CN101703930A - Palladium/carbon nanotube catalyst for hydrogenation of cinnamaldehyde and preparation method thereof - Google Patents
Palladium/carbon nanotube catalyst for hydrogenation of cinnamaldehyde and preparation method thereof Download PDFInfo
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- CN101703930A CN101703930A CN200910153977A CN200910153977A CN101703930A CN 101703930 A CN101703930 A CN 101703930A CN 200910153977 A CN200910153977 A CN 200910153977A CN 200910153977 A CN200910153977 A CN 200910153977A CN 101703930 A CN101703930 A CN 101703930A
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Abstract
The invention discloses a palladium/carbon nanotube catalyst for the hydrogenation of cinnamaldehyde and a preparation method thereof. The carrier of the catalyst is carbon nanotubes, and the active ingredient of the catalyst is noble metal palladium nanoparticles with an average particle size of 5 to 6 nanometers. The catalyst contains 0.1 to 5 mass percent of palladium and the balance of the carbon nanotubes. The preparation method of the catalyst comprises: 1) dissolving a palladium salt in deionized water to prepare 0.01 to 0.2 mol/L aqueous solution of the palladium salt, adding the carbon nanotubes into the aqueous solution of the palladium salt and subjecting the solution to ultrasonic dispersion for 0.5 to 1 hour; 2) with magnetic stirring, dripping reducer-containing aqueous solution till the ratio of the reducer and the palladium is 1:1 to 2:1, and continuously stirring for 1 to 2 hours after the dripping is finished; and 3) finally, stirring the solution in an oil bath for 1 to 2 hours, and obtaining the palladium/carbon nanotube catalyst by filtering, washing and drying. Compared with active carbon supported palladium catalyst, the palladium/carbon nanotube catalyst has high selectivity for the preparation of benzenepropana by the hydrogenation of cinnamaldehyde.
Description
Technical field
What the present invention relates to is that hydrogenation on cinnamic aldehyde prepares the Catalysts and its preparation method in the benzenpropanal reaction, especially relates to the preparation method of the palladium/carbon nano-tube catalyst that is used for spirit catalytic of cinnamaldehyde hydrogenation preparing benzenpropanal.
Background technology
α, β unsaturated aldehyde selective catalytic hydrogenation is an important reaction in fine chemistry industry and pharmaceuticals industry.α, β unsaturated aldehyde hydrogenation is selected appropriate catalyst, and product can be unsaturated aldehyde or saturated alcohols.Cinnamic acid is α, typical case's representative of β unsaturated aldehyde, and it has phenyl ring, the two keys of C=O and the two keys of C=C, forms a conjugated system, makes the two key selective hydrogenations of C=C increase certain difficulty.In recent years find that benzenpropanal is the important intermediate of AIDS resisting poison, people have developed some desirable catalyst of hydrogenation on cinnamic aldehyde generation benzenpropanal, and selectivity is still sixty-four dollar question.The catalyst of cinnamic acid selective catalytic hydrogenation is common to be the group VIII element, and well-known, palladium is typical C=C hydrogenation catalyst, because the conjugated structure of cinnamic acid, in palladium catalytic hydrogenation process, the C=O double-bond hydrogenation becomes easily, and the selectivity of C=C double-bond hydrogenation is descended.The product of cinnamic acid selective catalytic hydrogenation is a benzenpropanal, 3-phenylpropanol and phenylpropanol.Therefore improve the speed of C=C catalytic hydrogenation reaction, suppress or reduce the speed of C=O catalytic hydrogenation reaction, reduce cost, make the technical process greenization, have important significance for theories and practical value.
Pd nano particle as hydrogenation catalyst normally loads on certain carrier, and material with carbon element is the most frequently used carrier.Wherein, CNT is a kind of new carbon of finding over past ten years, because it has unique physics and chemical property, in a lot of fields, for example field such as microelectronic device and strengthening material is very extensive to the application of CNT.People are also very interested in as the research of catalyst carrier CNT recently, and this micro-structural is compared with the conventional catalyst agent carrier, has particular performances.In the liquid-phase hydrogenatin reaction, CNT is as catalyst carrier, existing report (Preparation, characterization and catalytichydroformylation properties of carbon nanotubes-supported Rh-phosphine catalyst, Applied Catalysis A:General, 1999,187:213-224).Therefore, utilize CNT to be used for hydrogenation on cinnamic aldehyde as carrier-supported precious metal palladium and prepare benzenpropanal, its result of study has significant practical applications very much.
Summary of the invention
The purpose of this invention is to provide a kind of palladium/carbon nano-tube catalyst and preparation method thereof with excellent Catalytic Hydrogenation Properties.Palladium/the carbon nano-tube catalyst of invention, the Metal Palladium that loads on the CNT is a nano particle, and high degree of dispersion, and particle diameter is 5～6nm, and the mass percent of palladium is 0.1～5% in the catalyst, and all the other are CNT.
The preparation method of palladium/carbon nano-tube catalyst who is used for hydrogenation on cinnamic aldehyde is as follows:
1) palladium salt is dissolved in the deionized water, compound concentration is the palladium saline solution of 0.01～0.2mol/L.In the palladium saline solution, add CNT then, ultrasonic dispersion 0.5～1h;
2) under the magnetic agitation effect, dropwise add the aqueous solution that contains reducing agent, making the ratio of reducing agent and palladium salt is 1: 1～2: 1, dropwises back continuation stirring 1～2h and makes the palladium salt in the solution be reduced to Pd nano particle fully;
3) in oil bath, stir 1～2h at last, after filtration, washing, oven dry obtain palladium/carbon nano-tube catalyst.
Said palladium salt is acid of chlorine palladium or potassium chloropalladate among the present invention. said reducing agent is formaldehyde or potassium borohydride.
The present invention has following beneficial effect compared with the prior art:
Palladium/carbon nano-tube catalyst that the present invention is prepared, the palladium that loads on the CNT is a nano particle, particle diameter is tiny and even, and high degree of dispersion is on carbon carrier.The synthetic catalyst of the inventive method is compared with activated carbon supported palladium catalyst, hydrogenation on cinnamic aldehyde is prepared benzenpropanal have very high selectivity.
The specific embodiment
Embodiment 1:
Pipetting 0.5mL concentration with pipette is that 0.05mol/L chlorine palladium aqueous acid joins in the 100mL three-necked bottle, and then adds the 30mL deionized water, adds the 263mg CNT under the magnetic agitation effect, and ultrasonic dispersion 1h is uniformly dispersed CNT.Under the magnetic agitation effect, dropwise add the solution of potassium borohydride that 10mL concentration is 0.005mol/L then, continue again after dropwising to stir 1.5h, make chlorine palladium acid solution be reduced to Pd nano particle fully.In 80 ℃ of oil baths, continue to stir 1.5h at last, till not having bubble to produce.Mixture is cooled to room temperature filters, fully wash, under 80 ℃ of temperature, dry with deionized water and absolute ethyl alcohol.Obtain palladium/carbon nano-tube catalyst (mass fraction of palladium is 1%).Transmission electron microscope shows that the Pd nano particle height is evenly dispersed on the CNT, and its average grain diameter size is 5.3nm.
As a comparison, as carrier, utilize said method synthesizing activity charcoal supported palladium nano-particle catalyst with active carbon.The activated carbon supported Pd nano particle average grain diameter of transmission electron microscope observing is 6.2nm.
Hydrogenation on cinnamic aldehyde prepares the benzenpropanal performance test relatively:
Catalytic hydrogenation reaction carries out in three mouthfuls of jacketed reaction bottles, and reaction bulb links to each other with the amounts of hydrogen tracheae of vavuum pump, automatic constant-pressure respectively, system super constant temperature trough temperature control.In three neck reaction bulbs, add absolute ethyl alcohol and palladium/carbon nano-tube catalyst or activated carbon supported palladium catalyst etc., with the gas in the hydrogen exchange reaction bulb three times, again with find time gas in the reaction bulb of vavuum pump, charge into hydrogen, pass through the silicon rubber of sealing then, in reaction bulb, inject cinnamic acid, with the volume of eudiometer tube record hydrogen.Catalytic hydrogenation reaction carries out under 303K, normal pressure, and the reaction time is fixed as 240min, when reacting less than 240min, no longer consumes hydrogen and then stops reaction.Product is with carrying out quantitative analysis on the Perkin-XL gas chromatograph, fid detector, and SE-30 capillary column, biphenyl are internal standard compound.
Record palladium/carbon nano-tube catalyst under the same conditions activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal is respectively 94.5% and 91.2%; And activated carbon supported palladium catalyst is respectively 99.1% and 25.3% to activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal, and this illustrates that the former has higher selectivity than the latter to hydrogenation on cinnamic aldehyde.
Embodiment 2:
Pipetting 2.5mL concentration with pipette is that 0.1mol/L chlorine palladium aqueous acid joins in the 100mL three-necked bottle, and then adds the 40mL deionized water, adds the 505mg CNT under the magnetic agitation effect, and ultrasonic dispersion 2h is uniformly dispersed CNT.Under the magnetic agitation effect, dropwise add the solution of potassium borohydride that 10mL concentration is 0.05mol/L then, continue again after dropwising to stir 2h, make chlorine palladium acid solution be reduced to Pd nano particle fully.In 80 ℃ of oil baths, continue to stir 2h at last, till not having bubble to produce.Mixture is cooled to room temperature filters, fully wash, under 80 ℃ of temperature, dry with deionized water and absolute ethyl alcohol.Obtain palladium/carbon nano-tube catalyst (mass fraction of palladium is 5%) transmission electron microscope and show that the Pd nano particle height is evenly dispersed on the CNT, its average grain diameter size is 5.8nm.
As a comparison, as carrier, utilize said method synthesizing activity charcoal supported palladium nano-particle catalyst with active carbon.The activated carbon supported Pd nano particle average grain diameter of transmission electron microscope observing is 6.8nm.
Carry out hydrogenation on cinnamic aldehyde according to the method among the embodiment 1 and prepare the benzenpropanal performance test relatively.
Record palladium/carbon nano-tube catalyst under the same conditions activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal is respectively 96.3% and 90.6%; And activated carbon supported palladium catalyst is respectively 100.0% and 26.6% to activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal, and this illustrates that the former has higher selectivity than the latter to hydrogenation on cinnamic aldehyde.
Embodiment 3:
Pipetting 1.0mL concentration with pipette is that 0.03mol/L chlorine palladium aqueous acid joins in the 100mL three-necked bottle, and then adds the 30mL deionized water, adds the 396mg CNT under the magnetic agitation effect, and ultrasonic dispersion 2h is uniformly dispersed CNT.Under the magnetic agitation effect, dropwise add the formalin that 10mL concentration is 0.006mol/L then, continue again after dropwising to stir 1.5h, make chlorine palladium acid solution be reduced to Pd nano particle fully.In 80 ℃ of oil baths, continue to stir 1.5h at last.Mixture is cooled to room temperature filters, fully wash, under 80 ℃ of temperature, dry with deionized water and absolute ethyl alcohol.Obtain palladium/carbon nano-tube catalyst (mass fraction of palladium is 0.8%) transmission electron microscope and show that the Pd nano particle height is evenly dispersed on the CNT, its average grain diameter size is 5.1nm.
As a comparison, as carrier, utilize said method synthesizing activity charcoal supported palladium nano-particle catalyst with active carbon.The activated carbon supported Pd nano particle average grain diameter of transmission electron microscope observing is 6.1nm.
Carry out hydrogenation on cinnamic aldehyde according to the method among the embodiment 1 and prepare the benzenpropanal performance test relatively.
Record palladium/carbon nano-tube catalyst under the same conditions activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal is respectively 95.5% and 92.3%; And activated carbon supported palladium catalyst is respectively 98.7% and 26.5% to activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal, and this illustrates that the former has higher selectivity than the latter to hydrogenation on cinnamic aldehyde.
Embodiment 4:
Pipetting 1.5mL concentration with pipette is that the 0.08mol/L potassium chloropalladate aqueous solution joins in the 100mL three-necked bottle, and then adds the 40mL deionized water, adds the 498mg CNT under the magnetic agitation effect, and ultrasonic dispersion 1h is uniformly dispersed CNT.Under the magnetic agitation effect, dropwise add the solution of potassium borohydride that 24mL concentration is 0.01mol/L then, continue again after dropwising to stir 1.5h, make potassium chloropalladate solution be reduced to Pd nano particle fully.In 80 ℃ of oil baths, continue to stir 2h at last, till not having bubble to produce.Mixture is cooled to room temperature filters, fully wash, under 80 ℃ of temperature, dry with deionized water and absolute ethyl alcohol.Obtain palladium/carbon nano-tube catalyst (mass fraction of palladium is 2.5%) transmission electron microscope and show that the Pd nano particle height is evenly dispersed on the CNT, its average grain diameter size is 5.7nm.
As a comparison, as carrier, utilize said method synthesizing activity charcoal supported palladium nano-particle catalyst with active carbon.The activated carbon supported Pd nano particle average grain diameter of transmission electron microscope observing is 6.5nm.
Carry out hydrogenation on cinnamic aldehyde according to the method among the embodiment 1 and prepare the benzenpropanal performance test relatively.
Record palladium/carbon nano-tube catalyst under the same conditions activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal is respectively 96.4% and 91.1%; And activated carbon supported palladium catalyst is respectively 99.2% and 26.3% to activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal, and this illustrates that the former has higher selectivity than the latter to hydrogenation on cinnamic aldehyde.
Claims (4)
1. one kind is used for hydrogenation on cinnamic aldehyde palladium/carbon nano-tube catalyst and preparation method thereof, it is characterized in that described catalyst carrier is a CNT, and active component is the precious metal palladium nano particle, and its average grain diameter size is 5～6nm.The mass fraction of palladium is 0.1～5% in the catalyst, and all the other are CNT.
2. a kind of preparation method who is used for hydrogenation on cinnamic aldehyde palladium/carbon nano-tube catalyst according to claim 1 is characterized in that following steps:
1) palladium salt is dissolved in the deionized water, compound concentration is the palladium saline solution of 0.01～0.2mol/L.In the palladium saline solution, add CNT then, ultrasonic dispersion 0.5～1h;
2) under the magnetic agitation effect, dropwise add the aqueous solution that contains reducing agent, making the ratio of reducing agent and palladium salt is 1: 1～2: 1, dropwises the back and continues to stir 1～2h;
3) in oil bath, stir 1～2h at last, after filtration, washing, oven dry obtain palladium/carbon nano-tube catalyst.
3. a kind of preparation method who is used for hydrogenation on cinnamic aldehyde palladium/carbon nano-tube catalyst according to claim 2 is characterized in that said palladium salt is acid of chlorine palladium or potassium chloropalladate.
4. a kind of preparation method who is used for hydrogenation on cinnamic aldehyde palladium/carbon nano-tube catalyst according to claim 2 is characterized in that said reducing agent is formaldehyde or potassium borohydride.
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| CN101862654A (en) * | 2010-05-28 | 2010-10-20 | 上海市七宝中学 | Method for preparing multi-wall carbon nanotube-palladium composite material and use thereof |
| CN102139234A (en) * | 2011-01-06 | 2011-08-03 | 梁耀彰 | Loaded reduced precious metal catalyst as well as preparation method and application thereof |
| CN108855072A (en) * | 2018-08-16 | 2018-11-23 | 无锡威孚环保催化剂有限公司 | A kind of three-way catalyst of high-temperature aging resisting and preparation method thereof |
| WO2019200894A1 (en) * | 2018-04-17 | 2019-10-24 | 清华大学 | Method for synthesizing atomically dispersed metal catalyst |
| CN112191246A (en) * | 2020-10-15 | 2021-01-08 | 东北石油大学 | Supported palladium monatomic catalyst and application thereof in selective hydrogenation of cinnamaldehyde |
| CN112705197A (en) * | 2019-10-25 | 2021-04-27 | 中国科学院大连化学物理研究所 | Carbon nano tube supported palladium-calcium monolithic catalyst and application thereof in cinnamaldehyde hydrogenation |
| CN112724005A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Method for preparing phenylpropyl aldehyde from cinnamyl aldehyde |
| CN113354603A (en) * | 2021-06-02 | 2021-09-07 | 中科国生(杭州)科技有限公司 | Preparation method of 2, 5-tetrahydrofuran dicarboxylic acid |
| CN115595624A (en) * | 2021-07-07 | 2023-01-13 | 天津大学（Cn） | Catalyst for electrocatalytic hydrogenation of cinnamaldehyde and preparation method thereof |
| CN115595625A (en) * | 2021-07-07 | 2023-01-13 | 天津大学（Cn） | Palladium catalyst, preparation method and application in cinnamyl alcohol electrosynthesis |
| CN115957794A (en) * | 2023-01-31 | 2023-04-14 | 大连理工大学 | Supported palladium/carbon catalyst for preparing hydrocinnamaldehyde by hydrogenation of cinnamaldehyde and preparation method thereof |
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- 2009-11-30 CN CN200910153977A patent/CN101703930A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101862654A (en) * | 2010-05-28 | 2010-10-20 | 上海市七宝中学 | Method for preparing multi-wall carbon nanotube-palladium composite material and use thereof |
| CN102139234A (en) * | 2011-01-06 | 2011-08-03 | 梁耀彰 | Loaded reduced precious metal catalyst as well as preparation method and application thereof |
| WO2019200894A1 (en) * | 2018-04-17 | 2019-10-24 | 清华大学 | Method for synthesizing atomically dispersed metal catalyst |
| CN108855072B (en) * | 2018-08-16 | 2021-10-22 | 无锡威孚环保催化剂有限公司 | High-temperature-aging-resistant three-way catalyst and preparation method thereof |
| CN108855072A (en) * | 2018-08-16 | 2018-11-23 | 无锡威孚环保催化剂有限公司 | A kind of three-way catalyst of high-temperature aging resisting and preparation method thereof |
| CN112705197B (en) * | 2019-10-25 | 2022-08-12 | 中国科学院大连化学物理研究所 | Carbon nano tube supported palladium-calcium monolithic catalyst and application thereof in cinnamaldehyde hydrogenation |
| CN112705197A (en) * | 2019-10-25 | 2021-04-27 | 中国科学院大连化学物理研究所 | Carbon nano tube supported palladium-calcium monolithic catalyst and application thereof in cinnamaldehyde hydrogenation |
| CN112724005A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Method for preparing phenylpropyl aldehyde from cinnamyl aldehyde |
| CN112724005B (en) * | 2019-10-28 | 2022-07-12 | 中国石油化工股份有限公司 | Method for preparing phenylpropyl aldehyde from cinnamyl aldehyde |
| CN112191246A (en) * | 2020-10-15 | 2021-01-08 | 东北石油大学 | Supported palladium monatomic catalyst and application thereof in selective hydrogenation of cinnamaldehyde |
| CN113354603A (en) * | 2021-06-02 | 2021-09-07 | 中科国生(杭州)科技有限公司 | Preparation method of 2, 5-tetrahydrofuran dicarboxylic acid |
| CN115595624A (en) * | 2021-07-07 | 2023-01-13 | 天津大学（Cn） | Catalyst for electrocatalytic hydrogenation of cinnamaldehyde and preparation method thereof |
| CN115595625A (en) * | 2021-07-07 | 2023-01-13 | 天津大学（Cn） | Palladium catalyst, preparation method and application in cinnamyl alcohol electrosynthesis |
| CN115957794A (en) * | 2023-01-31 | 2023-04-14 | 大连理工大学 | Supported palladium/carbon catalyst for preparing hydrocinnamaldehyde by hydrogenation of cinnamaldehyde and preparation method thereof |
| CN115957794B (en) * | 2023-01-31 | 2024-04-26 | 大连理工大学 | Supported palladium/carbon catalyst for preparing phenylpropionaldehyde by cinnamaldehyde hydrogenation and preparation method thereof |
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Open date: 20100512 |