CN106379912A - Preparation method of hierarchical porous titanium silicalite molecular sieves - Google Patents
Preparation method of hierarchical porous titanium silicalite molecular sieves Download PDFInfo
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- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
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- B01J29/00—Catalysts comprising molecular sieves
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Abstract
The invention relates to a preparation method of hierarchical porous titanium silicalite molecular sieves. The preparation method comprises the following steps: slowly adding a template into a silicon source under the condition of continuous stirring, and obtaining a colorless transparent solution after the silicon source is completely hydrolyzed; slowly adding a mixed solution of a titanium source and isopropanol into the above solution, removing alcohol, fully mixing with an aqueous solution of polyvinyl alcohol, carrying out hydrothermal crystallization, centrifuging, washing, drying, and roasting to obtain the hierarchical porous titanium silicalite molecular sieves. In comparison with the prior art, the prepared titanium silicalite molecular sieves have rich mesoporous channels, which are interconnected. The product has an excellent catalytic effect in the aspect of macromolecular catalytic oxidation, especially in the aspect of oxidation of dibenzothiophenes and 4,6-dimethyl dibenzothiophenes.
Description
Technical field
The present invention relates to a kind of preparation method of molecular sieve, especially relate to a kind of preparation of multi-stage porous titanium si molecular sieves
Method.
Background technology
Titanium-silicon molecular sieve TS-1 is synthesized (USP 4410501) early than nineteen eighty-three, by its excellent catalytic oxidative
Can and be widely used in phenol hydroxylation, alkene epoxidation, Ammonia epoxidation, oxidation of alkanes etc..Using TS-1 as catalyst,
Catalytic reaction is with the H of environmental protection2O2As oxidant, reaction condition is gentle, and byproduct of reaction is mainly water.
The active center of HTS is primarily present in its abundant micropore canals (0.55nm), however, less
Aperture is unfavorable for the diffusion in its duct of reactant and product molecule, and kinetic diameter cannot more than the molecule of channel diameter simultaneously
Enter duct to contact with active center, these catalytic performances that all significantly limit TS-1 and range of application.For this reason, grinding in a large number
Study carefully work to be directed in TS-1, introducing bigger mesopore orbit, preparation has the multistage pore canal of micropore canals and mesopore orbit simultaneously
TS-1 can be good at solving the above problems.
Template is as the common method of synthesis multi-stage pore canal molecular sieve.Compare hard template method, soft template method has operation
Simply, the features such as structure and acid controllability are good and be widely used in the synthesis of multi-stage porous titanium si molecular sieves.Adopt at present more
With high molecular surfactant, cation high molecular etc. as soft template, however these templates exist synthesis technique complicated or
Expensive the problems such as, these all significantly limit the commercial Application of multistage pore canal TS-1.Polyvinyl alcohol (PVA) is as a kind of
Macromolecule cheap and easy to get, has abundant hydroxyl simultaneously in structure, can with the presoma preparing HTS have stronger
Active force, but PVA could not be used as soft template always, crucial problem is PVA meeting under the crystallization temperature of TS-1
Fast dewatering carbonization, seriously destroys the interaction of PVA and presoma, leads to serious being separated, causes PVA not
Original template action can be played.
Chinese patent CN 1500720A discloses the preparation method of pure silicon MCM-41 molecular sieves.Mainly solve conventional art
In have that crystallization temperature is high, synthesize the pure silicon MCM-41 molecular sieves specific surface area obtaining less, pore volume is big, average pore size
Greatly, the big problem of granularity.But the crystallization temperature of MCM-41 is below 100 DEG C, at such a temperature, PVA is relatively stable, but
Compared to MCM-41, the crystallization temperature of TS-1 higher (>140 DEG C), under the crystallization temperature of TS-1, PVA can quickly be dehydrated
Carbonization, is weakened significantly with precursor solution after PVA carbonization, thus leading to serious being separated, final PVA cannot play mould
Plate acts on.
Content of the invention
The purpose of the present invention is exactly to overcome the defect of above-mentioned prior art presence to provide a kind of conventional polymer PVA
Synthesize the preparation method of multi-stage porous titanium si molecular sieves as soft template.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of multi-stage porous titanium si molecular sieves, using following steps：
(1) under conditions of continuous stirring, template is slowly added to silicon source, obtains colourless after silicon source hydrolysis completely
Bright solution；
(2) mixed solution of titanium source and isopropanol is slowly added in the solution that step (1) obtains；
(3) solution that step (2) obtains, after except alcohol, is sufficiently mixed with the aqueous solution of polyvinyl alcohol, then carries out hydro-thermal
Crystallization, eventually passes centrifugation, washing, drying, after roasting, obtains multi-stage porous HTS.
As preferred technical scheme, the hydrothermal crystallizing in step (3) adopts two-step method, first solution is placed in 60～100
Crystallization 12～36h under conditions of DEG C, crystallization 6～48h under conditions of being subsequently placed in 150～180 DEG C.
As preferred technical scheme, the solution in step (3) is after centrifugation, washing, dry under the conditions of 100-150 DEG C
Dry, the solid obtaining is placed in 500-600 DEG C of roasting.
As preferred technical scheme, the mol ratio of silicon source, template, titanium source, water and PVA is 1：0.10～0.50：
0.01～0.03：50～100：5×10-4～1.5 × 10-3, wherein silicon source is to contain SiO2Meter.
As preferred technical scheme, silicon source is tetraethyl orthosilicate, Ludox or white carbon.
As preferred technical scheme, template is TPAOH or tetraethyl ammonium hydroxide.
As preferred technical scheme, titanium source is butyl titanate or titanium tetrachloride.
As preferred technical scheme, polyvinyl alcohol is PVA-1788, PVA-1797 or PVA-1799.
The technical solution adopted in the present invention is the method by multistep crystallization, and first passing through low temperature crystallized method will
PVA is fixed in the unformed body of HTS, then high temperature crystallization again, so both can guarantee that the effect of PVA and presoma
Power, can guarantee that PVA still can play template action such that it is able to prepare multi-stage porous using PVA as template after high temperature cabonization again
Road HTS.
Because PVA is relatively stable at 100 DEG C, PVA therefore to be allowed to play template action, it is necessary to assure crystallization temperature is less than
100 DEG C, but too low temperature can result in unformed overlong time, when forming unformed in order to be able to reduce as far as possible
Between avoid the carbonization of PVA again, first step crystallization adopts 60-100 DEG C of scope.The main purpose of the first step avoids PVA carbonization, protects
Card PVA plays template action.After the completion of the first step, PVA is uniformly scattered in unformed titanium silicalite material.Second step selects
150-180 DEG C of scope is mainly to ensure that amorphous body rapid crystallization obtains HTS, and temperature is too low to lead to crystallization time
Long and increase energy consumption, typically not greater than 180 DEG C of the synthesis temperature of HTS, furthermore, because preparation process belongs to hydro-thermal
Crystallization, water heating kettle uses safe temperature to be less than 200 DEG C.
Compared with prior art, the present invention passes through using the reaction system in quaternary ammonium base, silicon source and surfactant composition
The middle technical scheme adding polyvinyl alcohol, preferably solves PVA present in prior art and cannot play asking of template action
Topic, can be used for pure silicon MCM-41 molecular sieves industrially prepared in.The HTS of preparation has abundant mesopore orbit, duct
Between be mutually communicated, bulky molecular catalysis oxidation, the particularly oxidation side of dibenzothiophenes and 4,6- dimethyl Dibenzothiophene
Face has excellent catalytic effect.
Brief description
Fig. 1 is the XRD spectrum of comparative example 1, embodiment 2 and the titanium-silicon molecular sieve TS-1 prepared by embodiment 3.
Fig. 2 is the FT-IR collection of illustrative plates of comparative example 1, embodiment 2 and the titanium-silicon molecular sieve TS-1 prepared by embodiment 3.
Fig. 3 is the TEM photo of comparative example 1, embodiment 2 and the titanium-silicon molecular sieve TS-1 prepared by embodiment 3.
Fig. 4 is the catalysis oxidation dibenzo thiophene of comparative example 1, embodiment 2 and the titanium-silicon molecular sieve TS-1 prepared by embodiment 3
Fen (DBT) and the result of the test of 4,6- dimethyl Dibenzothiophene (4,6-DMDBT).
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Comparative example 1
Under conditions of continuous stirring, 23.4g TPAOH (20wt%) is slowly added to the positive silicic acid of 15.0g four
In ethyl ester, after tetraethyl orthosilicate hydrolysis completely, obtain colourless transparent solution A；Then, by 0.72g titanium source and 2.4g isopropanol
Mixed solution B be slowly added in solution A and obtain colourless transparent solution C；After solution C is removed alcohol 2h at 80 DEG C, solution is turned
Move in hydrothermal reaction kettle, crystallization 72h at 170 DEG C, the product obtaining after crystallization, after centrifugation, washing, is dried at 110 DEG C
Overnight, finally by the solid obtaining at 550 DEG C roasting 6h, finally give traditional titanium-silicon molecular sieve TS-1.
Embodiment 1
Under conditions of continuous stirring, 23.4g TPAOH (20wt%) is slowly added to the positive silicic acid of 15.0g four
In ethyl ester, after tetraethyl orthosilicate hydrolysis completely, obtain colourless transparent solution A；Then, by 0.72g titanium source and 2.4g isopropanol
Mixed solution B be slowly added in solution A and obtain colourless transparent solution C；After solution C is removed alcohol 2h at 80 DEG C, with equal matter
After the PVA solution (5.0wt%) of amount is sufficiently mixed, solution is transferred in hydrothermal reaction kettle, crystallization 24h at 90 DEG C first, so
After be warming up to crystallization 24h at 160 DEG C.The product obtaining, after centrifugation, washing, is dried overnight at 110 DEG C, finally will obtain
Solid roasting 6h at 550 DEG C, finally gives multistage pore canal TS-1.
Embodiment 2
Under conditions of continuous stirring, 23.4g TPAOH (20wt%) is slowly added to the positive silicic acid of 15.0g four
In ethyl ester, after tetraethyl orthosilicate hydrolysis completely, obtain colourless transparent solution A；Then, by 0.72g titanium source and 2.4g isopropanol
Mixed solution B be slowly added in solution A and obtain colourless transparent solution C；After solution C is removed alcohol 2h at 80 DEG C, with equal matter
After the PVA solution (10.0wt%) of amount is sufficiently mixed, solution is transferred in hydrothermal reaction kettle, crystallization 24h at 90 DEG C first, so
After be warming up to crystallization 24h at 160 DEG C.The product obtaining, after centrifugation, washing, is dried overnight at 110 DEG C, finally will obtain
Solid roasting 6h at 550 DEG C, finally gives multistage pore canal TS-1.
Embodiment 3
Under conditions of continuous stirring, 23.4g TPAOH (20wt%) is slowly added to the positive silicic acid of 15.0g four
In ethyl ester, after tetraethyl orthosilicate hydrolysis completely, obtain colourless transparent solution A；Then, by 0.72g titanium source and 2.4g isopropanol
Mixed solution B be slowly added in solution A and obtain colourless transparent solution C；After solution C is removed alcohol 2h at 80 DEG C, with equal matter
After the PVA solution (15.0wt%) of amount is sufficiently mixed, solution is transferred in hydrothermal reaction kettle, crystallization 24h at 90 DEG C first, so
After be warming up to crystallization 24h at 160 DEG C.The product obtaining, after centrifugation, washing, is dried overnight at 110 DEG C, finally will obtain
Solid roasting 6h at 550 DEG C, finally gives multistage pore canal TS-1.
Fig. 1 is the XRD spectrum of comparative example 1, embodiment 2 and the titanium-silicon molecular sieve TS-1 prepared by embodiment 3, can from figure
To find out, all samples all in 7.8 °, 8.8 °, 23.1 °, 24.0 °, 24.5 ° of strong diffraction maximums of appearance, belong to typical MFI and open up
Flutter structure, and the addition of PVA has not significant impact to the crystallization process of molecular sieve.Fig. 2 is comparative example 1, embodiment 2 and implements
The FT-IR collection of illustrative plates of the titanium-silicon molecular sieve TS-1 prepared by example 3, all samples are all in 970cm-1Absworption peak in place, belongs to Si-
O-Ti or by the Si-O vibration absorption peak that skeleton Ti is affected, shows that Ti enters framework of molecular sieve.Simultaneously in 550cm-1The absorption at place
Peak belongs to SiO4And TiO4Tetrahedral vibration absorption peak.Fig. 3 is comparative example 1, embodiment 2 and the titanium silicon prepared by embodiment 3
The TEM photo of molecular sieve TS-1, wherein, a, b are traditional titanium-silicon molecular sieve TS-1s that comparative example 1 prepares, and c, d are to implement
The multistage pore canal TS-1 that example 2 prepares, e, f are the multistage pore canal TS-1 that embodiment 3 prepares.It can be seen that
Traditional TS-1 (comparative example 1) does not have mesopore orbit, and the multistage pore canal TS-1 (embodiment 2 and embodiment 3) preparing is respectively provided with
Obvious and abundant mesopore orbit, the two step crystallization methods that show successfully make PVA play mesoporous template action.Fig. 4 is comparative example
1st, embodiment 2 and the catalysis oxidation dibenzothiophenes (DBT) of titanium-silicon molecular sieve TS-1 prepared by embodiment 3 and 4,6- dimethyl
The result of the test of dibenzothiophenes (4,6-DMDBT), compares traditional TS-1, and multistage pore canal TS-1 (embodiment 2 and embodiment 3) urges
Change oxidation DBT and 4,6-DMDBT activity significantly improve, reason be traditional TS-1 active center be primarily present in its enrich
Micropore canals in, and molecular diameter larger DBT and 4,6-DMDBT cannot be introduced into micropore canals (0.55nm) and can only pass
The outer surface of system TS-1 particle is oxidized.Multi-stage porous TS-1 have abundant mesopore orbit (>2nm), DBT and 4,6-DMDBT obtains
Oxidized with entrance mesopore orbit, thus effectively improving the catalysis activity for the larger molecule of molecular diameter for the TS-1.
Embodiment 4
A kind of preparation method of multi-stage porous titanium si molecular sieves, using following steps：
(1) under conditions of continuous stirring, template TPAOH is slowly added in tetraethyl orthosilicate, treats
Colourless transparent solution is obtained after tetraethyl orthosilicate hydrolysis completely；
(2) mixed solution of butyl titanate and isopropanol is slowly added in the solution that step (1) obtains；
(3) solution that step (2) obtains, after except alcohol, is sufficiently mixed with the aqueous solution of PVAC polyvinylalcohol -1788, positive silicon
The mol ratio of sour tetra-ethyl ester, template, butyl titanate, water and polyvinyl alcohol is 1：0.10：0.01：50：5×10-4, wherein just
Tetraethyl orthosilicate is to contain SiO2Meter.Then carry out hydrothermal crystallizing, using two-step method, under conditions of first solution being placed in 60 DEG C
Crystallization 36h, crystallization 48h under conditions of being subsequently placed in 150 DEG C, eventually pass centrifugation, washing, be dried under the conditions of 100 DEG C, obtain
Solid be placed in 500 DEG C of roastings, obtain multi-stage porous HTS.
Embodiment 5
A kind of preparation method of multi-stage porous titanium si molecular sieves, using following steps：
(1) under conditions of continuous stirring, template tetraethyl ammonium hydroxide is slowly added to Ludox, treats Ludox water
Colourless transparent solution is obtained after solution is complete；
(2) mixed solution of titanium tetrachloride and isopropanol is slowly added in the solution that step (1) obtains；
(3) solution that step (2) obtains, after except alcohol, is sufficiently mixed with the aqueous solution of PVAC polyvinylalcohol -1797, silicon is molten
The mol ratio of glue, template, titanium tetrachloride, water and polyvinyl alcohol is 1：0.30：0.02：80：8×10-4, wherein Ludox be with
Containing SiO2Meter, then carries out hydrothermal crystallizing, using two-step method, crystallization 24h under conditions of first solution being placed in 80 DEG C, then puts
Crystallization 24h under conditions of 160 DEG C, eventually passes centrifugation, washing, is dried under the conditions of 120 DEG C, the solid obtaining is placed in 550
DEG C roasting, obtains multi-stage porous HTS.
Embodiment 6
A kind of preparation method of multi-stage porous titanium si molecular sieves, using following steps：
(1) under conditions of continuous stirring, template tetraethyl ammonium hydroxide is slowly added to white carbon, treats Linesless charcoal Heisui River
Colourless transparent solution is obtained after solution is complete；
(2) mixed solution of titanium tetrachloride and isopropanol is slowly added in the solution that step (1) obtains；
(3) solution that step (2) obtains, after except alcohol, is sufficiently mixed with the aqueous solution of PVAC polyvinylalcohol -1799, Linesless charcoal
The mol ratio of black, template, titanium tetrachloride, water and polyvinyl alcohol is 1：0.50：0.03：100：1.5×10-3, wherein white carbon
It is to contain SiO2Meter, then carries out hydrothermal crystallizing, using two-step method, crystallization 12h under conditions of first solution being placed in 100 DEG C,
Crystallization 6h under conditions of being subsequently placed in 180 DEG C, eventually passes centrifugation, washing, is dried under the conditions of 150 DEG C, the solid obtaining is put
In 600 DEG C of roastings, obtain multi-stage porous HTS.
Claims (8)
1. a kind of preparation method of multi-stage porous titanium si molecular sieves is it is characterised in that the method adopts following steps：
(1) under conditions of continuous stirring, template is slowly added to silicon source, obtains water white transparency after silicon source hydrolysis completely molten
Liquid；
(2) mixed solution of titanium source and isopropanol is slowly added in the solution that step (1) obtains；
(3) solution that step (2) obtains, after except alcohol, is sufficiently mixed with the aqueous solution of polyvinyl alcohol, then carries out hydrothermal crystallizing,
Eventually pass centrifugation, washing, drying, after roasting, obtain multi-stage porous HTS.
2. a kind of preparation method of multi-stage porous titanium si molecular sieves according to claim 1 is it is characterised in that step (3)
In hydrothermal crystallizing adopt two-step method, crystallization 12～36h under conditions of first solution being placed in 60～100 DEG C, be subsequently placed in 150～
Crystallization 6～48h under conditions of 180 DEG C.
3. a kind of preparation method of multi-stage porous titanium si molecular sieves according to claim 1 is it is characterised in that step (3)
In solution after centrifugation, washing, be dried under the conditions of 100-150 DEG C, the solid obtaining is placed in 500-600 DEG C of roasting.
4. a kind of preparation method of multi-stage porous titanium si molecular sieves according to claim 1 is it is characterised in that silicon source, mould
The mol ratio of plate agent, titanium source, water and PVA is 1：0.10～0.50：0.01～0.03：50～100：5×10-4～1.5 × 10-3,
Wherein silicon source is to contain SiO2Meter.
5. a kind of preparation method of multi-stage porous titanium si molecular sieves according to claim 1 is it is characterised in that described silicon
Source is tetraethyl orthosilicate, Ludox or white carbon.
6. a kind of preparation method of multi-stage porous titanium si molecular sieves according to claim 1 is it is characterised in that described mould
Plate agent is TPAOH or tetraethyl ammonium hydroxide.
7. a kind of preparation method of multi-stage porous titanium si molecular sieves according to claim 1 is it is characterised in that described titanium
Source is butyl titanate or titanium tetrachloride.
8. a kind of preparation method of multi-stage porous titanium si molecular sieves according to claim 1 is it is characterised in that described is poly-
Vinyl alcohol is PVA-1788, PVA-1797 or PVA-1799.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107500308A (en) * | 2017-08-15 | 2017-12-22 | 上海交通大学 | A kind of preparation method of rare earth modified multi-stage porous titanium si molecular sieves |
| CN108855203A (en) * | 2018-06-14 | 2018-11-23 | 辽宁科技大学 | A method of preparing Ti-SBA-15 mesopore molecular sieve |
| CN110467193A (en) * | 2018-05-10 | 2019-11-19 | 中国科学院过程工程研究所 | A kind of Titanium Sieve Molecular Sieve, preparation method and application |
| CN111013531A (en) * | 2019-11-15 | 2020-04-17 | 石家庄汉创环保科技有限公司 | Preparation method of titanium dioxide zeolite molecular sieve for adsorbing volatile organic pollutants |
| CN111908483A (en) * | 2020-07-14 | 2020-11-10 | 西安工程大学 | Hierarchical pore molecular sieve TS-1 and preparation method thereof |
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| KR20210087526A (en) * | 2018-11-15 | 2021-07-12 | 달리안 인스티튜트 오브 케미컬 피직스, 차이니즈 아카데미 오브 사이언시즈 | Method for producing hierarchically porous TS-1 molecular sieve |
| KR20210087527A (en) * | 2018-11-15 | 2021-07-12 | 달리안 인스티튜트 오브 케미컬 피직스, 차이니즈 아카데미 오브 사이언시즈 | Method for producing hierarchically porous TS-1 molecular sieve |
| CN113353951A (en) * | 2021-07-21 | 2021-09-07 | 中国石油大学(北京) | Hierarchical pore titanium silicalite molecular sieve and preparation method and application thereof |
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| CN115181035A (en) * | 2021-03-17 | 2022-10-14 | 天津师范大学 | Hierarchical pore TS-1 molecular sieve with intra-crystal micropore-ultramicropore-mesopore and preparation method and application thereof |
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