1180587A (en) * | 1996-10-22 | 1998-05-06 | 中国石油化工总公司上海石油化工研究院 | Synthetic method for titaniam silicon molecular sieve |
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