CN102688760A - Fe3O4/CuO/pSiO2 catalyst and preparation method thereof - Google Patents

Fe3O4/CuO/pSiO2 catalyst and preparation method thereof Download PDF

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CN102688760A
CN102688760A CN2012101869710A CN201210186971A CN102688760A CN 102688760 A CN102688760 A CN 102688760A CN 2012101869710 A CN2012101869710 A CN 2012101869710A CN 201210186971 A CN201210186971 A CN 201210186971A CN 102688760 A CN102688760 A CN 102688760A
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psio
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CN102688760B (en
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王戈
张晓伟
黄铌
郭万春
高鸿毅
杨穆
王倩
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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Abstract

The invention relates to a Fe3O4/CuO/pSiO2 (porous silica) catalyst, a preparation method thereof and application thereof in olefin epoxidation reaction. The preparation method comprises the following processes of: obtaining Fe3O4 microspheres serving as magnetic cores by adopting a co-precipitation method, and modifying the surfaces of the Fe3O4 microspheres by using polyvinyl pyrrolidone (PVP) in order to improve the adsorption effect of the surfaces of the Fe3O4 microspheres on metal cations; coating a CuO nano shell layer on the surfaces of the Fe3O4 microspheres by using copper acetate as a copper source through hydrothermal synthesis; and finally, coating the porous silicon dioxide shell layer by using cetyl trimethyl ammonium bromide (CTAB) as a surfactant and using ethyl orthosilicate as a silicon source, and thus obtaining a composite catalytic material with a magnetic Fe3O4/CuO/pSiO2 core-shell structure. The catalytic performance of the composite material is researched by respectively using epoxidation reaction of styrene and cyclooctene as probe reaction, and the results prove that the catalytic material has high reaction activity and selectivity, and the catalytic material is easy to separate and recover by introducing the magnetic ores; and the catalytic material has a good circulating effect, still can keep excellent catalytic performance by dozens of times of circulation, and has a great application prospect.

Description

Fe 3O 4/ CuO/pSiO 2Catalysts and its preparation method
Technical field
The invention belongs to magnetic Nano catalysis material field, relate to a kind of Fe with nucleocapsid structure 3O 4/ CuO/pSiO 2The preparation of magnetic compound catalyze material and the application in epoxidation reaction of olefines thereof.
Background technology
Epoxidation reaction of olefines is one type of important catalytic oxidation; Its product " olefin epoxide " is described as " organic intermediate of most worthy "; Its downstream product is widely used in various fields such as petrochemical industry, Polymer Synthesizing, organic synthesis, fine chemistry industry, biological medicine; Have wide range of applications, the market demand is big, can produce huge economic benefit.But its production process must rely on catalysis material, with realize the protection environment, simplify technology, shorten the reaction time, improve output, a series of purposes such as reduce production costs.Therefore, alkene epoxidation is a research field that receives much concern with Preparation of catalysts with innovation always.
Because existing, homogeneous catalyst is difficult for separating from reaction system, the major defect that is difficult to recycle, and in recent years, the support type heterogeneous catalysis has obtained significant progress with its more segregative advantage.Wherein, the magnetic catalysis material with its unique magnetic response function, greatly reduces separating difficulty again, only needs can realize by externally-applied magnetic field the recovery rapidly and efficiently of catalysis material, in the life-span that recycles of greatly improving catalyst, effectively reduces the manufacture of materials cost.Thereby the research of magnetic catalysis material has become the new focus of catalytic field.
Cupric oxide is one type of important transition metal oxide, has a wide range of applications at aspects such as catalysis, gas sensor, solar energy conversion and high-temperature superconductors.At the alkene epoxidation catalytic field, because cupric oxide itself has narrower band gap, catalytic activity is higher, and price is low, pollutes for a short time, thereby has caused the increasing concern of researcher.People such as Linping Xu ( Chem. Mater. 2009, 21,1253 – 1259) adopt circumfluence method to prepare the CuO group bunch of sea urchin shape, it has certain catalytic effect (optimal result: 1 mmol alkene, reaction 24h, wherein, the conversion ratio of cyclo-octene is 64.3%, selectivity is 100%) to epoxidation reaction of olefines.People such as Guohong Qiu ( J. Phys. Chem. C 2012,116, 468 – 477) having prepared cupric oxide spherical and two kinds of different-shapes of flower shape, is substrate with 1 mmol alkene, reaction 24h, and cinnamic conversion ratio is 100%, selectivity has only 45%.More than catalytic reaction time of two kinds of researchs longer, and catalyst is difficult for reclaiming, and is dispersed and circulating effect is all relatively poor.Chaoqiu Chen research group ( J. Mater. Chem., 2011, 21,5774 – 5779) prepared the coating mesoporous SiO in CuO outside 2Hud typed catalyst, be substrate with 1 mmol alkene equally, the reaction 8h, the conversion ratio of cyclo-octene and selectivity are respectively 66.5% and 100%; Reaction 2h, cinnamic conversion ratio and selectivity are respectively 88.6% and 61.2%.The result shows that the catalytic activity of catalyst and circulating effect have all had significant improvement.But the recovery of catalyst need be by traditional isolation technics such as filtering, centrifugal, and consuming time longer, for nanometer materials, the equipment that needs is more complicated, and separating difficulty increases, and catalyst loss is also relatively more serious.
In sum, magnetic material is effectively combined with the advantage of composite on catalytic performance in the function aspect the Separation and Recovery rapidly and efficiently, can produce good advantage coupling effect.
Summary of the invention
To above-mentioned situation, the objective of the invention is to combine the magnetic responsiveness and the CuO/SiO of magnetic material 2The advantage of aspects such as the catalytic performance of material provides a kind of hud typed Fe 3O 4/ CuO/pSiO 2(porous silica) magnetic compound catalyze material and preparation method thereof, and the catalytic performance of this new catalyst is inquired into as probe reaction with the epoxidation reaction of styrene and cyclo-octene.
The present invention provides a kind of Fe 3O 4/ CuO/pSiO 2Catalyst, wherein " p " representes porous, " pSiO 2" expression porous SiO 2Said Fe 3O 4/ CuO/pSiO 2Catalyst is with the Fe through finishing 3O 4As the magnetic function core, CuO is as active component, porous SiO 2Core-shell structure magnetic composite catalyst as protective layer.
Above-mentioned Fe 3O 4/ CuO/pSiO 2The Preparation of catalysts method is characterized in that comprising following preparation process:
(1) described Fe 3O 4Coprecipitation is adopted in the preparation of magnetic microsphere, and its specifically preparation process is: with a certain amount of FeCl 36H 2O is dissolved in the deionized water, and making solution concentration is 0.16 ~ 0.24mol/L, and stirring and the lasting high pure nitrogen that feeds are (until obtaining Fe under the room temperature 3O 4Magnetic microsphere), stir speed (S.S.) 200 ~ 350rpm, mixing time 10 ~ 40min adds an amount of FeCl 24H 2O continues reaction 20 ~ 60min; Be warming up to 80 ℃, add a certain amount of NH rapidly 3H 2O; For increasing its surface hydrophilicity, dropwise inject citric acid solution; After dropwising, reaction 45 ~ 90min; Vacuum drying obtains Fe 3O 4Magnetic microsphere; Wherein, FeCl 24H 2O, FeCl 36H 2The mol ratio of O, ammoniacal liquor and citric acid is about 1:2:200:2;
Described Fe 3O 4The finishing of magnetic microsphere is as surfactant with polyvinylpyrrolidone (PVP); Concrete operations are: at first, take by weighing a certain amount of PVP (molecular weight 58000) and be dissolved in the deionized water, preparation PVP (molecular weight 58000) solution a; Secondly, add an amount of above-mentioned Fe that makes 3O 4Magnetic microsphere, Fe 3O 4With the mol ratio of PVP be 42.9:1 ~ 53.6:1; Ultrasonic dispersion places shaking bath to react at a certain temperature then; Wash at last and carry out the room temperature vacuum drying, obtain the Fe of surface modification 3O 4Magnetic microsphere;
(2) load of described CuO nanometer shell, concrete preparation process is: take by weighing a certain amount of Schweinfurt green (C 4H 6CuO 4H 2O) in an amount of absolute ethyl alcohol, preparation obtains the ethanolic solution of Schweinfurt green, and ultrasonic being dispersed to entirely dissolved; In solution, add an amount of urea again, the mol ratio of Schweinfurt green and urea is 0.4:1 ~ 0.6:1, continues ultrasonic agitation to all dissolvings; Add a certain amount of Fe after PVP modifies then 3O 4And ultrasonic being dispersed to entirely dissolved Schweinfurt green and Fe 3O 4(PVP) mass ratio is 4:1 ~ 12:1; With solution be transferred to carry out hydro-thermal reaction in the agitated reactor after, wash with deionized water and absolute ethyl alcohol, carry out the room temperature vacuum drying at last and obtain Fe 3O 4/ CuO magnetic microsphere;
(3) described porous SiO 2The coating of shell, concrete operations are: the mixed solution b of preparation deionized water and absolute ethyl alcohol; Take by weighing an amount of softex kw (CTAB) and be dissolved in above-mentioned solution b, ultrasonic being dispersed to entirely dissolved; Add the Fe that has prepared 3O 4/ CuO magnetic microsphere, Fe 3O 4The mass ratio of/CuO and CTAB is 2.7:1 ~ 5.0:1, stirs 1 ~ 2h under 20 ~ 30 ℃ of temperature; Add proper ammonia (containing ammonia 25%～28%), dropwise drip a certain amount of ethyl orthosilicate (TEOS), the volume ratio of ammoniacal liquor, TEOS and mixed solution b is 0.28 ~ 0.8:0.17 ~ 0.26:100, continues to stir 6 ~ 15h, and washing is also removed surfactant.Obtain Fe 3O 4/ CuO/pSiO 2The magnetic composite catalyst.
The concentration that adds citric acid solution in the said step (1) is 1.0 ~ 1.2mol/L; The NH of said adding 3H 2O contains ammonia 25 ~ 28%; The concentration of the said PVP that makes (molecular weight 58000) solution a is 3.44 ~ 4.31mol/L.Further, the time of ultrasonic dispersion is 10 ~ 30min in the said step (1), and the temperature and time that in shaking bath, reacts is respectively 25 ~ 35 ℃ and 20 ~ 30h.
Adopt the synthetic Fe of coprecipitation in the said preparation process 1 3O 4Microballoon, purpose are the magnetic core that provides less, thereby effectively control the whole particle diameter of catalyst, so that when introducing the magnetic recovery function, keep advantages of high catalytic activity; Add a certain amount of citric acid, in order to increase Fe 3O 4Surface hydrophilicity, thereby improve its degree of scatter in water; Adopt polyvinylpyrrolidone to Fe 3O 4Microballoon carries out finishing, and purpose is to improve magnetic core and Cu 2+Interaction, promote effective coating of CuO shell.
The concentration of the ethanolic solution of preparation Schweinfurt green is 0.010 ~ 0.015mol/L in the said step (2); The temperature of said hydro-thermal reaction is 160 ~ 180 ℃, and the reaction time is 40 ~ 80min.In the said preparation process 2, Dichlorodiphenyl Acetate copper and Fe 3O 4(PVP) addition is controlled, mainly be because: if Fe 3O 4(PVP) add very few, the excessive independent balling-up of Schweinfurt green meeting, do not have magnetic function; If Fe 3O 4(PVP) add too much then excessive Fe 3O 4(PVP) can not realize effective coating of CuO shell in agitated reactor bottom sedimentation.Therefore, control Schweinfurt green and Fe 3O 4When mass ratio (PVP) was 4:1 ~ 12:1, CuO was better in the surface coated effect of magnetic core.
Described in the said step (3) among the mixed solution b of deionized water and absolute ethyl alcohol the volume ratio of deionized water and absolute ethyl alcohol be 1.3:1 ~ 1.5:1; The concentration of said softex kw (CTAB) in mixed solution b is 0.05 ~ 0.08mol/L, Fe 3O 4The mass ratio of/CuO and CTAB is 2.7:1 ~ 5.0:1, and the volume ratio that adds ammoniacal liquor, ethyl orthosilicate and mixed solution b is 0.28 ~ 0.8:0.17 ~ 0.26:100.
The removal of surfactant described in the said step (3) can be adopted the fast ion exchange method, and the ethanolic solution of preparation ammonium nitrate is as extractant, and its concentration is 0.18 ~ 0.25mol/L, washs at last and the room temperature vacuum drying; Or the removal of the high-temperature calcination under employing nitrogen protection surfactant, temperature is controlled at 450 ~ 550 ℃, calcining 3 ~ 6h.
In the said preparation process 3, the volume ratio of deionized water and absolute ethyl alcohol is controlled at 1.3:1 ~ 1.5:1, and Fe 3O 4The mass ratio of/CuO and CTAB is set at 2.7:1 ~ 5.0:1, is to realize porous SiO 2The crucial preparation condition that shell effectively coats; Adopt the fast ion exchange technology to remove surfactant, consider that mainly its gentle reaction condition is less to the influence of magnetic core, and the reaction time is short; Adopt the high-temperature calcination under the nitrogen protection to remove surfactant, easy to operation, and removal of surfactant is complete.
Fe of the present invention 3O 4/ CuO/pSiO 2Catalyst is mainly used in the catalytic oxidation epoxidation reaction of olefines, and can realize the quick recovery of catalyst through Magnetic Isolation, reaches the good effect that recycles.Being set at of described epoxidation reaction of olefines condition: substrate (alkene): 0.3mmol; Fe 3O 4/ CuO/pSiO 2Catalyst: 10 ~ 30mg; Solvent: acetonitrile, 5ml ~ 10ml; Oxygen source: TBHP, 0.6 ~ 1.5ml; Reaction temperature: 60 ~ 75 ℃; Reaction time: 9h; Catalytic result: cinnamic conversion ratio is near 100%, and the selectivity of Styryl oxide reaches more than 80%; The conversion ratio of cyclo-octene is about 70%, and the selectivity of epoxide ring octane is near 100%; Still can keep through tens of circulation catalytic effects.
In sum, the invention provides a kind of hud typed Fe 3O 4/ CuO/pSiO 2The preparation of magnetic compound catalyze material and for the research of the catalytic performance of epoxidation reaction of olefines, its characteristics are: on the one hand, adopt Fe 3O 4Microballoon can be realized the Separation and Recovery rapidly and efficiently of catalysis material as the magnetic core, effectively reduces catalyst loss, improves cyclic utilization rate, prolongs catalyst service life, reduces its production and maintenance cost greatly; On the other hand, to small particle diameter Fe 3O 4Microballoon carries out finishing, can realize green inexpensive CuO activated centre and porous SiO 2The introducing of magnetic response function had both been accomplished in effective coating of shell, had guaranteed the high activity and the selectivity of catalyst again.
Description of drawings
The hud typed Fe of accompanying drawing 1 the present invention preparation 3O 4/ CuO/pSiO 2The high-resolution-ration transmission electric-lens figure of magnetic compound catalyze material.
The specific embodiment
Below by embodiment technical scheme of the present invention is further described.
Embodiment 1:
(1) Fe 3O 4The preparation of magnetic microsphere: take by weighing a certain amount of FeCl 36H 2O is dissolved in the deionized water, and concentration is 0.24mol/L, stir under the room temperature and the lasting high pure nitrogen that feeds, and stir speed (S.S.) 280rpm, mixing time 40min adds an amount of FeCl 24H 2O, and continue reaction 30min; Be warming up to 80 ℃, add a certain amount of NH rapidly 3H 2O (containing ammonia 25 ~ 28%) for increasing its surface hydrophilicity, dropwise injects the citric acid solution of 1.2mol/L; After dropwising, reaction 60min; Vacuum drying obtains Fe 3O 4Magnetic microsphere.Wherein, FeCl 24H 2O, FeCl 36H 2The mol ratio of O, ammoniacal liquor and citric acid is about 1:2:200:2.
Take by weighing a certain amount of PVP (molecular weight 58000) and be dissolved in the deionized water, compound concentration is the solution of 3.6mol/L; Secondly, add an amount of above-mentioned Fe that makes 3O 4Magnetic microsphere, ultrasonic dispersion 30min, Fe 3O 4With the mol ratio of PVP be 50:1; Place shaking bath then, 30 ℃ of reaction 24h; Wash at last and carry out the room temperature vacuum drying, obtain the Fe of surface modification 3O 4Magnetic microsphere.
(2) load of CuO nanometer shell: take by weighing a certain amount of Schweinfurt green (C 4H 6CuO 4H 2O) in an amount of absolute ethyl alcohol, the ethanolic solution of preparation 0.012mol/L Schweinfurt green, ultrasonic being dispersed to entirely dissolved; In solution, add an amount of urea again, the mol ratio of Schweinfurt green and urea is 0.4:1, continues ultrasonic agitation to all dissolvings; Add a certain amount of Fe after PVP modifies then 3O 4And ultrasonic being dispersed to entirely dissolved Schweinfurt green and Fe 3O 4(PVP) mass ratio is 8:1; Solution is transferred in the agitated reactor, and 180 ℃ of reaction 70min wash with deionized water and absolute ethyl alcohol, carry out the room temperature vacuum drying at last, obtain Fe 3O 4/ CuO magnetic microsphere.
(3) porous SiO 2The coating of shell: the mixed solution of preparation deionized water and absolute ethyl alcohol, the volume ratio of deionized water and absolute ethyl alcohol is 1.5:1; Take by weighing an amount of softex kw (CTAB) and be dissolved in above-mentioned solution, ultrasonic being dispersed to entirely dissolved, and the concentration of CTAB in mixed solution is 0.08mol/L; Add the Fe that has prepared 3O 4/ CuO magnetic microsphere, Fe 3O 4The mass ratio of/CuO and CTAB is 3.0:1, stirs 1h under 25 ℃ of temperature; Add proper ammonia (containing ammonia 25%～28%), dropwise drip a certain amount of ethyl orthosilicate (TEOS), the volume ratio of ammoniacal liquor, TEOS and mixed solution is 0.4:0.18:100, continues to stir 12h, washing; The fast ion exchange method is adopted in the removal of surfactant, and the ethanolic solution of promptly preparing ammonium nitrate is as extractant, and its concentration is 0.20mol/L; Wash at last and the room temperature vacuum drying, obtain Fe 3O 4/ CuO/pSiO 2The magnetic composite catalyst.
(4) epoxidation reaction of olefines condition: styrene: 0.3mmol, cyclo-octene: 0.3mmol; The catalyst that makes in the present embodiment: 10mg; Solvent: acetonitrile, 5ml; Oxygen source: TBHP, 0.75ml; Reaction temperature: 70 ℃; Reaction time: 9h; Loop test: 8 times.
Under the epoxidation reaction of olefines condition that the present invention sets, adopt GC-MS to carry out the catalytic activity test, to the cinnamic catalytic effect of 0.3mmol be: cinnamic conversion ratio is 99.2%, the selectivity of Styryl oxide is 88.4%.Circulate after 8 times, cinnamic conversion ratio is 99.0%, and the selectivity of Styryl oxide is 88.3%.Catalytic effect to the 0.3mmol cyclo-octene is: the conversion ratio of cyclo-octene is 72.4%, and the selectivity of epoxide ring octane is 99.8%.Circulate after 8 times, the conversion ratio of cyclo-octene is 72.0%, and the selectivity of epoxide ring octane is 99.7%.
Embodiment 2:
(1) Fe 3O 4The preparation of magnetic microsphere: take by weighing a certain amount of FeCl 36H 2O is dissolved in the deionized water, and concentration is 0.20mol/L, stir under the room temperature and the lasting high pure nitrogen that feeds, and stir speed (S.S.) 300rpm, mixing time 30min adds an amount of FeCl 24H 2O, and continue reaction 40min; Be warming up to 80 ℃, add a certain amount of NH rapidly 3H 2O (containing ammonia 25 ~ 28%) for increasing its surface hydrophilicity, dropwise injects the citric acid solution of 1.1mol/L; After dropwising, reaction 70min; Vacuum drying obtains Fe 3O 4Magnetic microsphere.Wherein, FeCl 24H 2O, FeCl 36H 2The mol ratio of O, ammoniacal liquor and citric acid is about 1:2:200:2.
Take by weighing a certain amount of PVP (molecular weight 58000) and be dissolved in the deionized water, compound concentration is the solution of 4.0mol/L; Secondly, add an amount of above-mentioned Fe that makes 3O 4Magnetic microsphere, ultrasonic dispersion 20min, Fe 3O 4With the mol ratio of PVP be 46:1; Place shaking bath then, 25 ℃ of reaction 30h; Wash at last and carry out the room temperature vacuum drying, obtain the Fe of surface modification 3O 4Magnetic microsphere.
(2) load of CuO nanometer shell: take by weighing a certain amount of Schweinfurt green (C 4H 6CuO 4H 2O) in an amount of absolute ethyl alcohol, the ethanolic solution of preparation 0.015mol/L Schweinfurt green, ultrasonic being dispersed to entirely dissolved; In solution, add an amount of urea again, the mol ratio of Schweinfurt green and urea is 0.5:1, continues ultrasonic agitation to all dissolvings; Add a certain amount of Fe after PVP modifies then 3O 4And ultrasonic being dispersed to entirely dissolved Schweinfurt green and Fe 3O 4(PVP) mass ratio is 6:1; Solution is transferred in the agitated reactor, and 170 ℃ of reaction 90min wash with deionized water and absolute ethyl alcohol, carry out the room temperature vacuum drying at last, obtain Fe 3O 4/ CuO magnetic microsphere.
(3) porous SiO 2The coating of shell: the mixed solution of preparation deionized water and absolute ethyl alcohol, the volume ratio of deionized water and absolute ethyl alcohol is 1.4:1; Take by weighing an amount of softex kw (CTAB) and be dissolved in above-mentioned solution, ultrasonic being dispersed to entirely dissolved, and the concentration of CTAB in mixed solution is 0.06mol/L; Add the Fe that has prepared 3O 4/ CuO magnetic microsphere, Fe 3O 4The mass ratio of/CuO and CTAB is 4.0:1, stirs 1h under 30 ℃ of temperature; Add proper ammonia (containing ammonia 25%～28%), dropwise drip a certain amount of ethyl orthosilicate (TEOS), the volume ratio of ammoniacal liquor, TEOS and mixed solution is 0.6:0.20:100, continues to stir 15h, washing; The fast ion exchange method is adopted in the removal of surfactant, and the ethanolic solution of promptly preparing ammonium nitrate is as extractant, and its concentration is 0.18mol/L; Wash at last and the room temperature vacuum drying, obtain Fe 3O 4/ CuO/pSiO 2The magnetic composite catalyst.
(4) epoxidation reaction of olefines condition: styrene: 0.3mmol, cyclo-octene: 0.3mmol; Catalyst: 15mg; Solvent: acetonitrile, 10ml; Oxygen source: TBHP, 0.60ml; Reaction temperature: 70 ℃; Reaction time: 9h; Loop test: 10 times.
Under the epoxidation reaction of olefines condition that the present invention sets, adopt GC-MS to carry out the catalytic activity test, to the cinnamic catalytic effect of 0.3mmol be: cinnamic conversion ratio is 99.5%, the selectivity of Styryl oxide is 86.2%.Circulate after 10 times, cinnamic conversion ratio is 99.3%, and the selectivity of Styryl oxide is 85.7%.Catalytic effect to the 0.3mmol cyclo-octene is: the conversion ratio of cyclo-octene is 70.5%, and the selectivity of epoxide ring octane is 99.9%.Circulate after 10 times, the conversion ratio of cyclo-octene is 70.3%, and the selectivity of epoxide ring octane is 99.7%.
Embodiment 3:
(1) Fe 3O 4The preparation of magnetic microsphere: take by weighing a certain amount of FeCl 36H 2O is dissolved in the deionized water, and concentration is 0.22mol/L, stir under the room temperature and the lasting high pure nitrogen that feeds, and stir speed (S.S.) 310rpm, mixing time 25min adds an amount of FeCl 24H 2O, and continue reaction 25min; Be warming up to 80 ℃, add a certain amount of NH rapidly 3H 2O (containing ammonia 25 ~ 28%) for increasing its surface hydrophilicity, dropwise injects the citric acid solution of 1.2mol/L; After dropwising, reaction 90min; Vacuum drying obtains Fe 3O 4Magnetic microsphere.Wherein, FeCl 24H 2O, FeCl 36H 2The mol ratio of O, ammoniacal liquor and citric acid is about 1:2:200:2.
Take by weighing a certain amount of PVP (molecular weight 58000) and be dissolved in the deionized water, compound concentration is the solution of 3.8mol/L; Secondly, add an amount of above-mentioned Fe that makes 3O 4Magnetic microsphere, ultrasonic dispersion 15min, Fe 3O 4With the mol ratio of PVP be 48:1; Place shaking bath then, 25 ℃ of reaction 26h; Wash at last and carry out the room temperature vacuum drying, obtain the Fe of surface modification 3O 4Magnetic microsphere.
(2) load of CuO nanometer shell: take by weighing a certain amount of Schweinfurt green (C 4H 6CuO 4H 2O) in an amount of absolute ethyl alcohol, the ethanolic solution of preparation 0.010mol/L Schweinfurt green, ultrasonic being dispersed to entirely dissolved; In solution, add an amount of urea again, the mol ratio of Schweinfurt green and urea is 0.45:1, continues ultrasonic agitation to all dissolvings; Add a certain amount of Fe after PVP modifies then 3O 4And ultrasonic being dispersed to entirely dissolved Schweinfurt green and Fe 3O 4(PVP) mass ratio is 10:1; Solution is transferred in the agitated reactor, and 180 ℃ of reaction 65min wash with deionized water and absolute ethyl alcohol, carry out the room temperature vacuum drying at last, obtain Fe 3O 4/ CuO magnetic microsphere.
(3) porous SiO 2The coating of shell: the mixed solution of preparation deionized water and absolute ethyl alcohol, the volume ratio of deionized water and absolute ethyl alcohol is 1.33:1; Take by weighing an amount of softex kw (CTAB) and be dissolved in above-mentioned solution, ultrasonic being dispersed to entirely dissolved, and the concentration of CTAB in mixed solution is 0.05mol/L; Add the Fe that has prepared 3O 4/ CuO magnetic microsphere, Fe 3O 4The mass ratio of/CuO magnetic microsphere and CTAB is 3.6:1, stirs 1h under 25 ℃ of temperature; Add proper ammonia (containing ammonia 25%～28%), dropwise drip a certain amount of ethyl orthosilicate (TEOS), the volume ratio of ammoniacal liquor, TEOS and mixed solution is 0.5:0.24:100, continues to stir 10h, washing, vacuum drying; Adopt the high-temperature calcination under the nitrogen protection to remove surfactant at last, calcine 4h down, obtain Fe for 500 ℃ 3O 4/ CuO/pSiO 2The magnetic composite catalyst.
(4) epoxidation reaction of olefines condition: styrene: 0.3mmol, cyclo-octene: 0.3mmol; Catalyst: 20mg; Solvent: acetonitrile, 7ml; Oxygen source: TBHP, 0.80ml; Reaction temperature: 75 ℃; Reaction time: 9h; Loop test: 12 times.
Under the epoxidation reaction of olefines condition that the present invention sets, adopt GC-MS to carry out the catalytic activity test, to the cinnamic catalytic effect of 0.3mmol be: cinnamic conversion ratio is 99.9%, the selectivity of Styryl oxide is 86.0%.Circulate after 12 times, cinnamic conversion ratio is 99.2%, and the selectivity of Styryl oxide is 85.5%.Catalytic effect to the 0.3mmol cyclo-octene is: the conversion ratio of cyclo-octene is 67.3%, and the selectivity of epoxide ring octane is 99.5%.Circulate after 12 times, the conversion ratio of cyclo-octene is 65.5%, and the selectivity of epoxide ring octane is 99.3%.
Embodiment 4:
(1) Fe 3O 4The preparation of magnetic microsphere: take by weighing a certain amount of FeCl 36H 2O is dissolved in the deionized water, and concentration is 0.18mol/L, stir under the room temperature and the lasting high pure nitrogen that feeds, and stir speed (S.S.) 290rpm, mixing time 35min adds an amount of FeCl 24H 2O, and continue reaction 45min; Be warming up to 80 ℃, add a certain amount of NH rapidly 3H 2O (containing ammonia 25 ~ 28%) for increasing its surface hydrophilicity, dropwise injects the citric acid solution of 1.2mol/L; After dropwising, reaction 70min; Vacuum drying obtains Fe 3O 4Magnetic microsphere.Wherein, FeCl 24H 2O, FeCl 36H 2The mol ratio of O, ammoniacal liquor and citric acid is about 1:2:200:2.
Take by weighing a certain amount of PVP (molecular weight 58000) and be dissolved in the deionized water, compound concentration is the solution of 4.3mol/L; Secondly, add an amount of above-mentioned Fe that makes 3O 4Magnetic microsphere, ultrasonic dispersion 18min, Fe 3O 4With the mol ratio of PVP be 53:1; Place shaking bath then, 30 ℃ of reaction 20h; Wash at last and carry out the room temperature vacuum drying, obtain the Fe of surface modification 3O 4Magnetic microsphere.
(2) load of CuO nanometer shell: take by weighing a certain amount of Schweinfurt green (C 4H 6CuO 4H 2O) in an amount of absolute ethyl alcohol, the ethanolic solution of preparation 0.013mol/L Schweinfurt green, ultrasonic being dispersed to entirely dissolved; In solution, add an amount of urea again, the mol ratio of Schweinfurt green and urea is 0.52:1, continues ultrasonic agitation to all dissolvings; Add a certain amount of Fe after PVP modifies then 3O 4And ultrasonic being dispersed to entirely dissolved Schweinfurt green and Fe 3O 4(PVP) mass ratio is 9:1; Solution is transferred in the agitated reactor, and 175 ℃ of reaction 70min wash with deionized water and absolute ethyl alcohol, carry out the room temperature vacuum drying at last, obtain Fe 3O 4/ CuO magnetic microsphere.
(3) porous SiO 2The coating of shell: the mixed solution of preparation deionized water and absolute ethyl alcohol, the volume ratio of deionized water and absolute ethyl alcohol is 1.5:1; Take by weighing an amount of softex kw (CTAB) and be dissolved in above-mentioned solution, ultrasonic being dispersed to entirely dissolved, and the concentration of CTAB in mixed solution is 0.07mol/L; Add the Fe that has prepared 3O 4/ CuO magnetic microsphere, Fe 3O 4The mass ratio of/CuO and CTAB is 4.0:1, stirs 1.5h under 25 ℃ of temperature; Add proper ammonia (containing ammonia 25%～28%), dropwise drip a certain amount of ethyl orthosilicate (TEOS), the volume ratio of ammoniacal liquor, TEOS and mixed solution is 0.7:0.2:100, continues to stir 8h, washing, vacuum drying; Adopt the high-temperature calcination under the nitrogen protection to remove surfactant at last, calcine 3h down, obtain Fe for 550 ℃ 3O 4/ CuO/pSiO 2The magnetic composite catalyst.
(4) epoxidation reaction of olefines condition: styrene: 0.3mmol, cyclo-octene: 0.3mmol; Catalyst: 25mg; Solvent: acetonitrile, 8ml; Oxygen source: TBHP, 0.80ml; Reaction temperature: 70 ℃; Reaction time: 9h; Loop test: 15 times.
Under the epoxidation reaction of olefines condition that the present invention sets, adopt GC-MS to carry out the catalytic activity test, to the cinnamic catalytic effect of 0.3mmol be: cinnamic conversion ratio is 99.7%, the selectivity of Styryl oxide is 84.9%.Circulate after 15 times, cinnamic conversion ratio is 99.3%, and the selectivity of Styryl oxide is 83.6%.Catalytic effect to the 0.3mmol cyclo-octene is: the conversion ratio of cyclo-octene is 68.2%, and the selectivity of epoxide ring octane is 99.7%.Circulate after 15 times, the conversion ratio of cyclo-octene is 63.9%, and the selectivity of epoxide ring octane is 99.3%.

Claims (9)

1. Fe 3O 4/ CuO/pSiO 2Catalyst is characterized in that: said Fe 3O 4/ CuO/pSiO 2Catalyst is with the Fe through finishing 3O 4As the magnetic function core, CuO is as active component, porous SiO 2Core-shell structure magnetic composite catalyst as protective layer.
2. a kind of Fe as claimed in claim 1 3O 4/ CuO/pSiO 2The Preparation of catalysts method is characterized in that comprising following preparation process:
(1) described Fe 3O 4Coprecipitation is adopted in the preparation of magnetic microsphere, and its specifically preparation process is: with a certain amount of FeCl 36H 2O is dissolved in the deionized water, and making solution concentration is 0.16 ~ 0.24mol/L, stir under the room temperature and the lasting high pure nitrogen that feeds, and stir speed (S.S.) 200 ~ 350rpm, mixing time 10 ~ 40min adds an amount of FeCl 24H 2O continues reaction 20 ~ 60min; Be warming up to 80 ℃, add a certain amount of NH rapidly 3H 2O; For increasing its surface hydrophilicity, dropwise inject citric acid solution; After dropwising, reaction 45 ~ 90min; Vacuum drying obtains Fe 3O 4Magnetic microsphere; Wherein, FeCl 24H 2O, FeCl 36H 2The mol ratio of O, ammoniacal liquor and citric acid is about 1:2:200:2;
Described Fe 3O 4The finishing of magnetic microsphere is as surfactant with polyvinylpyrrolidone (PVP); Concrete operations are: at first, take by weighing a certain amount of PVP (molecular weight 58000) and be dissolved in the deionized water, preparation PVP (molecular weight 58000) solution a; Secondly, add an amount of above-mentioned Fe that makes 3O 4Magnetic microsphere, Fe 3O 4With the mol ratio of PVP be 42.9:1 ~ 53.6:1; Ultrasonic dispersion places shaking bath to react at a certain temperature then; Wash at last and carry out the room temperature vacuum drying, obtain the Fe of surface modification 3O 4Magnetic microsphere;
(2) load of described CuO nanometer shell, concrete preparation process is: take by weighing a certain amount of Schweinfurt green (C 4H 6CuO 4H 2O) in an amount of absolute ethyl alcohol, preparation obtains the ethanolic solution of Schweinfurt green, and ultrasonic being dispersed to entirely dissolved; In solution, add an amount of urea again, the mol ratio of Schweinfurt green and urea is 0.4:1 ~ 0.6:1, continues ultrasonic agitation to all dissolvings; Add a certain amount of Fe after PVP modifies then 3O 4And ultrasonic being dispersed to entirely dissolved Schweinfurt green and Fe 3O 4(PVP) mass ratio is 4:1 ~ 12:1; With solution be transferred to carry out hydro-thermal reaction in the agitated reactor after, wash with deionized water and absolute ethyl alcohol, carry out the room temperature vacuum drying at last and obtain Fe 3O 4/ CuO magnetic microsphere;
(3) described porous SiO 2The coating of shell, concrete operations are: the mixed solution b of preparation deionized water and absolute ethyl alcohol; Take by weighing an amount of softex kw (CTAB) and be dissolved in above-mentioned solution b, ultrasonic being dispersed to entirely dissolved; Add the Fe that has prepared 3O 4/ CuO magnetic microsphere, Fe 3O 4The mass ratio of/CuO and CTAB is 2.7:1 ~ 5.0:1, stirs 1 ~ 2h under 20 ~ 30 ℃ of temperature; Add proper ammonia (containing ammonia 25%～28%), dropwise drip a certain amount of ethyl orthosilicate (TEOS), the volume ratio of ammoniacal liquor, TEOS and mixed solution b is 0.28 ~ 0.8:0.17 ~ 0.26:100, continues to stir 6 ~ 15h, and washing is also removed surfactant; Obtain Fe 3O 4/ CuO/pSiO 2The magnetic composite catalyst.
3. a kind of Fe according to claim 2 3O 4/ CuO/pSiO 2The Preparation of catalysts method is characterized in that: the concentration that adds citric acid solution in the said step (1) is 1.0 ~ 1.2mol/L; The NH of said adding 3H 2O contains ammonia 25 ~ 28%; The concentration of the said PVP that makes (molecular weight 58000) solution a is 3.44 ~ 4.31mol/L.
4. a kind of Fe according to claim 2 3O 4/ CuO/pSiO 2The Preparation of catalysts method is characterized in that: the time of ultrasonic dispersion is 10 ~ 30min in the said step (1), and the temperature and time that in shaking bath, reacts is respectively 25 ~ 35 ℃ and 20 ~ 30h.
5. a kind of Fe according to claim 2 3O 4/ CuO/pSiO 2The Preparation of catalysts method is characterized in that: the concentration of the ethanolic solution of preparation Schweinfurt green is 0.010 ~ 0.015mol/L in the said step (2).
6. a kind of Fe according to claim 2 3O 4/ CuO/pSiO 2The Preparation of catalysts method is characterized in that: the temperature of hydro-thermal reaction is 160 ~ 180 ℃ described in the said step (2), and the reaction time is 40 ~ 80 min.
7. a kind of Fe according to claim 2 3O 4/ CuO/pSiO 2The Preparation of catalysts method; It is characterized in that: described in the said step (3) among the mixed solution b of deionized water and absolute ethyl alcohol the volume ratio of deionized water and absolute ethyl alcohol be 1.3:1 ~ 1.5:1; The concentration of said softex kw (CTAB) in mixed solution b is 0.05 ~ 0.08mol/L, Fe 3O 4The mass ratio of/CuO and CTAB is 2.7:1 ~ 5.0:1, and the volume ratio that adds ammoniacal liquor, ethyl orthosilicate and mixed solution b is 0.28 ~ 0.8:0.17 ~ 0.26:100.
8. a kind of Fe according to claim 2 3O 4/ CuO/pSiO 2The Preparation of catalysts method; It is characterized in that: the removal of surfactant described in the said step (3) can be adopted the fast ion exchange method; The ethanolic solution of preparation ammonium nitrate is as extractant, and its concentration is 0.18 ~ 0.25mol/L, washs at last and the room temperature vacuum drying; Or the removal of the high-temperature calcination under employing nitrogen protection surfactant, temperature is controlled at 450 ~ 550 ℃, calcining 3 ~ 6h.
9. according to claim 1 and 2 described a kind of Fe 3O 4/ CuO/pSiO 2Catalyst is characterized in that this catalyst is mainly used in the catalytic oxidation epoxidation reaction of olefines, and can realize the quick recovery of catalyst through Magnetic Isolation, reaches the good effect that recycles.
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