CN103691431A - Palladium carbon catalyst as well as preparation method and application thereof - Google Patents
Palladium carbon catalyst as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a palladium carbon catalyst which comprises the following components: (1) nanometer TiO2-modified active carbons are used as composite carriers; (2) Pd nanometer particles are used as active components, wherein the strong interaction between metals and the carriers exists in the active components and TiO2 on the composite carriers to form a Pd@TiO2 structure so as to form structural Pd@TiO2/active carbons of the catalyst.
Description
Technical field
The present invention relates to catalyst field, be specifically related to a kind of palladium-carbon catalyst and its preparation method and application, particularly relate to this catalyst and prepare the application application in cyclohexanone in phenol selective hydrogenation.
Background technology
Loaded nano noble metal catalyst has good Hydrogenation, at the catalytic hydrogenation of all kinds of unsaturated organic compounds of the industries such as petrochemical industry, pharmacy, dyestuff, agricultural chemicals.Nano Pd catalyst, as a kind of hydrogenation catalyst of function admirable, is usually used in the selective hydrogenation of eneyne hydrocarbon, nitro, nitroso, ketone, aldehyde etc., occupies extremely important status on chemical industry.It is generally acknowledged, the loaded nano palladium catalyst of function admirable structurally should have following characteristics: 1) active component palladium microcrystal grain wants little of nanoscale, and it is high that content is wanted, and it is many that surface exposure atom is wanted; 2) carrier specific area is large, and active component is at carrier surface good dispersion.
The character of catalyst except depend on form and content, also closely related with the preparation method of catalyst and process conditions etc., same raw material, identical composition and content, during preparation method's difference, the activity and selectivity of catalyst may have very large difference.Palladium-carbon catalyst will be realized efficient catalytic performance, should have Technique of Nano Pd crystallite good dispersion, the feature that content is high.At present, the main method of preparing palladium-carbon catalyst is both at home and abroad chemical reduction method, comprises gas phase reduction process and liquid phase reduction.Gas phase reduction process is that palladium salt is carried on palladium presoma on carrier by the method for flooding or depositing, and forming palladium oxide crystallite through high-temperature calcination, then in H2 atmosphere, carries out high temperature vapour phase reduction.The method easily makes in high-temperature calcination and high temperature reduction process that crystallite moves at carrier surface, agglomeration.Liquid phase reduction is that palladium salt is in being added with carrier and protectant liquid phase environment; through performic acid, formaldehyde, glucose, sodium formate, sodium borohydride, metaphosphoric acid sodium dihydrogen, hydrazine hydrate; the reduction of the reducing agents such as polyalcohol, is carried on metal simple-substance palladium on carrier.The method is by adding protective agent (polymer; surfactant) control the granular size of palladium particle; but need to remove protective agent through follow-up high-temperature oxidation process, carry out activating catalyst, this process can make palladium crystallite generation agglomeration, in the dispersiveness reduction of carrier surface.
Existing some exemplary of mentioning about preparing the patent of nano Pd catalyst aspect, but still have problem or weak point separately:
Chinese patent CN1519052A(load P d hydrogenation catalyst and preparation method thereof, is used the method for the preparing cyclohexanone from phenol of this catalyst) utilize conventional infusion process to prepare Pd/SiO
2catalyst.By the synthetic carrier S iO of xerogel method
2be immersed in PdCl
2in solution, in 100 ℃ dry, in 200 ℃ of N
2middle insulation 2-4 hour.Then at the H of 400 ℃
2middle reduction 4-6 hour.The method needs high-temperature process, and palladium crystallite particle diameter is restive, and the dispersiveness on carrier is bad.
Mono-kind of Chinese patent CN102125838A(prepares high selectivity Pd/TiO
2the method of-C hydrogenation catalyst) by pH swing method repeatedly, palladium ion is deposited to TiO
2on-C powder, then reduce processing by a kind of or its combination in formaldehyde, formic acid, hydrazine hydrate, glucose, sodium formate, sodium borohydride, paraformaldehyde, more after filtration, washing, the dry Pd/TiO that to obtain
2-C catalyst.This invention needs to consume a large amount of alkali lye and reducing agent, and operating process is complicated.
Chinese patent CN101612566A(mono-kind low platinum carbon-supported nano Pd-Pt alloy catalyst, preparation method and application thereof) by Na
2pdCl
4solution and K
2ptC1
4solution joins water, ethanol, in the dispersion solvents such as isopropyl alcohol, then add ethylenediamine, natrium citricum, ammoniacal liquor, the complexing agents such as ethylenediamine tetra-acetic acid, after being warming up to 40~80 ℃, keep stirring making complexing agent and Pd ion, the abundant complexing of Pt ion, regulate pH value to 7~11 of mixed liquor, add charcoal carrier, sonic oscillation also adds strong mixing, make Pd and Pt active material dispersed at carbon surface, make raw material charcoal slurry, pass into inert gas, remove dissolved oxygen wherein, dropwise add sodium borohydride, dimethylamino borine, the reducing agents such as ascorbic acid, abundant reduction Pd, Pt, filter, washing, after dry, obtain carbon-supported nano Pd-Pt alloy catalyst.The complexing agent that the method adds can be coated the active phase of Pd, Pt of reduction, makes catalyst activity reduction.
Chinese patent CN102463352A(hexahedral method of synthetic bimetallic Pd-Au core-shell) utilize two-step method synthetic Pd-Au core-shell hexahedron in water.First with H
2pdCl
4for palladium source, ascorbic acid is reducing agent, take cetyl ammonium bromide as the synthetic hexahedral Pd seed of stabilizing agent, then by crystal epitaxy method, with HAuCl
4for Au source, ascorbic acid is reducing agent, take cetyl pyridinium bromide as stabilizing agent, has synthesized bimetallic Pd-Au core-shell hexahedron in water.The method has added protective agent, and purposes is restricted.
Chinese patent CN102476051A(noble metal/TiO
2-C Catalysts and its preparation method) by TiO
2-C complex carrier impregnated in containing in the precious metal salt solutions such as palladium salt, ruthenium salt, obtain catalyst precarsor, again through 100 ℃ of dry 2h, with any or its combination in reducing agent formaldehyde, formic acid, hydrazine hydrate, paraformaldehyde, glucose, sodium formate, sodium borohydride or hydrogen, reduce again, obtain noble metal/TiO
2-C catalyst.The bad dispersibility of active phase prepared by the method, nano-sized crystal content is low.
Chinese patent CN102513100A(activated carbon supported Catalysts and its preparation method and application) in catalyst take active carbon as carrier, take the bimetallic catalyst that platinum and palladium be active component.Preparation method: the active carbon through salpeter solution immersion treatment be impregnated in to H
2pdCl
4the aqueous solution and H
2ptCl
64~8h in the aqueous solution, dipping finishes with alkali lye, to regulate reactant liquor pH=9 afterwards, filter, filter cake is washed to neutrality, the filter cake of acquisition add hydrazine hydrate reduction agent in l0~50 ℃ reaction l~5h, after filtration, washing, dry after, make activated carbon supported catalyst.The shortcoming of the method is active component bad dispersibility on carrier, and grain diameter is restive.
Chinese patent CN102806105A(load type gold palladium catalyst and preparation and application) using ion exchange resin as carrier, resin is processed with acid, neutralizing treatment successively, then itself and golden palladium metal precursor water solution are carried out to ion-exchange, with reducing agents such as ammonia borine, sodium borohydride, vitamin Cs, reduce again, after being dried, obtain catalyst.The carrier using in the method is expensive, and the scope of application is restricted.
Mono-kind of Chinese patent CN102553582A(prepares the method that carbon carries golden platinum or golden palladium bimetallic catalyst) synthetic golden platinum or the golden palladium composite Nano colloid of high temperature high pressure process chemistry co-reducing process that utilize microwave to produce in autoclave, induce golden platinum or the modification of golden palladium bimetal nano particles, the bimetal nano particles of modification is being deposited on to carbon carrier surface, and the carbon that obtains having high electrocatalytic active carries golden platinum or golden palladium catalyst.When chemical coreduction, added polyvinylpyrrolidone to cook protective agent.
Chinese patent CN102895970A(organic aerogel load P d compound is prepared method and the Pd/C catalyst of Pd/C catalyst) take organic aerogel as carbon matrix precursor and catalyst carrier, water-soluble Pd compound is catalyst activity component source, utilize equi-volume impregnating, by dip loading, ageing, high temperature cabonization, hydrogen reducing step, be prepared from.The method needs 600 ℃ of above high temperature cabonizations, and condition is harsher, and energy consumption is high.
Chinese patent CN102916201A(carbon carries palladium nanocatalyst and preparation method thereof) adopt liquid phase reactor method two-step oxidation Modified Activated Carbon carrier and Pd particle be dispersed in to the surface of above-mentioned charcoal carrier by liquid complexing coreduction approach.Complexing agent used is disodium ethylene diamine tetraacetate, natrium citricum, 1,2-diaminocyclohexane tetraacetic acid salt, acetylacetone,2,4-pentanedione or sodium tartrate, and reducing agent used is sodium borohydride, ethylene glycol, citric acid or formic acid.The coated active phase of complexing agent that the method is used, reduces catalytic activity.
Mono-kind of Chinese patent CN102872861A(utilizes ethanol reduction to prepare the method for Technique of Nano Pd eelctro-catalyst) utilize the reduction of ethanol and cosolvent effect by palladium bichloride (PdCl
2) be reduced to Metal Palladium (Pd) nano particle, first configure ethanol water; Then by PdCl
2a kind of being added in ethanolic solution in powder and protective agent lauryl sodium sulfate, polyvinylpyrrolidone, softex kw, logical protection gas N
2or Ar stir 1-3h at 60-80 ℃, make palladium cation generation reduction reaction obtain Pd nano particle; Centrifugation obtains black precipitate after completion of the reaction, uses ethanol, acetone to wash rear dry, obtains Technique of Nano Pd eelctro-catalyst.
Chinese patent CN102784642A(load type double-metal alloy catalyst and its production and use) described catalyst is to take ceria as carrier, take Metal Palladium and silver as active component.By two step synthesis, be about to ceria and impregnated in silver salt solution, after dipping balance, evaporating solvent, air calcination, then by gained sample double-steeping in palladium salting liquid, dipping balance after, evaporating solvent, in air, calcine, obtain palladium-silver bimetallic catalyst precursor, during use, pass through again H
2high-temperature activation.The method need to be carried out high-temperature process, makes activity that agglomeration occur mutually, and the dispersiveness of active phase is poor.
Chinese patent CN1026009900A(load type gold palladium bimetallic catalyst and preparation method thereof) magnesium oxide carrier is immersed in the maceration extract being formed by gold chloride and palladium bichloride, reach after dipping balance the metal ion then adsorbing with reducing plant extracts such as cacumen biotae, Chinese hackberry leaf, lotus leaves.Then filtration washing is dry, then obtains load type gold palladium bimetallic catalyst through calcination activation.
Chinese patent CN102544531A(Pd/TiO
2/ C composite nano-catalyst and its preparation method and application) by pretreated Vulcan XC-72 activated carbon powder and the synthetic nano-TiO of hydro-thermal method
2powder fully mixes, and adding concentration is 25% glycol water, and strong stirring, obtains active carbon and TiO
2the mixed solution of the carrier forming; Palladium chloride solution and stabilizing agent trisodium citrate, then to drip excessive sodium borohydride be reducing agent, after reaction 3h, through suction filtration after washing to noresidue chlorion, in vacuum drying, final Pd/TiO
2/ C composite nano-catalyst.
Chinese patent CN103055852A(is for high dispersive palladium/carbon nano-tube catalyst and the preparation method of anthraquinone hydrogenation) palladium bichloride hydrochloric acid solution is joined to carbon nano tube suspension, with aqueous slkali, regulate the pH to 9-12 of suspension, palladium ion is precipitated, add again excessive reductant formaldehyde (or sodium formate, glucose), at 40-60 ℃, carry out reduction reaction, after filtration, washing and the dry palladium/carbon nano-tube catalyst that to obtain.
Various the improving one's methods that above-mentioned patent is mentioned, object is mainly to improve content and the dispersive property of nanometer metal palladium crystallite.In fact, in existing preparation method, the control of Metal Palladium content of crystallite is not very desirable, and dispersive property is not high.In liquid-phase reduction process; by adding protective agent, control the particle size of palladium crystallite; at high-temperature oxydation, remove in protectant process, have the migration of palladium crystallite in various degree and grow up, and the reduction of Pd ion all needs by adding excessive reductant to realize.
Cyclohexanone is to have to be permitted multiduty industrial chemicals, mainly for the preparation of synthetic fibers nylon 6 and nylon 66, also can be used as the important intermediate of the fine chemicals such as medicine, coating, dyestuff.Phenol hydrogenation is an important approach preparing cyclohexanone.Because general catalyst is active low under temperate condition, and cyclohexanone easily further hydrogenation generate the accessory substances such as cyclohexanol, selectively not high.Even for example temperature is greater than 100 ℃ at 120-160 ℃, pressure 2-10MPa under harsh conditions, reaches the high selectivity (>95%) that realizes cyclohexanone under the condition of higher conversion (>80%) and remain a catalysis difficult problem with challenge.Therefore,, under temperate condition, the direct selective hydrogenation of phenol is prepared cyclohexanone and is still a challenge.Efficiently, highly selective synthesizing cyclohexanone is a challenge difficult problem always.
Summary of the invention
The object of the present invention is to provide hydrogenation catalyst of a kind of excellent performance and preparation method thereof, its dispersive property is good, and especially Pyrogentisinic Acid's selective hydrogenation has fine catalytic performance, overcomes the deficiency of existing palladium-carbon catalyst technology of preparing.
The invention provides a kind of palladium-carbon catalyst, comprising:
1) with nano-TiO
2the active carbon of modifying and decorating is complex carrier;
2) take Pd nano particle as active component;
Wherein, the TiO on described active component and described complex carrier
2there is the strong interaction of metal and carrier, form Pd@TiO
2structure, so forms the structure Pd@TiO of described catalyst
2/ active carbon.
In a preferred embodiment of the present invention, described nano-TiO
2with single or multiple lift dispersity, be carried on the active carbon outer surface of modification and the TiO that duct inner surface forms
2/ AC(active carbon) complex carrier.
In a preferred embodiment of the present invention, the particle diameter of described nano particle is 1-10nm, preferred 1-5nm, described TiO
2particle diameter be 1-20nm.
In a preferred embodiment of the present invention, TiO
2the active carbon of modifying and decorating is the TiO of complex carrier
2mass content account for the 1-15% of described complex carrier gross mass, preferred 5.0-12%.
In a preferred embodiment of the present invention, the mass content of described active component accounts for the 0.1-8% of catalyst gross mass, preferably 0.5%-3.0%.
In a preferred embodiment of the present invention, described active carbon is preferably cocoanut active charcoal.
The final structure of catalyst of the present invention is Pd@TiO
2/ AC.
The preparation method who the invention provides a kind of described palladium-carbon catalyst, comprising:
I) will to active carbon, carry out modification with salpeter solution and obtain modified active Carbon Materials;
Ii) by TiO
2be carried on step I) on the modified active Carbon Materials that obtains, obtain TiO
2/ activated carbon composite carrier material;
Iii) by step I i) TiO that obtains
2/ activated carbon composite carrier dispersion of materials is to containing stirring every light in the solution of Pd, then under UV-irradiation, filters, dryly obtains described Pd@TiO
2/ active carbon.
In a preferred embodiment of the present invention, described by TiO
2being carried on step I) step of the modified active Carbon Materials that obtains comprises:
Configure containing Ti solution, modified activated carbon dispersion of materials is contained in Ti solution in described, regulate pH value to 2-4, and carry out sonic oscillation, make to enter in the duct of described modified active Carbon Materials containing Ti solution, then standing plastic, finally calcines and obtains described TiO
2/ activated carbon composite carrier material.
In present invention further optimization embodiment, the compound method of described titaniferous solution is:
A) the ethanolic solution A of configuration butyl titanate;
B) the mixed solution B of configuration water and absolute ethyl alcohol;
C) under the condition stirring, solution B is dropwise joined in solution A, form mixed solution C, obtain described containing Ti solution.
Described mixed solution C is for being generally sol-gel state.
Concrete, the preparation method of catalyst of the present invention comprises:
1) carrier active carbon (AC) pretreatment
By through washing, boiled the salpeter solution that the cocoanut active charcoal of 2~3 times is placed in variable concentrations, in 60~70 ℃ of water-baths, add hot reflux 4h, deionized water washing and filtering, is neutral to pH, dry at 80 ℃, obtains through HNO
3the absorbent charcoal material of solution modification.
2) complex carrier TiO
2the preparation of/AC
Sol-gel process load TiO
2: the ethanolic solution A of configuration butyl titanate; The mixed solution B of configuration water and absolute ethyl alcohol; Under the condition stirring, solution B is dropwise joined in solution A, form sol-gel shape solution C, obtain described containing Ti solution.The modified activated carbon dispersion of materials that step 1) is obtained in mixed solution C, enriching HNO
3adjust pH to 3, stir 5~10min, then sonic oscillation 10min enters in AC duct colloidal sol, stop stirring and be settled into gel, dry at 80 ℃, calcine 2h at 500 ℃, obtain TiO
2/ AC composite carrier.Wherein, described solution C is a kind of sol-gel state.
3) load of active metal
Photo catalytic reduction load P d or Pd-Au: get step 2) TiO that makes
2/ AC composite carrier dispersed with stirring is in deionized water, add methyl alcohol, 5-15min is stirred in dark place, add the sub-palladium acid solution of a certain amount of chlorine, concentrated hydrochloric acid is adjusted pH to 3~5, dark place rapid stirring 0.1-1h again, then be placed in radiation 5~6h under ultraviolet light, washing, be filtered to filtrate and be neutral, vacuum drying at 50-90 ℃, obtains Pd@TiO
2/ AC catalyst.
The present invention also provides the application of a kind of described palladium-carbon catalyst in catalytic hydrogenation reaction, catalytic dehydrogenating reaction, catalytic oxidation and carbon carbon coupling reaction.Especially described palladium-carbon catalyst is prepared the application in cyclohexanone in phenol selective hydrogenation.
Compare with existing palladium-carbon catalyst technology of preparing, the present invention has following beneficial effect: adopt photocatalysis direct-reduction process to prepare nano-noble metal catalyst Pd@TiO
2/ AC.
1, the method utilizes photo catalytic reduction principle can make palladium cation Restore All for corresponding simple substance, and even reaches complete as long as light application time long enough just can make the load factor of palladium approach;
2, save operating procedure rambunctious, do not needed high-temperature calcination, can avoid Pd nano particle to reunite or sintering under hot conditions;
3, without any need for reducing agent reduction, do not need the protections such as surfactant yet, removed the palladium that high-temperature oxydation removal protective agent causes, the reunion of golden nanometer particle from and grown up;
4, between nanometer metal palladium and titanium dioxide, there is the strong interaction of metal and carrier, in conjunction with firmly, change the electronic state of Technique of Nano Pd, migration and the reunion of restriction Pd nano particle;
5, the palladium crystallite particle diameter of nano Pd catalyst only has 1-10nm, and even 1-5nm, is evenly distributed, good dispersion, and catalytic performance is good;
6, preparation condition is gentle, is easy to operate and control granular size;
7, preparation technology is simple; With H
2for reducing agent is investigated the nano-noble metal catalyst Pd@TiO preparing
2the catalytic performance of/AC catalysis of phenol selective hydrogenation, nano Pd catalyst catalytic performance prepared by the method is good, good stability.
Accompanying drawing explanation
Fig. 1 is the preparation flow schematic diagram of embodiment 1.
Fig. 2 is the nano Pd catalyst Pd@TiO of embodiment 1 preparation
2the XRD figure of/AC.
Fig. 3 is the nano Pd catalyst Pd@TiO of embodiment 2 preparations
2the XRD figure of/AC.
The specific embodiment
Below with reference to drawings and Examples, describe embodiments of the present invention in detail, to the present invention, how application technology means solve technical problem whereby, and the implementation procedure of reaching technique effect can fully understand and implement according to this.It should be noted that, only otherwise form conflict, each embodiment in the present invention and each feature in each embodiment can mutually combine, and formed technical scheme is all within protection scope of the present invention.
Embodiment 1
1) Activated Carbon Pretreatment: by through washing, boiling the cocoanut active charcoal of 2~3 times, to be placed in mass fraction be 10.94% salpeter solution, in~60 ℃ of water-baths, add hot reflux 4h, deionized water filters, wash to pH and be neutral, at 110 ℃, dry 12h, obtains the modified activated carbon through oxidation processes;
2) sol-gel process load TiO
2: configuration solution A and solution B, under the condition of magnetic agitation, B is dropwise slowly joined in solution A, form mixed solution C colloidal sol, the 12.03g modified activated carbon that step 1) is obtained is distributed in solution C, enriching HNO
3(66-68 quality %) adjusts pH to 3, stirs 5~10min, then sonic oscillation 10min enters in AC duct colloidal sol, stops stirring being settled into gel, and dry 12h at 80 ℃, calcines 2h at 500 ℃, obtains TiO
2carrying capacity is 9.95% composite carrier TiO
2/ AC.Wherein, solution A: 5.664g(~6ml) butyl titanate is scattered in the absolute ethyl alcohol of 25ml; Solution B: 1ml ultra-pure water is scattered in the absolute ethyl alcohol of 15ml
3) TiO photo catalytic reduction load P d: get step 2) making
2/ AC composite carrier 5.316g, dispersed with stirring is in 300ml ultra-pure water, the methyl alcohol that adds 10ml, 10min is stirred in dark place, then adds the sub-palladium acid solution of chlorine that 2.458ml palladium content is 20g/L, with the concentrated hydrochloric acid of mass concentration 37%, adjust pH to 3~5, dark place rapid stirring 1h, is then placed in radiation 5h under the ultraviolet light of 15w, filters, washs to filtrate and be neutral, vacuum drying 12h at 90 ℃, obtains Pd@TiO
2/ AC catalyst, the mass fraction 0.916% of palladium.
As described in Figure 1, the monocrystalline peak of Pa is very obvious as seen from Figure 1 for the XRD figure of the catalyst that the present embodiment obtains, as seen on this catalyst load the Pa crystal grain of monocrystalline.
Embodiment 2
By sol-gel process by TiO
2load on the active carbon of modification, obtain complex carrier TiO
2/ AC.The method of recycling photo catalytic reduction loads to complex carrier TiO by Metal Palladium
2/ AC is upper, through follow-up filtration, washing, dry run, obtains Pd@TiO
2/ AC.
Specific implementation process is with embodiment 1, and that different is HNO
3concentration is 11.13%, complex carrier TiO
2tiO in/AC
2mass content is 9.89%, catalyst P d@TiO
2in/AC, the mass content of palladium is 0.5%.
As described in Figure 2, the monocrystalline peak of Pa is very obvious as seen from Figure 2 for the XRD figure of the catalyst that the present embodiment obtains, as seen on this catalyst load the Pa crystal grain of monocrystalline.
Embodiment 3
With embodiment 1, that different is complex carrier TiO
2tiO in/AC
2mass content is 15%, catalyst P d@TiO
2in/AC, Pd content is 0.5 quality %.
Embodiment 4
With embodiment 1, that different is complex carrier TiO
2tiO in/AC
2content is 20 quality %, catalyst P d@TiO
2in/AC, Pd content is 0.5 quality %.
With embodiment 1, different is that concentration of nitric acid is 15 quality %, complex carrier TiO
2tiO in/AC
2mass content is 20%, catalyst P d@TiO
2in/AC, Pd mass content is 0.5%.
Embodiment 6
The nano Pd catalyst of preparation in 1~5 of above-described embodiment is prepared to cyclohexanone reaction for catalysis of phenol selective hydrogenation.Reaction is carried out in 300mL autoclave, adds successively catalyst 0.5~4g, 40mL cyclohexane (or carrene) and 0.1~1g phenol, passes into H
2air 5~8 times in displacement still, high-speed stirred under 800rpm, when temperature in the kettle rises to temperature required 80~100 ℃ of experiment, passes into H
2make pressure maintain 1.0MPa, reaction 2~6h.After reaction finishes, reactant liquor is at room temperature cooling in still, and the cyclohexanol in product, cyclohexanone content be take chlorobenzene by Agilent6890N gas chromatograph employing internal standard method and analyzed as internal standard compound.
Embodiment 7
With embodiment 6, add the catalyst 4g of embodiment 1 preparation, phenol 0.8g, 100 ℃ of reaction temperatures, solvent is carrene, and the reaction time is 2h, and phenol conversion is 73.0%, and cyclohexanone is selectively 95.7%.
Embodiment 8
With embodiment 6, add the catalyst 4g of embodiment 1 preparation, phenol 0.8g, 100 ℃ of reaction temperatures, solvent is carrene, and the reaction time is 6h, and phenol conversion is 76.4%, and cyclohexanone is selectively 94.9%.
Embodiment 9
With embodiment 6, add the catalyst 4g of embodiment 1 preparation, phenol 0.8g, 100 ℃ of reaction temperatures, solvent is cyclohexane, and the reaction time is 2h, and phenol conversion is 84.5%, and cyclohexanone is selectively 83.7%.
With embodiment 6, add the catalyst 4g of embodiment 2 preparations, phenol 0.8g, 100 ℃ of reaction temperatures, solvent is carrene, and the reaction time is 6h, and phenol conversion is 52.7%, and cyclohexanone is selectively 92.0%.
Embodiment 11
With embodiment 1, different is that concentration of nitric acid is 10 quality %, complex carrier TiO
2tiO in/AC
2content is 10%, catalyst P d@TiO
2the Pd content adding in/AC is 2 quality %.
With embodiment 6, different is that reaction is carried out in 50mL autoclave, adds the catalyst 0.24g of above-mentioned preparation, phenol 0.35g, 80 ℃ of reaction temperatures, solvent is carrene, reaction time is 2h, and phenol conversion is more than 99%, and cyclohexanone is selectively 98.9%.
With embodiment 1, different is that concentration of nitric acid is 10 quality %, complex carrier TiO
2tiO in/AC
2content is 10%, catalyst P d@TiO
2the Pd content adding in/AC is 2 quality %.
With embodiment 6, different is that reaction is carried out in 50mL autoclave, adds the catalyst 0.24g of above-mentioned preparation, phenol 0.35g, 90 ℃ of reaction temperatures, solvent is carrene, reaction time is 2h, and phenol conversion is 99.9%, and cyclohexanone is selectively 90.89%.
Embodiment 13
With embodiment 1, different is that concentration of nitric acid is 10 quality %, complex carrier TiO
2tiO in/AC
2content is 10%, catalyst P d@TiO
2the Pd content adding in/AC is 2 quality %.
With embodiment 6, different is that reaction is carried out in 50mL autoclave, adds the catalyst 0.24g of above-mentioned preparation, phenol 0.35g, 100 ℃ of reaction temperatures, solvent is carrene, reaction time is 2h, and phenol conversion is 99.9%, and cyclohexanone is selectively 87.8%.
Claims (10)
1. a palladium-carbon catalyst, comprising:
1) with nano-TiO
2the active carbon of modifying and decorating is complex carrier;
2) take Pd nano particle as active component;
Wherein, the TiO on described active component and described complex carrier
2there is the strong interaction of metal and carrier, form Pd@TiO
2structure, so forms the structure Pd@TiO of described catalyst
2/ active carbon.
2. catalyst according to claim 1, is characterized in that, described nano-TiO
2the activated carbon surface that is carried on modification with single or multiple lift dispersity forms TiO
2/ activated carbon composite carrier.
3. catalyst according to claim 1, is characterized in that, the particle diameter of described nano particle is 1-10nm, preferably 1-5nm; Described TiO
2particle diameter be 1-20nm.
4. according to the catalyst described in any one in claim 1-3, it is characterized in that TiO
2the active carbon of modifying and decorating is the TiO of complex carrier
2mass content account for the 1-15% of described complex carrier gross mass, preferred 5.0-12%.
5. according to the catalyst described in any one in claim 1-3, it is characterized in that, the mass content of described active component accounts for the 0.1-8% of catalyst gross mass, preferably 0.5-5.0%.
6. according to a preparation method for palladium-carbon catalyst described in any one in claim 1-5, comprising:
I) with salpeter solution, active carbon is carried out to modification and obtain modified active Carbon Materials;
Ii) by TiO
2be carried on step I) on the absorbent charcoal material that obtains, obtain TiO
2/ activated carbon composite carrier material;
Ii) by step I i) TiO that obtains
2/ activated carbon composite carrier dispersion of materials is to containing stirring every light in the solution of Pd, then under UV-irradiation, filters, dryly obtains described Pd@TiO
2/ active carbon.
7. method according to claim 6, is characterized in that, described by TiO
2being carried on step I) step of the absorbent charcoal material that obtains comprises:
Configuration contains Ti solution, and absorbent charcoal material is scattered in to described containing in Ti solution, regulates pH value to 2-4, and carries out sonic oscillation, makes to enter in the duct of described absorbent charcoal material containing Ti solution, and then standing plastic, finally calcines and obtain described TiO
2/ activated carbon composite carrier material.
8. according to the method described in claim 6 or 7, it is characterized in that, the compound method of described titaniferous solution is:
A) the ethanolic solution A of configuration butyl titanate;
B) the mixed solution B of configuration water and absolute ethyl alcohol;
C) under the condition stirring, solution B is dropwise joined in solution A, form mixed solution C, obtain described containing Ti solution.
9. the application in catalytic hydrogenation reaction, catalytic dehydrogenating reaction, catalytic oxidation and carbon carbon coupling reaction according to the palladium-carbon catalyst described in any one in claim 1-5.
10. according to the palladium-carbon catalyst described in any one in claim 1-5, in phenol selective hydrogenation, prepare the application in cyclohexanone for one kind.
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