CN101181687B - Ag-Fe3O4 magnetic nano catalyst and its application in phenylethene epoxidation - Google Patents

Ag-Fe3O4 magnetic nano catalyst and its application in phenylethene epoxidation Download PDF

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CN101181687B
CN101181687B CN2007101935660A CN200710193566A CN101181687B CN 101181687 B CN101181687 B CN 101181687B CN 2007101935660 A CN2007101935660 A CN 2007101935660A CN 200710193566 A CN200710193566 A CN 200710193566A CN 101181687 B CN101181687 B CN 101181687B
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catalyst
composite magnetic
nanocatalyst
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magnetic nanocatalyst
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CN101181687A (en
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陈接胜
张东慧
李国栋
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Jilin University
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Abstract

The invention pertains to a magnetic catalyst field, which relates to a compound Ag-Fe3O4 magnetic nano catalyst and application in a styrene catalytic epoxidation system under polymer effect. Generating method is: Fe3Cl6 . 6H2O, AgNO3 are taken as raw materials, and with the assistance of polymer PVP, Ag-Fe3O4 compound magnetic nano catalyst is generated in a glycol system which contains NaAc bysolvothermal technology; the catalyst can be applied to the styrene catalytic epoxidation system which adopts TBHP as oxidizer and toluol as solvent. The invention has the advantages of simple preparation method, ready availability of reactants, less solvent pollution, less generating time consumption, and the catalyst can be separated from reaction system conveniently under foreign field, and challenge of hard recycling of non magnetic nano catalyst; the catalyst prepared by the invention shows excellent catalytic activity and stability to styrene epoxidation, epoxy vinylbenzene yield reaches to 84.0 percent, and no de-activity phenomenon appears in reuse process.

Description

Ag-Fe 3O 4Magnetic nano-catalyst and the application in epoxidation of styrene
Technical field
The invention belongs to the magnetic catalyst field, be specifically related to a kind of magnetic Nano composite catalyst and application, it refers to Ag-Fe compound under the polymer effect 3O 4Magnetic nano-catalyst and its application in styrene catalysis epoxidation system.
Background technology
Heterogeneous catalyst has the characteristics of easily separating owing to it and plays an important role in chemistry and fine chemistry industry process from catalystic converter system.As everyone knows, the more little catalytic activity that they show of the granularity of heterogeneous catalyst is high more, the catalyst of nanoscale is owing to have bigger specific area, surface exposure has a large amount of avtive spots, reactant molecule can be gone up at nearly " molecular level " with the catalyst activity position fully to be contacted, thereby demonstrate the catalytic activity that is superior to corresponding block materials far away, relevant report is also very many.Yet, also just because of the very little (1nm=10 of particle diameter of nanocatalyst -9M) make them that a significant disadvantages be arranged: be difficult to be told from reaction system with traditional method centrifugal and that filter, this makes the recovery of nanocatalyst become an engineering difficult point.The one class nanocatalyst capable of magnetic separating (hereinafter to be referred as magnetic nano-catalyst) of development in recent years makes the catalyst of nanoscale to tell from reaction system easily under the effect of outside magnetic field.This magnetic catalyst is a kind of catalyst that magnetisable material is combined with active component, and this makes magnetic nano-catalyst have high activity and easily separated these two characteristics concurrently.In view of magnetic nano-catalyst has the characteristics of the above two kinds of excellence, people have invented a lot of methods and have prepared magnetic nano-catalyst.The preparation scheme of the magnetic nano-catalyst of bibliographical information comprises two big classes at present: 1. magnetic component (comprises Fe 3O 4, γ-Fe 2O 3, Ni etc.) and catalyst between (mainly be SiO by " rigidity cushion " 2, C and polymer) compound.For example, the people such as Canadian Alper is earlier at Fe 3O 4Outer cladding one deck SiO 2Then with catalytic active component [Rh (COD) Cl] 2Carry out compound prepared magnetic nano-catalyst (referring to document: J.Am.Chem.Soc.2006,128,5279) 2. magnetic component modify behind the flexible organic molecule with difunctional and the catalyst coupling.For example, the people such as Lin Wenbin of U.S. North Carolina university are with Fe 3O 4With catalyst activity component [Ru (BINAP-PO 3) (DPEN) Cl 2] directly get up to have prepared magnetic nano-catalyst (referring to document: J.Am.Chem.Soc.2005,127,12486) by the organic molecule coupling with difunctional.Yet it is various to prepare the magnetic catalyst step with this two classes scheme, the process complexity.This has limited to a great extent them and has used on a large scale in industrial production.Thereby the preparation method who seek that a kind of step is few, process is simple, is fit to the large-scale magnetic nano-catalyst that uses in the industrial production becomes problem demanding prompt solution.
Alkene epoxidation is the important chemical reaction of a class, and epoxidation product also is the very important organic intermediate of a class.The Ag catalyst is as ethene and O 2The special efficacy catalyst of reaction preparation oxirane can use in industrial production on a large scale.Yet effect was but not really desirable when the Ag catalyst was used for the epoxidation aspect of other alkene.Styryl oxide can be used as diluent, UV-absorbent, fumet, the dyestuff of epoxy resin, it also is the important intermediate of fine chemistry industry, pharmaceuticals industry, for example the bata-phenethyl alcohol that makes of Styryl oxide hydrogenation is attar of rose, caryophyllus oil, flores aurantii main body of oil, and is widely used in synthetic food, tobacco, soap and cosmetic essence.Recent domestic is to the demand sharp increase of bata-phenethyl alcohol and medical levamisol, and supply falls short of demand for Styryl oxide, has brought vast potential for future development for the research of preparation Styryl oxide.People attempted having prepared various modifieds Ag catalyst and estimated their activity when styrene catalyzed preparation Styryl oxide.People such as Spain scientist F.Medina find that alkali metal Cs is the promoter (referring to document: J.Mol.Catal.A:Chem.2006,258,346) of Ag catalysis epoxidation vinyl benzene.At present, the design synthesizing efficient can be recycled, and can remain a major challenge at the styrene catalyzed epoxidation catalyst that liquid phase is carried out.
Summary of the invention
Purpose of the present invention is exactly the deficiency that will overcome background technology, adopts simple method to synthesize a kind of novel capable of magnetic separating, efficient Ag-Fe through a solvent heat process 3O 4Magnetic nano-catalyst, and the application of this catalyst in styrene catalysis epoxidation system is provided, this catalyst is reused does not repeatedly have deactivation phenomenom afterwards, has actual application value.
Ag-Fe 3O 4The concrete synthetic method of composite magnetic nanocatalyst is as follows:
Have the middle order of certain deliquescent reproducibility alcohol (as: ethylene glycol, 1,3-glycerine, phenmethylol etc.) to 30～50ml and add Fe 3Cl 66H 2O, acetate (as: the sodium acetate CH of certain deliquescent long-chain polymer (as: PVP, epoxy ethane-epoxy propane-ethylene oxide block polymer (PEO-PPO-PEO), Sodium Polyacrylate (PAAS) etc.), soluble alkali metal or alkaline-earth metal is arranged in alcohol 3COONa, potassium acetate CH 3COOK or calcium acetate (CH 3COO) 2Ca etc.) and AgNO 3, Fe wherein 3Cl 66H 2The concentration of O is 0.0425～0.170mol/L, AgNO 3Concentration be 0.0425～0.170mol/L, the concentration of the acetate of alkali metal or alkaline-earth metal is 0.170～4.25mol/L, the concentration of polymer is 0.085～0.510mol/L (by monomer), the molecular weight of PVP (Mr) is 10000～58000, lucifuge stirs up to forming uniform suspension, then this suspension is transferred to and had in the stainless steel cauldron that the polytetrafluoroethyllining lining capacity is 50ml, 180～185 ℃ of reactions 0.5～4 hour, 200～210 ℃ of reactions 4～72 hours, naturally cool to room temperature;
With sedimentation separation under the effect of gained brownish black product outside magnetic field, and will precipitate again to be dispersed in the absolute ethyl alcohol and clean, so circulate 2～3 times, some ions on surface, unnecessary polymer and other impurity will be washed off; At last with the gained solid in the room temperature vacuum drying, namely get particle size range at the Ag-Fe of 178～306nm 3O 4The composite magnetic nanocatalyst.
The present invention is with ferric trichloride, silver nitrate be raw material under the assistance of polymer poly vinylpyrrolidone (PVP) etc., in containing the systems such as ethylene glycol of sodium acetate, synthesize a kind of Ag-Fe by the solvent heat synthetic technology 3O 4The composite magnetic nanocatalyst, this catalyst is being oxidant with TBHP (TBHP), toluene is to show excellent catalytic activity in the epoxidation of styrene system of solvent, can from reaction system, separate easily by the method that applies external magnetic field, and same catalyst is reused no deactivation phenomenom five times.
Preparating mechanism of the present invention can be described as: work as AgNO 3Join and comprise Fe 3Cl 66H 2O, PVP, CH 3During the ethylene glycol solution of COONa, AgCl at first forms, then in the process of 180 ℃ and 200 ℃ reactions, AgCl is reduced to Nano silver grain by solvent ethylene glycol earlier, the ferric ion of a part is reduced into ferrous ion and generates ferriferrous oxide nano-particle with remaining ferric ion co-precipitation then, and the ferriferrous oxide nano-particle of formation and Nano silver grain are combined into Ag-Fe in connection, the winding of PVP under assisting 3O 4The composite magnetic nano particle, two processes are carried out simultaneously.
The present invention prepares Ag-Fe 3O 4Used polymer P VP plays and assists Ag and Fe in the composite magnetic nano-catalytic agent method 3O 4The effect of nanocomposite.When other condition in the building-up process is identical when just not adding PVP, nonmagnetic portion has appearred in the products obtained therefrom, we have carried out the power spectrum sign to nonmagnetic portion, from can spectrogram as can be known the non magnetic product overwhelming majority be Ag, only comprise a small amount of Fe, Ag and Fe 3O 4Separate, can not be combined into Ag-Fe 3O 4The composite magnetic nanocatalyst particles.
Gained Ag-Fe of the present invention 3O 4The applicating evaluating system of composite magnetic nanocatalyst in epoxidation of styrene is as follows: toluene is solvent, TBHP is oxidant, styrene is substrate, counterflow condition, every secondary response finishes, and catalyst can add magnet by one and separate easily (each recyclable more than 90%) from reaction system; Same catalyst is reused no deactivation phenomena five times, and the result that catalyst uses for the 5th time is as follows: when reaction proceeded to 13 hours, the styrene conversion rate was 100%, and the productive rate of Styryl oxide is 84.0%, and the productive rate of benzaldehyde is 11.1%.
The toluene of using in the evaluating catalyst system is through air-distillation, and styrene is after distillation under reduced pressure, and TBHP then is that existing usefulness now extracts, and product is analyzed by gas-chromatography.
The present invention has following obvious advantage:
1.) to compare method of the present invention simply direct with the existing method for preparing magnetic catalyst, used reactant green, cheap and easy to get, and solvent for use pollutes little, and building-up process is consuming time few, gained Ag-Fe 3O 4The particle diameter of composite magnetic nanocatalyst can be between 178～306nm modulation;
2.) gained catalyst of the present invention has the advantages that to separate from reaction system easily under can outside magnetic field, has solved the difficult problem that non magnetic nanocatalyst is difficult to reclaim;
3.) gained catalyst of the present invention shows excellent catalytic activity and stability in the epoxidation of styrene system, reuses no deactivation phenomena five times;
4.) the polymer poly vinylpyrrolidone plays in building-up process and assists Ag and Fe 3O 4The effect of nanocomposite, this method can be widely used in catalyst and the Fe such as Pd, Au, Ru 3O 4Nanocomposite prepares the process of magnetic catalyst.
Description of drawings
Fig. 1: Ag-Fe 3O 4The powder x-ray diffraction spectrogram (XRD) of composite magnetic nanocatalyst;
Fig. 2: Ag-Fe 3O 4The stereoscan photograph of composite magnetic nanocatalyst (SEM);
Fig. 3: Ag-Fe 3O 4The transmission electron microscope photo of composite magnetic nanocatalyst (TEM);
Fig. 4: Ag-Fe 3O 4The high-resolution-ration transmission electric-lens photo (HRTEM) of a particle of composite magnetic nanocatalyst;
Fig. 5: Ag-Fe 3O 4Catalytic activity phenogram when the composite magnetic nanocatalyst uses for the 5th time in cinnamic catalysis epoxidation system;
Fig. 6: Ag-Fe 3O 4Composite magnetic nanocatalyst when (a) temperature is 4K and (b) temperature is 300 o'clock hysteresis curve.
As shown in Figure 1, wherein diamond symbols represents the diffraction maximum of Ag, and triangle represents Fe 3O 4Diffraction maximum.
As shown in Figure 5, abscissa is the reaction time, and ordinate is the productive rate of Styryl oxide.
The specific embodiment
Embodiment 1:
Preparation Ag-Fe 3O 4Composite magnetic nanocatalyst: with 2.975 mmol FeCl 36H 210000), 29.75mmol CH O, 8.925mmol PVP (K30 molecular weight: 3COONa, 2.975mmol AgNO 3Order joins in the 35mL ethylene glycol, the solution lucifuge that forms stirred until form uniform suspension, transferring to this suspension with the polytetrafluoroethyllining lining capacity then was in the stainless steel cauldron of 50ml, 180 ℃ of reactions 1 hour, 200 ℃ of reactions naturally cooled to room temperature after 8 hours; The sedimentation separation under the magnet effect of gained brownish black product, and again be dispersed in the absolute ethyl alcohol and clean, so circulate 3 times, some ions on surface, unnecessary polymer and other impurity are washed off; The gained solid is final that pressed powder 0.555 restrains in the room temperature vacuum drying, i.e. Ag-Fe 3O 4The composite magnetic nanocatalyst.
Fig. 1 is gained Ag-Fe 3O 4The XRD spectra of composite magnetic nanocatalyst not only contains Ag but also contain Fe in the product as known in the figure 3O 4
Fig. 2 is gained Ag-Fe 3O 4The SEM of composite magnetic nanocatalyst, as seen from Figure 2 Ag-Fe 3O 4The composite magnetic nanocatalyst is regular sphere, and each nano composite sphere is made up of some littler elementary cells.
Fig. 3 is gained Ag-Fe 3O 4The TEM of composite magnetic nanocatalyst, as seen from Figure 3 gained Ag-Fe 3O 4Nano composite sphere is medicine ball, and average grain diameter is 230nm (result who averages by measuring on a plurality of TEM the size of totally 127 particles).
Fig. 4 is Ag-Fe 3O 4The high-resolution-ration transmission electric-lens photo (HRTEM) of a particle of composite magnetic nanocatalyst.From the high resolution electron microscopy photo, on same nano spherical particle, not only can see the lattice of Ag but also can see Fe 3O 4Lattice, Ag and Fe are described 3O 4The nano particle unit under the connection of PVP, winding effect, jointly be combined into an Ag-Fe 3O 4The composite magnetic nanocatalyst particles.
Embodiment 2:
Similar with the step of embodiment 1,1 hour, 200 ℃ reactions of 185 ℃ of reactions 8 hours, the same Ag-Fe that gets 3O 4Composite magnetic nanocatalyst particles, average grain diameter are 225nm.
Embodiment 3:
Similar with the step of embodiment 1,1 hour, 210 ℃ reactions of 180 ℃ of reactions 8 hours, the same Ag-Fe that gets 3O 4Composite magnetic nanocatalyst particles, average grain diameter are 306nm.
Embodiment 4:
Similar with the step of embodiment 1, just with FeCl 36H 2The concentration of O becomes 1.4875mmol, AgNO 3Concentration become 1.4875mmol (mol ratio FeCl 36H 2O: AgNO 3=1: 1), obtain Ag-Fe equally 3O 4Composite magnetic nanocatalyst particles, average grain diameter are 178nm.
Embodiment 5:
Similar with the step of embodiment 1, just with FeCl 36H 2The concentration of O becomes 5.95mmol, AgNO 3Concentration become 5.95mmol (mol ratio FeCl 36H 2O: AgNO 3=1: 1), obtain Ag-Fe equally 3O 4Composite magnetic nanocatalyst particles, average grain diameter are 244nm.
Embodiment 6:
Similar with the step of embodiment 1, just with molecular weight be 10000 PVP to change molecular weight into be 58000 PVP, obtain equally Ag-Fe 3O 4Composite magnetic nanocatalyst particles, average grain diameter are 221nm.
Embodiment 7:
Similar with the step of embodiment 1,1 hour, 200 ℃ reactions of 180 ℃ of reactions 4 hours, obtain equally Ag-Fe 3O 4Composite magnetic nanocatalyst particles, average grain diameter are 227nm.
Embodiment 8:
Similar with the step of embodiment 1,1 hour, 200 ℃ reactions of 180 ℃ of reactions 12 hours, obtain equally Ag-Fe 3O 4Composite magnetic nanocatalyst particles, average grain diameter are 221nm.
Embodiment 9:
Similar with the step of embodiment 1,1 hour, 200 ℃ reactions of 180 ℃ of reactions 24 hours, obtain equally Ag-Fe 3O 4Composite magnetic nanocatalyst particles, average grain diameter are 242nm.
Embodiment 10:
Similar with the step of embodiment 1,1 hour, 200 ℃ reactions of 180 ℃ of reactions 48 hours, obtain equally Ag-Fe 3O 4Composite magnetic nanocatalyst particles, average grain diameter are 268nm.
Embodiment 11:
Similar with the step of embodiment 1,1 hour, 200 ℃ reactions of 180 ℃ of reactions 72 hours, obtain equally Ag-Fe 3O 4Composite magnetic nanocatalyst particles, average grain diameter are 220nm.
Embodiment 12:
Similar with the step of embodiment 1,0.5 hour, 200 ℃ reactions of 180 ℃ of reactions 8 hours, obtain equally Ag-Fe 3O 4Composite magnetic nanocatalyst particles, average grain diameter are 213nm.
Embodiment 13:
Similar with the step of embodiment 1, but be used in 2 hours, 200 ℃ reactions of 180 ℃ of reactions 8 hours, obtain equally Ag-Fe 3O 4Composite magnetic nanocatalyst particles, average grain diameter are 203nm.
Embodiment 14:
Similar with the step of embodiment 1,4 hours, 200 ℃ reactions of 180 ℃ of reactions 8 hours, obtain equally Ag-Fe 3O 4Composite magnetic nanocatalyst particles, average grain diameter are 225nm.
Embodiment 15:
The catalytically active assessment of catalyst: contain the styrene that adds the 10mmol decompression distillation in the three-neck flask of the distilled toluene of 10ml to 50ml and by the synthetic 100mg Ag-Fe of embodiment 1 3O 4The composite magnetic nanocatalyst, on the Electromagnetic Heating agitator, be heated to while stirring then and begin to reflux, after continuing to keep refluxing 0.5 hour, will dropwise add in three flasks with the TBHP (containing approximately toluene 4ml, TBHP 6ml) of the new extraction of toluene, cause catalytic reaction; Take out about 0.5ml sample with glass syringe from reaction system at set intervals and analyze with day island proper Tianjin SHIMADZU GC-14C gas-chromatography, chromatographic column is capillary column.After experiment finished, catalyst was processed through reclaiming, as the experiment of next round catalytic reaction; So loop five times, catalyst does not have deactivation phenomena.
Fig. 5 is Ag-Fe 3O 4Catalytic activity phenogram when the composite magnetic nanocatalyst uses for the 5th time in cinnamic catalysis epoxidation system, reaction proceeds to 13 hours as we know from the figure, the productive rate of Styryl oxide is 84.0%, this moment, cinnamic conversion ratio was 100%, and the productive rate of benzaldehyde is 11.1% (primary product except the epoxy vinylbenzene).For the first time during catalytic reaction, the productive rate of Styryl oxide is 54.0%, cinnamic conversion ratio is 88.1%, the productive rate of benzaldehyde is 14.1%.
The recovery of catalyst, processing: each catalytic reaction finishes, and catalyst is all told from reaction system by applying externally-applied magnetic field, again is dispersed in then to clean in the distilled toluene 3～4 times, after the room temperature vacuum drying, namely can be used for next time catalytic reaction.
Fig. 6 is Ag-Fe 3O 4The hysteresis curve of composite magnetic nanocatalyst, 300k (Fig. 6 a) time this product do not have hysteresis curve, and an obvious hysteresis curve has appearred when 4k (Fig. 6 b), the Ag-Fe among the present invention is described 3O 4The composite magnetic nanocatalyst has the character of superparamagnetic in room temperature.The character of this superparamagnetic is so that this catalyst can easily enrichment, recovery when applying external magnetic field, can be scattered in easily in the solution again when removing external magnetic field, in the recovery lecture experiment of catalyst, one magnet is put near the sample bottle, and the catalyst that was dispersed in a minute in the toluene just is enriched to bottle wall one side.

Claims (9)

1.Ag-Fe 3O 4The composite magnetic nanocatalyst, it is prepared by following method: have in the deliquescent reproducibility alcohol order to 30～50ml and add Fe 3Cl 66H 2O, acetate and the AgNO of certain deliquescent long-chain polymer, soluble alkali metal or alkaline-earth metal are arranged in alcohol 3, Fe wherein 3Cl 66H 2The concentration of O is 0.0425～0.170mol/L, AgNO 3Concentration be 0.0425～0.170mol/L, the concentration of the acetate of alkali metal or alkaline-earth metal is 0.170～4.25mol/L, concentration by the monomer polymer is 0.085～0.510mol/L, lucifuge stirs until form uniform suspension, transferring to this suspension with the polytetrafluoroethyllining lining capacity then is in the stainless steel cauldron of 50ml, 180～185 ℃ of reactions 0.5～4 hour, 200～210 ℃ of reactions 4～72 hours, naturally cool to room temperature; Then with sedimentation separation under the effect of gained brownish black product outside magnetic field, and will precipitate again to be dispersed in the absolute ethyl alcohol and clean, so circulate 2～3 times, at last with the gained solid in the room temperature vacuum drying, namely get particle size range at the Ag-Fe of 178～306nm 3O 4The composite magnetic nanocatalyst.
2. Ag-Fe as claimed in claim 1 3O 4The composite magnetic nanocatalyst is characterized in that: reproducibility alcohol is ethylene glycol, 1,3-glycerine or phenmethylol.
3. Ag-Fe as claimed in claim 2 3O 4The composite magnetic nanocatalyst is characterized in that: reproducibility alcohol is ethylene glycol.
4. Ag-Fe as claimed in claim 1 3O 4The composite magnetic nanocatalyst is characterized in that: long-chain polymer is polyvinylpyrrolidone, epoxy ethane-epoxy propane-ethylene oxide block polymer or Sodium Polyacrylate.
5. Ag-Fe as claimed in claim 4 3O 4The composite magnetic nanocatalyst is characterized in that: long-chain polymer is polyvinylpyrrolidone.
6. Ag-Fe as claimed in claim 5 3O 4The composite magnetic nanocatalyst is characterized in that: the Mr molecular weight of polyvinylpyrrolidone is 10000～58000.
7. Ag-Fe as claimed in claim 1 3O 4The composite magnetic nanocatalyst is characterized in that: the acetate of soluble alkali metal or alkaline-earth metal is sodium acetate, potassium acetate or calcium acetate.
8. Ag-Fe as claimed in claim 7 3O 4The composite magnetic nanocatalyst is characterized in that: the acetate of soluble alkali metal or alkaline-earth metal is sodium acetate.
9. any one described Ag-Fe of claim 1-8 3O 4The application of composite magnetic nanocatalyst in epoxidation of styrene.
CN2007101935660A 2007-12-18 2007-12-18 Ag-Fe3O4 magnetic nano catalyst and its application in phenylethene epoxidation Expired - Fee Related CN101181687B (en)

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