CN100560493C - Dendritic titanium silicon molecular screen film and preparation method - Google Patents
Dendritic titanium silicon molecular screen film and preparation method Download PDFInfo
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- CN100560493C CN100560493C CNB2008100520161A CN200810052016A CN100560493C CN 100560493 C CN100560493 C CN 100560493C CN B2008100520161 A CNB2008100520161 A CN B2008100520161A CN 200810052016 A CN200810052016 A CN 200810052016A CN 100560493 C CN100560493 C CN 100560493C
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Abstract
The present invention relates to a kind of dendritic titanium silicon molecular screen film and preparation method, dendritic titanium silicon molecular screen film diffuse reflectance infrared spectroscopy of the present invention peak is 960cm
-1X-ray diffraction Fig. 2 θ=7.8 ° 8.8 ° 23.1 ° 23.8 ° 24.4 °, the preparation method of dendritic titanium silicon molecular screen film of the present invention is: be the titanium source with the tetrabutyl titanate, tetraethyl orthosilicate is the silicon source, TPAOH is template RN, the invention has the advantages that the HTS crystal is the dendrimer sieve membrane, and be carried on the cordierite carrier, can be applied to carry out in the monolith honeycomb reactor cyclohexanone oxamidinating reaction, the molecular sieve catalyst utilization ratio of avoiding the molecular screen membrane because of intensive form to cause reduces, reactant is difficult for diffusing into the problem of molecular screen membrane, and saved separating of reaction solution and catalyzer, reduced the loss of catalyzer.
Description
Technical field
The invention belongs to the inorganic material film field, particularly a kind of dendritic titanium silicon molecular screen film and preparation method.
Background technology
The reaction of HTS (TS-1) catalysis of pimelinketone oxamidine is a typical green chemical industry process.It is the cyclohexanone-oxime metallization processes of being developed the earliest by gondola Enichem company, and it is a raw material with pimelinketone, ammonia and hydrogen peroxide, titanium-silicon molecular sieve TS-1 catalysis with under the normal pressure synthesis cyclohexanone-oxime.This process byproducts is few, can overcome the shortcoming of traditional technology substantially, is expected to realize zero release, reaches the purpose of cleaner production.But the particle diameter of TS-1 sieve particle is very little, is about 0.2 ~ 0.5 μ m, with the separation difficulty of liquid reactants.
Patent CN1432560A has described the method that adopts Powdered HTS (TS-1) catalysis of pimelinketone oxamidine, and reaction product is separated in settling vessel with HTS.And when adopting intensive molecular screen membrane to react, the conclusion that Chen Xiaohui etc. obtain is a thickness and catalytic performance relation not in direct ratio, the transformation efficiency of hydrogen peroxide is 9.2% when thickness reaches 25 μ m, and this illustrates that the film of intensive form can influence the diffusion of reactant, causes side reaction to take place.
Summary of the invention
For solving the deficiencies in the prior art, the present invention proposes a kind of dendritic titanium silicon molecular screen film and preparation method, adopt the method for load that HTS is loaded on the trichroite, make the form of dendrimer sieve membrane, help the diffusion of reactant on molecular screen membrane, improve the utilization ratio of molecular screen membrane, reduce the generation of side reaction.
It is 960cm that dendritic titanium silicon molecular screen film of the present invention, molecular sieve have the diffuse reflectance infrared spectroscopy peak
-1X-ray diffraction Fig. 2 θ=7.8 ° 8.8 ° 23.1 ° 23.8 ° 24.4 °.As shown in Figure 4 and Figure 5.
The preparation method of dendritic titanium silicon molecular screen film of the present invention is: be the titanium source with the tetrabutyl titanate, tetraethyl orthosilicate is the silicon source, and TPAOH is template RN, and its feature comprises following process:
1) carrier pre-treatment: cylindric porous cordierite carrier was put into 20%～37% hydrochloric acid soaking at room temperature 3～6 hours, put into after the drying at room temperature that to naturally cool to room temperature after 200～400 ℃ of roastings of retort furnace standby, the trichroite surface after the processing as shown in Figure 1;
2) synthetic liquid configuration: wherein the mol ratio of each material is TiO in the synthetic liquid of molecular screen membrane
2: RN: H
2O: SiO
2=0.015～0.05: 0.15～0.35: 30～150: 1; Tetraethyl orthosilicate and tetrabutyl titanate are mixed stirring 10～30 minutes under 0～20 ℃ of condition, the dropping mass ratio is 10～20% the TPAOH aqueous solution, the dropping process avoids white precipitate to produce, after template dropwises, consecutive low temperature and stirring state are after 10～30 minutes, with the heating of the speed of 2～5 ℃/min and be warming up to 80～100 ℃ and removed alcohol 2～5 hours, to replenish distilled water in the heat-processed, make synthetic liquid keep initial volume.
3) hydrothermal crystallizing and weathering process: with step 2) synthetic liquid add in the stainless steel crystallizing kettle that has poly-tetrafluoro liner, again pretreated cylindric carrier in the step 1) is immersed in the synthetic liquid, put into baking oven behind the good seal crystallizing kettle and carry out crystallization, crystallization is 1～3 day under autogenous pressure, and crystallization temperature is 150～170 ℃.Carry out weathering process then, crystallizing kettle worn out 1～3 day under 30～100 ℃ of conditions,, crystallizing kettle was put into the baking oven crystallization 3～5 days again, crystallization temperature is 160～180 ℃;
4) aftertreatment: crystallizing kettle is taken out the back cooling bath be cooled to room temperature rapidly from baking oven, after Ti-Si molecular sieve membrane/carrier taking-up, be washed with distilled water to washing lotion and be neutral, 20～80 ℃ of dryings 1～3 day, 400～600 ℃ of following roastings obtained dendritic titanium silicon molecular screen film after 6～12 hours in retort furnace again, the molecular screen membrane that obtains learns that through infrared spectra and X-ray powder diffraction result the synthetic molecular screen membrane is Ti-Si molecular sieve membrane (TS-1), shown in Figure 4 and 5 shown in Fig. 2 and 3.
The invention has the advantages that the HTS crystal is the dendrimer sieve membrane, and be carried on the cordierite carrier, can be applied to carry out in the monolith honeycomb reactor cyclohexanone oxamidinating reaction, the molecular sieve catalyst utilization ratio of avoiding the molecular screen membrane because of intensive form to cause reduces, reactant is difficult for diffusing into the problem of molecular screen membrane, and saved separating of reaction solution and catalyzer, reduced the loss of catalyzer.
Description of drawings
Fig. 1: the surface of blank cordierite;
Fig. 2: the trichroite surface behind the growth molecular screen membrane;
Fig. 3: the side-view of molecular screen membrane;
Fig. 4: the infrared spectra of Ti-Si molecular sieve membrane;
Fig. 5: the x-ray diffractogram of powder of Ti-Si molecular sieve membrane; The characteristic diffraction peak of Ti-Si molecular sieve membrane on the characteristic diffraction peak b trichroite of a trichroite.
Embodiment
Embodiment 1: with cylindric porous cordierite carrier (2MgO2Al
2O
35SiO
2, Φ 3 * 4mm) put into 37% hydrochloric acid soaking at room temperature 6 hours, put into after the drying at room temperature that to naturally cool to room temperature after 400 ℃ of roastings of retort furnace standby.The mol ratio of each material is TiO in the synthetic liquid of molecular screen membrane
2/ SiO
2=0.015, RN/SiO
2=0.35, H
2O/SiO
2=120.Tetraethyl orthosilicate and tetrabutyl titanate are mixed stirring 30 minutes under 0 ℃ of condition, the dropping mass ratio is 20% the TPAOH aqueous solution, avoid white precipitate to produce in the dropping process,, continue to drip template again after should precipitating disappearance by the time if produce white flocks in the process.After template dropwised, consecutive low temperature and stirring state added quantitative distilled water after 30 minutes, with the heating of the speed of 2 ℃/min and be warming up to 90 ℃ and removed alcohol 4 hours, will suitably replenish distilled water in the heat-processed, made the initial volume of synthetic liquid maintenance.Synthetic liquid is added in the stainless steel crystallizing kettle that has poly-tetrafluoro liner, more pretreated cylindric carrier is immersed in the synthetic liquid, put into baking oven behind the good seal crystallizing kettle and carry out the first step crystallization, crystallization is 1 day under autogenous pressure, and crystallization temperature is 160 ℃.Aging then, crystallizing kettle is slowly lowered the temperature, under 30 ℃ of conditions, wore out 2 days, crystallizing kettle was put into the baking oven crystallization 4 days again, crystallization temperature is 170 ℃.Crystallizing kettle is taken out the back cooling bath be cooled to room temperature rapidly from baking oven, after Ti-Si molecular sieve membrane/carrier taking-up, be washed with distilled water to washing lotion and be neutral, 80 ℃ of dryings 1 day, 600 ℃ of following roastings obtaining after 12 hours is used for the cyclohexanone oxamidinating reaction in retort furnace again and load on Ti-Si molecular sieve membrane on the cordierite carrier.The Ti-Si molecular sieve membrane that makes is applied to the cyclohexanone oxamidinating reaction, and the pimelinketone transformation efficiency that obtains and the selectivity of cyclohexanone-oxime are respectively 87% and 92%.
Embodiment 2: with cylindric porous cordierite carrier (2MgO2Al
2O
35SiO
2, Φ 3 * 4mm) put into 20% hydrochloric acid soaking at room temperature 3 hours, put into after the drying at room temperature that to naturally cool to room temperature after 200 ℃ of roastings of retort furnace standby.The mol ratio of each material is TiO in the synthetic liquid of molecular screen membrane
2/ SiO
2=0.02, RN/SiO
2=0.15, H
2O/SiO
2=30.Tetraethyl orthosilicate and tetrabutyl titanate are mixed stirring 20 minutes under 4 ℃ of conditions, slowly the dropping mass ratio is 18% the TPAOH aqueous solution, avoid white precipitate to produce in the dropping process, if produce white flocks in the process, continue to drip template again after should precipitating disappearance by the time.After template dropwised, consecutive low temperature and stirring state added quantitative distilled water after 10 minutes, with the heating of the speed of 5 ℃/min and be warming up to 80 ℃ and removed alcohol 5 hours, will suitably replenish distilled water in the heat-processed, made the initial volume of synthetic liquid maintenance.Synthetic liquid is added in the stainless steel crystallizing kettle that has poly-tetrafluoro liner, more pretreated cylindric carrier is immersed in the synthetic liquid, put into baking oven behind the good seal crystallizing kettle and carry out the first step crystallization, crystallization is 2 days under autogenous pressure, and crystallization temperature is 150 ℃.Aging then, crystallizing kettle is slowly lowered the temperature, under 50 ℃ of conditions, wore out 3 days, crystallizing kettle was put into the baking oven crystallization 5 days again, crystallization temperature is 160 ℃.Crystallizing kettle is taken out the back cooling bath be cooled to room temperature rapidly from baking oven, after Ti-Si molecular sieve membrane/carrier taking-up, be washed with distilled water to washing lotion and be neutral, 60 ℃ of dryings 2 days, 500 ℃ of following roastings obtaining after 8 hours is used for the cyclohexanone oxamidinating reaction in retort furnace again and load on Ti-Si molecular sieve membrane on the cordierite carrier.The Ti-Si molecular sieve membrane that makes is applied to the cyclohexanone oxamidinating reaction, and the pimelinketone transformation efficiency that obtains and the selectivity of cyclohexanone-oxime are respectively 84% and 89%.
Embodiment 3: with cylindric porous cordierite carrier (2MgO2Al
2O
35SiO
2, Φ 3 * 4mm) put into 30% hydrochloric acid soaking at room temperature 4 hours, put into after the drying at room temperature that to naturally cool to room temperature after 300 ℃ of roastings of retort furnace standby.The mol ratio of each material is TiO in the synthetic liquid of molecular screen membrane
2/ SiO
2=0.05, RN/SiO
2=0.25, H
2O/SiO
2=150.Tetraethyl orthosilicate and tetrabutyl titanate are mixed stirring 10 minutes under 20 ℃ of conditions, the dropping mass ratio is 10% the TPAOH aqueous solution, avoid white precipitate to produce in the dropping process, if produce white flocks in the process, continue to drip template again after should precipitating disappearance by the time.After template dropwised, consecutive low temperature and stirring state added quantitative distilled water after 20 minutes, with the heating of the speed of 3 ℃/min and be warming up to 100 ℃ and removed alcohol 2 hours, will suitably replenish distilled water in the heat-processed, made the initial volume of synthetic liquid maintenance.Synthetic liquid is added in the stainless steel crystallizing kettle that has poly-tetrafluoro liner, more pretreated cylindric carrier is immersed in the synthetic liquid, put into baking oven behind the good seal crystallizing kettle and carry out the first step crystallization, crystallization is 3 days under autogenous pressure, and crystallization temperature is 170 ℃.Aging then, crystallizing kettle is slowly lowered the temperature, under 100 ℃ of conditions, wore out 1 day, crystallizing kettle was put into the baking oven crystallization 3 days again, crystallization temperature is 180 ℃.Crystallizing kettle is taken out the back cooling bath be cooled to room temperature rapidly from baking oven, after Ti-Si molecular sieve membrane/carrier taking-up, be washed with distilled water to washing lotion and be neutral, 20 ℃ of dryings 3 days, 400 ℃ of following roastings obtaining after 6 hours is used for the cyclohexanone oxamidinating reaction in retort furnace again and load on Ti-Si molecular sieve membrane on the cordierite carrier.The Ti-Si molecular sieve membrane that makes is applied to the cyclohexanone oxamidinating reaction, and the pimelinketone transformation efficiency that obtains and the selectivity of cyclohexanone-oxime are respectively 72% and 81%.
Dendritic titanium silicon molecular screen film and preparation method that the present invention discloses and discloses can be by using for reference this paper disclosure.Although method of the present invention is described by preferred embodiment, but those skilled in the art obviously can change method as herein described in not breaking away from content of the present invention, spirit and scope, more particularly, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (1)
1. the preparation method of dendritic titanium silicon molecular screen film, it is 960cm that molecular sieve has the diffuse reflectance infrared spectroscopy peak
-1X-ray diffraction Fig. 2 θ=7.8 ° 8.8 ° 23.1 ° 23.8 ° 24.4 °; It is characterized in that the preparation method is as follows:
1) carrier pre-treatment: cylindric porous cordierite carrier was put into 20%～37% hydrochloric acid soaking at room temperature 3～6 hours, put into after the drying at room temperature that to naturally cool to room temperature after 200～400 ℃ of roastings of retort furnace standby;
2) synthetic liquid configuration: wherein the mol ratio of each material is TiO in the synthetic liquid of molecular screen membrane
2: TPAOH: H
2O: SiO
2=0.015～0.05: 0.15～0.35: 30～150: 1; Tetraethyl orthosilicate and tetrabutyl titanate are mixed stirring 10～30 minutes under 0～20 ℃ of condition, the dropping mass ratio is 10～20% the TPAOH aqueous solution, the dropping process avoids white precipitate to produce, after template dropwises, consecutive low temperature and stirring state are after 10～30 minutes, with the heating of the speed of 2～5 ℃/min and be warming up to 80～100 ℃ and removed alcohol 2～5 hours, to replenish distilled water in the heat-processed, make synthetic liquid keep initial volume;
3) hydrothermal crystallizing and weathering process: with step 2) synthetic liquid add in the stainless steel crystallizing kettle that has poly-tetrafluoro liner, again pretreated cylindric carrier in the step 1) is immersed in the synthetic liquid, put into baking oven behind the good seal crystallizing kettle and carry out crystallization, crystallization is 1～3 day under autogenous pressure, and crystallization temperature is 150～170 ℃; Carry out weathering process then, crystallizing kettle was worn out 1～3 day under 30～100 ℃ of conditions, crystallizing kettle was put into the baking oven crystallization 3～5 days again, crystallization temperature is 160～180 ℃;
4) aftertreatment: crystallizing kettle is taken out the back cooling bath be cooled to room temperature rapidly from baking oven, after Ti-Si molecular sieve membrane/carrier taking-up, be washed with distilled water to washing lotion and be neutral, 20～80 ℃ of dryings 1～3 day, 400～600 ℃ of following roastings obtained dendritic titanium silicon molecular screen film after 6～12 hours in retort furnace again.
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| CN102530982A (en) * | 2012-01-09 | 2012-07-04 | 河北科技大学 | Method for preparing titanium silicalite film by dynamic in-situ hydrothermal method |
| CN103285905B (en) * | 2012-02-29 | 2015-03-04 | 北京安耐吉能源工程技术有限公司 | Overall structure catalyst, preparation method of overall structure catalyst, and method for preparing caprolactam |
| CN104477935B (en) * | 2014-11-21 | 2016-08-24 | 常州大学 | The method that salt particulate templates method prepares hydridization duct molecular sieve |
| CN104528761B (en) * | 2014-12-25 | 2016-08-24 | 中国天辰工程有限公司 | A kind of synthetic method of high skeleton Ti content HTS |
| CN104841415B (en) * | 2015-04-13 | 2017-10-24 | 中国天辰工程有限公司 | A kind of preparation method for the catalyst that caprolactam is prepared for cyclohexanone one-step method |
| CN112076782B (en) | 2019-06-14 | 2022-03-11 | 大连理工大学 | Alkali metal ion modified titanium-silicon molecular sieve for propylene and hydrogen peroxide gas phase epoxidation reaction and preparation method thereof |
| CN110180586B (en) * | 2019-06-14 | 2022-03-11 | 大连理工大学 | Alkali metal ion modified titanium silicalite TS-1 for propylene and hydrogen peroxide gas phase epoxidation reaction and preparation method thereof |
Citations (1)
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Non-Patent Citations (2)
| Title |
|---|
| 钛硅分子筛膜的合成及其催化性能的研究. 陈晓辉等.化工进展，第23卷第11期. 2004 |
| 钛硅分子筛膜的合成及其催化性能的研究. 陈晓辉等.化工进展，第23卷第11期. 2004 * |
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