CN104445257A - Preparation method for high-stable-activity titanium silicalite molecular sieve catalyst - Google Patents
Preparation method for high-stable-activity titanium silicalite molecular sieve catalyst Download PDFInfo
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- CN104445257A CN104445257A CN201410685345.5A CN201410685345A CN104445257A CN 104445257 A CN104445257 A CN 104445257A CN 201410685345 A CN201410685345 A CN 201410685345A CN 104445257 A CN104445257 A CN 104445257A
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- molecular sieve
- soxylat
- titanium
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- sieve catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
Abstract
The invention discloses a preparation method for a high-stable-activity titanium silicalite molecular sieve catalyst. The method comprises the following steps: uniformly mixing tetraethoxysilane, tetrapropylammonium hydroxide, polyoxyethylene ether-polypropylethylene ether-polyoxyethylene ether (P123), polyether modified fluorine-containing polydimethylsiloxane and distilled water, and producing a hydrolysis reaction to obtain a tetraethoxysilane hydrolysis solution; adding tetrabutyl titanate, isopropanol and 8-fluoro-4-hydroxy-2-trifluoromethylquinoline, mixing to obtain a mixed solution, producing an ageing reaction of the mixed solution, filtering a product, washing with water, and drying to obtain a titanium silicalite molecular sieve immediate product; roasting to obtain the titanium silicalite molecular sieve catalyst. Due to the adoption of the fluorosilicone structure, the acid and alkali resistance of a molecular sieve framework is improved, the silicon dissolution loss of the molecular sieve framework of the catalyst is inhibited, and the inherent structure of a molecular sieve is kept; 8-fluoro-4-hydroxy-2-trifluoromethylquinoline and titanium form a chelate, so that the catalyst on the molecular sieve framework is relatively firm in position and difficult in loss, and the service life of the catalyst is prolonged.
Description
Technical field
The present invention relates to a kind of preparation method of molecular sieve catalyst, particularly a kind of preparation method of titanium-silicon molecular sieve catalyst.
Background technology
The application of molecular sieve in fine chemical product is produced, not only can change the environmental pollution that traditional processing technology brings, have good social benefit, and its value-added content of product is higher, can produce good economic benefit.The successful exploitation of titanium-silicon molecular sieve catalyst is considered to the milestone of the zeolite catalysis eighties in 20th century, for hydrocarbon oxidization, the developing green technique studying highly selective is laid a good foundation.There are reports for the domestic and international technology of preparing about similar catalyzer: patent US4410501 adopts two kinds of hydrothermal methods to synthesize first successfully, method does silicon source with tetraethoxy (TEOS) or silica gel, positive tetraethyl titanate (TEOT) is titanium source, template is tetrapropyl oxyammonia (TPAOH), according to a certain ratio, synthesis mother liquid synthesizes in the hot method of 448 K pressure by water, crystallization time about 10 days.When with silicon sol as silicon source time, need in mixture to add H
2o
2, titanium is existed with pertitanic acid ionic species.Patent CN103896301A discloses a kind of method of synthesis of titanium silicon molecular sieve, first organosilicon acid esters and titanium source are dissolved in the alkali source template aqueous solution and obtain mixture A, mixture A is proceeded in sealed reactor in 100 ~ 180 DEG C of crystallization 1 ~ 12h after organic silicic acid Ester hydrolysis, contact mixing with silica gel or silicon sol again after crystallization and obtain mixture B, again by mixture B in sealed reactor in 120 ~ 200 DEG C of crystallization 6 ~ 36h, and reclaim product.The method comparatively conventional art has saved cost, and yield and relative crystallinity improve.But HTS prepared by prior art exists many defects, in use there is de-titanium problem to a certain degree.The inducement of de-titanium is that silicon dissolves, and silicon dissolves and takes off titanium process and changes along with surface acidity enhancing and catalytic performance, causes reactivity worth to decline.
Summary of the invention
The object of this invention is to provide a kind of preparation method of titanium-silicon molecular sieve catalyst of high stable activity.
It is such that the present invention solves the technical scheme that its technical problem takes: a kind of preparation method of titanium-silicon molecular sieve catalyst of high stable activity, comprises the following steps:
(1) raw material is prepared by following mass parts
Component (mass parts)
Tetraethyl orthosilicate 30 ~ 60
Four third class ammonium hydroxide 10 ~ 20
Soxylat A 25-7-poly-third Vinyl Ether-Soxylat A 25-7 (P123) 0.01 ~ 0.1
Polyether-modified fluorine-containing polydimethylsiloxane 0.001 ~ 0.005
Tetrabutyl titanate 1 ~ 4
Anhydrous isopropyl alcohol 5 ~ 15
The fluoro-4-hydroxyl of 8--2-Trifluoromethylquinocarboxylic 0.001 ~ 0.005
Distilled water 100
(2) preparation of colloid
By proportioning in step (1) by tetraethyl orthosilicate, four third class ammonium hydroxide, Soxylat A 25-7-poly-third Vinyl Ether-Soxylat A 25-7 (P123), polyether-modified fluorine-containing polydimethylsiloxane, distilled water mixes, be hydrolyzed reaction at normal temperatures, reaction times 1 ~ 5h, obtain the hydrating solution of tetraethyl orthosilicate, tetrabutyl titanate is added in gained hydrating solution, anhydrous isopropyl alcohol, the fluoro-4-hydroxyl of 8--2-Trifluoromethylquinocarboxylic, obtain mixing solutions, by the mixing solutions heating obtained, at 60 ~ 90 DEG C, stir 1 ~ 5h obtain clear colloid,
(3) ageing reaction
The colloid that step (2) obtains is transferred in the reactor of sealing, at 150 ~ 190 DEG C, places 120 ~ 240 h, carry out ageing reaction, product is filtered, is washed to pH=7, dry, obtain HTS intermediate product;
(4) roasting
HTS intermediate product step (3) obtained obtains titanium-silicon molecular sieve catalyst product through 400 ~ 600 DEG C of roasting 2 ~ 8h.
Raw material used in the present invention is commercially available, is easy to get.As the product that tetraethyl orthosilicate can select Sichuan Yinbang Silicon Industry Co., Ltd. to produce; The product that four third class ammonium hydroxide can select Heze City, Shandong Province three and source Chemical Co., Ltd. to produce; The product that Soxylat A 25-7-poly-third Vinyl Ether-Soxylat A 25-7 (P123) can select AlfaAesar (China) Chemical Co., Ltd. to produce; The product that polyether-modified fluorine-containing polydimethylsiloxane can select Hangzhou Bao Er get organosilicon company limited to produce; The product that tetrabutyl titanate can select Li Jin chemical inc, Changzhou to produce; The product that Virahol can select the Five continents, Beijing century Red Star chemical industry limited liability company to produce
;the product that ancient cooking vessel vast chemical Science and Technology Ltd. in 8-fluoro-4-hydroxyl-2-Trifluoromethylquinocarboxylic optional Shanghai produces.
The present invention obtains following beneficial effect:
The present invention by adding Soxylat A 25-7-poly-third Vinyl Ether-Soxylat A 25-7 (P123), polyether-modified fluorine-containing polydimethylsiloxane in synthesis technique, fluorine silicon structure improves framework of molecular sieve acid-proof alkaline, catalyst molecule is inhibit to sieve the loss by dissolution of framework silicon, maintain the inherent structure of molecular sieve, the fluoro-4-hydroxyl of 8--2-Trifluoromethylquinocarboxylic and titanium elements form inner complex, make it more firm on framework of molecular sieve, not easily run off, significantly improve the life-span of catalyzer.
Embodiment
Following examples are for illustration of the present invention.But require emphasis, the following examples, only for illustration of the present invention, do not limit the scope of protection of the invention.
The preparation method of the titanium-silicon molecular sieve catalyst of embodiment 1 one kinds of high stable activity, comprises the following steps:
(1) get the raw materials ready according to the following ratio
Component (mass unit) kg
Tetraethyl orthosilicate 45
Four third class ammonium hydroxide 15
Soxylat A 25-7-poly-third Vinyl Ether-Soxylat A 25-7 (P123) 0.05
Polyether-modified fluorine-containing polydimethylsiloxane 0.003
Tetrabutyl titanate 2
Anhydrous isopropyl alcohol 10
The fluoro-4-hydroxyl of 8--2-Trifluoromethylquinocarboxylic 0.003
Distilled water 100
(2) preparation of colloid
In 500L stainless steel cauldron, by proportioning in step (1), tetraethyl orthosilicate, four third class ammonium hydroxide, Soxylat A 25-7-poly-third Vinyl Ether-Soxylat A 25-7 (P123), polyether-modified fluorine-containing polydimethylsiloxane, distilled water are mixed the reaction that is hydrolyzed at normal temperatures, reaction times 2h, obtain the hydrating solution of tetraethyl orthosilicate, tetrabutyl titanate, Virahol, the mixing of the fluoro-4-hydroxyl of 8--2-Trifluoromethylquinocarboxylic is added by above proportioning in hydrolyzed solution, by the mixing solutions heating obtained, at 80 DEG C, stir 3h obtain clear colloid;
(3) ageing reaction
Transferred to by the colloid obtained in step (2) in the stainless steel cauldron of 500L sealing, at 165 DEG C, placing 7 days, (168 h), carries out ageing reaction, and product after filtration, is washed to pH=7, dry, obtains HTS intermediate product;
(4) roasting
HTS intermediate product step (3) obtained obtains the titanium-silicon molecular sieve catalyst of high stable activity through 500 DEG C of roasting 5h, product designation MB-1.
The preparation method of the titanium-silicon molecular sieve catalyst of embodiment 2 one kinds of high stable activity, comprises the following steps:
(1) get the raw materials ready according to the following ratio
Component (mass unit) kg
Tetraethyl orthosilicate 30
Four third class ammonium hydroxide 10
Soxylat A 25-7-poly-third Vinyl Ether-Soxylat A 25-7 (P123) 0.01
Polyether-modified fluorine-containing polydimethylsiloxane 0.001
Tetrabutyl titanate 1
Anhydrous isopropyl alcohol 5
The fluoro-4-hydroxyl of 8--2-Trifluoromethylquinocarboxylic 0.001
Distilled water 100
(2) preparation of colloid
In 500L stainless steel cauldron, by proportioning in step (1), tetraethyl orthosilicate, four third class ammonium hydroxide, Soxylat A 25-7-poly-third Vinyl Ether-Soxylat A 25-7 (P123), polyether-modified fluorine-containing polydimethylsiloxane, distilled water are mixed the reaction that is hydrolyzed, reaction times 1h, obtain the hydrating solution of tetraethyl orthosilicate, tetrabutyl titanate, Virahol, the mixing of the fluoro-4-hydroxyl of 8--2-Trifluoromethylquinocarboxylic is added by above proportioning in hydrolyzed solution, by the mixing solutions heating obtained, at 60 DEG C, stir 5h obtain clear colloid;
(3) ageing reaction
Transferred to by the colloid that step (2) obtains in the stainless steel cauldron of 500L sealing, at 150 DEG C, placing 10 days, (240 h), carries out ageing reaction, and product after filtration, is washed to pH=7, dry, obtains HTS intermediate product;
(4) roasting
HTS intermediate product step (3) obtained obtains the titanium-silicon molecular sieve catalyst of high stable activity through 400 DEG C of roasting 2h, product designation MB-2.
The preparation method of the titanium-silicon molecular sieve catalyst of embodiment 3 one kinds of high stable activity, comprises the following steps:
(1) get the raw materials ready according to the following ratio
Component: (mass unit) kg
Tetraethyl orthosilicate 60
Four third class ammonium hydroxide 20
Soxylat A 25-7-poly-third Vinyl Ether-Soxylat A 25-7 (P123) 0.1
Polyether-modified fluorine-containing polydimethylsiloxane 0.005
Tetrabutyl titanate 4
Anhydrous isopropyl alcohol 15
The fluoro-4-hydroxyl of 8--2-Trifluoromethylquinocarboxylic 0.005
Distilled water 100
(2) preparation of colloid
In 500L stainless steel cauldron, by proportioning in step (1), tetraethyl orthosilicate, four third class ammonium hydroxide, Soxylat A 25-7-poly-third Vinyl Ether-Soxylat A 25-7 (P123), polyether-modified fluorine-containing polydimethylsiloxane, distilled water are mixed the reaction that is hydrolyzed, reaction times 5h, obtain the hydrating solution of tetraethyl orthosilicate, tetrabutyl titanate, Virahol, the mixing of the fluoro-4-hydroxyl of 8--2-Trifluoromethylquinocarboxylic is added by above proportioning in hydrolyzed solution, by the solution heating obtained, at 90 DEG C, stir 1h obtain clear colloid;
(3) ageing reaction
Transferred to by the colloid obtained in step (2) in the reactor of 500L sealing, at 190 DEG C, placing 5 days, (120 h), carries out ageing reaction, and product after filtration, is washed to pH=7, dry, obtains HTS intermediate product;
(4) roasting
HTS intermediate product step (3) obtained obtains the titanium-silicon molecular sieve catalyst of high stable activity through 600 DEG C of roasting 2h, product designation MB-3.
Comparative example 1
Do not add Soxylat A 25-7-poly-third Vinyl Ether-Soxylat A 25-7 (P123) in this example, other condition is complete
Entirely be same as embodiment 1, obtained titanium-silicon molecular sieve catalyst, product designation MB-4.
Comparative example 2
Do not add polyether-modified fluorine-containing polydimethylsiloxane in this example, other condition is same as embodiment completely
1, obtained titanium-silicon molecular sieve catalyst, product designation MB-5.
Comparative example 3
Do not add the fluoro-4-hydroxyl of 8--2-Trifluoromethylquinocarboxylic in this example, other condition is same as embodiment completely
1, obtained titanium-silicon molecular sieve catalyst, product designation MB-6.
Embodiment 4 catalysis of phenol hydroxylating
First adopt the titanium-silicon molecular sieve catalyst of standard probe reaction-phenol hydroxylation proportioning to test, and using the obtained molecular sieve catalyst of embodiment 1-3 and comparative example 1-3 as Comparison of standards, product detect at liquid chromatograph.Detected result is in table 2.
1, detect the transformation efficiency of phenol, reaction parameter is as table 1.
The phenol amount of the phenol amount/input of transformation efficiency X (the phenol)=consumption of phenol
2, catalyzer Ti turnover rate (%).
Ti constituent content composition measuring: adopt VARIAN Oncology Systems VISIA-AX type inductively coupled plasma atomic emission spectrometer to carry out ICP/AES test.
Catalyzer Ti turnover rate (%)=(using procatalyst Ti constituent content-use rear catalyst Ti constituent content)/use procatalyst Ti constituent content.
Table 1: phenol hydroxylation reaction parameter
Table 2: detected result
Can find out that the turnover rate of titanium-silicon molecular sieve catalyst MB-1, MB-2, MB-3 catalyzer Ti catalyzed reaction application obtained by embodiment 1, embodiment 2 and embodiment 3 is lower than comparative example 1, comparative example 2, comparative example 3 from detected result, illustrate that the framework of molecular sieve of the titanium-silicon molecular sieve catalyst prepared by the inventive method is more firm, Ti not easily runs off.
Claims (1)
1. a preparation method for titanium-silicon molecular sieve catalyst, is characterized in that comprising the following steps:
(1) raw material is prepared by following mass fraction
Component (mass parts)
Tetraethyl orthosilicate 30 ~ 60
Four third class ammonium hydroxide 10 ~ 20
Soxylat A 25-7-poly-third Vinyl Ether-Soxylat A 25-7 0.01 ~ 0.1
Polyether-modified fluorine-containing polydimethylsiloxane 0.001 ~ 0.005
Tetrabutyl titanate 1 ~ 4
Anhydrous isopropyl alcohol 5 ~ 15
The fluoro-4-hydroxyl of 8--2-Trifluoromethylquinocarboxylic 0.001 ~ 0.005
Distilled water 100
(2) preparation of colloid
By proportioning in step (1), tetraethyl orthosilicate, four third class ammonium hydroxide, Soxylat A 25-7-poly-third Vinyl Ether-Soxylat A 25-7, polyether-modified fluorine-containing polydimethylsiloxane, distilled water are mixed, carry out ordinary-temp hydrolysis reaction, reaction times 1 ~ 5h, obtain the hydrating solution of tetraethyl orthosilicate, in gained hydrating solution, add tetrabutyl titanate, anhydrous isopropyl alcohol, the fluoro-4-hydroxyl of 8--2-Trifluoromethylquinocarboxylic obtain mixing solutions, by the mixing solutions heating obtained, at 60 ~ 90 DEG C, stir 1 ~ 5h obtain clear colloid;
(3) ageing reaction
The colloid that step (2) obtains is transferred in the reactor of sealing, at 150 ~ 190 DEG C, places 120 ~ 240h, carry out ageing reaction, products therefrom is filtered, is washed to pH=7, dry, obtain HTS intermediate product;
(4) roasting
HTS intermediate product step (3) obtained obtains titanium-silicon molecular sieve catalyst product through 400 ~ 600 DEG C of roasting 2 ~ 8h.
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Citations (6)
| 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 |
| CN1428296A (en) * | 2001-12-28 | 2003-07-09 | 中国科学院大连化学物理研究所 | Method for synthesizing new titanium-silicone metapore molecular sieve |
| CN101767036A (en) * | 2009-12-25 | 2010-07-07 | 湘潭大学 | Titanium silicalite TS-1 catalyst preparation method |
| CN102745710A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Preparation method of hierarchical pore structure titanium-silicon molecular sieve material |
| CN103418432A (en) * | 2013-08-03 | 2013-12-04 | 大连理工大学 | Hierarchical-pore titanium silicon molecular sieve catalyst synthesized with assistance of aerosol and preparation method of hierarchical-pore titanium silicon molecular sieve catalyst |
| CN103896301A (en) * | 2012-12-28 | 2014-07-02 | 中国石油化工股份有限公司 | Method for synthesizing titanium-silicalite molecular sieve |
-
2014
- 2014-11-25 CN CN201410685345.5A patent/CN104445257B/en active Active
Patent Citations (6)
| 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 |
| CN1428296A (en) * | 2001-12-28 | 2003-07-09 | 中国科学院大连化学物理研究所 | Method for synthesizing new titanium-silicone metapore molecular sieve |
| CN101767036A (en) * | 2009-12-25 | 2010-07-07 | 湘潭大学 | Titanium silicalite TS-1 catalyst preparation method |
| CN102745710A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Preparation method of hierarchical pore structure titanium-silicon molecular sieve material |
| CN103896301A (en) * | 2012-12-28 | 2014-07-02 | 中国石油化工股份有限公司 | Method for synthesizing titanium-silicalite molecular sieve |
| CN103418432A (en) * | 2013-08-03 | 2013-12-04 | 大连理工大学 | Hierarchical-pore titanium silicon molecular sieve catalyst synthesized with assistance of aerosol and preparation method of hierarchical-pore titanium silicon molecular sieve catalyst |
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