CN103230804B - 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
- Publication number
- CN103230804B CN103230804B CN201310167376.7A CN201310167376A CN103230804B CN 103230804 B CN103230804 B CN 103230804B CN 201310167376 A CN201310167376 A CN 201310167376A CN 103230804 B CN103230804 B CN 103230804B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- magnetic
- mcnt
- add
- night
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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 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, Pt metal catalyst is at α, in beta-unsaturated aldehyde selective hydrogenation, have good C=O key hydrogenation selectivity, Pt particle size has material impact to catalytic performance, and size homogeneous, the metallic being 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 the aspects such as mineral separation and material purification at present.The magnetic catalyst of tool, 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 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 separate with liquid-phase reaction system is efficient 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 is selectively 0.
In preparation process for magnetic catalyst, face following major issue: the Pt that 1) adopts traditional deposition reducing process to prepare is catalyst based, tend to cause Pt particle size inequality, thereby reduce 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 making, and the particle diameter of particle is larger, cause magnetic-particle easily to come off, affect the separating property of magnetic catalyst, catalytic performance is also had to larger impact simultaneously.
Summary of the invention
The problems such as the magnetic-particle that the present invention is directed to existing magnetic catalyst existence easily comes off, Hydrogenation is not good, provide that a kind of magnetic-particle particle diameter is less, Pt even particle size, catalytic performance are good, easy recovery 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 is magnetic composite, is made up of active component, magnetisable material and carrier, it is characterized in that: described active component is Pt, magnetic component is Fe
3o
4particle, carrier is multi-walled carbon nano-tubes (MCNT), wherein the load capacity of active component Pt is 1-10wt.%, magnetic component Fe
3o
4load capacity is 1-10wt.%.
The preparation method of above-mentioned catalyst, is characterized in that comprising the steps:
(1) Fe
3o
4the preparation of magnetic nanoparticle: this preparation method is with reference to the people such as Sun (J. Am. Chem. Soc.; 2004; 126 (1); pp 273 – 279) report, the ferric acetyl acetonade adding successively in diphenyl ether, 1,2-hexadecane glycol, oleyl amine and oleic acid; then under nitrogen protection, add hot reflux; be cooled to room temperature, add ethanol, obtain Fe
3o
4nanoparticle precipitate.
(2) Fe
3o
4magnetic nanoparticle loads to MCNT surface: the Fe that step 1 is obtained
3o
4nano particle with ethanol washing, is distributed in n-hexane repeatedly, adds a certain amount of MCNT by proportioning, and stirring is spent the night, and suction filtration is dried at 100 DEG C and spent the night, and obtains Fe
3o
4-MCNT magnetic composite.
(3) preparation of Pt nano particle: this preparation method, with reference to the report of the people such as Zhong (chem.Mater.2005,17,3086-3091), in toluene solution, adds four n-octyl bromination ammoniums, chloroplatinic acid, stirs until water becomes colorless.Then add oleyl amine, stir, add fresh sodium borohydride solution, stir.In the product obtaining, add ethanol, centrifugal, use respectively ethanol, distilled water washing obtains Pt nano particle.
(4) 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 toluene, adds a certain amount of Fe by proportioning
3o
4-MCNT, ultrasonic, stir spend the night after suction filtration, dry at 80 DEG C and spend the night, obtain magnetic catalyst.
(5) magnetic catalyst activates: under nitrogen atmosphere, the flow velocity of nitrogen is 30ml/min, and temperature is 400 DEG C, processing time 2h, 0.5 DEG C/min of heating rate.
This catalyst is applied to α, in the selective hydrogenation of beta-unsaturated aldehyde.Concrete steps are as follows: by 0.10 g Pt-Fe3O4-MCNT catalyst, the α of 2.0 mL, beta-unsaturated aldehyde, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, first use hydrogen purge 8 times (0.6 MPa/ time), then be heated to 80 DEG C of temperature, stir speed (S.S.) is about 300 rmin-1, is filled with immediately the hydrogen of 1.4Mpa, and keeps Hydrogen Vapor Pressure constant, magnetic agitation speed is adjusted to about 1000 rmin-1, the reaction time is 3h simultaneously.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 butenol selectively up to more than 98%.
Catalyst prepared by the present invention, 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, between 2-3nm.This catalyst is at α simultaneously, and beta-unsaturated aldehyde hydrogenation reaction has higher activity and selectivity, and separative efficiency is high, and the recycling rate of waterused of catalyst is high.Reuse after four times, to selectively reaching more than 96% of cinnamyl alcohol, and to 3-methyl-2 butenol selectively up to more than 98%.
Brief description of the 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
Detailed description of the invention
Further illustrate the present invention below in conjunction with specific embodiment, but the present invention is not limited to embodiment.
Embodiment 1
In 50ml quartz there-necked flask, add successively diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 of 20 ml, 2-hexadecane glycol, the oleyl amine of 2mmol and the oleic acid of 2mmol, in ultrasonic pond, ultrasonic 30 min mix.Then pass into nitrogen 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 DEG C with the heating rate of 1 DEG C/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3o
4pitchy nanoparticle precipitate.Ethanol washing 5 times, finally adds the n-hexane (adding a small amount of oleic acid and oleyl amine) of 20 ml to disperse.Finally add respectively the MCNT of 3.2g, ultrasonic 1 h, room temperature magnetic agitation is spent the night, suction filtration, 100 DEG C are dry.Fe in this catalyst
3o
4load capacity be 5 wt %.
In the round-bottomed flask of toluene solution that 20 ml are housed, add the platinum acid chloride solution that 0.1 g tetra-n-octyl bromination ammoniums, 3.98ml concentration are 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, illustrate that chloroplatinic acid anion all transfers in organic phase.Then syringe pipettes 0.05ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stirs 1 h solution and becomes milky, finally adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stirs 2 h.In the product obtaining, add 100 ml ethanol, centrifugal 10 min of 3500 r/min, the precipitation obtaining is used respectively ethanol again, distilled water washing 3 times.Pt nanoparticle is distributed to again to the toluene of 30 ml, adds the Fe of 0.5g
3o
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration, dries at 80 DEG C and spends the night.Catalyst Pt-Fe
3o
4-MCNT is placed under nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 DEG C, processing time 2h, 0.5 DEG C/min of heating rate.The load capacity of active component platinum is 3 wt.%.
By 0.10 g Pt-Fe3O4-MCNT catalyst, cinnamic acid/3-methyl-2-butene aldehyde of 2.0 mL, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, first use hydrogen purge 8 times (0.6 MPa/ time), be then heated to 80 DEG C of temperature, stir speed (S.S.) is about 300 rmin-1, be filled with immediately the hydrogen of 1.4Mpa, and keep Hydrogen Vapor Pressure constant, and magnetic agitation speed being adjusted to about 1000 rmin-1 simultaneously, the reaction time is 3h.Reaction result is in table one.
Embodiment 2
In 50ml quartz there-necked flask, add successively diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 of 20 ml, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, in ultrasonic pond, ultrasonic 30 min mix.Then pass into nitrogen 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 DEG C with the heating rate of 1 DEG C/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3o
4pitchy nanoparticle precipitate.Ethanol washing 5 times, finally adds the n-hexane (adding a small amount of oleic acid and oleyl amine) of 20 ml to disperse.Finally add respectively the MCNT of 3.2g, ultrasonic 1 h, room temperature magnetic agitation is spent the night, suction filtration, 100 DEG C are dry.Fe in this catalyst
3o
4load capacity be 5 wt %.
In the round-bottomed flask of toluene solution that 20 ml are housed, add the platinum acid chloride solution that 0.1 g tetra-n-octyl bromination ammoniums, 3.98ml concentration are 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, illustrate that chloroplatinic acid anion all transfers in organic phase.Then syringe pipettes 0.05ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stirs 1 h solution and becomes milky, finally adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stirs 2 h.In the product obtaining, add 100 ml ethanol, centrifugal 10 min of 3500 r/min, the precipitation obtaining is used respectively ethanol again, distilled water washing 3 times.Pt nanoparticle is distributed to again to the toluene of 30 ml, adds the Fe of 0.5g
3o
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration, dries at 80 DEG C and spends the night.Catalyst Pt-Fe
3o
4-MCNT is placed under nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 DEG C, processing time 2h, 0.5 DEG C/min of heating rate.The load capacity of active component platinum is 3 wt.%.
Gained catalyst is carried out to XRD(Fig. 1), TEM(Fig. 2) characterize, result shows, magnetic ferroferric oxide nanometer particle can load on multi-walled carbon nano-tubes uniformly, the size of particle is at 2-3nm, pattern is spherical or oval.And Pt nanoparticle also can load on magnetic carbon nano-tube equably, the particle diameter of Pt nanoparticle is 3-4 nanometer, narrow diameter distribution, and it is spherical that pattern mostly is.High-resolution photo shows that in magnetic composite, spacing of lattice is that 0.26 nm belongs to Fe
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 MCNT outer surface with Pt.
By 0.10 g Pt-Fe3O4-MCNT catalyst, cinnamic acid/3-methyl-2-butene aldehyde of 2.0 mL, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, first use hydrogen purge 8 times (0.6 MPa/ time), be then heated to 80 DEG C of temperature, stir speed (S.S.) is about 300 rmin-1, be filled with immediately the hydrogen of 1.4Mpa, and keep Hydrogen Vapor Pressure constant, and magnetic agitation speed being adjusted to about 1000 rmin-1 simultaneously, the reaction time is 3h.Reaction result is in table one.
Embodiment 3
In 50ml quartz there-necked flask, add successively diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 of 20 ml, 2-hexadecane glycol, the oleyl amine of 10 mmol and the oleic acid of 10mmol, in ultrasonic pond, ultrasonic 30 min mix.Then pass into nitrogen 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 DEG C with the heating rate of 1 DEG C/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3o
4pitchy nanoparticle precipitate.Ethanol washing 5 times, finally adds the n-hexane (adding a small amount of oleic acid and oleyl amine) of 20 ml to disperse.Finally add respectively the MCNT of 3.2g, ultrasonic 1 h, room temperature magnetic agitation is spent the night, suction filtration, 100 DEG C are dry.Fe in this catalyst
3o
4load capacity be 5 wt %.
In the round-bottomed flask of toluene solution that 20 ml are housed, add the platinum acid chloride solution that 0.1 g tetra-n-octyl bromination ammoniums, 3.98ml concentration are 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, illustrate that chloroplatinic acid anion all transfers in organic phase.Then syringe pipettes 0.05ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stirs 1 h solution and becomes milky, finally adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stirs 2 h.In the product obtaining, add 100 ml ethanol, centrifugal 10 min of 3500 r/min, the precipitation obtaining is used respectively ethanol again, distilled water washing 3 times.Pt nanoparticle is distributed to again to the toluene of 30 ml, adds the Fe of 0.5g
3o
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration, dries at 80 DEG C and spends the night.Catalyst Pt-Fe
3o
4-MCNT is placed under nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 DEG C, processing time 2h, 0.5 DEG C/min of heating rate.The load capacity of active component platinum is 3 wt.%.
By 0.10 g Pt-Fe3O4-MCNT catalyst, cinnamic acid/3-methyl-2-butene aldehyde of 2.0 mL, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, first use hydrogen purge 8 times (0.6 MPa/ time), be then heated to 80 DEG C of temperature, stir speed (S.S.) is about 300 rmin-1, be filled with immediately the hydrogen of 1.4Mpa, and keep Hydrogen Vapor Pressure constant, and magnetic agitation speed being adjusted to about 1000 rmin-1 simultaneously, the reaction time is 3h.Reaction result is in table one.
Embodiment 4
In 50ml quartz there-necked flask, add successively diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 of 20 ml, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, in ultrasonic pond, ultrasonic 30 min mix.Then pass into nitrogen 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 DEG C with the heating rate of 1 DEG C/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3o
4pitchy nanoparticle precipitate.Ethanol washing 5 times, finally adds the n-hexane (adding a small amount of oleic acid and oleyl amine) of 20 ml to disperse.Finally add respectively the MCNT of 15.5 g, ultrasonic 1 h, room temperature magnetic agitation is spent the night, suction filtration, 100 DEG C are dry.Fe in this catalyst
3o
4load capacity be 1 wt %.
In the round-bottomed flask of toluene solution that 20 ml are housed, add the platinum acid chloride solution that 0.1 g tetra-n-octyl bromination ammoniums, 3.98ml concentration are 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, illustrate that chloroplatinic acid anion all transfers in organic phase.Then syringe pipettes 0.05ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stirs 1 h solution and becomes milky, finally adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stirs 2 h.In the product obtaining, add 100 ml ethanol, centrifugal 10 min of 3500 r/min, the precipitation obtaining is used respectively ethanol again, distilled water washing 3 times.Pt nanoparticle is distributed to again to the toluene of 30 ml, adds the Fe of 0.5g
3o
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration, dries at 80 DEG C and spends the night.Catalyst Pt-Fe
3o
4-MCNT is placed under nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 DEG C, processing time 2h, 0.5 DEG C/min of heating rate.The load capacity of active component platinum is 3 wt.%.
By 0.10 g Pt-Fe3O4-MCNT catalyst, cinnamic acid/3-methyl-2-butene aldehyde of 2.0 mL, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, first use hydrogen purge 8 times (0.6 MPa/ time), be then heated to 80 DEG C of temperature, stir speed (S.S.) is about 300 rmin-1, be filled with immediately the hydrogen of 1.4Mpa, and keep Hydrogen Vapor Pressure constant, and magnetic agitation speed being adjusted to about 1000 rmin-1 simultaneously, the reaction time is 3h.Reaction result is in table one.
Embodiment 5
In 50ml quartz there-necked flask, add successively diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 of 20 ml, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, in ultrasonic pond, ultrasonic 30 min mix.Then pass into nitrogen 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 DEG C with the heating rate of 1 DEG C/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3o
4pitchy nanoparticle precipitate.Ethanol washing 5 times, finally adds the n-hexane (adding a small amount of oleic acid and oleyl amine) of 20 ml to disperse.Finally add respectively the MCNT of 1.8g, ultrasonic 1 h, room temperature magnetic agitation is spent the night, suction filtration, 100 DEG C are dry.Fe in this catalyst
3o
4load capacity be 10wt %.
In the round-bottomed flask of toluene solution that 20 ml are housed, add the platinum acid chloride solution that 0.1 g tetra-n-octyl bromination ammoniums, 3.98ml concentration are 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, illustrate that chloroplatinic acid anion all transfers in organic phase.Then syringe pipettes 0.05ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stirs 1h solution and becomes milky, finally adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stirs 2 h.In the product obtaining, add 100 ml ethanol, centrifugal 10 min of 3500 r/min, the precipitation obtaining is used respectively ethanol again, distilled water washing 3 times.Pt nanoparticle is distributed to again to the toluene of 30 ml, adds the Fe of 0.5g
3o
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration, dries at 80 DEG C and spends the night.Catalyst Pt-Fe
3o
4-MCNT is placed under nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 DEG C, processing time 2h, 0.5 DEG C/min of heating rate.The load capacity of active component platinum is 3 wt.%.
By 0.10 g Pt-Fe3O4-MCNT catalyst, cinnamic acid/3-methyl-2-butene aldehyde of 2.0 mL, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, first use hydrogen purge 8 times (0.6 MPa/ time), be then heated to 80 DEG C of temperature, stir speed (S.S.) is about 300 rmin-1, be filled with immediately the hydrogen of 1.4Mpa, and keep Hydrogen Vapor Pressure constant, and magnetic agitation speed being adjusted to about 1000 rmin-1 simultaneously, the reaction time is 3h.Reaction result is in table one.
Embodiment 6
In 50ml quartz there-necked flask, add successively diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 of 20 ml, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, in ultrasonic pond, ultrasonic 30 min mix.Then pass into nitrogen 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 DEG C with the heating rate of 1 DEG C/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3o
4pitchy nanoparticle precipitate.Ethanol washing 5 times, finally adds the n-hexane (adding a small amount of oleic acid and oleyl amine) of 20 ml to disperse.Finally add respectively the MCNT of 3.2 g, ultrasonic 1 h, room temperature magnetic agitation is spent the night, suction filtration, 100 DEG C are dry.Fe in this catalyst
3o
4load capacity be 5 wt %.
In the round-bottomed flask of toluene solution that 20 ml are housed, add the platinum acid chloride solution that 0.1 g tetra-n-octyl bromination ammoniums, 3.98ml concentration are 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, illustrate that chloroplatinic acid anion all transfers in organic phase.Then syringe pipettes 0.03ml oleyl amine (chloroplatinic acid: oleyl amine=1:1), stirs 1 h solution and becomes milky, finally adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stirs 2 h.In the product obtaining, add 100 ml ethanol, centrifugal 10 min of 3500 r/min, the precipitation obtaining is used respectively ethanol again, distilled water washing 3 times.Pt nanoparticle is distributed to again to the toluene of 30 ml, adds the Fe of 0.5g
3o
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration, dries at 80 DEG C and spends the night.Catalyst Pt-Fe
3o
4-MCNT is placed under nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 DEG C, processing time 2h, 0.5 DEG C/min of heating rate.The load capacity of active component platinum is 3 wt.%.
By 0.10 g Pt-Fe3O4-MCNT catalyst, cinnamic acid/3-methyl-2-butene aldehyde of 2.0 mL, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, first use hydrogen purge 8 times (0.6 MPa/ time), be then heated to 80 DEG C of temperature, stir speed (S.S.) is about 300 rmin-1, be filled with immediately the hydrogen of 1.4Mpa, and keep Hydrogen Vapor Pressure constant, and magnetic agitation speed being adjusted to about 1000 rmin-1 simultaneously, the reaction time is 3h.Reaction result is in table one.
Embodiment 7
In 50ml quartz there-necked flask, add successively diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 of 20 ml, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, in ultrasonic pond, ultrasonic 30 min mix.Then pass into nitrogen 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 DEG C with the heating rate of 1 DEG C/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3o
4pitchy nanoparticle precipitate.Ethanol washing 5 times, finally adds the n-hexane (adding a small amount of oleic acid and oleyl amine) of 20 ml to disperse.Finally add respectively the MCNT of 3.2 g, ultrasonic 1 h, room temperature magnetic agitation is spent the night, suction filtration, 100 DEG C are dry.Fe in this catalyst
3o
4load capacity be 5 wt %.
In the round-bottomed flask of toluene solution that 20 ml are housed, add the platinum acid chloride solution that 0.1 g tetra-n-octyl bromination ammoniums, 3.98ml concentration are 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, illustrate that chloroplatinic acid anion all transfers in organic phase.Then syringe pipettes 0.13ml oleyl amine (chloroplatinic acid: oleyl amine=1:5), stirs 1 h solution and becomes milky, finally adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stirs 2 h.In the product obtaining, add 100 ml ethanol, centrifugal 10 min of 3500 r/min, the precipitation obtaining is used respectively ethanol again, distilled water washing 3 times.Pt nanoparticle is distributed to again to the toluene of 30 ml, adds the Fe of 0.5g
3o
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration, dries at 80 DEG C and spends the night.Catalyst Pt-Fe
3o
4-MCNT is placed under nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 DEG C, processing time 2h, 0.5 DEG C/min of heating rate.The load capacity of active component platinum is 3 wt.%.
By 0.10 g Pt-Fe3O4-MCNT catalyst, cinnamic acid/3-methyl-2-butene aldehyde of 2.0 mL, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, first use hydrogen purge 8 times (0.6 MPa/ time), be then heated to 80 DEG C of temperature, stir speed (S.S.) is about 300 rmin-1, be filled with immediately the hydrogen of 1.4Mpa, and keep Hydrogen Vapor Pressure constant, and magnetic agitation speed being adjusted to about 1000 rmin-1 simultaneously, the reaction time is 3h.Reaction result is in table one.
Embodiment 8
In 50ml quartz there-necked flask, add successively diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 of 20 ml, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, in ultrasonic pond, ultrasonic 30 min mix.Then pass into nitrogen 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 DEG C with the heating rate of 1 DEG C/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3o
4pitchy nanoparticle precipitate.Ethanol washing 5 times, finally adds the n-hexane (adding a small amount of oleic acid and oleyl amine) of 20 ml to disperse.Finally add respectively the MCNT of 3.2 g, ultrasonic 1 h, room temperature magnetic agitation is spent the night, suction filtration, 100 DEG C are dry.Fe in this catalyst
3o
4load capacity be 5 wt %.
In the round-bottomed flask of toluene solution that 20 ml are housed, add the platinum acid chloride solution that 0.1 g tetra-n-octyl bromination ammoniums, 3.98ml concentration are 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, illustrate that chloroplatinic acid anion all transfers in organic phase.Then syringe pipettes 0.26ml oleyl amine (chloroplatinic acid: oleyl amine=1:10), stirs 1h solution and becomes milky, finally adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stirs 2 h.In the product obtaining, add 100 ml ethanol, centrifugal 10 min of 3500 r/min, the precipitation obtaining is used respectively ethanol again, distilled water washing 3 times.Pt nanoparticle is distributed to again to the toluene of 30 ml, adds the Fe of 0.5g
3o
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration, dries at 80 DEG C and spends the night.Catalyst Pt-Fe
3o
4-MCNT is placed under nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 DEG C, processing time 2h, 0.5 DEG C/min of heating rate.The load capacity of active component platinum is 3 wt.%.
By 0.10 g Pt-Fe3O4-MCNT catalyst, cinnamic acid/3-methyl-2-butene aldehyde of 2.0 mL, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, first use hydrogen purge 8 times (0.6 MPa/ time), be then heated to 80 DEG C of temperature, stir speed (S.S.) is about 300 rmin-1, be filled with immediately the hydrogen of 1.4Mpa, and keep Hydrogen Vapor Pressure constant, and magnetic agitation speed being adjusted to about 1000 rmin-1 simultaneously, the reaction time is 3h.Reaction result is in table one.
Embodiment 9
In 50ml quartz there-necked flask, add successively diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 of 20 ml, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, in ultrasonic pond, ultrasonic 30 min mix.Then pass into nitrogen 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 DEG C with the heating rate of 1 DEG C/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3o
4pitchy nanoparticle precipitate.Ethanol washing 5 times, finally adds the n-hexane (adding a small amount of oleic acid and oleyl amine) of 20 ml to disperse.Finally add respectively the MCNT of 3.2 g, ultrasonic 1 h, room temperature magnetic agitation is spent the night, suction filtration, 100 DEG C are dry.Fe in this catalyst
3o
4load capacity be 5 wt %.
In the round-bottomed flask of toluene solution that 20 ml are housed, add the platinum acid chloride solution that 0.1 g tetra-n-octyl bromination ammoniums, 1.33ml concentration are 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, illustrate that chloroplatinic acid anion all transfers in organic phase.Then syringe pipettes 0.02ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stirs 1 h solution and becomes milky, finally adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stirs 2 h.In the product obtaining, add 100 ml ethanol, centrifugal 10 min of 3500 r/min, the precipitation obtaining is used respectively ethanol again, distilled water washing 3 times.Pt nanoparticle is distributed to again to the toluene of 30 ml, adds the Fe of 0.5g
3o
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration, dries at 80 DEG C and spends the night.Catalyst Pt-Fe
3o
4-MCNT is placed under nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 DEG C, processing time 2h, 0.5 DEG C/min of heating rate.The load capacity of active component platinum is 1 wt.%.
By 0.10 g Pt-Fe3O4-MCNT catalyst, cinnamic acid/3-methyl-2-butene aldehyde of 2.0 mL, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, first use hydrogen purge 8 times (0.6 MPa/ time), be then heated to 80 DEG C of temperature, stir speed (S.S.) is about 300 rmin-1, be filled with immediately the hydrogen of 1.4Mpa, and keep Hydrogen Vapor Pressure constant, and magnetic agitation speed being adjusted to about 1000 rmin-1 simultaneously, the reaction time is 3h.Reaction result is in table one.
Embodiment 10
In 50ml quartz there-necked flask, add successively diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 of 20 ml, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, in ultrasonic pond, ultrasonic 30 min mix.Then pass into nitrogen 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 DEG C with the heating rate of 1 DEG C/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3o
4pitchy nanoparticle precipitate.Ethanol washing 5 times, finally adds the n-hexane (adding a small amount of oleic acid and oleyl amine) of 20 ml to disperse.Finally add respectively the MCNT of 3.2 g, ultrasonic 1 h, room temperature magnetic agitation is spent the night, suction filtration, 100 DEG C are dry.Fe in this catalyst
3o
4load capacity be 5 wt %.
In the round-bottomed flask of toluene solution that 20 ml are housed, add the platinum acid chloride solution that 0.1 g tetra-n-octyl bromination ammoniums, 6.64ml concentration are 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, illustrate that chloroplatinic acid anion all transfers in organic phase.Then syringe pipettes 0.08ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stirs 1 h solution and becomes milky, finally adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stirs 2 h.In the product obtaining, add 100 ml ethanol, centrifugal 10 min of 3500 r/min, the precipitation obtaining is used respectively ethanol again, distilled water washing 3 times.Pt nanoparticle is distributed to again to the toluene of 30 ml, adds the Fe of 0.5g
3o
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration, dries at 80 DEG C and spends the night.Catalyst Pt-Fe
3o
4-MCNT is placed under nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 DEG C, processing time 2h, 0.5 DEG C/min of heating rate.The load capacity of active component platinum is 5 wt.%.
By 0.10 g Pt-Fe3O4-MCNT catalyst, cinnamic acid/3-methyl-2-butene aldehyde of 2.0 mL, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, first use hydrogen purge 8 times (0.6 MPa/ time), be then heated to 80 DEG C of temperature, stir speed (S.S.) is about 300 rmin-1, be filled with immediately the hydrogen of 1.4Mpa, and keep Hydrogen Vapor Pressure constant, and magnetic agitation speed being adjusted to about 1000 rmin-1 simultaneously, the reaction time is 2h.Reaction result is in table one.
Embodiment 11
In 50ml quartz there-necked flask, add successively diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 of 20 ml, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, in ultrasonic pond, ultrasonic 30 min mix.Then pass into nitrogen 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 DEG C with the heating rate of 1 DEG C/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3o
4pitchy nanoparticle precipitate.Ethanol washing 5 times, finally adds the n-hexane (adding a small amount of oleic acid and oleyl amine) of 20 ml to disperse.Finally add respectively the MCNT of 3.2 g, ultrasonic 1 h, room temperature magnetic agitation is spent the night, suction filtration, 100 DEG C are dry.Fe in this catalyst
3o
4load capacity be 5 wt %.
In the round-bottomed flask of toluene solution that 20 ml are housed, add the platinum acid chloride solution that 0.1 g tetra-n-octyl bromination ammoniums, 6.64ml concentration are 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, illustrate that chloroplatinic acid anion all transfers in organic phase.Then syringe pipettes 0.17ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stirs 1 h solution and becomes milky, finally adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stirs 2 h.In the product obtaining, add 100 ml ethanol, centrifugal 10 min of 3500 r/min, the precipitation obtaining is used respectively ethanol again, distilled water washing 3 times.Pt nanoparticle is distributed to again to the toluene of 30 ml, adds the Fe of 0.5g
3o
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration, dries at 80 DEG C and spends the night.Catalyst Pt-Fe
3o
4-MCNT is placed under nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 DEG C, processing time 2h, 0.5 DEG C/min of heating rate.The load capacity of active component platinum is 10 wt.%.
By 0.10 g Pt-Fe3O4-MCNT catalyst, cinnamic acid/3-methyl-2-butene aldehyde of 2.0 mL, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, first use hydrogen purge 8 times (0.6 MPa/ time), be then heated to 80 DEG C of temperature, stir speed (S.S.) is about 300 rmin-1, be filled with immediately the hydrogen of 1.4Mpa, and keep Hydrogen Vapor Pressure constant, and magnetic agitation speed being adjusted to about 1000 rmin-1 simultaneously, the reaction time is 1h.Reaction result is in table one.
Embodiment 12
In 50ml quartz there-necked flask, add successively diphenyl ether, the ferric acetyl acetonade of 2 mmol, 10 mmol 1 of 20 ml, the oleyl amine of 2-hexadecane glycol, 6 mmol and the oleic acid of 6 mmol, in ultrasonic pond, ultrasonic 30 min mix.Then pass into nitrogen 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 DEG C with the heating rate of 1 DEG C/min, add hot reflux 1h, be cooled to room temperature; add 40 ml ethanol, the centrifugal Fe that obtains
3o
4pitchy nanoparticle precipitate.Ethanol washing 5 times, finally adds the n-hexane (adding a small amount of oleic acid and oleyl amine) of 20 ml to disperse.Finally add respectively the MCNT of 3.2g, ultrasonic 1 h, room temperature magnetic agitation is spent the night, suction filtration, 100 DEG C are dry.Fe in this catalyst
3o
4load capacity be 5 wt %.
In the round-bottomed flask of toluene solution that 20 ml are housed, add the platinum acid chloride solution that 0.1 g tetra-n-octyl bromination ammoniums, 3.98ml concentration are 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, illustrate that chloroplatinic acid anion all transfers in organic phase.Then syringe pipettes 0.05ml oleyl amine (chloroplatinic acid: oleyl amine=1:2), stirs 1 h solution and becomes milky, finally adds fresh sodium borohydride solution (chloroplatinic acid: sodium borohydride=1:10), stirs 2 h.In the product obtaining, add 100 ml ethanol, centrifugal 10 min of 3500 r/min, the precipitation obtaining is used respectively ethanol again, distilled water washing 3 times.Pt nanoparticle is distributed to again to the toluene of 30 ml, adds the Fe of 0.5g
3o
4-MCNT, ultrasonic 1 h, stirring is spent the night.Last suction filtration, dries at 80 DEG C and spends the night.Catalyst Pt-Fe
3o
4-MCNT is placed under nitrogen atmosphere, and the flow velocity of nitrogen is 30ml/min, and temperature is 400 DEG C, processing time 2h, 0.5 DEG C/min of heating rate.The load capacity of active component platinum is 3 wt.%.
Gained catalyst is carried out to XRD(Fig. 1), TEM(Fig. 2) characterize, result shows, magnetic ferroferric oxide nanometer particle can load on multi-walled carbon nano-tubes uniformly, the size of particle is at 2-3nm, pattern is spherical or oval.And Pt nanoparticle also can load on magnetic carbon nano-tube equably, the particle diameter of Pt nanoparticle is 3-4 nanometer, narrow diameter distribution, and it is spherical that pattern mostly is.High-resolution photo shows that in magnetic composite, spacing of lattice is that 0.26 nm belongs to Fe
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 MCNT outer surface with Pt.
By 0.10 g Pt-Fe3O4-MCNT catalyst, cinnamic acid/3-methyl-2-butene aldehyde of 2.0 mL, the absolute ethyl alcohol of 16.0 mL, the deionized water of 2.0 mL, add successively in the autoclave of 50 mL, first use hydrogen purge 8 times (0.6 MPa/ time), be then heated to 80 DEG C of temperature, stir speed (S.S.) is about 300 rmin-1, be filled with immediately the hydrogen of 1.4Mpa, and keep Hydrogen Vapor Pressure constant, and magnetic agitation speed being adjusted to about 1000 rmin-1 simultaneously, the reaction time is 3h.Under the effect of last outside magnetic field, catalyst is separated with reaction system, ethanol washing, 80 DEG C of vacuum drying, recycling, reaction result is in table 2.Measure the hysteresis curve of the catalyst of circulation after four times, result shows simultaneously, and saturated magnetic intensity does not significantly change, and illustrates that Fe3O4 does not come off.Catalyst is being reused after 4 times, still has good catalytic activity and selective, and catalyst has shown good stability.
Table 1: the hydrogenation activity of embodiment catalyst and selective list
Table 2: the reusing of catalyst
Cycle-index | Cinnamic acid conversion ratio (%) | Cinnamyl alcohol selective (%) | 3-methyl-2-butene aldehyde conversion ratio (%) | 3-methyl-2 butenol 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 (1)
1. for a α, the preparation method of the catalyst of beta-unsaturated aldehyde selective hydrogenation, this catalyst is magnetic composite, is made up of active component, magnetisable material and carrier, and described active component is Pt, and magnetic component is Fe
3o
4particle, carrier is MCNT, wherein the load capacity of active component Pt is 1-10wt.%, magnetic component Fe
3o
4load capacity is 1-10wt.%, it is characterized in that comprising the steps:
(1) Fe
3o
4the preparation of magnetic nanoparticle: add successively ferric acetyl acetonade, 1 in diphenyl ether, 2-hexadecane glycol, oleyl amine and oleic acid then add hot reflux under nitrogen protection, are cooled to room temperature, add ethanol, obtain Fe
3o
4nanoparticle precipitate;
(2) Fe
3o
4magnetic nanoparticle loads to MCNT surface: the Fe that step (1) is obtained
3o
4nano particle with ethanol washing, is distributed in n-hexane repeatedly, adds a certain amount of MCNT by proportioning, and stirring is spent the night, and suction filtration is dried at 100 DEG C 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, stir until water becomes colorless, then add oleyl amine, stir, add fresh sodium borohydride solution, stir, in the product obtaining, add ethanol, centrifugal, use respectively ethanol, distilled water washing obtains Pt nano particle;
(4) 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 toluene, adds a certain amount of Fe by proportioning
3o
4-MCNT, ultrasonic, stir spend the night after suction filtration, dry at 80 DEG C and spend the night, obtain magnetic catalyst;
(5) magnetic catalyst activates.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310167376.7A CN103230804B (en) | 2013-05-09 | 2013-05-09 | Catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method of catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310167376.7A CN103230804B (en) | 2013-05-09 | 2013-05-09 | Catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method of catalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103230804A CN103230804A (en) | 2013-08-07 |
CN103230804B true CN103230804B (en) | 2014-12-10 |
Family
ID=48878912
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310167376.7A Expired - Fee Related CN103230804B (en) | 2013-05-09 | 2013-05-09 | Catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method of catalyst |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103230804B (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107983382B (en) * | 2017-11-09 | 2020-04-17 | 中国科学院上海硅酸盐研究所 | Catalyst for selective hydrogenation of liquid-phase α -unsaturated aldehyde and preparation method thereof |
CN108971516B (en) * | 2018-07-02 | 2022-05-03 | 湖北大学 | Platinum nano-particles and preparation method 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 |
CN111151268B (en) * | 2020-01-16 | 2021-02-26 | 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 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008044655A1 (en) * | 2008-08-27 | 2010-03-04 | Bayer Materialscience Ag | Preparing di- or poly-amines from di- or poly-aldehydes, comprises dissolving aldehyde in a solvent and transforming reaction solution in presence of hydrogenation catalyst with ammonia and hydrogen in a trickle-bed reactor |
CN102151575B (en) * | 2011-01-29 | 2013-04-17 | 浙江师范大学 | Method for preparing carbon nanometer tube loaded type catalyst |
-
2013
- 2013-05-09 CN CN201310167376.7A patent/CN103230804B/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN103230804A (en) | 2013-08-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103230804B (en) | Catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method of catalyst | |
Marquardt et al. | The use of microwave irradiation for the easy synthesis of graphene-supported transition metal nanoparticles in ionic liquids | |
CN106064087B (en) | A method of preparing VOCs catalyst for catalytic combustion | |
Le et al. | Fibrous nano-silica supported palladium nanoparticles: An efficient catalyst for the reduction of 4-nitrophenol and hydrodechlorination of 4-chlorophenol under mild conditions | |
Yang et al. | Pt nanoparticles entrapped in titanate nanotubes (TNT) for phenol hydrogenation: the confinement effect of TNT | |
Liu et al. | MOFs-Derived Co@ CN bi-functional catalysts for selective transfer hydrogenation of α, β-unsaturated aldehydes without use of base additives | |
CN102336404B (en) | Preparation method of graphene oxide quantum dot based on photocatalytic oxidation | |
Rossi et al. | Recent advances in the development of magnetically recoverable metal nanoparticle catalysts | |
CN103566935A (en) | Preparation method of monatomic dispersion catalyst with high catalytic performance | |
CN104722276B (en) | A kind of melon ring/graphene oxide magnetic composite and preparation method thereof | |
Kaboudin et al. | Polymer supported gold nanoparticles: synthesis and characterization of functionalized polystyrene-supported gold nanoparticles and their application in catalytic oxidation of alcohols in water | |
CN102151575B (en) | Method for preparing carbon nanometer tube loaded type catalyst | |
CN103263921A (en) | Metal/graphene catalyst and preparation method thereof | |
Zhao et al. | Controlled synthesis of metal-organic frameworks coated with noble metal nanoparticles and conducting polymer for enhanced catalysis | |
CN104043481A (en) | Preparation method for functionalized graphene loaded noble metal nano-crystalline composite catalyst | |
CN104069882A (en) | Preparation method of nanocrystalline metal catalyst loaded with carbon and nitrogen materials | |
CN106563507A (en) | Nanometer supported metal organic framework palladium composite catalyst, preparation method and applications thereof | |
CN107252685B (en) | A kind of hydroxyl aminated compounds functional magnetic graphene oxide catalysis material and its preparation method and application | |
CN106076361A (en) | A kind of nickel foam/graphene/nanometer metal/composite material and preparation method thereof | |
Sun et al. | Immobilization of palladium (II) complexes on ethylenediamine functionalized core–shell magnetic nanoparticles: An efficient and recyclable catalyst for aerobic oxidation of alcohols and carbonylative Suzuki coupling reaction | |
CN103599794A (en) | Fe3O4-Au magnetic nano composite material, and preparation method and application thereof | |
CN103566950A (en) | Preparation method of catalyst for selectively hydrogenating alpha, beta-unsaturated aldehyde | |
Sun et al. | Extended Stöber method to synthesize core-shell magnetic composite catalyst Fe3O4@ C-Pd for Suzuki coupling reactions | |
CN112337462A (en) | Atomic-level dispersed Pd catalyst prepared by nitric acid steam method and application thereof | |
CN108525675A (en) | It is a kind of to prepare magnetic carbon/palladium-cobalt multiplex catalyst of aminated compounds, preparation method and application for being catalyzed reduction amination |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141210 Termination date: 20170509 |