CN101862676B - Large-aperture SBA-15 mesoporous material-copper trifluoromethanesulfonate composite catalyst, preparation method and application - Google Patents
Large-aperture SBA-15 mesoporous material-copper trifluoromethanesulfonate composite catalyst, preparation method and application Download PDFInfo
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- CN101862676B CN101862676B CN2009100824180A CN200910082418A CN101862676B CN 101862676 B CN101862676 B CN 101862676B CN 2009100824180 A CN2009100824180 A CN 2009100824180A CN 200910082418 A CN200910082418 A CN 200910082418A CN 101862676 B CN101862676 B CN 101862676B
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Abstract
The invention relates to a large-aperture mesoporous material loaded with copper trifluoromethanesulfonate, a preparation method thereof and a process for utilizing the material as a catalyst for catalyzing the condensation reaction of 1,2-epoxypropane and ketone. The SBA-15 mesoporous material loaded with the copper trifluoromethanesulfonate comprises a mesoporous material with an aperture of 10-11 nm and loaded copper trifluoromethanesulfonate. The mesoporous material is adopted as a catalyst for the condensation reaction of the 1,2-epoxypropane and the ketone to prepare food industry perfume 2,4-dimethyl-2-ethyl-1,3-dioxolane (named as butanone-1,2 propanediol ketal) and has higher reaction activity, easy separation of the catalyst and a product, difficult corrosion of instruments and recycling, and the reaction process for producing the food industry perfume 2,4-dimethyl-2-ethyl-1,3-dioxolane at present becomes an environmental-friendly reaction process.
Description
Technical field
The invention belongs to the catalyst synthesis technical field; Be specifically related to macropore SBA-15 mesoporous material and preparation method thereof and this catalyst 1 of a kind of load copper trifluoromethanesulfcomposite; 2-expoxy propane and butanone react and obtain a kind of spices 2 of food industry; 4-dimethyl-2-ethyl-1,3-dioxolanes (another name: reaction process butanone-1,2 propane diols ketal).
Background technology
Butanone-1,2-propane diols ketal has fresh fruital fragrance, can be used in the multiple daily chemical essence prescription.Its traditional synthetic method is under the Bronsted acid effect, and by butanone and 1, the 2-propane diols is synthetic, and used Bronsted acid generally is sulfuric acid, phosphoric acid, hydrochloric acid, p-methyl benzenesulfonic acid, oxalic acid etc.Its advantage is that catalyst is cheap and easy to get, product yield is high, but has side reaction many (sulfonation, oxidation, dehydrations etc.), and product purity is not high; Color and luster is darker; Equipment corrosion is serious, in the post processing discharging of a large amount of acid waste water cause drawbacks such as environmental pollution (some ring ketal flavor compounds synthetic. Wang Shaohua, Zhong Xiangju; He Jian etc., organic chemistry 8 (1988) 375; Sodium bisulfate catalysis synthesizes butanone 1, the research of 2-propane diols ketal. Gong Churu, and Dong Jinghua, Zhang Liande uses chemical industry 35 (2006) 270).Therefore, the scientific worker is seeking the new catalyst of function admirable always.
Mesoporous material SBA-15 is a kind of novel mesopore molecular sieve, has large aperture (6-30nm), the pore volume (1.0cm of high-sequential
3/ g), the high mechanical properties that keeps of thicker hole wall (4-6nm) and good catalysis absorption property (Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300Angstrom Pores.D.Y.Zhao; J..Feng, Q.S.Huo, N.Melosh; G.H.Fredrickson; B.F.Chmelka, G.D.Stucky, Science 279 (1998) 548; Zhao Dongyuan, Yu Chengzhong, Yu Yonghao. a kind of preparation method of mesonic pore molecular sieve carrier material, CN1341553A).Become the focus that scientific circles pay close attention to gradually with its Subjective and Objective that is basis assembling compound system at present, be about to homogeneous catalyst and load on a kind of carrier, can prepare a kind of heterogeneous novel mesoporous material catalyst.This novel mesoporous material does not have corrosivity, separates with product easily, and environmentally safe or pollute for a short time is a kind of environmentally friendly new material of heterogeneousization of homogeneous catalysis.Can assemble multiple compound in the mesoporous material duct, like heteropoly acid, cadmium sulfide, zirconium sulfate and organic palladium compound etc.
Copper trifluoromethanesulfcomposite is the lewis acid with good acid catalysis performance, is a kind of homogeneous catalyst preferably, so the present invention just combines the good catalytic of copper trifluoromethanesulfcomposite and the stronger load performance of SBA-15, synthesizes SBA-Cu (OTf)
2, it is used for catalysis 1, the 2-expoxy propane is also prepared the spices 2 of food industry, 4-dimethyl-2-ethyl-1,3-dioxolanes (butanone-1,2-propane diols ketal).
Yet mesoporous material SBA-15 aperture commonly used at present is many at 6-7nm, and pore volume and specific area are at 1.0cm
3/ g and 500m
2About/g, load capacity is limited, and also just directly it influences its catalytic performance for this.As expand the mesoporous material aperture to 10nm and improve pore volume and specific area after load compound (TriblockCopolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores.D.Y.Zhao again; J.L.Feng, Q.S.Huo, N.Melosh; G.H.Fredrickson; B.F.Chmelka, G.D.Stucky, Science 279 (1998) 548; Zhao Dongyuan, Yu Chengzhong, Yu Yonghao. a kind of preparation method of mesonic pore molecular sieve carrier material, CN1341553A), the mesoporous material load capacity will increase to some extent, and the catalytic performance of the mesoporous material of load also will increase.Therefore to intend and adopt wide-aperture mesoporous material SBA-15 be support materials in the present invention.
Summary of the invention
A kind of large-aperture SBA-15 mesoporous material-copper trifluoromethanesulfcomposite composite catalyst of the present invention, at outer surface and the inner duct load copper trifluoromethanesulfcomposite of big-pore mesoporous material SBA-15, wherein the aperture of mesoporous material SBA-15 is at 10～11nm.
The expression formula of a kind of large-aperture SBA-15 mesoporous material-copper trifluoromethanesulfcomposite composite catalyst provided by the invention is SBA-Cu (OTf)
2, Cu (OTf) wherein
2Represent copper trifluoromethanesulfcomposite, SBA representes the mesoporous material SBA-15 with its load.
A kind of load copper trifluoromethanesulfcomposite Preparation of catalysts method is characterized in that concrete steps are following:
The mesoporous material SBA-15 that with the aperture is 10-11nm was at 25-200 ℃ of following vacuum drying 1-24 hour; After being cooled to room temperature; Take by weighing the mesoporous material SBA-15 of handling well through above-mentioned steps; Butanone and copper trifluoromethanesulfcomposite are put into the teflon-lined agitated reactor in the lump, and the mass ratio of mesoporous material SBA-15, butanone and copper trifluoromethanesulfcomposite is 1: 1～20: 0.5～2: preferred 1: 12～18: 0.5～1, and the capping still; In the oil bath temperature scope is to stir 1～72 hour under 25～150 ℃ of conditions, preferably under 25～50 ℃ of conditions of oil bath, stirs 15～30 hours.Be cooled to room temperature, impurity was removed in 1～24 hour 25～200 ℃ of following vacuum drying in the centrifugation back, obtained solid product SBA-Cu (OTf)
2
A kind of described large-aperture SBA-15 mesoporous material-copper trifluoromethanesulfcomposite composite catalyst SBA-Cu (OTf) that utilizes
2Catalysis 1,2-expoxy propane and reactive ketone technology, concrete steps are following:
In the polytetrafluoroethyllining lining agitated reactor, add SBA-Cu (OTf) successively
2, butanone and 1,2-expoxy propane, SBA-Cu (OTf)
2, butanone and 1, the mass ratio of 2-expoxy propane is 1: 15～300: 5～100, preferred 1: 19～110: 6～60; The capping still; In under the stirring condition in oil bath 25～150 ℃ the reaction 1～72 hour, preferably in oil bath 25～50 ℃ the reaction 15～30 hours, the centrifugation; Liquid is surveyed GC-MS, solid product SBA-Cu (OTf)
2, 25～200 ℃ of following vacuum drying utilize again after removing impurity in 1～24 hour and reclaim.
The present invention adopts the SBA-Cu (OTf) of preparation
2Catalyst 1, the condensation reaction of 2-expoxy propane and butanone, reactant 1, the conversion ratio of 2-expoxy propane reaches 100%, the SBA-Cu of recovery (OTf)
2Composite catalyst utilizes and still has higher catalytic effect, its reactant 1, and the conversion ratio of 2-expoxy propane reaches 95%.And catalyst S BA-Cu (OTf)
2Still keep the distinctive orderly hexagonal hole road structure of mesoporous material SBA-15, see Fig. 1.Wherein figure (1) a is the XRD spectra of SBA-15, and figure (1) b is the XRD spectra of the SBA-15 behind the load copper trifluoromethanesulfcomposite, and figure (1) c is the SBA-Cu (OTf) after the catalytic reaction
2XRD spectra.Low-angle spectrum peak by XRD spectra occurs can know, behind the SBA-15 load copper trifluoromethanesulfcomposite and the hexagonal hole road structure of the sequential 2 D that carries out still keeping orderly after the catalytic reaction.
Analyze the microscopic pattern of mesoporous material SBA-15 load copper trifluoromethanesulfcomposite and see Fig. 2 and Fig. 3, wherein figure (2) a is SBA-15 microscopic appearance figure, and figure (2) b is the SBA-15 microscopic appearance figure (SBA-Cu (OTf) behind the load copper trifluoromethanesulfcomposite
2), figure (2) c is the SBA-Cu (OTf) after the catalytic reaction
2Microscopic appearance figure.Can know that by figure microstructure remains unchanged behind the SBA-15 load copper trifluoromethanesulfcomposite and after carrying out catalytic reaction.Wherein figure (3) a is the pore structure sketch map of SBA-15, and figure (3) b is the pore structure sketch map (SBA-Cu (OTf) of the SBA-15 behind the load copper trifluoromethanesulfcomposite
2), figure (3) c is SBA-Cu (OTf)
2SBA-Cu (OTf) after twice catalytic reaction
2The pore structure sketch map.Can know by figure, behind the SBA-15 load copper trifluoromethanesulfcomposite and the pore structure of carrying out after the catalytic reaction remain unchanged.
The invention has the beneficial effects as follows:
The present invention adopts a kind of composite catalyst of large aperture SBA-15 mesoporous material load copper trifluoromethanesulfcomposite gained, and with this catalyst applications in catalysis 1, the condensation reaction technology of 2-expoxy propane and ketone; The spices 2 of reacted food industry, 4-dimethyl-2-ethyl-1,3-dioxolanes (another name: butanone-1; 2 propane diols ketals) in the middle of the reaction, have high reaction activity and high, catalyst and product are easily separated; Not perishable instrument; And catalyst can use repeatedly, the spices 2 that makes present production food industry, 4-dimethyl-2-ethyl-1; (another name: reaction process butanone-1,2 propane diols ketal) becomes a kind of eco-friendly course of reaction to the 3-dioxolanes.
Description of drawings
Fig. 1 is the comparison diagram of the structure of the SBA-15 before and after the load copper trifluoromethanesulfcomposite.
Fig. 2 is the SBA-15 microscopic appearance figure before and after the load copper trifluoromethanesulfcomposite.
Fig. 3 is the pore structure sketch map of SBA-15 for load copper trifluoromethanesulfcomposite front and back.
The specific embodiment
Conversion ratio of the following example and selectivity, the result who analyzes based on gas chromatography-mass spectrography calculates and gets.In the computational process, confirming of each concrete material is to provide according to given mass spectrogram and the standard spectrogram contrast that is input in the computer.
Embodiment 1: a kind of preparation of load copper trifluoromethanesulfcomposite mesoporous material
The mesoporous material SBA-15 that with the aperture is 10～11nm was 150 ℃ of following vacuum drying 6 hours; After being cooled to room temperature, take by weighing 1g, take by weighing 20ml butanone and 1g copper trifluoromethanesulfcomposite again and put into 100ml teflon-lined agitated reactor; The capping still; After temperature is to stir 8 hours under 25 ℃ of conditions, after the centrifugation, obtain solid product SBA-Cu (OTf) behind the filter liquide
2, behind its 150 ℃ of vacuum drying removal impurity, be weighed as 1.2g.
Fig. 1 provides SBA-15 (a), SBA-Cu (OTf)
2(b) and SBA-Cu (OTf)
2(c) carry out the XRD spectra after the catalytic reaction twice.Can know that by above-mentioned three spectrograms macroporous/mesoporous material SBA-15 has orderly meso-hole structure, behind the load copper trifluoromethanesulfcomposite, still maintain ordered meso-porous structure, and order mesoporous structure still remains unchanged after carrying out twice catalytic reaction.
Embodiment 2: a kind of preparation of load copper trifluoromethanesulfcomposite mesoporous material
The mesoporous material SBA-15 that with the aperture is 10～11nm was 150 ℃ of following vacuum drying 6 hours; After being cooled to room temperature, take by weighing 1g, take by weighing 20ml butanone and 1g copper trifluoromethanesulfcomposite again and put into 100ml teflon-lined agitated reactor; The capping still; After temperature is to stir 8 hours under 35 ℃ of conditions, after the centrifugation, obtain solid product SBA-Cu (OTf) behind the filter liquide
2, behind its 150 ℃ of vacuum drying removal impurity, be weighed as 1.2g.
Embodiment 3: a kind of preparation and application of load copper trifluoromethanesulfcomposite mesoporous material
The mesoporous material SBA-15 that with the aperture is 10～11nm was 150 ℃ of following vacuum drying 6 hours; After being cooled to room temperature; Take by weighing 1g, take by weighing 20ml butanone and 1g copper trifluoromethanesulfcomposite again and put into 100ml teflon-lined agitated reactor, capping still; In temperature is to stir 8 hours under 25 ℃ of conditions, centrifugalizes and obtain solid product SBA-Cu (OTf)
2
In 100ml polytetrafluoroethyllining lining agitated reactor, add 1 successively, 2-expoxy propane 7.7g, butanone 22g, SBA-Cu (OTf)
21.2g in 55 ℃ of oil baths, reacting 24 hours under the stirring condition, centrifugation utilizes gas chromatographic analysis reaction product liquid composition, and 1,2-expoxy propane conversion ratio 100%, 2,4-dimethyl-2-ethyl-1,3-dioxolanes selectivity 75%., solid catalyst SBA-Cu (OTf)
2150 ℃ of following vacuum drying 6 hours, be cooled to room temperature after, utilize again after the recovery.
Embodiment 4: catalyst recovery is used
With the SBA-Cu (OTf) that recycles
2150 ℃ of following vacuum drying 6 hours, be cooled to room temperature after, take by weighing 1.2g, take by weighing 1 again; 2-expoxy propane 7.7g, butanone 22g adds in the 100ml polytetrafluoroethyllining lining agitated reactor, under stirring condition successively; Reaction is 24 hours in 55 ℃ of oil baths, and centrifugation utilizes gas chromatographic analysis reaction product liquid composition, 1; 2-expoxy propane conversion ratio 95%, 2,4-dimethyl-2-ethyl-1,3-dioxolanes selectivity 50%.
Table 1 is the pore structure parameter of the SBA-15 before and after the load copper trifluoromethanesulfcomposite; Can know that by table mesoporous material SBA-15 is behind the load copper trifluoromethanesulfcomposite, pore volume and specific area all reduce to some extent; And pore wall thickness increases, and explains that copper trifluoromethanesulfcomposite enters in the duct of mesoporous material.
Table 1
| Sample | ?Cu(OTf) 2Load | d 100 (nm) | Cell parameter (nm | Pore wall thickness (nm) | Specific area (m 2/g) | Pore volume (ml/g) | Aperture (nm) |
| ?SBA-15 | ?- | 10.4 | 12.3 | 2.1 | 623 | 1.6 | 10.2 |
| ?SBA-Cu(OTf) 2 | + | 15.5 | 18.0 | 5.6 | 332 | 1.0 | 12.4 |
Claims (5)
1. a large-aperture SBA-15 mesoporous material-copper trifluoromethanesulfcomposite composite catalyst is characterized in that, at outer surface and the inner duct load copper trifluoromethanesulfcomposite of big-pore mesoporous material SBA-15, wherein the aperture of mesoporous material SBA-15 is at 10～11nm; The expression formula of described large-aperture SBA-15 mesoporous material-copper trifluoromethanesulfcomposite composite catalyst is SBA-Cu (OTf)
2, Cu (OTf) wherein
2Represent copper trifluoromethanesulfcomposite, SBA representes the mesoporous material SBA-15 with its load.
2. the described large-aperture SBA-15 mesoporous material-copper trifluoromethanesulfcomposite method for preparing composite catalyst of claim 1 is characterized in that, comprises the steps:
With the aperture at the mesoporous material SBA-15 of 10～11nm 25～200 ℃ of following vacuum drying 1～24 hour; After being cooled to room temperature; In the teflon-lined agitated reactor, add mesoporous material SBA-15, butanone and copper trifluoromethanesulfcomposite, wherein the mass ratio of mesoporous material SBA-15, butanone and copper trifluoromethanesulfcomposite is 1: 1～20: 0.5～2; Closed reactor stirs under 25～150 ℃ of temperature conditions and reacted 1～72 hour; Be cooled to that centrifugal solid-liquid separates after the room temperature, then with solid phase 25～200 ℃ of following vacuum drying 1～24 hour, obtain solid catalyst product S BA-Cu (OTf)
2
3. large-aperture SBA-15 mesoporous material-copper trifluoromethanesulfcomposite method for preparing composite catalyst according to claim 2; It is characterized in that; The mass ratio of mesoporous material SBA-15, butanone and copper trifluoromethanesulfcomposite is 1: 12～18: 0.5～1, under 25～50 ℃ of temperature conditions, stirs and reacts 15～30 hours.
4. the described large-aperture SBA-15 mesoporous material-copper trifluoromethanesulfcomposite composite catalyst of one of claim 1～3 is in catalysis 1, the application in the reaction of 2-expoxy propane, and concrete steps are following:
(1) in the polytetrafluoroethyllining lining agitated reactor, adds SBA-Cu (OTf) successively
2, butanone and 1,2-expoxy propane, wherein SBA-Cu (OTf)
2, butanone and 1, the mass ratio of 2-expoxy propane is 1: 15～300: 5～100, the capping still, stirring reaction is 1～72 hour under 25～150 ℃ of temperature conditions, the centrifugation, in liquid phase, obtain product, liquid is surveyed GC-MS;
(2) SBA-Cu (OTf)
2Catalyst recovery reaches and utilizes: solid product SBA-Cu (OTf)
2, 25～200 ℃ of following vacuum drying utilize again after removing impurity in 1～24 hour and reclaim.
5. large-aperture SBA-15 mesoporous material-copper trifluoromethanesulfcomposite composite catalyst according to claim 4 is in catalysis 1, and the application in the reaction of 2-expoxy propane is characterized in that, wherein SBA-Cu (OTf)
2, butanone and 1, the mass ratio of 2-expoxy propane is 1: 19～110: 6～60, stirring reaction is 15～30 hours under 25～50 ℃ of temperature conditions.
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| CN103586086B (en) * | 2012-08-14 | 2016-03-30 | 中国石油化工股份有限公司 | The preparation method of a kind of support type copper trifluoromethanesulfcomposite Catalysts and its preparation method and application and cyclohexanone ethylene ketal |
| CN103586071B (en) * | 2012-08-14 | 2015-08-19 | 中国石油化工股份有限公司 | The preparation method of a kind of support type copper trifluoromethanesulfcomposite Catalysts and its preparation method and application and cyclohexanone ethylene ketal |
| CN105964297B (en) * | 2016-05-13 | 2018-07-13 | 浙江师范大学 | Preparation method for the solid-supported catalyst for synthesizing oximido benzofuran derivatives |
| CN114515597B (en) * | 2020-11-19 | 2023-05-09 | 中国石油化工股份有限公司 | Esterification catalyst, preparation method thereof and application thereof in esterification synthesis reaction of acetic acid and alcohol |
| CN112892560B (en) * | 2021-01-27 | 2022-10-25 | 南开大学 | Fluorine-containing weakly coordinated anion modified copper-based catalyst for acetylene hydrochlorination reaction and preparation method and application thereof |
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