CN103566950A - Preparation method of catalyst for selectively hydrogenating alpha, beta-unsaturated aldehyde - Google Patents

Preparation method of catalyst for selectively hydrogenating alpha, beta-unsaturated aldehyde Download PDF

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CN103566950A
CN103566950A CN201310537743.8A CN201310537743A CN103566950A CN 103566950 A CN103566950 A CN 103566950A CN 201310537743 A CN201310537743 A CN 201310537743A CN 103566950 A CN103566950 A CN 103566950A
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catalyst
mass ratio
magnetic
preparation
noble metal
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肖强
余建雁
严力
叶向荣
钟依均
朱伟东
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Zhejiang Normal University CJNU
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Zhejiang Normal University CJNU
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Abstract

The invention relates to a preparation method of a catalyst for selectively hydrogenating alpha, beta-unsaturated aldehyde. The catalyst consists of a carrier of shell-core-structured carbon-coated ferroferric oxide and an active component (noble metal nano-particles), wherein the mass ratio of ferroferric oxide which is a magnetic component to carbon which is an auxiliary component is 9:1-5:5, and the mass ratio of the carrier to the active component is 9:1-100:1. According to the preparation method, Fe3O4 magnetic nano-particles are firstly prepared, then shell-core-structured Fe3O4@C is prepared, and finally the noble metal nano-particles are loaded to the surface of the Fe3O4@C, so as to obtain the catalyst. The catalyst prepared by utilizing the preparation method is applied to the selective hydrogenation reaction of the alpha, beta-unsaturated aldehyde and has the characteristics of time and labor saving, high efficiency in separation and recyclable use.

Description

A α, the preparation method of the catalyst of beta-unsaturated aldehyde selective hydrogenation
Technical field
The present invention relates to a kind of for α, the preparation method of the catalyst of beta-unsaturated aldehyde selective hydrogenation, metal catalyst preparation field, especially with C parcel Fe 3o 4the magnetic composite of nucleocapsid structure be the method that carrier is prepared noble metal support type magnetic catalyst.
Background technology
α, beta-unsaturated aldehyde selective hydrogenation is the important reaction of a class in industrial circle, α, in beta-unsaturated aldehyde, C=O hydrogenation products unsaturated alcohol is important source material and the intermediate of medicine, spices, agricultural chemicals etc.Exploitation high activity and high-selectivity catalyst are α, the key of beta-unsaturated aldehyde selective hydrogenation.Research report, the catalyst that the noble metal of take is active component, at α, has good hydrogenation selectivity and hydrogenation activity in beta-unsaturated aldehyde selective hydrogenation.Pd is catalyst based at α, shows superior hydrogenation activity in beta-unsaturated aldehyde selective hydrogenation, and Pt is catalyst based, shows good C=O key hydrogenation selectivity.Noble metal size has material impact to catalytic performance, and size homogeneous, the metallic being of moderate size are the keys that obtains high selectivity.
Although industrial, adopted heterogeneous catalysis, greatly improved the recovery utilization rate of catalyst, yet the current separated recycling for solid catalyst and liquid-phase reaction system, mainly based on filtration cycle, but this conventional method not only process is loaded down with trivial details time-consuming, and very easily cause the loss of catalyst and active component, therefore how to make solid-phase catalyst is industrial problem anxious to be resolved with the fast simple separated of liquid-phase reaction system always.Magnetic separation technique is a kind of conventional physical isolation technics, mainly utilizes each material magnetic contrast each other to realize effective separation of material.It is the magnetic responsiveness that utilizes magnetic nano-particle, can reach high efficiente callback and the recycling of catalyst under additional magnetic fields.
Patent of invention (CN102151575A) discloses a kind of preparation method of carbon nanometer tube loaded type catalyst, and its preparation is to deposit or assemble magnetic nanoparticle by CNT, then load active component, makes magnetic catalyst.This catalyst can be efficiently separated with liquid-phase reaction system under externally-applied magnetic field, and shown the good performance that recycles.This preparation method is by magnetisable material presoma and the directly deposition reduction on CNT of metal component presoma, thereby on the magnetic catalyst making, magnetic nanoparticle and metal active constituent granular size are uneven, cause the problems such as magnetic-particle easily comes off, Hydrogenation is not good.As Pd/Fe 3o 4-MCNT magnetic catalyst has shown superior activity to hydrogenation on cinnamic aldehyde, yet very poor to C=O hydrogenation selectivity, and cinnamyl alcohol is selectively 0.
Although the open report of existing magnetic catalyst, and shown the good performance that recycles, but magnetic catalyst prepared by prior art means is magnetic component and active component to be loaded on simultaneously to the surface of carrier, will cause like this existing competition load between the two, under hydrogenation conditions, there is the problems such as magnetic-particle comes off, cause magnetic catalyst to there is no actual application prospect.
Summary of the invention
The present invention is directed to the problems such as the magnetic-particle of existing magnetic catalyst existence easily comes off, and separating property is not good, the preparation method of a kind of time saving and energy saving, efficient separation with the nucleocapsid structure loaded catalyst can be recycled is provided.
For solving this technical problem, the technical solution used in the present invention is as follows:
A α, the preparation method of the catalyst of beta-unsaturated aldehyde selective hydrogenation, catalyst is by the carbon coated ferroferric oxide (Fe of nucleocapsid structure 3o 4c) carrier and active constituent noble metal nano particles form, magnetic component tri-iron tetroxide (Fe 3o 4) and the mass ratio of helper component carbon (C) be 9: 1～5: 5, carrier and active component mass ratio are 9: 1～100: 1, described noble metal nano particles is selected from a kind of in Pt, Pd, Ru.
The presoma of helper component C is glucose.
Above-mentioned method for preparing catalyst comprises the following steps:
(1) Fe 3o 4the preparation of magnetic nanoparticle:
In ethylene glycol, add successively FeCl 36H 2o, polyethylene glycol, anhydrous sodium acetate, stir, and is then placed in reactor and at 160～240 ℃, keeps one section of 4～8h, and heating rate is 0.5～5 ℃/min, is cooled to room temperature, washs rear 80 ℃ of dry Fe that obtain 3o 4nano particle, FeCl 36H 2o: polyethylene glycol mass ratio is 1: 0～1: 5, FeCl 36H 2o: anhydrous sodium acetate mass ratio is 1: 1～1: 10.
(2) nucleocapsid structure Fe 3o 4the preparation of C: the Fe that step (1) is obtained 3o 4nanoparticulate dispersed is to ultrasonic in rare nitric acid, wash to being distributed to after neutrality in the middle of the glucose solution of 0.5M, be then placed in reactor and at 160～240 ℃, keep one section of 4～8h, heating rate is 0.5～5 ℃/min, be cooled to room temperature, wash rear 80 ℃ of dry Fe that obtain 3o 4c nanoparticulate carriers.
(3) noble metal nano particles loads to Fe 3o 4c surface: the Fe that step (2) is obtained 3o 4c nanoparticulate dispersed is to ethylene glycol, then add dodecyl sodium sulfate, mechanical agitation, rises to 140～180 ℃ after ultrasonic, then add noble metal precursor body-ethylene glycol mixed solution, condensing reflux: reflux temperature is 140～180 ℃, return time 1～5h, heating rate is 0.5～5 ℃/min, after wash after being cooled to room temperature, 70 ℃ of vacuum drying 8h, obtain catalyst, Fe 3o 4c: dodecyl sodium sulfate mass ratio is 1: 1～1: 10,
Described noble metal precursor body is a kind of in palladium bichloride, ruthenic chloride, chloroplatinic acid.
Catalyst of the present invention and common for α; beta-unsaturated aldehyde selective liquid-phase hydrogenation magnetic catalyst is compared difference and is to have realized the inside that magnetic component is wrapped in to carrier; well protected magnetic component unaffected; and under the effect of externally-applied magnetic field, catalyst is separated rapidly with liquid-phase system.Catalyst of the present invention is for α for this reason, and beta-unsaturated aldehyde selective hydrogenation has higher activity, selective and stability.
Accompanying drawing explanation
Fig. 1 is Fe 3o 4(a), Fe 3o 4c (b), Pt-Fe 3o 4the X-ray diffractogram of C (c)
Fig. 2 is Fe 3o 4(a, b), Fe 3o 4c (c), Pt-Fe 3o 4the transmission electron microscope photo of C (d)
Fig. 3 is Pt-Fe 3o 4the room temperature magnetization curve of C
Fig. 4 is Pt-Fe 3o 4the magnetism testing photo of C
The specific embodiment
The present invention is further described by the following embodiment, but the present invention is not limited to following example, the present invention is also applicable to take the different-phase catalyst that base metal, oxide etc. are catalytic active substance, and the high-performance that can simultaneously realize catalyst in applications such as electrochemical catalysis, photochemical catalysis, magnetic target medicine, cell separation and even clean environments is with efficient separated and recycle.
Embodiment 1
Take 1.35gFeCl 3.6H 2o and 1.0g polyethylene glycol add in 40ml ethylene glycol, stir it is dissolved completely.Then take 3.6g anhydrous sodium acetate, join in above-mentioned mixed liquor, stir 30min, finally put into reactor, heating rate is 5 ℃/min, keeps 8h after rising to 200 ℃.Water and ethanol washing 3-5 time, 80 ℃ obtain Fe after being dried 3o 4magnetic nanoparticle.
Take 0.2gFe 3o 4put into beaker, add 20ml0.1M HNO 3ultrasonic 10min, is washed with distilled water to neutrality, and the 40ml0.5M glucose solution configuring is joined to the Fe after washing 3o 4in the middle of, after ultrasonic 10min, the solution mixing is poured into 180 ℃ of maintenance 6h in reactor, heating rate is 5 ℃/min.Distilled water supersound washing 3-5 time, 80 ℃ obtain Fe after dry 3o 4c magnetic nano-particle carrier.Through thermogravimetric analyzer analysis, draw Fe 3o 4with the mass ratio of C be 9: 1.
By 0.15gFe 3o 4c and 0.76g dodecyl sodium sulfate add in 30ml ethylene glycol, and ultrasonic 60min after mechanical agitation 30min is then heated to 160 ℃, and heating rate is 5 ℃/min, more slowly adds 10ml H 2ptCl 6-ethylene glycol mixed solution, 160 ℃ of condensing reflux 3h.Be cooled to room temperature, distilled water and absolute ethanol washing, 70 ℃ of vacuum drying 8h, obtain Pt/Fe 3o 4c catalyst, obtains Fe through inductively coupled plasma atomic emission spectrometer analysis 3o 4c and Pt mass ratio are 100: 5.
By 0.10g Pt/Fe 3o 4c catalyst, the cinnamic acid of 2.0mL, the absolute ethyl alcohol of 16.0mL, the deionized water of 2.0mL, adds in the autoclave of 50mL successively, is then heated to 80 ℃ of temperature, and stir speed (S.S.) is about 500rmin -1, be filled with immediately the hydrogen of 2.0Mpa, and keep Hydrogen Vapor Pressure constant, magnetic agitation speed is adjusted to about 1000rmin simultaneously -1, the reaction time is 12h.Hydrogenation products is analyzed in Shimadzu GC-2014 gas-chromatography, and quantitative analysis is calculated with area normalization method, the results are shown in Table 1.
What Fig. 1 showed is the X-ray diffractogram of central three kinds of particles, with a, b, c, represents respectively Fe 3o 4, Fe 3o 4c and Pt-Fe 3o 4c.A and b go out peak position and peak intensity is roughly the same, illustrate that C is unformed C, in the middle of catalyst, only play protection Fe 3o 4with the effect that supports Pt.In c, at 39.8 °, locate to occur a new characteristic peak, be attributed to the characteristic diffraction peak of Pt.What Fig. 2 showed is the transmission electron microscope photo of central three kinds of particles, with a, b, c, d, represents respectively Fe 3o 4, Fe 3o 4c and Pt-Fe 3o 4c.
In figure, can obviously see Fe 3o 4the thickness of the size of nano particle and C layer and the loading condition of Pt.That Fig. 3 shows is central Pt-Fe 3o 4the room temperature magnetization curve of C, curve shows catalyst has good superparamagnetism.That Fig. 4 shows is central Pt-Fe 3o 4the separating effect figure of C under externally-applied magnetic field.
Embodiment 2
Take 1.35gFeCl 3.6H 2o and 1.0g polyethylene glycol add in 40ml ethylene glycol, stir it is dissolved completely.Then take 3.6g anhydrous sodium acetate, join in above-mentioned mixed liquor, stir 30min, finally put into reactor, 200 ℃ keep 8h, and heating rate is 5 ℃/min.Water and ethanol washing 3-5 time, 80 ℃ obtain Fe after being dried 3o 4magnetic nanoparticle.
Take 0.2gFe 3o 4put into beaker, add 20ml0.1M HNO 3ultrasonic 10min, is washed with distilled water to neutrality, and the 40ml0.5M glucose solution configuring is joined to the Fe after washing 3o 4in the middle of, after ultrasonic 10min, the solution mixing is poured into 180 ℃ of maintenance 6h in reactor, heating rate is 5 ℃/min.Distilled water supersound washing 3-5 time, 80 ℃ obtain Fe after dry 3o 4c magnetic nano-particle carrier.Through thermogravimetric analyzer analysis, draw Fe 3o 4with the mass ratio of C be 9: 1.
By 0.15gFe 3o 4c and 0.76g dodecyl sodium sulfate add in 30ml ethylene glycol, and ultrasonic 60min after mechanical agitation 30min is then heated to 160 ℃, and heating rate is 5 ℃/min, more slowly adds 10ml PdCl 2-ethylene glycol mixed solution, 160 ℃ of condensing reflux 3h.Be cooled to room temperature, distilled water and absolute ethanol washing, 70 ℃ of vacuum drying 8h, obtain Pd/Fe 3o 4c catalyst, obtains Fe through inductively coupled plasma atomic emission spectrometer analysis 3o 4c and Pd mass ratio are 100: 5.
By 0.10g Pd/Fe 3o 4c catalyst, the cinnamic acid of 2.0mL, the absolute ethyl alcohol of 16.0mL, the deionized water of 2.0mL, adds in the autoclave of 50mL successively, is then heated to 80 ℃ of temperature, and stir speed (S.S.) is about 500rmin -1, be filled with immediately the hydrogen of 2.0Mpa, and keep Hydrogen Vapor Pressure constant, magnetic agitation speed is adjusted to about 1000rmin simultaneously -1, the reaction time is 2h.Hydrogenation products is analyzed in Shimadzu GC-2014 gas-chromatography, and quantitative analysis is calculated with area normalization method.
Embodiment 3
Take 1.35gFeCl 3.6H 2o and 1.0g polyethylene glycol add in 40ml ethylene glycol, stir it is dissolved completely.Then take 3.6g anhydrous sodium acetate, join in above-mentioned mixed liquor, stir 30min, finally put into reactor, 200 ℃ keep 8h, and heating rate is 5 ℃/min.Water and ethanol washing 3-5 time, 80 ℃ obtain Fe after being dried 3o 4magnetic nanoparticle.
Take 0.2gFe 3o 4put into beaker, add 20ml0.1M HNO 3ultrasonic 10min, is washed with distilled water to neutrality, and the 40ml0.5M glucose solution configuring is joined to the Fe after washing 3o 4in the middle of, after ultrasonic 10min, the solution mixing is poured into 180 ℃ of maintenance 6h in reactor, heating rate is 5 ℃/min.Distilled water supersound washing 3-5 time, 80 ℃ obtain Fe after dry 3o 4c magnetic nano-particle carrier.Through thermogravimetric analyzer analysis, draw Fe 3o 4with the mass ratio of C be 9: 1.
By 0.15gFe 3o 4c and 0.76g dodecyl sodium sulfate add in 30ml ethylene glycol, and ultrasonic 60min after mechanical agitation 30min is then heated to 160 ℃, and heating rate is 5 ℃/min.Slowly add again 10ml RuCl 3-ethylene glycol mixed solution, 160 ℃ of condensing reflux 3h.Be cooled to room temperature, distilled water and absolute ethanol washing, 70 ℃ of vacuum drying 8h, Ru/Fe 3o 4c catalyst, obtains Fe through inductively coupled plasma atomic emission spectrometer analysis 3o 4c and Ru mass ratio are 100: 5.
By 0.10g Ru/Fe 3o 4c catalyst, the cinnamic acid of 2.0mL, the absolute ethyl alcohol of 16.0mL, the deionized water of 2.0mL, adds in the autoclave of 50mL successively, is then heated to 80 ℃ of temperature, and stir speed (S.S.) is about 500rmin -1, be filled with immediately the hydrogen of 2.0Mpa, and keep Hydrogen Vapor Pressure constant, magnetic agitation speed is adjusted to about 1000rmin simultaneously -1, the reaction time is 3h.Hydrogenation products is analyzed in Shimadzu GC-2014 gas-chromatography, and quantitative analysis is calculated with area normalization method.
Enforcement case row 4
Take 1.35gFeCl 3.6H 2o and 0g polyethylene glycol add in 40ml ethylene glycol, stir it is dissolved completely.Then take 1.35g anhydrous sodium acetate, join in above-mentioned mixed liquor, stir 30min, finally put into reactor, heating rate is 5 ℃/min, keeps 4h after rising to 160 ℃.Water and ethanol washing 3-5 time, 80 ℃ obtain Fe after being dried 3o 4magnetic nanoparticle.
Take 0.2gFe 3o 4put into beaker, add 20ml0.1M HNO 3ultrasonic 10min, is washed with distilled water to neutrality, and the 40ml0.5M glucose solution configuring is joined to the Fe after washing 3o 4in the middle of, after ultrasonic 10min, the solution mixing is poured into 240 ℃ of maintenance 8h in reactor, heating rate is 5 ℃/min.Distilled water supersound washing 3-5 time, 80 ℃ obtain Fe after dry 3o 4c magnetic nano-particle carrier.Through thermogravimetric analyzer analysis, draw Fe 3o 4with the mass ratio of C be 5: 5.
By 0.15gFe 3o 4c and 0.15g dodecyl sodium sulfate add in 30ml ethylene glycol, and ultrasonic 60min after mechanical agitation 30min is then heated to 140 ℃, and heating rate is 5 ℃/min, more slowly adds 10ml H 2ptCl 6-ethylene glycol mixed solution, 140 ℃ of condensing reflux 1h.Be cooled to room temperature, distilled water and absolute ethanol washing, 70 ℃ of vacuum drying 8h, obtain Pt/Fe 3o 4c catalyst, obtains Fe through inductively coupled plasma atomic emission spectrometer analysis 3o 4c and Pt mass ratio are 100: 1.
By 0.10g Pt/Fe 3o 4c catalyst, the cinnamic acid of 2.0mL, the absolute ethyl alcohol of 16.0mL, the deionized water of 2.0mL, adds in the autoclave of 50mL successively, is then heated to 80 ℃ of temperature, and stir speed (S.S.) is about 500rmin -1, be filled with immediately the hydrogen of 2.0Mpa, and keep Hydrogen Vapor Pressure constant, magnetic agitation speed is adjusted to about 1000rmin simultaneously -1, the reaction time is 12h.Hydrogenation products is analyzed in Shimadzu GC-2014 gas-chromatography, and quantitative analysis is calculated with area normalization method.
Enforcement case row 5
Take 1.35gFeCl 3.6H 2o and 6.75g polyethylene glycol add in 40ml ethylene glycol, stir it is dissolved completely.Then take 13.5g anhydrous sodium acetate, join in above-mentioned mixed liquor, stir 30min, finally put into reactor, heating rate is 0.5 ℃/min, keeps 8h after rising to 240 ℃.Water and ethanol washing 3-5 time, 80 ℃ obtain Fe after being dried 3o 4magnetic nanoparticle.
Take 0.2gFe 3o 4put into beaker, add 20ml0.1M HNO 3ultrasonic 10min, is washed with distilled water to neutrality, and the 40ml0.5M glucose solution configuring is joined to the Fe after washing 3o 4in the middle of, after ultrasonic 10min, the solution mixing is poured into 160 ℃ of maintenance 4h in reactor, heating rate is 0.5 ℃/min.Distilled water supersound washing 3-5 time, 80 ℃ obtain Fe after dry 3o 4c magnetic nano-particle carrier.Through thermogravimetric analyzer analysis, draw Fe 3o 4with the mass ratio of C be 9: 1.
By 0.15gFe 3o 4c and 1.5g dodecyl sodium sulfate add in 30ml ethylene glycol, and ultrasonic 60min after mechanical agitation 30min is then heated to 180 ℃, and heating rate is 0.5 ℃/min, more slowly adds 10ml H 2ptCl 6-ethylene glycol mixed solution, 180 ℃ of condensing reflux 5h.Be cooled to room temperature, distilled water and absolute ethanol washing, 70 ℃ of vacuum drying 8h, obtain Pt/Fe 3o 4c catalyst, obtains Fe through inductively coupled plasma atomic emission spectrometer analysis 3o 4c and Pt mass ratio are 100: 5.
By 0.10g Pt/Fe 3o 4c catalyst, the cinnamic acid of 2.0mL, the absolute ethyl alcohol of 16.0mL, the deionized water of 2.0mL, adds in the autoclave of 50mL successively, is then heated to 80 ℃ of temperature, and stir speed (S.S.) is about 500rmin -1, be filled with immediately the hydrogen of 2.0Mpa, and keep Hydrogen Vapor Pressure constant, magnetic agitation speed is adjusted to about 1000rmin simultaneously -1, the reaction time is 12h.Hydrogenation products is analyzed in Shimadzu GC-2014 gas-chromatography, and quantitative analysis is calculated with area normalization method.
Enforcement case row 6
Take 1.35gFeCl 3.6H 2o and 6.75g polyethylene glycol add in 40ml ethylene glycol, stir it is dissolved completely.Then take 13.5g anhydrous sodium acetate, join in above-mentioned mixed liquor, stir 30min, finally put into reactor, heating rate is 0.5 ℃/min, keeps 8h after rising to 240 ℃.Water and ethanol washing 3-5 time, 80 ℃ obtain Fe after being dried 3o 4magnetic nanoparticle.
Take 0.2gFe 3o 4put into beaker, add 20ml0.1M HNO 3ultrasonic 10min, is washed with distilled water to neutrality, and the 40ml0.5M glucose solution configuring is joined to the Fe after washing 3o 4in the middle of, after ultrasonic 10min, the solution mixing is poured into 160 ℃ of maintenance 4h in reactor, heating rate is 0.5 ℃/min.Distilled water supersound washing 3-5 time, 80 ℃ obtain Fe after dry 3o 4c magnetic nano-particle carrier.Through thermogravimetric analyzer analysis, draw Fe 3o 4with the mass ratio of C be 9: 1.
By 0.15gFe 3o 4c and 1.5g dodecyl sodium sulfate add in 30ml ethylene glycol, and ultrasonic 60min after mechanical agitation 30min is then heated to 180 ℃, and heating rate is 0.5 ℃/min, more slowly adds 10ml PdCl 2-ethylene glycol mixed solution, 180 ℃ of condensing reflux 5h.Be cooled to room temperature, distilled water and absolute ethanol washing, 70 ℃ of vacuum drying 8h, obtain Pd/Fe 3o 4c catalyst, obtains Fe through inductively coupled plasma atomic emission spectrometer analysis 3o 4c and Pd mass ratio are 100: 5.
By 0.10g Pd/Fe 3o 4c catalyst, the cinnamic acid of 2.0mL, the absolute ethyl alcohol of 16.0mL, the deionized water of 2.0mL, adds in the autoclave of 50mL successively, is then heated to 80 ℃ of temperature, and stir speed (S.S.) is about 500rmin -1, be filled with immediately the hydrogen of 2.0Mpa, and keep Hydrogen Vapor Pressure constant, magnetic agitation speed is adjusted to about 1000rmin simultaneously -1, the reaction time is 2h.Hydrogenation products is analyzed in Shimadzu GC-2014 gas-chromatography, and quantitative analysis is calculated with area normalization method.
Enforcement case row 7
Take 1.35gFeCl 3.6H 2o and 0g polyethylene glycol add in 40ml ethylene glycol, stir it is dissolved completely.Then take 1.35g anhydrous sodium acetate, join in above-mentioned mixed liquor, stir 30min, finally put into reactor, heating rate is 5 ℃/min, keeps 4h after rising to 160 ℃.Water and ethanol washing 3-5 time, 80 ℃ obtain Fe after being dried 3o 4magnetic nanoparticle.
Take 0.2gFe 3o 4put into beaker, add 20ml0.1M HNO 3ultrasonic 10min, is washed with distilled water to neutrality, and the 40ml0.5M glucose solution configuring is joined to the Fe after washing 3o 4in the middle of, after ultrasonic 10min, the solution mixing is poured into 240 ℃ of maintenance 8h in reactor, heating rate is 5 ℃/min.Distilled water supersound washing 3-5 time, 80 ℃ obtain Fe after dry 3o 4c magnetic nano-particle carrier.Through thermogravimetric analyzer analysis, draw Fe 3o 4with the mass ratio of C be 5: 5.
By 0.15gFe 3o 4c and 0.15g dodecyl sodium sulfate add in 30ml ethylene glycol, and ultrasonic 60min after mechanical agitation 30min is then heated to 160 ℃, and heating rate is 5 ℃/min, more slowly adds 10ml PdCl 2-ethylene glycol mixed solution, 140 ℃ of condensing reflux 1h.Be cooled to room temperature, distilled water and absolute ethanol washing, 70 ℃ of vacuum drying 8h, obtain Pd/Fe 3o 4c catalyst, obtains Fe through inductively coupled plasma atomic emission spectrometer analysis 3o 4c and Pd mass ratio are 100: 1.
By 0.10g Pd/Fe 3o 4c catalyst, the cinnamic acid of 2.0mL, the absolute ethyl alcohol of 16.0mL, the deionized water of 2.0mL, adds in the autoclave of 50mL successively, is then heated to 80 ℃ of temperature, and stir speed (S.S.) is about 500rmin -1, be filled with immediately the hydrogen of 2.0Mpa, and keep Hydrogen Vapor Pressure constant, magnetic agitation speed is adjusted to about 1000rmin simultaneously -1, the reaction time is 2h.Hydrogenation products is analyzed in Shimadzu GC-2014 gas-chromatography, and quantitative analysis is calculated with area normalization method.
Enforcement case row 8
Take 1.35gFeCl 3.6H 2o and 6.75g polyethylene glycol add in 40ml ethylene glycol, stir it is dissolved completely.Then take 13.5g anhydrous sodium acetate, join in above-mentioned mixed liquor, stir 30min, finally put into reactor, heating rate is 0.5 ℃/min, keeps 8h after rising to 240 ℃.Water and ethanol washing 3-5 time, 80 ℃ obtain Fe after being dried 3o 4magnetic nanoparticle.
Take 0.2gFe 3o 4put into beaker, add 20ml0.1M HNO 3ultrasonic 10min, is washed with distilled water to neutrality, and the 40ml0.5M glucose solution configuring is joined to the Fe after washing 3o 4in the middle of, after ultrasonic 10min, the solution mixing is poured into 160 ℃ of maintenance 4h in reactor, heating rate is 0.5 ℃/min.Distilled water supersound washing 3-5 time, 80 ℃ obtain Fe after dry 3o 4c magnetic nano-particle carrier.Through thermogravimetric analyzer analysis, draw Fe 3o 4with the mass ratio of C be 9: 1.
By 0.15gFe 3o 4c and 1.5g dodecyl sodium sulfate add in 30ml ethylene glycol, and ultrasonic 60min after mechanical agitation 30min is then heated to 180 ℃, and heating rate is 0.5 ℃/min, more slowly adds 10ml RuCl 3-ethylene glycol mixed solution, 180 ℃ of condensing reflux 5h.Be cooled to room temperature, distilled water and absolute ethanol washing, 70 ℃ of vacuum drying 8h, obtain Ru/Fe 3o 4c catalyst, obtains Fe through inductively coupled plasma atomic emission spectrometer analysis 3o 4c and Ru mass ratio are 100: 5.
By 0.10g Ru/Fe 3o 4c catalyst, the cinnamic acid of 2.0mL, the absolute ethyl alcohol of 16.0mL, the deionized water of 2.0mL, adds in the autoclave of 50mL successively, is then heated to 80 ℃ of temperature, and stir speed (S.S.) is about 500rmin -1, be filled with immediately the hydrogen of 2.0Mpa, and keep Hydrogen Vapor Pressure constant, magnetic agitation speed is adjusted to about 1000rmin simultaneously -1, the reaction time is 3h.Hydrogenation products is analyzed in Shimadzu GC-2014 gas-chromatography, and quantitative analysis is calculated with area normalization method.
Enforcement case row 9
Take 1.35gFeCl 3.6H 2o and 0g polyethylene glycol add in 40ml ethylene glycol, stir it is dissolved completely.Then take 1.35g anhydrous sodium acetate, join in above-mentioned mixed liquor, stir 30min, finally put into reactor, heating rate is 5 ℃/min, keeps 4h after rising to 160 ℃.Water and ethanol washing 3-5 time, 80 ℃ obtain Fe after being dried 3o 4magnetic nanoparticle.
Take 0.2gFe 3o 4put into beaker, add 20ml0.1M HNO 3ultrasonic 10min, is washed with distilled water to neutrality, and the 40ml0.5M glucose solution configuring is joined to the Fe after washing 3o 4in the middle of, after ultrasonic 10min, the solution mixing is poured into 240 ℃ of maintenance 8h in reactor, heating rate is 5 ℃/min.Distilled water supersound washing 3-5 time, 80 ℃ obtain Fe after dry 3o 4c magnetic nano-particle carrier.Through thermogravimetric analyzer analysis, draw Fe 3o 4with the mass ratio of C be 5: 5.
By 0.15gFe 3o 4c and 0.15g dodecyl sodium sulfate add in 30ml ethylene glycol, and ultrasonic 60min after mechanical agitation 30min is then heated to 160 ℃, and heating rate is 5 ℃/min, more slowly adds 10ml RuCl 3-ethylene glycol mixed solution, 140 ℃ of condensing reflux 1h.Be cooled to room temperature, distilled water and absolute ethanol washing, 70 ℃ of vacuum drying 8h, obtain Ru/Fe 3o 4c catalyst, obtains Fe through inductively coupled plasma atomic emission spectrometer analysis 3o 4c and Ru mass ratio are 100: 1.
By 0.10g Ru/Fe 3o 4c catalyst, the cinnamic acid of 2.0mL, the absolute ethyl alcohol of 16.0mL, the deionized water of 2.0mL, adds in the autoclave of 50mL successively, is then heated to 80 ℃ of temperature, and stir speed (S.S.) is about 500rmin -1, be filled with immediately the hydrogen of 2.0Mpa, and keep Hydrogen Vapor Pressure constant, magnetic agitation speed is adjusted to about 1000rmin simultaneously -1, the reaction time is 3h.Hydrogenation products is analyzed in Shimadzu GC-2014 gas-chromatography, and quantitative analysis is calculated with area normalization method.
Table 1Pt/Fe 3o 4the result of C in hydrogenation on cinnamic aldehyde reaction
Figure BDA0000407875060000091

Claims (2)

1. one kind for α, the preparation method of the catalyst of beta-unsaturated aldehyde selective hydrogenation, this catalyst is comprised of carrier and the active constituent noble metal nano particles of the carbon coated ferroferric oxide of nucleocapsid structure, the mass ratio of magnetic component tri-iron tetroxide and helper component carbon is 9: 1～5: 5, and carrier and active component mass ratio are 9: 1～100: 1; Described noble metal nano particles is selected from a kind of in Pt, Pd, Ru, it is characterized in that: comprise the following steps:
(1) Fe 3o 4the preparation of magnetic nanoparticle:
In ethylene glycol, add successively FeCl 36H 2o, polyethylene glycol, anhydrous sodium acetate, stir, and is then placed in reactor and at 160～240 ℃, keeps one section of 4～8h, and heating rate is 0.5～5 ℃/min, is cooled to room temperature, washs rear 80 ℃ of dry Fe that obtain 3o 4nano particle, FeCl 36H 2o: polyethylene glycol mass ratio is 1: 0～1: 5, FeCl 36H 2o: anhydrous sodium acetate mass ratio is 1: 1～1: 10;
(2) nucleocapsid structure Fe 3o 4the preparation of C: the Fe that step (1) is obtained 3o 4nanoparticulate dispersed is to ultrasonic in rare nitric acid, wash to being distributed to after neutrality in the middle of the glucose solution of 0.5M, be then placed in reactor and at 160～240 ℃, keep one section of 4～8h, heating rate is 0.5～5 ℃/min, be cooled to room temperature, wash rear 80 ℃ of dry Fe that obtain 3o 4c nanoparticulate carriers;
(3) noble metal nano particles loads to Fe 3o 4c surface: the Fe that step (2) is obtained 3o 4c nanoparticulate dispersed is to ethylene glycol, then add dodecyl sodium sulfate, mechanical agitation, rises to 140～180 ℃ after ultrasonic, then add noble metal precursor body-ethylene glycol mixed solution, condensing reflux: reflux temperature is 140～180 ℃, return time 1～5h, heating rate is 0.5～5 ℃/min, after wash after being cooled to room temperature, 70 ℃ of vacuum drying 8h, obtain catalyst, Fe 3o 4c: dodecyl sodium sulfate mass ratio is 1: 1～1: 10.
2. method according to claim 1, is characterized in that: described noble metal precursor body is a kind of in palladium bichloride, ruthenic chloride, chloroplatinic acid.
CN201310537743.8A 2013-11-04 2013-11-04 Preparation method of catalyst for selectively hydrogenating alpha, beta-unsaturated aldehyde Pending CN103566950A (en)

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