CN101711980A - Novel attapulgite supported palladium hydrogenation catalyst and preparation method thereof - Google Patents
Novel attapulgite supported palladium hydrogenation catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a novel attapulgite supported palladium hydrogenation catalyst and a preparation method thereof. Acidized attapulgite clay is used as a carrier, potassium borohydride or hydrazine hydrate is used as a reducer, and a soluble palladium salt is reduced to palladium nano particles which are loaded on the acidized attapulgite clay. In the attapulgite loaded palladium hydrogenation catalyst prepared by the method of the invention, the palladium nano particles are fine and uniform and are highly dispersed on the surfaces of carbon nano tubes, and compared with the active carbon or graphite loaded palladium catalyst, the attapulgite loaded palladium hydrogenation catalyst has high activity and selectivity for hydrogenating cinnamyl aldehyde to prepare phenylpropyl aldehyde.
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, specifically relates to be used for the attapulgite supported palladium Preparation of catalysts method of spirit catalytic of cinnamaldehyde hydrogenation preparing benzenpropanal.
Background technology
Cinnamic acid is as a kind of important α, beta-unsaturated aldehyde, and its hydrogenation products cinnamyl alcohol and benzenpropanal all are intermediates important in the fine chemistry industry.Therefore benzenpropanal is a kind of additive of foodstuff flavouring, it is found that recently benzenpropanal also is the important intermediate of preparation AIDS drug, and the research to the C=C key selective catalytic hydrogenation of cinnamic acid receives much attention.Because cinnamic acid has two keys of C=C and the two keys of C=O simultaneously, and and kinds of aromatic ring conjugation, the two key selective hydrogenation products of control C=C are just more difficult during hydrogenation.The catalyst that the cinnamic acid catalytic hydrogenation is commonly used is platinum, palladium, iridium, ruthenium etc., and wherein palladium is that spirit catalytic of cinnamaldehyde C=C double-bond hydrogenation generates the most effective catalyst of benzenpropanal.Studies show that catalyst carrier, reaction condition, solvent, additive etc. all have significant effects to the hydrogenation performance of cinnamic acid.Therefore palladium catalyst normally loads on the various carriers, as carbon carrier, molecular sieve, zeolite and metal oxide etc.On the one hand, above-mentioned carrier loaded palladium catalyst awaits further to improve to selectivity and the activity that hydrogenation on cinnamic aldehyde prepares benzenpropanal; On the other hand, because the carrier costliness causes catalyst cost height, be unfavorable for industrial applications.
Attapulgite clay (Attapulgite) claims palygorskite (Palygorskite) again, be a kind of tool chain layer structure contain Shuifu County's zeopan clay mineral, it has special fibre structure, unusual colloid and absorption property.China is the country of attapulgite clay reserves maximum in the world.Though the application of attapulgite clay in catalysis in recent years more and more paid close attention to, be that carrier loaded nano Pd catalyst and the research that applies it to spirit catalytic of cinnamaldehyde hydrogenation preparing benzenpropanal do not see as yet that but report is arranged with it.The price of comprehensive carrier and active component and catalytic performance etc. are many-sided to be considered, to being that the preparation method of carrier loaded palladium catalyst and the research of catalytic applications are a significant job with attapulgite clay.
Summary of the invention
The purpose of this invention is to provide a kind of novel attapulgite supported palladium hydrogenation catalyst and preparation method thereof with excellent Catalytic Hydrogenation Properties.The catalyst carrier of invention is an attapulgite clay, and active component is the precious metal palladium nano particle, and its average grain diameter size is 3～5nm.The mass fraction of palladium is 0.2～3% in the catalyst, and all the other are attapulgite clay.
The attapulgite supported palladium Preparation of catalysts method that is used for hydrogenation on cinnamic aldehyde is as follows:
1) be that the acid solution of 1～6mol/L mixes with a certain amount of attapulgite clay and concentration, making solid-to-liquid ratio is 6: 1～12: 1, and the room temperature lower magnetic force stirs 8～16h, centrifugal, washing, dry for standby;
2) palladium salt is dissolved in the deionized water, compound concentration is the palladium saline solution of 0.02～0.3mol/L.In the palladium saline solution, add the attapulgite clay after the acidification then, ultrasonic dispersion 2～3h;
3) 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;
4) in oil bath, stir 1～2h at last, obtain attapulgite supported palladium hydrogenation catalyst through centrifugal, washing, oven dry.
Said acid solution is hydrochloric acid or nitric acid among the present invention.Said palladium salt is acid of chlorine palladium or potassium chloropalladate.Said reducing agent is potassium borohydride or hydrazine hydrate.
The present invention has following beneficial effect compared with the prior art:
The attapulgite supported palladium hydrogenation catalyst that the present invention is prepared, the palladium that loads on the concavo-convex rod is a nano particle, particle diameter is tiny and even, and high degree of dispersion is on concavo-convex rod surface.The synthetic catalyst of the inventive method is compared with the palladium catalyst of other carbon carrier loads, and cost is lower, and hydrogenation on cinnamic aldehyde is prepared benzenpropanal has very high selectivity.
The specific embodiment
Embodiment 1:
The attapulgite clay that takes by weighing certain mass is 8: 1 adding 4mol/L hydrochloric acid by liquid-solid ratio in beaker, and the room temperature lower magnetic force stirs 12h, and is centrifugal then, the distilled water washing, and 105 ℃ of oven dry, it is standby to put into drier after the grinding.Pipetting 2.0mL concentration with pipette is that 0.02mol/L chlorine palladium aqueous acid joins in the 150mL three-necked bottle, and then adds the 50mL deionized water, adds 528mg acidifying attapulgite clay under the magnetic agitation effect, and ultrasonic dispersion 2.5h is uniformly dispersed concavo-convex rod.Under the magnetic agitation effect, dropwise add the solution of potassium borohydride that 10mL concentration is 0.008mol/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 2h at last, till not having bubble to produce.It is centrifugal that mixture is cooled to room temperature, fully washs with deionized water and absolute ethyl alcohol, dries under 110 ℃ of temperature.Obtain attapulgite supported palladium hydrogenation catalyst (mass fraction of palladium is 0.8%).Transmission electron microscope shows that the Pd nano particle height is evenly dispersed on the concavo-convex rod, and its average grain diameter size is 4.1nm.
As a comparison, as carrier, utilize said method synthesizing activity charcoal supported palladium nano-particle catalyst and the agent of mineral carbon load palladium nano particle catalysis with active carbon and graphite.The activated carbon supported Pd nano particle average grain diameter of transmission electron microscope observing is 6.5nm, and the Pd nano particle average grain diameter of mineral carbon load is 14.5nm.
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 attapulgite loaded palladium catalyst or other carbon carrier loaded palladium catalysts, 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 120min, when reacting less than 120min, 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 attapulgite supported palladium hydrogenation catalyst under the same conditions activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal is respectively 99.1% and 90.2%; And activated carbon supported palladium catalyst is respectively 99.5% and 25.3% to activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal, the mineral carbon load palladium catalyst is respectively 45.6% and 19.5% to activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal, and this explanation attapulgite supported palladium hydrogenation catalyst has higher activity and selectivity than two kinds of carbon carrier loaded palladium catalysts to hydrogenation on cinnamic aldehyde.
Embodiment 2:
The attapulgite clay that takes by weighing certain mass is 10: 1 adding 2mol/L nitric acid by liquid-solid ratio in beaker, and the room temperature lower magnetic force stirs 10h, and is centrifugal then, the distilled water washing, and 105 ℃ of oven dry, it is standby to put into drier after the grinding.Pipetting 1.0mL concentration with pipette is that 0.05mol/L chlorine palladium aqueous acid joins in the 150mL three-necked bottle, and then adds the 60mL deionized water, adds 438mg acidifying attapulgite clay under the magnetic agitation effect, and ultrasonic dispersion 2h is uniformly dispersed concavo-convex rod.Under the magnetic agitation effect, dropwise add the solution of potassium borohydride that 10mL concentration is 0.01mol/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 2h at last, till not having bubble to produce.It is centrifugal that mixture is cooled to room temperature, fully washs with deionized water and absolute ethyl alcohol, dries under 110 ℃ of temperature.Obtain attapulgite supported palladium hydrogenation catalyst (mass fraction of palladium is 1.2%).Transmission electron microscope shows that the Pd nano particle height is evenly dispersed on the concavo-convex rod, and its average grain diameter size is 4.3nm.
As a comparison, as carrier, utilize said method synthesizing activity charcoal supported palladium nano-particle catalyst and the agent of mineral carbon load palladium nano particle catalysis with active carbon and graphite.The activated carbon supported Pd nano particle average grain diameter of transmission electron microscope observing is 6.8nm, and the Pd nano particle average grain diameter of mineral carbon load is 15.1nm.
Carry out hydrogenation on cinnamic aldehyde according to the method among the embodiment 1 and prepare the benzenpropanal performance test relatively.
Record attapulgite supported palladium hydrogenation catalyst under the same conditions activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal is respectively 100.0% and 92.1%; And activated carbon supported palladium catalyst is respectively 98.8% and 26.3% to activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal, the mineral carbon load palladium catalyst is respectively 44.4% and 18.6% to activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal, and this explanation attapulgite supported palladium hydrogenation catalyst has higher activity and selectivity than two kinds of carbon carrier loaded palladium catalysts to hydrogenation on cinnamic aldehyde.
Embodiment 3:
The attapulgite clay that takes by weighing certain mass is 10: 1 adding 4mol/L hydrochloric acid by liquid-solid ratio in beaker, and the room temperature lower magnetic force stirs 14h, and is centrifugal then, the distilled water washing, and 105 ℃ of oven dry, it is standby to put into drier after the grinding.Pipetting 1.0mL concentration with pipette is that the 0.1mol/L potassium chloropalladate aqueous solution joins in the 150mL three-necked bottle, and then adds the 80mL deionized water, adds 344mg acidifying attapulgite clay under the magnetic agitation effect, and ultrasonic dispersion 2h is uniformly dispersed concavo-convex rod.Under the magnetic agitation effect, dropwise add the solution of potassium borohydride that 10mL concentration is 0.02mol/L then, continue again after dropwising to stir 1.5h, make the potassium chloropalladate in the 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.It is centrifugal that mixture is cooled to room temperature, fully washs with deionized water and absolute ethyl alcohol, dries under 110 ℃ of temperature.Obtain attapulgite supported palladium hydrogenation catalyst (mass fraction of palladium is 3%).Transmission electron microscope shows that the Pd nano particle height is evenly dispersed on the concavo-convex rod, and its average grain diameter size is 4.9nm.
As a comparison, as carrier, utilize said method synthesizing activity charcoal supported palladium nano-particle catalyst and the agent of mineral carbon load palladium nano particle catalysis with active carbon and graphite.The activated carbon supported Pd nano particle average grain diameter of transmission electron microscope observing is 7.4nm, and the Pd nano particle average grain diameter of mineral carbon load is 16.3nm.
Carry out hydrogenation on cinnamic aldehyde according to the method among the embodiment 1 and prepare the benzenpropanal performance test relatively.
Record attapulgite supported palladium hydrogenation catalyst under the same conditions activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal is respectively 98.9% and 91.3%; And activated carbon supported palladium catalyst is respectively 98.5% and 22.7% to activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal, the mineral carbon load palladium catalyst is respectively 40.8% and 16.2% to activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal, and this explanation attapulgite supported palladium hydrogenation catalyst has higher activity and selectivity than two kinds of carbon carrier loaded palladium catalysts to hydrogenation on cinnamic aldehyde.
Embodiment 4:
The attapulgite clay that takes by weighing certain mass is 12: 1 adding 3mol/L hydrochloric acid by liquid-solid ratio in beaker, and the room temperature lower magnetic force stirs 13h, and is centrifugal then, the distilled water washing, and 105 ℃ of oven dry, it is standby to put into drier after the grinding.Pipetting 1.5mL concentration with pipette is that 0.03mol/L chlorine palladium aqueous acid joins in the 150mL three-necked bottle, and then adds the 50mL deionized water, adds 594mg acidifying attapulgite clay under the magnetic agitation effect, and ultrasonic dispersion 3h is uniformly dispersed concavo-convex rod.Under the magnetic agitation effect, dropwise add the hydrazine hydrate solution that 10mL concentration is 0.009mol/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.It is centrifugal that mixture is cooled to room temperature, fully washs with deionized water and absolute ethyl alcohol, dries under 110 ℃ of temperature.Obtain attapulgite supported palladium hydrogenation catalyst (mass fraction of palladium is 0.8%).Transmission electron microscope shows that the Pd nano particle height is evenly dispersed on the concavo-convex rod, and its average grain diameter size is 4.2nm.
As a comparison, as carrier, utilize said method synthesizing activity charcoal supported palladium nano-particle catalyst and the agent of mineral carbon load palladium nano particle catalysis with active carbon and graphite.The activated carbon supported Pd nano particle average grain diameter of transmission electron microscope observing is 6.7nm, and the Pd nano particle average grain diameter of mineral carbon load is 14.3nm.
Carry out hydrogenation on cinnamic aldehyde according to the method among the embodiment 1 and prepare the benzenpropanal performance test relatively.
Record attapulgite supported palladium hydrogenation catalyst under the same conditions activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal is respectively 100.0% and 93.1%; And activated carbon supported palladium catalyst is respectively 99.3% and 28.0% to activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal, the mineral carbon load palladium catalyst is respectively 47.2% and 21.3% to activity and the selectivity that hydrogenation on cinnamic aldehyde prepares benzenpropanal, and this explanation attapulgite supported palladium hydrogenation catalyst has higher activity and selectivity than two kinds of carbon carrier loaded palladium catalysts to hydrogenation on cinnamic aldehyde.
Claims (5)
1. novel attapulgite supported palladium hydrogenation catalyst and preparation method thereof is characterized in that described catalyst carrier is an attapulgite clay, and active component is the precious metal palladium nano particle, and its average grain diameter size is 3～5nm.The mass fraction of palladium is 0.2～3% in the catalyst, and all the other are attapulgite clay.
2. the preparation method of a kind of novel attapulgite supported palladium hydrogenation catalyst according to claim 1 is characterized in that following steps:
1) be that the acid solution of 1～6mol/L mixes with a certain amount of attapulgite clay and concentration, making solid-to-liquid ratio is 6: 1～12: 1, and the room temperature lower magnetic force stirs 8～16h, centrifugal, washing, dry for standby;
2) palladium salt is dissolved in the deionized water, compound concentration is the palladium saline solution of 0.01～0.05mol/L.In the palladium saline solution, add the attapulgite clay after the acidification then, ultrasonic dispersion 2～3h;
3) 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;
4) in oil bath, stir 1～2h at last, obtain attapulgite supported palladium hydrogenation catalyst through centrifugal, washing, oven dry.
3. the preparation method of a kind of novel attapulgite supported palladium hydrogenation catalyst according to claim 2 is characterized in that said acid solution is hydrochloric acid or nitric acid.
4. the preparation method of a kind of novel attapulgite supported palladium hydrogenation catalyst according to claim 2 is characterized in that said palladium salt is acid of chlorine palladium or potassium chloropalladate.
5. the preparation method of a kind of novel attapulgite supported palladium hydrogenation catalyst according to claim 2 is characterized in that said reducing agent is potassium borohydride or hydrazine hydrate.
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