CN110451522A - A method of preparing TS-1 microspherical catalyst - Google Patents
A method of preparing TS-1 microspherical catalyst Download PDFInfo
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- CN110451522A CN110451522A CN201910835061.2A CN201910835061A CN110451522A CN 110451522 A CN110451522 A CN 110451522A CN 201910835061 A CN201910835061 A CN 201910835061A CN 110451522 A CN110451522 A CN 110451522A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract
The present invention provides a kind of methods for preparing TS-1 microspherical catalyst, the technical solution uses hydrothermal synthesis method, it is silicon source using butyl titanate as titanium source, tetraethyl orthosilicate, tetrapropylammonium hydroxide is that template is mixed, is filtered, washed, dried, roasting synthesis TS-1 fine catalyst, using spray shaping method, TS-1 microspherical catalyst is prepared.The catalytic mechanical intensity of synthesis is good, and catalytic activity is good, and easily separates with reaction system liquid phase substance, the industrial production suitable for scale.The present invention is prepared for powdered TS-1 catalyst using hydrothermal synthesis method, prepares TS-1 microballoon using the method for spray shaping on this basis.The catalytic activity of powder catalyst synthesized by hydrothermal synthesis method is not only remained, but also microspheric catalyst avoids the defect that powder catalyst is not readily separated during the reaction.
Description
Technical field
The present invention relates to inorganic chemical synthesis technical fields, and in particular to a method of prepare TS-1 microspherical catalyst.
Background technique
TS-1 molecular sieve is made of the hetero-atom molecular-sieve of skeleton structure silicon and titanium, has MFI topological structure and three-dimensional
Ten-ring duct isolates the catalytic active center that existing four-coordination titanium is TS-1 molecular sieve on skeleton.Itself and hydrogen peroxide group
At oxidation system good selectivity is shown to reactions such as alkene epoxidation, ketone ammonia deuteration and oxidation of alkanes.TS-1 exists
Excellent catalytic oxidation performance is shown in the selective oxidation system of hydrogen peroxide composition, and by-product only has water, is a kind of ring
The catalyst of border close friend.Market is had a wide range of applications, and development prospect is wide.
Currently, there are mainly three types of the synthetic methods of TS-1 molecular sieve: isomorphous substitution method, dry gel conversion method and hydrothermal synthesis
Method.
Gas-solid phase isomorphous replacement process is the aluminium atom and boron original replaced in existing MFI topological structure molecular sieve with titanium atom
Son, is bonded into TS-1.Kraushaawr etc. is parent using ZSM-5 molecular sieve, is pre-processed by hydrochloric acid solution to remove
Aluminium atom in ZSM-5 forms framework of molecular sieve defect, then uses TiCl under gas phase condition4As titanium source, lacked with there is skeleton
Sunken ZSM-5 reaction, titanium atom are successfully embedded in lattice vacancy, finally remove extra surface titanium to obtain TS-1.The method
Easy to operate, synthesis cost is low, but due to the more difficult removal of aluminium atom on acidic site, the TS-1 catalytic for causing the method to synthesize
It can be poor.Gas-solid phase isomorphous replacement process process is complex, and is confined to process conditions, is not suitable for large-scale industrial production.
Dry gel conversion method be during preparing TS-1 catalyst using gel conversion method mixture solution is made it is molten
Crystallization obtains TS-1 catalyst after glue.Zhang little Ming etc. using different titanium sources, silicon source and template, using dry gel conversion method at
Function has synthesized TS-1 molecular sieve, but has only investigated the crystalline structure of products obtained therefrom, and to synthesis condition to TS-1 molecular sieve
Synthesis and the influence of catalytic performance do not study further.Dry gel conversion method process conditions are complicated, and the TS-1 prepared is urged
Agent catalytic activity is not high.
Hydrothermal synthesis method is the conventional method for preparing TS-1 catalyst, and nineteen eighty-three, Taramasso etc. uses hydrothermal synthesis method
TS-1 is successfully synthesized for the first time, and titanium, which enters, forms active sites in framework of molecular sieve, greatly improve the catalytic performance of TS-1.But by
It is very fast in titanium source hydrolysis rate, cause a large amount of titanium oxides to generate, catalytic performance is affected.So, in hydrothermal synthesis method
In, how further to improve the catalytic activity and mechanical strength of TS-1 catalyst, becomes technical problem urgently to be resolved.This
Outside, powdered finished catalyst is not easy to separate from reaction system, this affects process efficiency to a certain extent.
Summary of the invention
The present invention is directed to be directed to the technological deficiency of the prior art, a kind of method for preparing TS-1 microspherical catalyst is provided, with
Solve in the prior art, when using hydrothermal synthesis method preparation TS-1 catalyst, how to further increase by process modification
The catalytic activity of product.
Another technical problem to be solved by the present invention is that powdered finished catalyst is not easy to separate from reaction system.
To realize the above technical purpose, the invention adopts the following technical scheme:
A method of TS-1 microspherical catalyst being prepared, this method belongs to hydrothermal synthesis method, in the method, with metatitanic acid four
Butyl ester is titanium source, using tetraethyl orthosilicate as silicon source, using tetrapropylammonium hydroxide as template.
A method of preparing TS-1 microspherical catalyst, comprising the following steps:
1) with SiO in tetraethyl orthosilicate2Molal quantity: the molal quantity of tetrapropylammonium hydroxide: TiO in butyl titanate2's
Molal quantity: the molal quantity of water is 1:0.3~1:0.02~0.05:30~50 ratio, by the aqueous solution of tetrapropylammonium hydroxide
It is uniformly mixed with the aqueous solution of tetraethyl orthosilicate, is then under agitation added thereto butyl titanate, mix, it is quiet
Set 8~12h；
2) by step 1) products therefrom with 80~90 DEG C of crystallization for 24 hours, then with 110~130 DEG C of 2~10h of crystallization, then with
160~180 DEG C of crystallization for 24 hours, product are filtered, washed, is dried, is roasted to get TS-1 fine catalyst is arrived；
3) step 2) products therefrom is uniformly mixed with the silicon dioxde solution that mass fraction is 30%, is sprayed onto high speed rotation
On turntable, it is centrifuged material of dishing out, is fallen in 400 DEG C of nitrogen atmospheres, collects the dry matter fallen to get micro- to the TS-1
Sphere catalyst.
Preferably, in step 1), it is described to be added thereto butyl titanate under stirring parts, with vigorous stirring will be
Butyl titanate is slowly added thereto.
Preferably, crystallization described in step 2), is completed in a high pressure reaction kettle.
Preferably, the partial size of the TS-1 microspherical catalyst is 2~100 μm.
The present invention provides a kind of method for preparing TS-1 microspherical catalyst, which uses hydrothermal synthesis method, with
Butyl titanate is titanium source, tetraethyl orthosilicate is silicon source, tetrapropylammonium hydroxide is that template is mixed, be filtered, washed, done
Dry, roasting synthesis TS-1 fine catalyst prepares TS-1 microspherical catalyst using spray shaping method.The catalyst machine of synthesis
Tool intensity is good, and catalytic activity is good, and easily separates with reaction system liquid phase substance, the industrial production suitable for scale.The present invention
It is prepared for powdered TS-1 catalyst using hydrothermal synthesis method, it is micro- using the method preparation TS-1 of spray shaping on this basis
Ball.The catalytic activity of powder catalyst synthesized by hydrothermal synthesis method is not only remained, but also microspheric catalyst avoids
The defect that powder catalyst is not readily separated during the reaction.
Specific embodiment
Below by specific embodiments of the present invention will be described in detail.In order to avoid excessive unnecessary details, In
It will not be described in detail in following embodiment to belonging to well known structure or function.Approximation used in following embodiment
Language can be used for quantitative expression, show to allow quantity to have certain variation in the case where not changing basic function.It is fixed except having
Adopted outer, technical and scientific term used in following embodiment has the phase being commonly understood by with those skilled in the art of the invention
Same meaning.
Embodiment 1
By the SiO in silicon source2: template: the TiO in titanium source2:H2O (molar ratio)=1:0.3:0.02:30, first by 4 third
Base Ammonia is uniformly mixed with tetraethyl orthosilicate solution, is with vigorous stirring slowly added to butyl titanate
Solution is stated, is stirred evenly, 12h is placed；Above-mentioned reaction mixture is transferred to autoclave, for 24 hours in 80 DEG C of crystallization, then in
Crystallization 2h at 110 DEG C, finally at 160 DEG C crystallization for 24 hours, after the good reaction mixture of crystallization is filtered, washed, is dried, being roasted
Obtain TS-1 fine catalyst.The powdered TS-1 catalyst made is mixed with the silicon dioxde solution that mass fraction is 30%
It is even, it is sprayed on high speed rotation turntable.It is centrifuged material of dishing out, is fallen in 400 DEG C of nitrogen atmospheres.Material has been done when reaching tank bottom
It is dry, form TS-1 microballoon.
Embodiment 2
By the SiO in silicon source2: template: the TiO in titanium source2:H2O (molar ratio)=1:0.5:0.02:30, first by 4 third
Base Ammonia is uniformly mixed with tetraethyl orthosilicate solution, is with vigorous stirring slowly added to butyl titanate
Solution is stated, is stirred evenly, 12h is placed；Above-mentioned reaction mixture is transferred to autoclave, for 24 hours in 80 DEG C of crystallization, then in
Crystallization 2h at 110 DEG C, finally at 180 DEG C crystallization for 24 hours, after the good reaction mixture of crystallization is filtered, washed, is dried, being roasted
Obtain TS-1 fine catalyst.The powdered TS-1 catalyst made is mixed with the silicon dioxde solution that mass fraction is 30%
It is even, it is sprayed on high speed rotation turntable.It is centrifuged material of dishing out, is fallen in 400 DEG C of nitrogen atmospheres.Material has been done when reaching tank bottom
It is dry, form TS-1 microballoon.
Embodiment 3
By the SiO in silicon source2: template: the TiO in titanium source2:H2O (molar ratio)=1:0.7:0.02:30, first by 4 third
Base Ammonia is uniformly mixed with tetraethyl orthosilicate solution, is with vigorous stirring slowly added to butyl titanate
Solution is stated, is stirred evenly, 8h is placed；Above-mentioned reaction mixture is transferred to autoclave, for 24 hours in 80 DEG C of crystallization, then in
Crystallization 2h at 110 DEG C, finally at 175 DEG C crystallization for 24 hours, after the good reaction mixture of crystallization is filtered, washed, is dried, being roasted
Obtain TS-1 fine catalyst.The powdered TS-1 catalyst made is mixed with the silicon dioxde solution that mass fraction is 30%
It is even, it is sprayed on high speed rotation turntable.It is centrifuged material of dishing out, is fallen in 400 DEG C of nitrogen atmospheres.Material has been done when reaching tank bottom
It is dry, form TS-1 microballoon.
Embodiment 4
By the SiO in silicon source2: template: the TiO in titanium source2:H2O (molar ratio)=1:0.9:0.02:30, first by 4 third
Base Ammonia is uniformly mixed with tetraethyl orthosilicate solution, is with vigorous stirring slowly added to butyl titanate
Solution is stated, is stirred evenly, 10h is placed；Above-mentioned reaction mixture is transferred to autoclave, for 24 hours in 80 DEG C of crystallization, then in
Crystallization 2h at 110 DEG C, finally at 165 DEG C crystallization for 24 hours, after the good reaction mixture of crystallization is filtered, washed, is dried, being roasted
Obtain TS-1 fine catalyst.The powdered TS-1 catalyst made is mixed with the silicon dioxde solution that mass fraction is 30%
It is even, it is sprayed on high speed rotation turntable.It is centrifuged material of dishing out, is fallen in 400 DEG C of nitrogen atmospheres.Material has been done when reaching tank bottom
It is dry, form TS-1 microballoon.
Embodiment 5
By the SiO in silicon source2: template: the TiO in titanium source2:H2O (molar ratio)=1:0.4:0.02:30, first by 4 third
Base Ammonia is uniformly mixed with tetraethyl orthosilicate solution, is with vigorous stirring slowly added to butyl titanate
Solution is stated, is stirred evenly, 12h is placed；Above-mentioned reaction mixture is transferred to autoclave, for 24 hours in 80 DEG C of crystallization, then in
Crystallization 2h at 120 DEG C, finally at 170 DEG C crystallization for 24 hours, after the good reaction mixture of crystallization is filtered, washed, is dried, being roasted
Obtain TS-1 fine catalyst.The powdered TS-1 catalyst made is mixed with the silicon dioxde solution that mass fraction is 30%
It is even, it is sprayed on high speed rotation turntable.It is centrifuged material of dishing out, is fallen in 400 DEG C of nitrogen atmospheres.Material has been done when reaching tank bottom
It is dry, form TS-1 microballoon.
Embodiment 6
By the SiO in silicon source2: template: the TiO in titanium source2:H2O (molar ratio)=1:0.3:0.02:35, first by 4 third
Base Ammonia is uniformly mixed with tetraethyl orthosilicate solution, is with vigorous stirring slowly added to butyl titanate
Solution is stated, is stirred evenly, 12h is placed；Above-mentioned reaction mixture is transferred to autoclave, for 24 hours in 80 DEG C of crystallization, then in
Crystallization 2h at 110 DEG C, finally at 180 DEG C crystallization for 24 hours, after the good reaction mixture of crystallization is filtered, washed, is dried, being roasted
Obtain TS-1 fine catalyst.The powdered TS-1 catalyst made is mixed with the silicon dioxde solution that mass fraction is 30%
It is even, it is sprayed on high speed rotation turntable.It is centrifuged material of dishing out, is fallen in 400 DEG C of nitrogen atmospheres.Material has been done when reaching tank bottom
It is dry, form TS-1 microballoon.
The embodiments of the present invention have been described in detail above, but content is only the preferred embodiment of the present invention,
It is not intended to limit the invention.All any modifications, equivalent replacements, and improvements etc. done in application range of the invention, should all
It is included within protection scope of the present invention.
Claims (5)
1. a kind of method for preparing TS-1 microspherical catalyst, this method belong to hydrothermal synthesis method, which is characterized in that in this method
In, using butyl titanate as titanium source, using tetraethyl orthosilicate as silicon source, using tetrapropylammonium hydroxide as template.
2. a kind of method for preparing TS-1 microspherical catalyst according to claim 1, it is characterised in that the following steps are included:
1) with SiO in tetraethyl orthosilicate2Molal quantity: the molal quantity of tetrapropylammonium hydroxide: TiO in butyl titanate2Mole
Number: the molal quantity of water is 1:0.3~1:0.02~0.05:30~50 ratio, by the aqueous solution and silicon of tetrapropylammonium hydroxide
The aqueous solution of sour tetra-ethyl ester is uniformly mixed, and is then under agitation added thereto butyl titanate, is mixed, and stands 8
~12h；
2) by step 1) products therefrom with 80~90 DEG C of crystallization for 24 hours, then with 110~130 DEG C of 2~10h of crystallization, then with 160
~180 DEG C of crystallization for 24 hours, product are filtered, washed, is dried, is roasted to get TS-1 fine catalyst is arrived；
3) step 2) products therefrom is uniformly mixed with the silicon dioxde solution that mass fraction is 30%, is sprayed onto high speed rotation turntable
On, it is centrifuged material of dishing out, is fallen in 400 DEG C of nitrogen atmospheres, is collected the dry matter fallen and urged to get to the TS-1 microballoon
Agent.
3. a kind of method for preparing TS-1 microspherical catalyst according to claim 2, which is characterized in that in step 1), institute
It states and is added thereto butyl titanate under stirring parts, be with vigorous stirring to be slowly added thereto butyl titanate.
4. a kind of method for preparing TS-1 microspherical catalyst according to claim 2, which is characterized in that described in step 2)
Crystallization is completed in a high pressure reaction kettle.
5. a kind of method for preparing TS-1 microspherical catalyst according to claim 2, which is characterized in that the TS-1 microballoon
The partial size of catalyst is 2~100 μm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618579A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation method of iron-molybdenum catalyst for fluidized bed, catalyst and application |
| CN115845916A (en) * | 2022-12-23 | 2023-03-28 | 大连理工大学 | Preparation method and application of Au/TS-1 nano microsphere catalyst for propylene gas phase epoxidation |
-
2019
- 2019-09-05 CN CN201910835061.2A patent/CN110451522A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618579A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation method of iron-molybdenum catalyst for fluidized bed, catalyst and application |
| CN114618579B (en) * | 2020-12-11 | 2023-06-02 | 中国科学院大连化学物理研究所 | Preparation method of iron-molybdenum catalyst for fluidized bed, catalyst and application |
| CN115845916A (en) * | 2022-12-23 | 2023-03-28 | 大连理工大学 | Preparation method and application of Au/TS-1 nano microsphere catalyst for propylene gas phase epoxidation |
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Application publication date: 20191115 |