CN107262148A - A kind of strip crystallite titanium-silicon molecular sieve and its synthetic method and application - Google Patents
A kind of strip crystallite titanium-silicon molecular sieve and its synthetic method and application Download PDFInfo
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- CN107262148A CN107262148A CN201710507878.8A CN201710507878A CN107262148A CN 107262148 A CN107262148 A CN 107262148A CN 201710507878 A CN201710507878 A CN 201710507878A CN 107262148 A CN107262148 A CN 107262148A
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- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- 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
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Abstract
The invention discloses a kind of synthesis and application of strip crystallite titanium-silicon molecular sieve.Using hydro-thermal method synthesis of titanium silicon molecular sieve, using positive esters of silicon acis as silicon source, titanate esters are titanium source, TPAOH is template, water and fatty alcohol are solvent, and ammonium citrate is additive, through hydrolysis, except the steps such as alcohol it is well mixed after, 48~120h of crystallization at 160~180 DEG C, then obtain HTS powder after filtering, washing, dry, roasting.The HTS that the present invention is synthesized has MFI topological structures, and grain shape is strip, and crystal grain length is 1~2 μm, because its crystal grain is larger, it is easy to the recovery after separation and use, and this catalyst has good catalytic performance in phenol hydroxylation reaction.
Description
Technical field
The invention belongs to field of preparation of molecular sieve material, be related to a kind of strip crystallite titanium-silicon molecular sieve synthetic method and
Its phenol hydroxylation reaction in application.
Background technology
Titanium-silicon molecular sieve TS-1 belongs to rhombic system, with ZSM-5 molecular sieve identical MFI topological structures.Due to mistake
The introducing of Titanium is crossed so that TS-1 is provided with the catalytic oxidation performance of uniqueness.TS-1 is widely used in alkene epoxidation, benzene
In the hydroxylating of phenol and benzene, the partial oxidation of alkane, oxidation of alcohols, the catalytic oxidation such as the oximate of ketone.
HTS is generally synthesized by hydro-thermal method, grain size between 100-500nm, due to crystallite dimension compared with
It is small, the recovery after separation and use is not easy to, the use cost in industrial applications is improved.Ensureing that catalytic performance is constant
In the case of, appropriate increase crystallite dimension is conducive to the recycling after the separation and use of catalyst.
Patent CN104495867A discloses a kind of preparation method of big particle diameter HTS, and this invention is by crystalline material
It is incorporated into the mixed liquor being made up of inorganic silicon source, inorganic ti sources, organic formwork agent and water, average grain diameter is obtained after hydrothermal crystallizing
HTS more than 5 μm.
Patent CN101696019A elaborates inorganic by adding in a kind of synthetic method of large blocked TS-1, building-up process
Additive H2O2The crystalline character of molecular sieve is changed, the molecular sieve of invention synthesis can be used in phenol hydroxylation reaction.
Patent CN101480622A also discloses that a kind of preparation method of big particle diameter HTS, using silica gel, particle diameter as
100~300nm HTS and tetraethyl orthosilicate is 0.2~5.1mm of Material synthesis big particle diameter titanium molecular sieve catalysis
Agent.The method building-up process is complicated, and production cost is higher.
The content of the invention
The purpose of the present invention is, by a kind of HTS of the method synthesis with compared with big crystal grain simple and easy to apply, to make it
It is easily isolated during synthesis and use, while ensureing higher catalytic performance.
Following scheme is used in order to achieve the above object：
A kind of synthetic method of strip crystallite titanium-silicon molecular sieve, it is characterised in that use hydro-thermal method synthesis of titanium silicon molecular sieve,
Using positive esters of silicon acis as silicon source, titanate esters are titanium source, and TPAOH is template, and water and fatty alcohol are solvent, citric acid
Ammonium is additive, after hydrolysis, being well mixed except steps such as alcohol, 48~120h of crystallization at 160~180 DEG C, then through filtering, washing
Wash, dry, be calcined after obtain HTS powder.
Comprise the following steps that：
(1) silicic acid ester hydrolysis：The aqueous solution of TPAOH, hydrolysis is added dropwise into positive esters of silicon acis at 25~40 DEG C
3~6h；
(2) metatitanic acid ester hydrolysis：Titanate esters are well mixed with solvent fatty alcohol, are added dropwise at 20~30 DEG C into mixture
The aqueous solution of TPAOH, hydrolyzes 1~4h；
(3) two kinds of hydrolyzates are well mixed, are removed at 80~90 DEG C and additive citric acid ammonium is added after alcohol, stirring is equal
It is even；
(4) it is fitted into the autoclave with polytetrafluoro liner, 48~120h of crystallization at 160~180 DEG C；
(5) filter, washing, dried at 80~100 DEG C, be calcined at 500~600 DEG C, obtain HTS powder.
Further, in above-mentioned synthetic method, described positive esters of silicon acis is tetraethyl orthosilicate or methyl silicate.
Further, in above-mentioned synthetic method, described titanate esters are butyl titanate.
Further, in above-mentioned synthetic method, described fatty alcohol is ethanol or isopropanol.
Further, in above-mentioned synthetic method, the mol ratio of each material is SiO2:TiO2:TPAOH:Fat
Fat alcohol:Ammonium citrate：H2O=1:0.015~0.05:0.1~0.5:1~2:0.05~0.3：25~50.(positive esters of silicon acis with
SiO2Meter, titanate esters are with TiO2Meter).
The present invention provides a kind of strip crystallite titanium-silicon molecular sieve of above-mentioned method synthesis, and crystal grain length is 1~2 μm.
A kind of HTS synthesized by the above method of present invention offer is applied to by solvent of acetone, hydrogen peroxide is
In the phenol hydroxylation reaction of oxidant.Specific reaction condition is that phenol is 3 with hydrogen peroxide mol ratio:1, acetone and phenol
Mol ratio is 3:1, catalyst amount is the 10% of phenol quality, and reaction temperature is 80 DEG C, and the reaction time is 6h.Using gas phase color
Spectrum is analyzed reaction result.
Brief description of the drawings
Fig. 1 is sample TS-1-3 XRD；
Fig. 2 schemes for sample TS-1-3 SEM.
Embodiment
The invention will be further described for following examples, but content not thereby limiting the invention.
Used in embodiment to reagent be commercially available chemically pure reagent.
Catalyst prepared by the present invention is used to can be applied to by solvent of acetone, hydrogen peroxide for oxidant phenol hydroxylation
In reaction, reaction result is analyzed using gas-chromatography, indicator reaction is phenol conversion (XPHE), benzenediol selectivity
(SCAT+HQ) and benzoquinones selectivity (SBQ)
Comparative example
At 30 DEG C, the 26.0g TPAOHs aqueous solution (0.76mol/L) is added dropwise into 19.6g tetraethyl orthosilicates,
Hydrolyze 4h；At 30 DEG C, 6.0g isopropanols are well mixed with 0.8g butyl titanates, 20.0g tetrapropyl hydrogen is added dropwise thereto
Aqueous ammonium (0.38mol/L) is aoxidized, 2h is hydrolyzed；Two kinds of hydrolyzates are well mixed, at 85 DEG C remove alcohol after add 30.0g go from
Sub- water；It is fitted into the autoclave with polytetrafluoro liner, the crystallization 72h at 180 DEG C；Go out after kettle, filter, washing, 100 DEG C
Lower drying, is calcined at 550 DEG C, obtains sample TS-1-1.
Embodiment 1
At 30 DEG C, the 26.0g TPAOHs aqueous solution (0.76mol/L) is added dropwise into 19.6g tetraethyl orthosilicates,
Hydrolyze 4h；At 30 DEG C, 6.0g isopropanols are well mixed with 0.8g butyl titanates, 20.0g tetrapropyl hydrogen is added dropwise thereto
Aqueous ammonium (0.38mol/L) is aoxidized, 2h is hydrolyzed；Two kinds of hydrolyzates are well mixed, at 85 DEG C remove alcohol after add 30.0g go from
Sub- water, under vigorous stirring, adds 1.14g ammonium citrates；It is fitted into the autoclave with polytetrafluoro liner, at 180 DEG C
Lower crystallization 72h；Go out after kettle, filter, wash, dried at 100 DEG C, be calcined at 550 DEG C, obtain sample TS-1-2.
Embodiment 2
At 30 DEG C, the 26.0g TPAOHs aqueous solution (0.76mol/L) is added dropwise into 19.6g tetraethyl orthosilicates,
Hydrolyze 4h；At 30 DEG C, 6.0g isopropanols are well mixed with 0.8g butyl titanates, 20.0g tetrapropyl hydrogen is added dropwise thereto
Aqueous ammonium (0.38mol/L) is aoxidized, 2h is hydrolyzed；Two kinds of hydrolyzates are well mixed, at 85 DEG C remove alcohol after add 30.0g go from
Sub- water, under vigorous stirring, adds 2.28g ammonium citrates；It is fitted into the autoclave with polytetrafluoro liner, at 180 DEG C
Lower crystallization 72h；Go out after kettle, filter, wash, dried at 100 DEG C, be calcined at 550 DEG C, obtain sample TS-1-3.Sample TS-1-3
XRD and SEM figures see accompanying drawing.
Embodiment 3
At 30 DEG C, the 26.0g TPAOHs aqueous solution (0.76mol/L) is added dropwise into 19.6g tetraethyl orthosilicates,
Hydrolyze 4h；At 30 DEG C, 6.0g isopropanols are well mixed with 0.8g butyl titanates, 20.0g tetrapropyl hydrogen is added dropwise thereto
Aqueous ammonium (0.38mol/L) is aoxidized, 2h is hydrolyzed；Two kinds of hydrolyzates are well mixed, at 85 DEG C remove alcohol after add 30.0g go from
Sub- water, under vigorous stirring, adds 4.56g ammonium citrates；It is fitted into the autoclave with polytetrafluoro liner, at 180 DEG C
Lower crystallization 72h；Go out after kettle, filter, wash, dried at 100 DEG C, be calcined at 550 DEG C, obtain sample TS-1-4.
Embodiment 4
At 30 DEG C, the 26.0g TPAOHs aqueous solution (0.76mol/L) is added dropwise into 19.6g tetraethyl orthosilicates,
Hydrolyze 4h；At 30 DEG C, 6.0g isopropanols are well mixed with 0.8g butyl titanates, 20.0g tetrapropyl hydrogen is added dropwise thereto
Aqueous ammonium (0.38mol/L) is aoxidized, 2h is hydrolyzed；Two kinds of hydrolyzates are well mixed, at 85 DEG C remove alcohol after add 30.0g go from
Sub- water, under vigorous stirring, adds 1.14g ammonium citrates；It is fitted into the autoclave with polytetrafluoro liner, at 160 DEG C
Lower crystallization 120h；Go out after kettle, filter, wash, dried at 100 DEG C, be calcined at 550 DEG C, obtain sample TS-1-5.
Embodiment 5
At 30 DEG C, the 26.0g TPAOHs aqueous solution (0.76mol/L) is added dropwise into 14.3g methyl silicates,
Hydrolyze 4h；At 30 DEG C, 6.0g isopropanols are well mixed with 0.8g butyl titanates, 20.0g tetrapropyl hydrogen is added dropwise thereto
Aqueous ammonium (0.38mol/L) is aoxidized, 2h is hydrolyzed；Two kinds of hydrolyzates are well mixed, at 85 DEG C remove alcohol after add 30.0g go from
Sub- water, under vigorous stirring, adds 1.14g ammonium citrates；It is fitted into the autoclave with polytetrafluoro liner, at 180 DEG C
Lower crystallization 72h；Go out after kettle, filter, wash, dried at 100 DEG C, be calcined at 550 DEG C, obtain sample TS-1-6.
Application examples
Phenol hydroxylation performance evaluation is carried out to the catalyst sample obtained by comparative example and embodiment respectively.Reaction is at four mouthfuls
Carried out in flask, acetone is solvent, hydrogen peroxide is oxidant, hydrogen peroxide is using being added to phenol and acetone by the way of dropwise addition
In mixture.Specific reaction condition is that phenol is 3 with hydrogen peroxide mol ratio:1, acetone is 3 with phenol mol ratio:1, catalysis
Agent consumption is the 10% of phenol quality, and reaction temperature is 80 DEG C, and the reaction time is 6h.Reaction result is carried out using gas-chromatography
Analysis.
Comparative example and the Evaluation results of sample obtained by embodiment are listed in Table 1 below.
The catalytic performance test result of each sample catalyst of table 1
| Sample catalyst is numbered | XPHE(%) | SCAT+HQ(%) | SBQ(%) |
| TS-1-1 | 21.4 | 98.13 | 1.75 |
| TS-1-2 | 21.6 | 98.00 | 1.99 |
| TS-1-3 | 21.1 | 98.41 | 1.58 |
| TS-1-4 | 21.3 | 98.06 | 1.92 |
| TS-1-5 | 20.7 | 97.88 | 2.09 |
| TS-1-6 | 21.0 | 97.95 | 2.02 |
| TS-1-3 is reclaimed | 21.3 | 98.38 | 1.60 |
XPHEPhenol conversion, SCAT+HQBenzenediol selectivity, SBQBenzoquinones selectivity
As can be seen from the above table, caused by additive the change of grain shape and size not to catalyst phenolic hydroxy
Change reactivity worth and produce influence, but this recycling changed after the separation and use that are conducive to catalyst.
Claims (8)
1. a kind of synthetic method of strip crystallite titanium-silicon molecular sieve, it is characterised in that use hydro-thermal method synthesis of titanium silicon molecular sieve, with
Positive esters of silicon acis is silicon source, and titanate esters are titanium source, and TPAOH is template, and water and fatty alcohol are solvent, ammonium citrate
For additive, through hydrolysis, except the steps such as alcohol it is well mixed after, 48~120h of crystallization at 160~180 DEG C, then through filtering, washing
Wash, dry, be calcined after obtain HTS powder.
2. synthetic method according to claim 1, it is characterised in that comprise the following steps that：
(1) silicic acid ester hydrolysis：At 25~40 DEG C into positive esters of silicon acis be added dropwise TPAOH the aqueous solution, hydrolysis 3~
6h；
(2) metatitanic acid ester hydrolysis：Titanate esters are well mixed with solvent fatty alcohol, 4 third are added dropwise into mixture at 20~30 DEG C
The aqueous solution of base ammonium hydroxide, hydrolyzes 1~4h；
(3) two kinds of hydrolyzates are well mixed, are removed at 80~90 DEG C and additive citric acid ammonium is added after alcohol, stirred；
(4) it is fitted into the autoclave with polytetrafluoro liner, 48~120h of crystallization at 160~180 DEG C；
(5) filter, washing, dried at 80~100 DEG C, be calcined at 500~600 DEG C, obtain HTS powder.
3. synthetic method according to claim 1 or 2, it is characterised in that described positive esters of silicon acis is for tetraethyl orthosilicate or just
Methyl silicate.
4. synthetic method according to claim 1 or 2, it is characterised in that described titanate esters are butyl titanate.
5. synthetic method according to claim 1 or 2, it is characterised in that described fatty alcohol is ethanol or isopropanol.
6. synthetic method according to claim 1 or 2, it is characterised in that silicon source is with SiO2Meter, titanium source is with TiO2Meter, each thing
The mol ratio of material is SiO2:TiO2:TPAOH:Fatty alcohol:Ammonium citrate：H2O=1:0.015~0.05:0.1~
0.5:1~2:0.05~0.3：25~50.
7. the strip crystallite titanium-silicon molecular sieve of the method synthesis as described in claim 1~6 any one, crystal grain length is 1~2
μm。
8. HTS as claimed in claim 7 by solvent of acetone, hydrogen peroxide it is anti-for the phenol hydroxylation of oxidant
Application in answering.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110813373A (en) * | 2019-11-27 | 2020-02-21 | 吉林大学 | Titanium-silicon molecular sieve catalyst, preparation method and application thereof in olefin epoxidation reaction |
| CN114082441A (en) * | 2021-11-23 | 2022-02-25 | 江苏科技大学 | MFI molecular sieve and preparation method and application thereof |
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|---|---|---|---|---|
| CN1401569A (en) * | 2002-08-26 | 2003-03-12 | 大连理工大学 | Method for quick synthesis of Ti-Si nano molecular sieve catalyst and use thereof |
| CN106348309A (en) * | 2015-07-18 | 2017-01-25 | 湖北申昙环保新材料有限公司 | Titanium silicon molecular sieve and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401569A (en) * | 2002-08-26 | 2003-03-12 | 大连理工大学 | Method for quick synthesis of Ti-Si nano molecular sieve catalyst and use thereof |
| CN106348309A (en) * | 2015-07-18 | 2017-01-25 | 湖北申昙环保新材料有限公司 | Titanium silicon molecular sieve and preparation method thereof |
Non-Patent Citations (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110813373A (en) * | 2019-11-27 | 2020-02-21 | 吉林大学 | Titanium-silicon molecular sieve catalyst, preparation method and application thereof in olefin epoxidation reaction |
| CN114082441A (en) * | 2021-11-23 | 2022-02-25 | 江苏科技大学 | MFI molecular sieve and preparation method and application thereof |
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