CN1853778A - Synthesis of SBA-15-SO3II solid-phase catalyst and Beckmann rearrangement, esterification catalytic performances - Google Patents
Synthesis of SBA-15-SO3II solid-phase catalyst and Beckmann rearrangement, esterification catalytic performances Download PDFInfo
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- CN1853778A CN1853778A CNA2005100664395A CN200510066439A CN1853778A CN 1853778 A CN1853778 A CN 1853778A CN A2005100664395 A CNA2005100664395 A CN A2005100664395A CN 200510066439 A CN200510066439 A CN 200510066439A CN 1853778 A CN1853778 A CN 1853778A
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Abstract
A strong-acidity solid SBA-15-Ph-SO3H catalyst for preparing synthetic fiber Nylon-6, cosmetics and food by Beckmann reforming reaction and esterifying reaction is prepared from ethyl n-silicate (TEDS) as Si source, triblock copolymer Pluronic 123 (P123) as template agent and 2-(4-phenylsulfuryl chloride) ethyl trimethyl silicate (CSPTMS) as phenylsulfonyl precursor. It has high catalytic activity to said two reactions.
Description
One, technical field
The present invention is the silicon source with ethyl orthosilicate (TEOS), Pluronic123 triblock copolymer (P123) is the template agent, 2-(4-benzene sulfonyl chloride) ethyl-trimethyl esters of silicon acis (CSPTMS) is the benzene sulfonic acid based precursor, preparation highly acid solid acid catalyst SBA-15-Ph-SO
3H, and be applied to liquid phase Beckmann rearrangement and esterification.
Two, background technology
Current, more and more stricter environmental regulation stimulates factory, enterprise constantly to reform its production technology, technology, so that production process can be more and environmentally compatible.With respect to " latter end improvement ", " source control " is a kind of more effective control whole world method of serious environmental pollution problem day by day.And be the foundational development new catalyst with the new material, be again a ring very important in " source control ".Emerging mesoporous molecular sieve (as MCM-41, MCM-48, HMS, SBA-15 or the like) has not only become a focus of present material research recently, also provides many opportunities for Green Chemistry simultaneously.For example, and the active hetero atom of introducing in the mesoporous molecular sieve skeleton (as Ti, Cu,, Fe or the like), or in the mesoporous molecular sieve duct, draw as active component, the duct is modified, and the new catalyst of preparation has shown catalytic activity and progressively industrialization preferably in many catalytic reactions.These raw catelysts have greatly solved the poor efficiency that old technology exists, corrosion, and accessory substance waits some problems relevant with environmental pollution more.Epsilon-caprolactams (brief note is CL) is synthetic fibers Nylon
6 important raw and processed materials, and ethyl caprilate also is widely used in cosmetics and food service industry.Traditionally, these two kinds of products of large-scale production often with liquid acid as catalyst, so just brought the unfriendly factor of environment such as recovery, corrosion of catalyst.Therefore, for many years, people wish to develop novel solid acid catalyst always and replace these liquid acid.Because with respect to these big molecular product, there is narrower (＜1nm) the fatal problem in aperture in the zeolites catalyst that yields unusually brilliant results in petrochemical industry and fine chemistry industry.So the appearing as to address this problem of mesoporous molecular sieve (aperture is at 2-50nm) provides good opportunity.In the mesoporous molecular sieve that has occurred at present, SBA-15 has bigger, adjustable pore passage structure, thereby, be more conducive to the transmission of macromolecular complex material in its duct.Since Al-SBA-15 acidity of catalyst that SBA-15 skeleton doped with Al atom obtains a little less than, can obtain acid stronger solid acid catalyst and in its duct, introduce highly acid group.At present, have some with highly acid sulfonic group (SO
3H) relevant report in the introducing SBA-15 duct.As: have plenty of by directly synthetic method and earlier sulfydryl (SH) is introduced the duct, used hydrogen peroxide (H again
2O
2) oxidation obtains sulfonic group; Has plenty of the method for modifying with in the SBA-15 duct of sulfonic group grafting after the roasting by the back.But these methods are all more loaded down with trivial details, are unfavorable for practical application, and do not investigate the catalytic performance of gained catalyst in liquid phase Beckmann rearrangement and esterification.
Three, summary of the invention
The present invention is the silicon source with ethyl orthosilicate (TEOS), Pluronic123 triblock copolymer (P123) is the template agent, 2-(4-benzene sulfonyl chloride) ethyl-trimethyl esters of silicon acis (CSPTMS) is the benzene sulfonic acid based precursor, and directly hydro-thermal has been synthesized highly acid solid acid catalyst SBA-15-Ph-SO
3H.Liquid phase Beckmann is reset this catalyst and esterification has all shown catalytic activity preferably.This industrial production for Beckmann rearrangement reaction and esterification provides a green approach.
The synthesis step of this method is as follows: 4g Pluronic123 copolymer is dissolved in the 125ml 2M hydrochloric acid solution, stirred 45 minutes.Add silicon source TEOS and 2-(4-benzene sulfonyl chloride) ethyl-trimethyl esters of silicon acis (CSPTMS) then.The mole of gained mixture consists of: 1+xSiO
2: x CSPTMS: 6.5HCl: 180H
2O is x=0.05 wherein, and 0.1,0.15,0.2.This mixture carries out self assembly again under 100 ℃ of static conditions behind 40 ℃ of stirring certain hours.Through extracting, roasting promptly obtains product after removing copolymer.
Synthetic material when hydrothermal condition is as follows:
(1) CSPTMS and SiO
2Mol ratio be 0.05-0.2;
(2) for 4g P123 triblock copolymer, other molar ratio of material is;
1-xSiO
2∶x?CSPTMS∶6.5HCl∶180H
2O
(3) concentration of CSPTMS is 0.4%～1.7%.
Synthesis condition of the present invention is better in following ranges:
(1) CSPTMS and SiO
2Mol ratio be 0.05-0.1
(2) concentration of CSPTMS is 0.6%～0.8%
(3) with ethanol extracting 24h;
(4) sintering temperature is between 180-200 ℃
Catalytic reaction condition is as follows:
(1) liquid phase Beckmann rearrangement reaction: with the catalyst of 0.05-0.1g, 0.1g cyclohexanone oxime, 20-30ml solvent (chlorobenzene, toluene) add 50ml to be furnished with in the two neck flasks of condenser pipe.In oil bath, under the 120-150 ℃ of temperature, take a sample behind the stirring 12-36h, analyze with GC-MAS (application of gas chromatorgraphy/mass).
(2) liquid-phase esterification: with the catalyst of 0.05-0.1g, 6-8mmol is sad, and 20-30ml ethanol adds 50ml to be furnished with in the two neck flasks of condenser pipe.In water-bath, under the 60-80 ℃ of temperature, take a sample behind the stirring 4-6h, analyze with GC-MAS (application of gas chromatorgraphy/mass).
The product of the present invention's preparation has still kept the p6m one-dimensional tunnel structure that SBA-15 had.But its BET, pore volume have been compared obvious reduction with pure silicon SBA-15.XRD result shows that the sample of low benzene sulfonic acid base introducing amount still has the typical diffraction maximum of p6m space structure; And, the sample (CSPTMS/SiO of high benzene sulfonic acid base introducing amount
2＞0.15) then loses this diffraction maximum.But, when the sample of high benzene sulfonic acid base introducing amount down after the roasting, occurs this diffraction maximum at high temperature (＞600 ℃) again.This pore passage structure that shows this sample does not suffer obvious destruction, just weakens owing to too much benzene sulfonic acid base group in the duct can cause the X ray scattering contrast between duct and the hole wall, thereby loses this diffraction maximum.After these groups were removed in high-temperature roasting, the scattering contrast was strengthened, and this diffraction maximum can be recovered again.Results of elemental analyses shows that the element sulphur content of low benzene sulfonic acid base introducing amount sample is basic suitable with initial rate of charge; The element sulphur content of high benzene sulfonic acid base introducing amount sample then is lower than initial rate of charge, but still can reach more than 70% of initial rate of charge.That is, can successfully the benzene sulfonic acid base be incorporated in the duct of SBA-15 by this method.The gained catalyst is to liquid phase Beckmann rearrangement reaction, and productive rate surpasses 30%.To liquid-phase esterification, productive rate then surpasses 90%.Simultaneously, this catalyst has showed different catalysis behaviors in above two reactions.To liquid phase Beckmann rearrangement reaction, the sample of high benzene sulfonic acid base introducing amount has shown best catalytic activity; And to liquid-phase esterification, the sample activity of low benzene sulfonic acid base introducing amount is best.
Fig. 1 is the nitrogen adsorption-desorption curve and the pore size distribution curve of the different SBA-15 samples of gained.Wherein:
A: pure silicon SBA-15; B:CSPTMS/SiO
2+ CSPTMS=0.05; C:
CSPTMS/SiO
2+CSPTMS＝0.1；d：CSPTMS/SiO
2+CSPTMS＝0.15；
E:CSPTMS/SiO
2+ CSPTMS=0.2; F: sample e after 600 ℃ of roastings, the gained sample.
Fig. 2 is the feature X-ray diffraction pattern (XRD) of the different SBA-15 samples of gained.Wherein: a: pure silicon SBA-15; B:CSPTMS/SiO
2+ CSPTMS=0.05; C:CSPTMS/SiO
2+ CSPTMS=0.1; D:CSPTMS/SiO
2+ CSPTMS=0.15; E:CSPTMS/SiO
2+ CSPTMS=0.2; F: sample e after 600 ℃ of roastings, the gained sample.
Table 1 is the specific surface and the pore volume result of the different SBA-15 samples of gained
Table 2 is the results of elemental analyses of the different SBA-15 samples of gained
Table 3 is the liquid phase Beckmann rearrangement reaction catalytic performance of the different SBA-15 samples of gained
Table 4 is the liquid-phase esterification catalytic performance of the different SBA-15 samples of gained
Four, the specific embodiment
Further describe feature of the present invention below by example.
Example 1:
Under the constant agitation speed, with a certain amount of TEOS, CSPTMS is added dropwise in the hydrochloric acid solution of 4g P123, and 40 ℃ are stirred down, obtain mole and consist of 1+xSiO
2: x CSPTMS: 6.5HCl: 180H
2The mixture of O, x=0.05 wherein, 0.1,0.15,0.2.This mixture is continued to stir 30h down at 40 ℃.Then, left standstill 1 day at 100 ℃, product after the drying, promptly obtains synthesis type SBA-15-Ph-SO through suction filtration
3H.This sample is behind ethanol extracting 20h, and direct 210 ℃ of roasting 6h in air promptly obtain required catalyst again.The N of sample
2Adsorption-desorption isothermal curve, XRD figure, specific surface, pore volume and results of elemental analyses are seen Fig. 1-Fig. 2 and Biao 1-table 2 respectively.
Example 2:
Produce synthesis type SBA-15-Ph-SO
3The process of H is got synthesis type SBA-15-Ph-SO with example 1
3Directly 210 ℃ of following roastings 6 hours in air of H can obtain SBA-15-Ph-SO
3The H catalyst
Example 3:
With the catalyst of 0.1g, 0.1g epsilon-caprolactams, 20ml toluene add 50ml to be furnished with in the two neck flasks of condenser pipe.In oil bath, take a sample behind 130 ℃ of stirring 24h, analyze with GC-MAS (application of gas chromatorgraphy/mass).
Example 4:
With the catalyst of 0.1g, 8mmol is sad, and 20ml ethanol adds 50ml to be furnished with in the two neck flasks of condenser pipe.In water-bath, take a sample behind 70 ℃ of stirring 6h, analyze with GC-MAS (application of gas chromatorgraphy/mass).
Claims (6)
1. one kind is the silicon source with ethyl orthosilicate (TEOS), Pluronic123 triblock copolymer (P123) is the template agent, 2-(4-benzene sulfonyl chloride) ethyl-trimethyl esters of silicon acis (CSPTMS) is the benzene sulfonic acid based precursor, preparation highly acid solid acid catalyst SBA-15-Ph-SO
3H, and be applied to that liquid phase Beckmann resets and the method for esterification.4g Pluronic123 copolymer is dissolved in the 125ml 2M hydrochloric acid solution, stirred 45 minutes.Add silicon source TEOS and 2-(4-benzene sulfonyl chloride) ethyl-trimethyl esters of silicon acis (CSPTMS) then.The mole of gained mixture consists of: 1+xSiO
2: x CSPTMS: 6.5HCl: 180H
2O is x=0.05 wherein, and 0.1,0.15,0.2.This mixture carries out self assembly again under 100 ℃ of static conditions behind 40 ℃ of stirring certain hours.Through extracting, roasting promptly obtains required catalyst after removing copolymer.Liquid phase Beckmann resets and esterification is carried out in 50ml is furnished with two neck flasks of condenser pipe.
When hydrothermal condition is as follows for the synthetic material of A:
(1) CSPTMS and SiO
2Mol ratio be 0.05-0.2;
(2) for 4g P123 triblock copolymer, other molar ratio of material is;
1+x?SiO
2∶x?CSPTMS∶6.5HCl∶180H
2O
(3) concentration of CSPTMS is 0.4%～1.7%.
The B catalytic reaction condition is as follows:
(1) liquid phase Beckmann rearrangement reaction: with a certain amount of catalyst, cyclohexanone oxime, solvent add 50ml to be furnished with in the two neck flasks of condenser pipe.In oil bath, under the uniform temperature, sample analysis behind the stirring certain hour is analyzed with application of gas chromatorgraphy/mass (GC-MAS).
(2) liquid-phase esterification: a certain amount of catalyst is sad, and ethanol adds 50ml to be furnished with in the two neck flasks of condenser pipe.In water-bath, under the uniform temperature, sample analysis behind the stirring certain hour is analyzed with application of gas chromatorgraphy/mass (GC-MAS).
2. directly synthetic solid acid catalyst SBA-15-Ph-SO of a step according to claim 1
3The method of H is characterized in that reaction system is the 2M hydrochloric acid solution.
3. directly synthetic solid acid catalyst SBA-15-Ph-SO of a step according to claim 1
3The method of H is characterized in that synthesis mother liquid stirs 20-30h at 40 ℃ earlier, and then at 100 ℃ of crystallization 20-30h.
4. directly synthetic solid acid catalyst SBA-15-Ph-SO of a step according to claim 1
3The method of H is characterized in that the former powder of synthesis type is earlier with ethanol extracting 20-30h.Then, direct 150～220 ℃ of roasting 5-10h in air again.
5. liquid phase Beckmann rearrangement reaction condition according to claim 1 is characterized in that catalyst consumption is 0.05-0.2g, and the amount of cyclohexanone oxime is 0.05-0.2g, and the consumption of solvent is 10-40ml.Reaction temperature is 70-150 ℃, and the reaction time is 12-48h.
6. liquid-phase esterification condition according to claim 1 is characterized in that catalyst consumption is 0.05-0.2g, and sad amount is 6-8mmol, and the amount of ethanol is 10-40ml.Reaction temperature is 30-80 ℃, and the reaction time is 2-8h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781223A (en) * | 2009-12-25 | 2010-07-21 | 华东师范大学 | Method for catalytically synthesizing aminated compounds by using carbon-silicon solid acid as catalysts |
| CN102039176B (en) * | 2009-10-20 | 2013-07-03 | 中国石油化工股份有限公司 | Aromatic hydrocarbon sulfo-copper ion-containing SBA-16 mesoporous material and preparation method and application thereof |
| CN105107547A (en) * | 2015-09-22 | 2015-12-02 | 河南工业大学 | High hydrophobic high-temperature-resistant solid acid catalyst |
| CN105772078A (en) * | 2016-03-22 | 2016-07-20 | 华南农业大学 | Application of modified SBA-15 catalyst to synthesizing of biomass-based chemicals |
| CN105854942A (en) * | 2016-03-31 | 2016-08-17 | 湘潭大学 | Method for preparing sulfonic acid group-modified mesoporous material-loaded heteropolyacid catalyst and application thereof during esterification reaction |
| CN115999638A (en) * | 2022-12-21 | 2023-04-25 | 浙江中硝康鹏化学有限公司 | Immobilized trifluoromethyl sulfonic acid and preparation method thereof |
-
2005
- 2005-04-26 CN CNA2005100664395A patent/CN1853778A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102039176B (en) * | 2009-10-20 | 2013-07-03 | 中国石油化工股份有限公司 | Aromatic hydrocarbon sulfo-copper ion-containing SBA-16 mesoporous material and preparation method and application thereof |
| CN101781223A (en) * | 2009-12-25 | 2010-07-21 | 华东师范大学 | Method for catalytically synthesizing aminated compounds by using carbon-silicon solid acid as catalysts |
| CN101781223B (en) * | 2009-12-25 | 2013-01-23 | 华东师范大学 | Method for catalytically synthesizing aminated compounds by using carbon-silicon solid acid as catalysts |
| CN105107547A (en) * | 2015-09-22 | 2015-12-02 | 河南工业大学 | High hydrophobic high-temperature-resistant solid acid catalyst |
| CN105772078A (en) * | 2016-03-22 | 2016-07-20 | 华南农业大学 | Application of modified SBA-15 catalyst to synthesizing of biomass-based chemicals |
| CN105854942A (en) * | 2016-03-31 | 2016-08-17 | 湘潭大学 | Method for preparing sulfonic acid group-modified mesoporous material-loaded heteropolyacid catalyst and application thereof during esterification reaction |
| CN105854942B (en) * | 2016-03-31 | 2018-08-17 | 湘潭大学 | A kind of preparation method of sulfonic group modification mesoporous material carried heteropoly acid catalyst and its application in the esterification reaction |
| CN115999638A (en) * | 2022-12-21 | 2023-04-25 | 浙江中硝康鹏化学有限公司 | Immobilized trifluoromethyl sulfonic acid and preparation method thereof |
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