CN103230804A - Catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method of catalyst - Google Patents
Catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method of catalyst Download PDFInfo
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Abstract
The invention relates to a catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde and a preparation method of the catalyst. The catalyst consists of an active component, a magnetic substance and a vector, wherein the active component is Pt, the magnetic component is Fe3O4 particles, and the vector is MCNT; the load capacity of the active component Pt is 1-10wt.%, and the load capacity of the magnetic component Fe3O4 is 1-10wt.%. The preparation method comprises the following steps: first preparing Fe3O4 magnetic nano particles, then loading the Fe3O4 magnetic nano particles to the MCNT surface to obtain an Fe3O4-MCNT magnetic composite material; and then preparing Pt nano particles, and then loading the Pt nano particles to the surface of the Fe3O4-MCNT magnetic composite material to obtain a magnetic catalyst, and finally activating the magnetic catalyst. The catalyst has relatively high activity and selectivity in alpha, beta-unsaturated aldehyde hydrogenation reaction, and is high in separation efficiency, and the reutilization rate of the catalyst is high.
Description
Technical field
The present invention relates to a kind of chemical catalyst and preparation method thereof, particularly a kind of for α, the Catalysts and its preparation method of beta-unsaturated aldehyde selective hydrogenation.
Background technology
α, beta-unsaturated aldehyde selective hydrogenation are the important reactions of a class in the industrial circle, α, and C=O hydrogenation products unsaturated alcohol is important source material and the intermediate of medicine, spices, agricultural chemicals etc. in the beta-unsaturated aldehyde.Exploitation high activity and high-selectivity catalyst are α, the key of beta-unsaturated aldehyde selective hydrogenation.The research report, metal Pt catalyst is at α, have good C=O key hydrogenation selectivity in the beta-unsaturated aldehyde selective hydrogenation, the Pt particle size has material impact to catalytic performance, and size homogeneous, the metallic that is of moderate size are the keys that obtains high selectivity.
In addition, for the recycling that separates of solid catalyst and liquid-phase reaction system, mainly based on filtration cycle, but not only process is loaded down with trivial details time-consuming for this conventional method, and very easily causes the loss of catalyst and active component at present.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.This technology is mainly used in aspects such as mineral separation and material purification at present.Catalyst with magnetic under the effect of certain external magnetic field, can reach high efficiente callback and the recycling of catalyst.
Patent of invention (CN102151575A) discloses a kind of carbon nanotube loaded type Preparation of catalysts method, and its preparation is that load active component makes magnetic catalyst again by CNT deposition or assembling magnetic nanoparticle.This catalyst can efficiently separate with liquid-phase reaction system under externally-applied magnetic field, and has shown the good performance that recycles.Pd/Fe
3O
4-MCNT magnetic catalyst is very poor to cinnamic acid C=O hydrogenation selectivity, and cinnamyl alcohol selectively is 0.
Face following major issue in the preparation process for magnetic catalyst: 1) adopt the Pt of traditional deposition reducing process preparation catalyst based, tend to cause Pt particle size inequality, thereby reduce the C=O hydrogenation selectivity.2) adopt magnetisable material presoma and the direct mixed deposit reduction of CNT, the big or small heterogeneity of magnetic nanoparticle on the magnetic catalyst that makes, and particle grain size is bigger, cause magnetic-particle easily to come off, influence the separating property of magnetic catalyst, simultaneously catalytic performance is also had bigger influence.
Summary of the invention
Problems such as the magnetic-particle that the present invention is directed to existing magnetic catalyst existence easily comes off, the hydrogenation performance is not good, provide that a kind of magnetic-particle particle diameter is less, Pt even particle size, catalytic performance are good, easy recovery be used for α, the Catalysts and its preparation method of beta-unsaturated aldehyde selective hydrogenation.
For solving this technical problem, the technical solution used in the present invention is as follows:
A kind of for α, the catalyst of beta-unsaturated aldehyde selective hydrogenation, this catalyst are magnetic composite, are made up of active component, magnetisable material and carrier, it is characterized in that: described active component is Pt, and magnetic component is Fe
3O
4Particle, carrier are multi-walled carbon nano-tubes (MCNT), and wherein the load capacity of active component Pt is 1-10wt.%, magnetic component Fe
3O
4Load capacity is 1-10wt.%.
Above-mentioned Preparation of catalysts method is characterized in that comprising the steps:
(1) Fe
3O
4The preparation of magnetic nanoparticle: this preparation method is with reference to people such as Sun (J. Am. Chem. Soc.; 2004; 126 (1); pp 273 – 279) report, the ferric acetyl acetonade, 1 that in diphenyl ether, adds successively, 2-hexadecane glycol, oleyl amine and oleic acid; under nitrogen protection, add hot reflux then; be cooled to room temperature, add ethanol, obtain Fe
3O
4Nanoparticle precipitate.
(2) Fe
3O
4Magnetic nanoparticle loads to the MCNT surface: the Fe that step 1 is obtained
3O
4Nano particle with the ethanol washing, is distributed in the n-hexane repeatedly, adds a certain amount of MCNT by proportioning, and stirring is spent the night, and suction filtration is dried down for 100 ℃ and spent the night, and obtains Fe
3O
4-MCNT magnetic composite.
(3) preparation of Pt nano particle: this preparation method with reference to people such as Zhong (chem.Mater.2005,17, report 3086-3091) in toluene solution, adds four n-octyl bromination ammoniums, chloroplatinic acid, stirs to become colorless up to water.Add oleyl amine then, stir, add fresh sodium borohydride solution, stir.Add ethanol in the product that obtains, centrifugal, use ethanol respectively, the distilled water washing obtains the Pt nano particle.
(4) the Pt nano particle is loaded to the Fe that step 2 obtains
3O
4-MCNT magnetic composite surface: the metal nanoparticle that step 3 is obtained is distributed in the toluene, adds a certain amount of Fe by proportioning
3O
4-MCNT, ultrasonic, stir the back suction filtration that spends the night, dry down for 80 ℃ and spend the night, get magnetic catalyst.
(5) magnetic catalyst activates: under nitrogen atmosphere, the flow velocity of nitrogen is 30ml/min, and temperature is 400 ℃, processing time 2h, 0.5 ℃/min of heating rate.
This catalyst is applied to α, in the selective hydrogenation of beta-unsaturated aldehyde.Concrete steps are as follows: with 0.10 g Pt-Fe3O4-MCNT catalyst, 2.0 the α of mL, beta-unsaturated aldehyde, 16.0 the absolute ethyl alcohol of mL, 2.0 the deionized water of mL, add successively in the autoclave of 50 mL, at first use hydrogen purge 8 times (0.6 MPa/ time), heat temperature raising to 80 ℃ temperature then, stir speed (S.S.) is about 300 rmin-1, charges into the hydrogen of 1.4Mpa immediately, and keeps Hydrogen Vapor Pressure constant, simultaneously magnetic agitation speed is transferred to about 1000 rmin-1, the reaction time is 3h.The conversion ratio of cinnamic acid can reach 90%, selectively the reaching more than 96% of cinnamyl alcohol.The conversion ratio of 3-methyl-2-butene aldehyde can reach 80%, to 3-methyl-2-butene alcohol selectively up to more than 98%.
The catalyst of the present invention's preparation, the less and big or small homogeneous of magnetic component Fe3O4 particle, difficult drop-off, Pt nano particle diameter narrowly distributing, big or small homogeneous is between 2-3nm.This catalyst is at α simultaneously, and the beta-unsaturated aldehyde hydrogenation reaction has higher activity and selective, separative efficiency height, and the recycling rate of waterused height of catalyst.After reusing four times, to selectively reaching more than 96% of cinnamyl alcohol, and to 3-methyl-2-butene alcohol selectively up to more than 98%.
Description of drawings
Fig. 1 is MCNT(a), Pt-3-MCNTb(b), Fe
3O
4-5-MCNT(c), Pt-3-Fe
3O
4-5-MCNT(d) XRD figure
Fig. 2 is Pt-3-Fe
3O
4The TEM figure of-5-MCNT
The specific embodiment
Further illustrate the present invention below in conjunction with specific embodiment, but the present invention is not limited to embodiment.
Embodiment 1
The diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 that in the quartzy there-necked flask of 50ml, add 20 ml successively, the oleyl amine of 2-hexadecane glycol, 2mmol and the oleic acid of 2mmol, ultrasonic 30 min mix in ultrasonic pond.Feed nitrogen then as protection gas, the flow velocity of protection gas is 30ml/min, and mechanical agitation speed is controlled at 800r/min; adopt electric jacket to rise to 300 ℃ with the heating rate of 1 ℃/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3O
4The pitchy nanoparticle precipitate.Ethanol washing 5 times, the n-hexane (adding a spot of oleic acid and oleyl amine) that adds 20 ml at last disperses.The MCNT that adds 3.2g at last respectively, ultrasonic 1 h, the room temperature magnetic agitation is spent the night, suction filtration, 100 ℃ of dryings.Fe in this catalyst
3O
4Load capacity be 5 wt %.
In the round-bottomed flask of the toluene solution that 20 ml are housed, add 0.1 g, four n-octyl bromination ammoniums, 3.98ml concentration is the platinum acid chloride solution of 0.01g/ml, stir 2 h, at this moment the organic phase of solution has the colourless yellowish-brown that becomes, and water does not have color substantially, illustrates that the chloroplatinic acid anion all transfers in the organic phase.Syringe pipettes the 0.05ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stir 1 h solution and become milky adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stir 2 h at last then.Add 100 ml ethanol in the product that obtains, centrifugal 10 min of 3500 r/min, the precipitation that obtains is used ethanol more respectively, distilled water washing 3 times.Pt nanoparticle is distributed to the toluene of 30 ml again, adds the Fe of 0.5g
3O
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration is dried down for 80 ℃ and is spent the night.Catalyst Pt-Fe
3O
4-MCNT places under the nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 ℃, processing time 2h, 0.5 ℃/min of heating rate.The load capacity of active component platinum is 3 wt.%.
With 0.10 g Pt-Fe3O4-MCNT catalyst, 2.0 the cinnamic acid of mL/3-methyl-2-butene aldehyde, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, at first use hydrogen purge 8 times (0.6 MPa/ time), heat temperature raising to 80 ℃ temperature then, stir speed (S.S.) is about 300 rmin-1, charge into the hydrogen of 1.4Mpa immediately, and keep Hydrogen Vapor Pressure constant, and simultaneously magnetic agitation speed being transferred to about 1000 rmin-1, the reaction time is 3h.Reaction result sees Table one.
Embodiment 2
The diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 that in the quartzy there-necked flask of 50ml, add 20 ml successively, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, ultrasonic 30 min mix in ultrasonic pond.Feed nitrogen then as protection gas, the flow velocity of protection gas is 30ml/min, and mechanical agitation speed is controlled at 800r/min; adopt electric jacket to rise to 300 ℃ with the heating rate of 1 ℃/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3O
4The pitchy nanoparticle precipitate.Ethanol washing 5 times, the n-hexane (adding a spot of oleic acid and oleyl amine) that adds 20 ml at last disperses.The MCNT that adds 3.2g at last respectively, ultrasonic 1 h, the room temperature magnetic agitation is spent the night, suction filtration, 100 ℃ of dryings.Fe in this catalyst
3O
4Load capacity be 5 wt %.
In the round-bottomed flask of the toluene solution that 20 ml are housed, add 0.1 g, four n-octyl bromination ammoniums, 3.98ml concentration is the platinum acid chloride solution of 0.01g/ml, stir 2 h, at this moment the organic phase of solution has the colourless yellowish-brown that becomes, and water does not have color substantially, illustrates that the chloroplatinic acid anion all transfers in the organic phase.Syringe pipettes the 0.05ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stir 1 h solution and become milky adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stir 2 h at last then.Add 100 ml ethanol in the product that obtains, centrifugal 10 min of 3500 r/min, the precipitation that obtains is used ethanol more respectively, distilled water washing 3 times.Pt nanoparticle is distributed to the toluene of 30 ml again, adds the Fe of 0.5g
3O
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration is dried down for 80 ℃ and is spent the night.Catalyst Pt-Fe
3O
4-MCNT places under the nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 ℃, processing time 2h, 0.5 ℃/min of heating rate.The load capacity of active component platinum is 3 wt.%.
The gained catalyst is carried out XRD(Fig. 1), TEM(Fig. 2) characterize, the result shows that the magnetic ferroferric oxide nanometer particle can load on the multi-walled carbon nano-tubes uniformly, the size of particle is at 2-3nm, pattern be sphere or oval.And Pt nanoparticle also can load on the magnetic carbon nano-tube equably, and the particle diameter of Pt nanoparticle is the 3-4 nanometer, and it is spherical that narrow diameter distribution, pattern mostly are.The high-resolution photo shows that spacing of lattice is that 0.26 nm belongs to Fe in the magnetic composite
3O
4(311) face, and (111) face of spacing of lattice to be 0.23 nm belong to Pt crystal confirms magnetic Fe
3O
4Successfully load to the MCNT outer surface with Pt.
With 0.10 g Pt-Fe3O4-MCNT catalyst, 2.0 the cinnamic acid of mL/3-methyl-2-butene aldehyde, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, at first use hydrogen purge 8 times (0.6 MPa/ time), heat temperature raising to 80 ℃ temperature then, stir speed (S.S.) is about 300 rmin-1, charge into the hydrogen of 1.4Mpa immediately, and keep Hydrogen Vapor Pressure constant, and simultaneously magnetic agitation speed being transferred to about 1000 rmin-1, the reaction time is 3h.Reaction result sees Table one.
Embodiment 3
The diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 that in the quartzy there-necked flask of 50ml, add 20 ml successively, the oleyl amine of 2-hexadecane glycol, 10 mmol and the oleic acid of 10mmol, ultrasonic 30 min mix in ultrasonic pond.Feed nitrogen then as protection gas, the flow velocity of protection gas is 30ml/min, and mechanical agitation speed is controlled at 800r/min; adopt electric jacket to rise to 300 ℃ with the heating rate of 1 ℃/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3O
4The pitchy nanoparticle precipitate.Ethanol washing 5 times, the n-hexane (adding a spot of oleic acid and oleyl amine) that adds 20 ml at last disperses.The MCNT that adds 3.2g at last respectively, ultrasonic 1 h, the room temperature magnetic agitation is spent the night, suction filtration, 100 ℃ of dryings.Fe in this catalyst
3O
4Load capacity be 5 wt %.
In the round-bottomed flask of the toluene solution that 20 ml are housed, add 0.1 g, four n-octyl bromination ammoniums, 3.98ml concentration is the platinum acid chloride solution of 0.01g/ml, stir 2 h, at this moment the organic phase of solution has the colourless yellowish-brown that becomes, and water does not have color substantially, illustrates that the chloroplatinic acid anion all transfers in the organic phase.Syringe pipettes the 0.05ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stir 1 h solution and become milky adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stir 2 h at last then.Add 100 ml ethanol in the product that obtains, centrifugal 10 min of 3500 r/min, the precipitation that obtains is used ethanol more respectively, distilled water washing 3 times.Pt nanoparticle is distributed to the toluene of 30 ml again, adds the Fe of 0.5g
3O
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration is dried down for 80 ℃ and is spent the night.Catalyst Pt-Fe
3O
4-MCNT places under the nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 ℃, processing time 2h, 0.5 ℃/min of heating rate.The load capacity of active component platinum is 3 wt.%.
With 0.10 g Pt-Fe3O4-MCNT catalyst, 2.0 the cinnamic acid of mL/3-methyl-2-butene aldehyde, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, at first use hydrogen purge 8 times (0.6 MPa/ time), heat temperature raising to 80 ℃ temperature then, stir speed (S.S.) is about 300 rmin-1, charge into the hydrogen of 1.4Mpa immediately, and keep Hydrogen Vapor Pressure constant, and simultaneously magnetic agitation speed being transferred to about 1000 rmin-1, the reaction time is 3h.Reaction result sees Table one.
Embodiment 4
The diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 that in the quartzy there-necked flask of 50ml, add 20 ml successively, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, ultrasonic 30 min mix in ultrasonic pond.Feed nitrogen then as protection gas, the flow velocity of protection gas is 30ml/min, and mechanical agitation speed is controlled at 800r/min; adopt electric jacket to rise to 300 ℃ with the heating rate of 1 ℃/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3O
4The pitchy nanoparticle precipitate.Ethanol washing 5 times, the n-hexane (adding a spot of oleic acid and oleyl amine) that adds 20 ml at last disperses.The MCNT that adds 15.5 g at last respectively, ultrasonic 1 h, the room temperature magnetic agitation is spent the night, suction filtration, 100 ℃ of dryings.Fe in this catalyst
3O
4Load capacity be 1 wt %.
In the round-bottomed flask of the toluene solution that 20 ml are housed, add 0.1 g, four n-octyl bromination ammoniums, 3.98ml concentration is the platinum acid chloride solution of 0.01g/ml, stir 2 h, at this moment the organic phase of solution has the colourless yellowish-brown that becomes, and water does not have color substantially, illustrates that the chloroplatinic acid anion all transfers in the organic phase.Syringe pipettes the 0.05ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stir 1 h solution and become milky adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stir 2 h at last then.Add 100 ml ethanol in the product that obtains, centrifugal 10 min of 3500 r/min, the precipitation that obtains is used ethanol more respectively, distilled water washing 3 times.Pt nanoparticle is distributed to the toluene of 30 ml again, adds the Fe of 0.5g
3O
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration is dried down for 80 ℃ and is spent the night.Catalyst Pt-Fe
3O
4-MCNT places under the nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 ℃, processing time 2h, 0.5 ℃/min of heating rate.The load capacity of active component platinum is 3 wt.%.
With 0.10 g Pt-Fe3O4-MCNT catalyst, 2.0 the cinnamic acid of mL/3-methyl-2-butene aldehyde, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, at first use hydrogen purge 8 times (0.6 MPa/ time), heat temperature raising to 80 ℃ temperature then, stir speed (S.S.) is about 300 rmin-1, charge into the hydrogen of 1.4Mpa immediately, and keep Hydrogen Vapor Pressure constant, and simultaneously magnetic agitation speed being transferred to about 1000 rmin-1, the reaction time is 3h.Reaction result sees Table one.
Embodiment 5
The diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 that in the quartzy there-necked flask of 50ml, add 20 ml successively, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, ultrasonic 30 min mix in ultrasonic pond.Feed nitrogen then as protection gas, the flow velocity of protection gas is 30ml/min, and mechanical agitation speed is controlled at 800r/min; adopt electric jacket to rise to 300 ℃ with the heating rate of 1 ℃/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3O
4The pitchy nanoparticle precipitate.Ethanol washing 5 times, the n-hexane (adding a spot of oleic acid and oleyl amine) that adds 20 ml at last disperses.The MCNT that adds 1.8g at last respectively, ultrasonic 1 h, the room temperature magnetic agitation is spent the night, suction filtration, 100 ℃ of dryings.Fe in this catalyst
3O
4Load capacity be 10wt %.
In the round-bottomed flask of the toluene solution that 20 ml are housed, add 0.1 g, four n-octyl bromination ammoniums, 3.98ml concentration is the platinum acid chloride solution of 0.01g/ml, stir 2 h, at this moment the organic phase of solution has the colourless yellowish-brown that becomes, and water does not have color substantially, illustrates that the chloroplatinic acid anion all transfers in the organic phase.Then syringe pipette the 0.05ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stir 1h solution and become milky, add fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stir 2 h at last.Add 100 ml ethanol in the product that obtains, centrifugal 10 min of 3500 r/min, the precipitation that obtains is used ethanol more respectively, distilled water washing 3 times.Pt nanoparticle is distributed to the toluene of 30 ml again, adds the Fe of 0.5g
3O
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration is dried down for 80 ℃ and is spent the night.Catalyst Pt-Fe
3O
4-MCNT places under the nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 ℃, processing time 2h, 0.5 ℃/min of heating rate.The load capacity of active component platinum is 3 wt.%.
With 0.10 g Pt-Fe3O4-MCNT catalyst, 2.0 the cinnamic acid of mL/3-methyl-2-butene aldehyde, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, at first use hydrogen purge 8 times (0.6 MPa/ time), heat temperature raising to 80 ℃ temperature then, stir speed (S.S.) is about 300 rmin-1, charge into the hydrogen of 1.4Mpa immediately, and keep Hydrogen Vapor Pressure constant, and simultaneously magnetic agitation speed being transferred to about 1000 rmin-1, the reaction time is 3h.Reaction result sees Table one.
Embodiment 6
The diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 that in the quartzy there-necked flask of 50ml, add 20 ml successively, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, ultrasonic 30 min mix in ultrasonic pond.Feed nitrogen then as protection gas, the flow velocity of protection gas is 30ml/min, and mechanical agitation speed is controlled at 800r/min; adopt electric jacket to rise to 300 ℃ with the heating rate of 1 ℃/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3O
4The pitchy nanoparticle precipitate.Ethanol washing 5 times, the n-hexane (adding a spot of oleic acid and oleyl amine) that adds 20 ml at last disperses.The MCNT that adds 3.2 g at last respectively, ultrasonic 1 h, the room temperature magnetic agitation is spent the night, suction filtration, 100 ℃ of dryings.Fe in this catalyst
3O
4Load capacity be 5 wt %.
In the round-bottomed flask of the toluene solution that 20 ml are housed, add 0.1 g, four n-octyl bromination ammoniums, 3.98ml concentration is the platinum acid chloride solution of 0.01g/ml, stir 2 h, at this moment the organic phase of solution has the colourless yellowish-brown that becomes, and water does not have color substantially, illustrates that the chloroplatinic acid anion all transfers in the organic phase.Syringe pipettes the 0.03ml oleyl amine (chloroplatinic acid: oleyl amine=1:1), stir 1 h solution and become milky adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stir 2 h at last then.Add 100 ml ethanol in the product that obtains, centrifugal 10 min of 3500 r/min, the precipitation that obtains is used ethanol more respectively, distilled water washing 3 times.Pt nanoparticle is distributed to the toluene of 30 ml again, adds the Fe of 0.5g
3O
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration is dried down for 80 ℃ and is spent the night.Catalyst Pt-Fe
3O
4-MCNT places under the nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 ℃, processing time 2h, 0.5 ℃/min of heating rate.The load capacity of active component platinum is 3 wt.%.
With 0.10 g Pt-Fe3O4-MCNT catalyst, 2.0 the cinnamic acid of mL/3-methyl-2-butene aldehyde, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, at first use hydrogen purge 8 times (0.6 MPa/ time), heat temperature raising to 80 ℃ temperature then, stir speed (S.S.) is about 300 rmin-1, charge into the hydrogen of 1.4Mpa immediately, and keep Hydrogen Vapor Pressure constant, and simultaneously magnetic agitation speed being transferred to about 1000 rmin-1, the reaction time is 3h.Reaction result sees Table one.
Embodiment 7
The diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 that in the quartzy there-necked flask of 50ml, add 20 ml successively, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, ultrasonic 30 min mix in ultrasonic pond.Feed nitrogen then as protection gas, the flow velocity of protection gas is 30ml/min, and mechanical agitation speed is controlled at 800r/min; adopt electric jacket to rise to 300 ℃ with the heating rate of 1 ℃/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3O
4The pitchy nanoparticle precipitate.Ethanol washing 5 times, the n-hexane (adding a spot of oleic acid and oleyl amine) that adds 20 ml at last disperses.The MCNT that adds 3.2 g at last respectively, ultrasonic 1 h, the room temperature magnetic agitation is spent the night, suction filtration, 100 ℃ of dryings.Fe in this catalyst
3O
4Load capacity be 5 wt %.
In the round-bottomed flask of the toluene solution that 20 ml are housed, add 0.1 g, four n-octyl bromination ammoniums, 3.98ml concentration is the platinum acid chloride solution of 0.01g/ml, stir 2 h, at this moment the organic phase of solution has the colourless yellowish-brown that becomes, and water does not have color substantially, illustrates that the chloroplatinic acid anion all transfers in the organic phase.Syringe pipettes the 0.13ml oleyl amine (chloroplatinic acid: oleyl amine=1:5), stir 1 h solution and become milky adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stir 2 h at last then.Add 100 ml ethanol in the product that obtains, centrifugal 10 min of 3500 r/min, the precipitation that obtains is used ethanol more respectively, distilled water washing 3 times.Pt nanoparticle is distributed to the toluene of 30 ml again, adds the Fe of 0.5g
3O
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration is dried down for 80 ℃ and is spent the night.Catalyst Pt-Fe
3O
4-MCNT places under the nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 ℃, processing time 2h, 0.5 ℃/min of heating rate.The load capacity of active component platinum is 3 wt.%.
With 0.10 g Pt-Fe3O4-MCNT catalyst, 2.0 the cinnamic acid of mL/3-methyl-2-butene aldehyde, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, at first use hydrogen purge 8 times (0.6 MPa/ time), heat temperature raising to 80 ℃ temperature then, stir speed (S.S.) is about 300 rmin-1, charge into the hydrogen of 1.4Mpa immediately, and keep Hydrogen Vapor Pressure constant, and simultaneously magnetic agitation speed being transferred to about 1000 rmin-1, the reaction time is 3h.Reaction result sees Table one.
Embodiment 8
The diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 that in the quartzy there-necked flask of 50ml, add 20 ml successively, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, ultrasonic 30 min mix in ultrasonic pond.Feed nitrogen then as protection gas, the flow velocity of protection gas is 30ml/min, and mechanical agitation speed is controlled at 800r/min; adopt electric jacket to rise to 300 ℃ with the heating rate of 1 ℃/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3O
4The pitchy nanoparticle precipitate.Ethanol washing 5 times, the n-hexane (adding a spot of oleic acid and oleyl amine) that adds 20 ml at last disperses.The MCNT that adds 3.2 g at last respectively, ultrasonic 1 h, the room temperature magnetic agitation is spent the night, suction filtration, 100 ℃ of dryings.Fe in this catalyst
3O
4Load capacity be 5 wt %.
In the round-bottomed flask of the toluene solution that 20 ml are housed, add 0.1 g, four n-octyl bromination ammoniums, 3.98ml concentration is the platinum acid chloride solution of 0.01g/ml, stir 2 h, at this moment the organic phase of solution has the colourless yellowish-brown that becomes, and water does not have color substantially, illustrates that the chloroplatinic acid anion all transfers in the organic phase.Then syringe pipette the 0.26ml oleyl amine (chloroplatinic acid: oleyl amine=1:10), stir 1h solution and become milky, add fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stir 2 h at last.Add 100 ml ethanol in the product that obtains, centrifugal 10 min of 3500 r/min, the precipitation that obtains is used ethanol more respectively, distilled water washing 3 times.Pt nanoparticle is distributed to the toluene of 30 ml again, adds the Fe of 0.5g
3O
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration is dried down for 80 ℃ and is spent the night.Catalyst Pt-Fe
3O
4-MCNT places under the nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 ℃, processing time 2h, 0.5 ℃/min of heating rate.The load capacity of active component platinum is 3 wt.%.
With 0.10 g Pt-Fe3O4-MCNT catalyst, 2.0 the cinnamic acid of mL/3-methyl-2-butene aldehyde, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, at first use hydrogen purge 8 times (0.6 MPa/ time), heat temperature raising to 80 ℃ temperature then, stir speed (S.S.) is about 300 rmin-1, charge into the hydrogen of 1.4Mpa immediately, and keep Hydrogen Vapor Pressure constant, and simultaneously magnetic agitation speed being transferred to about 1000 rmin-1, the reaction time is 3h.Reaction result sees Table one.
Embodiment 9
The diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 that in the quartzy there-necked flask of 50ml, add 20 ml successively, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, ultrasonic 30 min mix in ultrasonic pond.Feed nitrogen then as protection gas, the flow velocity of protection gas is 30ml/min, and mechanical agitation speed is controlled at 800r/min; adopt electric jacket to rise to 300 ℃ with the heating rate of 1 ℃/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3O
4The pitchy nanoparticle precipitate.Ethanol washing 5 times, the n-hexane (adding a spot of oleic acid and oleyl amine) that adds 20 ml at last disperses.The MCNT that adds 3.2 g at last respectively, ultrasonic 1 h, the room temperature magnetic agitation is spent the night, suction filtration, 100 ℃ of dryings.Fe in this catalyst
3O
4Load capacity be 5 wt %.
In the round-bottomed flask of the toluene solution that 20 ml are housed, add 0.1 g, four n-octyl bromination ammoniums, 1.33ml concentration is the platinum acid chloride solution of 0.01g/ml, stir 2 h, at this moment the organic phase of solution has the colourless yellowish-brown that becomes, and water does not have color substantially, illustrates that the chloroplatinic acid anion all transfers in the organic phase.Syringe pipettes the 0.02ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stir 1 h solution and become milky adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stir 2 h at last then.Add 100 ml ethanol in the product that obtains, centrifugal 10 min of 3500 r/min, the precipitation that obtains is used ethanol more respectively, distilled water washing 3 times.Pt nanoparticle is distributed to the toluene of 30 ml again, adds the Fe of 0.5g
3O
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration is dried down for 80 ℃ and is spent the night.Catalyst Pt-Fe
3O
4-MCNT places under the nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 ℃, processing time 2h, 0.5 ℃/min of heating rate.The load capacity of active component platinum is 1 wt.%.
With 0.10 g Pt-Fe3O4-MCNT catalyst, 2.0 the cinnamic acid of mL/3-methyl-2-butene aldehyde, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, at first use hydrogen purge 8 times (0.6 MPa/ time), heat temperature raising to 80 ℃ temperature then, stir speed (S.S.) is about 300 rmin-1, charge into the hydrogen of 1.4Mpa immediately, and keep Hydrogen Vapor Pressure constant, and simultaneously magnetic agitation speed being transferred to about 1000 rmin-1, the reaction time is 3h.Reaction result sees Table one.
The diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 that in the quartzy there-necked flask of 50ml, add 20 ml successively, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, ultrasonic 30 min mix in ultrasonic pond.Feed nitrogen then as protection gas, the flow velocity of protection gas is 30ml/min, and mechanical agitation speed is controlled at 800r/min; adopt electric jacket to rise to 300 ℃ with the heating rate of 1 ℃/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3O
4The pitchy nanoparticle precipitate.Ethanol washing 5 times, the n-hexane (adding a spot of oleic acid and oleyl amine) that adds 20 ml at last disperses.The MCNT that adds 3.2 g at last respectively, ultrasonic 1 h, the room temperature magnetic agitation is spent the night, suction filtration, 100 ℃ of dryings.Fe in this catalyst
3O
4Load capacity be 5 wt %.
In the round-bottomed flask of the toluene solution that 20 ml are housed, add 0.1 g, four n-octyl bromination ammoniums, 6.64ml concentration is the platinum acid chloride solution of 0.01g/ml, stir 2 h, at this moment the organic phase of solution has the colourless yellowish-brown that becomes, and water does not have color substantially, illustrates that the chloroplatinic acid anion all transfers in the organic phase.Syringe pipettes the 0.08ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stir 1 h solution and become milky adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stir 2 h at last then.Add 100 ml ethanol in the product that obtains, centrifugal 10 min of 3500 r/min, the precipitation that obtains is used ethanol more respectively, distilled water washing 3 times.Pt nanoparticle is distributed to the toluene of 30 ml again, adds the Fe of 0.5g
3O
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration is dried down for 80 ℃ and is spent the night.Catalyst Pt-Fe
3O
4-MCNT places under the nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 ℃, processing time 2h, 0.5 ℃/min of heating rate.The load capacity of active component platinum is 5 wt.%.
With 0.10 g Pt-Fe3O4-MCNT catalyst, 2.0 the cinnamic acid of mL/3-methyl-2-butene aldehyde, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, at first use hydrogen purge 8 times (0.6 MPa/ time), heat temperature raising to 80 ℃ temperature then, stir speed (S.S.) is about 300 rmin-1, charge into the hydrogen of 1.4Mpa immediately, and keep Hydrogen Vapor Pressure constant, and simultaneously magnetic agitation speed being transferred to about 1000 rmin-1, the reaction time is 2h.Reaction result sees Table one.
Embodiment 11
The diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 that in the quartzy there-necked flask of 50ml, add 20 ml successively, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, ultrasonic 30 min mix in ultrasonic pond.Feed nitrogen then as protection gas, the flow velocity of protection gas is 30ml/min, and mechanical agitation speed is controlled at 800r/min; adopt electric jacket to rise to 300 ℃ with the heating rate of 1 ℃/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3O
4The pitchy nanoparticle precipitate.Ethanol washing 5 times, the n-hexane (adding a spot of oleic acid and oleyl amine) that adds 20 ml at last disperses.The MCNT that adds 3.2 g at last respectively, ultrasonic 1 h, the room temperature magnetic agitation is spent the night, suction filtration, 100 ℃ of dryings.Fe in this catalyst
3O
4Load capacity be 5 wt %.
In the round-bottomed flask of the toluene solution that 20 ml are housed, add 0.1 g, four n-octyl bromination ammoniums, 6.64ml concentration is the platinum acid chloride solution of 0.01g/ml, stir 2 h, at this moment the organic phase of solution has the colourless yellowish-brown that becomes, and water does not have color substantially, illustrates that the chloroplatinic acid anion all transfers in the organic phase.Syringe pipettes the 0.17ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stir 1 h solution and become milky adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stir 2 h at last then.Add 100 ml ethanol in the product that obtains, centrifugal 10 min of 3500 r/min, the precipitation that obtains is used ethanol more respectively, distilled water washing 3 times.Pt nanoparticle is distributed to the toluene of 30 ml again, adds the Fe of 0.5g
3O
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration is dried down for 80 ℃ and is spent the night.Catalyst Pt-Fe
3O
4-MCNT places under the nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 ℃, processing time 2h, 0.5 ℃/min of heating rate.The load capacity of active component platinum is 10 wt.%.
With 0.10 g Pt-Fe3O4-MCNT catalyst, 2.0 the cinnamic acid of mL/3-methyl-2-butene aldehyde, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, at first use hydrogen purge 8 times (0.6 MPa/ time), heat temperature raising to 80 ℃ temperature then, stir speed (S.S.) is about 300 rmin-1, charge into the hydrogen of 1.4Mpa immediately, and keep Hydrogen Vapor Pressure constant, and simultaneously magnetic agitation speed being transferred to about 1000 rmin-1, the reaction time is 1h.Reaction result sees Table one.
Embodiment 12
The diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 that in the quartzy there-necked flask of 50ml, add 20 ml successively, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, ultrasonic 30 min mix in ultrasonic pond.Feed nitrogen then as protection gas, the flow velocity of protection gas is 30ml/min, and mechanical agitation speed is controlled at 800r/min; adopt electric jacket to rise to 300 ℃ with the heating rate of 1 ℃/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3O
4The pitchy nanoparticle precipitate.Ethanol washing 5 times, the n-hexane (adding a spot of oleic acid and oleyl amine) that adds 20 ml at last disperses.The MCNT that adds 3.2g at last respectively, ultrasonic 1 h, the room temperature magnetic agitation is spent the night, suction filtration, 100 ℃ of dryings.Fe in this catalyst
3O
4Load capacity be 5 wt %.
In the round-bottomed flask of the toluene solution that 20 ml are housed, add 0.1 g, four n-octyl bromination ammoniums, 3.98ml concentration is the platinum acid chloride solution of 0.01g/ml, stir 2 h, at this moment the organic phase of solution has the colourless yellowish-brown that becomes, and water does not have color substantially, illustrates that the chloroplatinic acid anion all transfers in the organic phase.Syringe pipettes the 0.05ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stir 1 h solution and become milky adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stir 2 h at last then.Add 100 ml ethanol in the product that obtains, centrifugal 10 min of 3500 r/min, the precipitation that obtains is used ethanol more respectively, distilled water washing 3 times.Pt nanoparticle is distributed to the toluene of 30 ml again, adds the Fe of 0.5g
3O
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration is dried down for 80 ℃ and is spent the night.Catalyst Pt-Fe
3O
4-MCNT places under the nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 ℃, processing time 2h, 0.5 ℃/min of heating rate.The load capacity of active component platinum is 3 wt.%.
The gained catalyst is carried out XRD(Fig. 1), TEM(Fig. 2) characterize, the result shows that the magnetic ferroferric oxide nanometer particle can load on the multi-walled carbon nano-tubes uniformly, the size of particle is at 2-3nm, pattern be sphere or oval.And Pt nanoparticle also can load on the magnetic carbon nano-tube equably, and the particle diameter of Pt nanoparticle is the 3-4 nanometer, and it is spherical that narrow diameter distribution, pattern mostly are.The high-resolution photo shows that spacing of lattice is that 0.26 nm belongs to Fe in the magnetic composite
3O
4(311) face, and (111) face of spacing of lattice to be 0.23 nm belong to Pt crystal confirms magnetic Fe
3O
4Successfully load to the MCNT outer surface with Pt.
With 0.10 g Pt-Fe3O4-MCNT catalyst, 2.0 the cinnamic acid of mL/3-methyl-2-butene aldehyde, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, at first use hydrogen purge 8 times (0.6 MPa/ time), heat temperature raising to 80 ℃ temperature then, stir speed (S.S.) is about 300 rmin-1, charge into the hydrogen of 1.4Mpa immediately, and keep Hydrogen Vapor Pressure constant, and simultaneously magnetic agitation speed being transferred to about 1000 rmin-1, the reaction time is 3h.Under the effect of last outside magnetic field, catalyst is separated with reaction system, the ethanol washing, 80 ℃ of vacuum drying, recycling, reaction result sees Table 2.Measure the hysteresis curve of the catalyst after the circulation four times simultaneously, the result shows that saturated magnetic intensity does not have obvious variation, illustrates that Fe3O4 does not come off.Catalyst still has catalytic activity and selective preferably after reusing 4 times, catalyst has shown good stable.
Table 1: the hydrogenation activity of embodiment catalyst and selective tabulation
Table 2: the repeated use of catalyst
| Cycle-index | Cinnamic acid conversion ratio (%) | Cinnamyl alcohol selective (%) | 3-methyl-2-butene aldehyde conversion ratio (%) | 3-methyl-2-butene alcohol selective (%) |
| 1 | 90.2 | 96.3 | 79.7 | 98.8 |
| 2 | 88.2 | 96.5 | 81.2 | 98.6 |
| 3 | 89.4 | 95.5 | 79.8 | 98.2 |
| 4 | 87.9 | 96.2 | 81.7 | 98.0 |
Claims (3)
1. one kind is used for α, and the catalyst of beta-unsaturated aldehyde selective hydrogenation, this catalyst are magnetic composite, are made up of active component, magnetisable material and carrier, it is characterized in that: described active component is Pt, and magnetic component is Fe
3O
4Particle, carrier are MCNT, and wherein the load capacity of active component Pt is 1-10wt.%, magnetic component Fe
3O
4Load capacity is 1-10wt.%.
2. the described Preparation of catalysts method of claim 1 is characterized in that comprising the steps:
(1) Fe
3O
4The preparation of magnetic nanoparticle: the ferric acetyl acetonade, 1 that adds successively in diphenyl ether, 2-hexadecane glycol, oleyl amine and oleic acid add hot reflux then under nitrogen protection, be cooled to room temperature, add ethanol, obtain Fe
3O
4Nanoparticle precipitate;
(2) Fe
3O
4Magnetic nanoparticle loads to the MCNT surface: the Fe that step 1 is obtained
3O
4Nano particle with the ethanol washing, is distributed in the n-hexane repeatedly, adds a certain amount of MCNT by proportioning, and stirring is spent the night, and suction filtration is dried down for 100 ℃ and spent the night, and obtains Fe
3O
4-MCNT magnetic composite;
(3) preparation of Pt nano particle: in toluene solution, add four n-octyl bromination ammoniums, chloroplatinic acid, stirring becomes colorless up to water; Add oleyl amine then, stir, add fresh sodium borohydride solution, stir; Add ethanol in the product that obtains, centrifugal, use ethanol respectively, the distilled water washing obtains the Pt nano particle;
(4) the Pt nano particle is loaded to the Fe that step 2 obtains
3O
4-MCNT magnetic composite surface: the metal nanoparticle that step 3 is obtained is distributed in the toluene, adds a certain amount of Fe by proportioning
3O
4-MCNT, ultrasonic, stir the back suction filtration that spends the night, dry down for 80 ℃ and spend the night, get magnetic catalyst;
(5) magnetic catalyst activates.
3. the described catalyst of claim 1 is at α, the application in the selective hydrogenation of beta-unsaturated aldehyde.
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| CN110947397A (en) * | 2019-10-23 | 2020-04-03 | 广东工业大学 | Cerium dioxide loaded low-dose PtCu superfine alloy catalyst and preparation method and application thereof |
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| CN111266119A (en) * | 2020-02-25 | 2020-06-12 | 南京工业大学 | α -unsaturated aldehyde ketone selective hydrogenation platinum-based catalyst, and preparation method and application thereof |
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| CN107983382A (en) * | 2017-11-09 | 2018-05-04 | 中国科学院上海硅酸盐研究所 | Catalyst for liquid phase alpha, beta-unsaturated aldehyde selective hydrogenation and preparation method thereof |
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| CN110947397A (en) * | 2019-10-23 | 2020-04-03 | 广东工业大学 | Cerium dioxide loaded low-dose PtCu superfine alloy catalyst and preparation method and application thereof |
| CN110947397B (en) * | 2019-10-23 | 2022-08-12 | 广东工业大学 | Cerium dioxide loaded low-dose PtCu superfine alloy catalyst and preparation method and application thereof |
| CN111151268A (en) * | 2020-01-16 | 2020-05-15 | 厦门大学 | aFe (OH)xOyApplication method of Pt catalyst as hydrogenation reaction catalyst |
| CN111266119A (en) * | 2020-02-25 | 2020-06-12 | 南京工业大学 | α -unsaturated aldehyde ketone selective hydrogenation platinum-based catalyst, and preparation method and application thereof |
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