CN103691431B - A kind of palladium-carbon catalyst and preparation method and application - Google Patents
A kind of palladium-carbon catalyst and preparation method and application Download PDFInfo
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- CN103691431B CN103691431B CN201310721791.2A CN201310721791A CN103691431B CN 103691431 B CN103691431 B CN 103691431B CN 201310721791 A CN201310721791 A CN 201310721791A CN 103691431 B CN103691431 B CN 103691431B
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- catalyst
- tio
- palladium
- activated carbon
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- 238000002360 preparation method Methods 0.000 title claims description 42
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- 238000000034 method Methods 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 46
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of palladium-carbon catalyst, including: 1) with nano-TiO2The activated carbon of modifying and decorating is complex carrier；2) with Pd nano-particle for active component；Wherein, described active component and the TiO on described complex carrier2There is the strong interaction of metal and carrier, form PdTiO2Structure, is thusly-formed the structure PdTiO of described catalyst2/ activated carbon.
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 apply for the application in Ketohexamethylene at phenol selectivity 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, pesticide.Nano Pd catalyst, as the hydrogenation catalyst of a kind of function admirable, is usually used in the selective hydrogenation of eneyne hydrocarbon, nitro, nitroso-group, ketone, aldehyde etc., occupies extremely important status on chemical industry.It is generally believed that the loaded nano palladium catalyst of function admirable structurally should have the following characteristics that 1) active component palladium microcrystal grain wants little of nanoscale, and content wants height, and surface exposure atom wants many；2) carrier specific surface area is big, and active component is at carrier surface good dispersion.
The character of catalyst is except depending on composition and content, also closely related with the preparation method of catalyst and process conditions etc., same raw material, identical composition and content, and during preparation method difference, the activity and selectivity of catalyst is likely to there is very big difference.Palladium-carbon catalyst to realize efficient catalytic performance, should have Technique of Nano Pd microcrystalline dispersion good, the feature that content is high.At present, the main method preparing palladium-carbon catalyst both at home and abroad is chemical reduction method, including gas phase reduction process and liquid phase reduction.Gas phase reduction process is that palladium presoma is carried on carrier by the method that palladium salt is passed through to impregnate or deposit, and forming palladium oxide crystallite through high-temperature calcination, then carries out hightemperature gas-phase reduction in H2 atmosphere.The method easily makes crystallite migrate at carrier surface in high-temperature calcination and high temperature reduction process, agglomeration.Liquid phase reduction is that palladium salt is added with, in 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 polyhydric alcohol, being carried on carrier by metal simple-substance palladium.The method is by adding protective agent (polymer; surfactant) control the granular size of palladium particle; but need to removing protective agent through subsequent high temperature oxidizing process and carry out activating catalytic agent, this process can make palladium crystallite generation agglomeration, and the dispersibility at carrier surface reduces.
Existing some exemplary mentioned about the patent prepared in nano Pd catalyst, but still have respective problem or weak point:
Chinese patent CN1519052A(load P d hydrogenation catalyst and preparation method thereof, the method using the preparing cyclohexanone from phenol of this catalyst) utilize conventional infusion process to prepare Pd/SiO2Catalyst.The carrier S iO that dry gel method is synthesized2It is immersed in PdCl2In solution, dry in 100 DEG C, in 200 DEG C of N2Middle insulation 2-4 hour.Then at the H of 400 DEG C2Middle reduction 4-6 hour.The method needs high-temperature process, and palladium crystallite particle diameter is difficult to control, the poor dispersion on carrier.
Chinese patent CN102125838A(mono-kind prepares high selectivity Pd/TiO2The method of-C hydrogenation catalyst) by repeatedly pH swing method, palladium ion is deposited to TiO2On-C powder body, carry out reduction treatment again through the one in formaldehyde, formic acid, hydrazine hydrate, glucose, sodium formate, sodium borohydride, paraformaldehyde or its combination, to obtain Pd/TiO then through filtering, wash, drying2-C catalyst.This invention need to consume a large amount of alkali liquor and reducing agent, and operating process is complicated.
The low platinum carbon-supported nano Pd-Pt alloy catalyst of Chinese patent CN101612566A(mono-kind, preparation method and application thereof) by Na2PdCl4Solution and K2PtC14Solution joins water, ethanol, in the dispersion solvent such as isopropanol, it is subsequently added into ethylenediamine, sodium citrate, ammonia, the chelating agent such as ethylenediaminetetraacetic acid, it is kept stirring for after being warming up to 40～80 DEG C making chelating agent and Pd ion, the abundant complexation of Pt ion, regulate the pH value of mixed liquor to 7～11, add high-area carbon, sonic oscillation also adds strong mixing, make Pd and Pt active substance dispersed at carbon surface, prepare raw material charcoal slurry, pass into noble gas, remove dissolved oxygen therein, it is added dropwise over sodium borohydride, dimethylamino borine, the reducing agents such as ascorbic acid, fully reduce Pd, Pt, filter, washing, dried carbon-supported nano Pd-Pt alloy catalyst.The chelating agent that the method adds can be coated with Pd, Pt activity phase of reduction, makes catalyst activity reduction.
Chinese patent CN102463352A(mono-kind synthesizes the hexahedral method of bimetallic Pd-Au core-shell) utilize two-step method to synthesize Pd-Au core-shell structure copolymer hexahedron in aqueous phase.First with H2PdCl4For palladium source, ascorbic acid is reducing agent, synthesizes hexahedral Pd seed with cetyl ammonium bromide for stabilizer, then passes through crystal epitaxy method, with HAuCl4For Au source, ascorbic acid is reducing agent, with cetyl pyridinium bromide for stabilizer, has synthesized bimetallic Pd-Au core-shell hexahedron in aqueous phase.The method adds protective agent, and purposes is restricted.
Chinese patent CN102476051A(noble metal/TiO2-C catalyst and preparation method thereof) by TiO2-C complex carrier impregnated in containing in the precious metal salt solutions such as palladium salt, ruthenium salt, obtain catalyst precarsor, then through 100 DEG C of dry 2h, reduce with any one in reducing agent formaldehyde, formic acid, hydrazine hydrate, paraformaldehyde, glucose, sodium formate, sodium borohydride or hydrogen or its combination again, obtain noble metal/TiO2-C catalyst.The bad dispersibility of active phase prepared by the method, nano-sized crystal content is low.
Catalysts and its preparation method that Chinese patent CN102513100A(is mono-kind activated carbon supported and application) in catalyst with activated carbon for carrier, the bimetallic catalyst being active component with platinum and palladium.Preparation method: the activated carbon through salpeter solution immersion treatment be impregnated in H2PdCl4Aqueous solution and H2PtCl64～8h in aqueous solution, dipping regulates reactant liquor pH=9 with alkali liquor after terminating, and filters, filter cake is washed to neutrality, it is thus achieved that filter cake add hydrazine hydrate reduction agent and react l～5h in l0～50 DEG C, through filtering, washing, dried, prepare activated carbon supported catalyst.The shortcoming of the method is active component bad dispersibility on carrier, and grain diameter is difficult to control.
Chinese patent CN102806105A(load type gold palladium catalyst and preparation thereof and application) using ion exchange resin as carrier, resin is processed with acid, neutralizing treatment successively, then it is carried out ion exchange with gold palladium metal precursor water solution, reduce with reducing agents such as ammonia borine, sodium borohydride, vitamin Cs again, dried catalyst.The carrier used in the method is expensive, and the scope of application is restricted.
Chinese patent CN102553582A(mono-kind prepares the method for carbon load gold platinum or gold palladium bimetallic catalyst) the golden platinum of the high temperature high pressure process chemistry co-reducing process synthesis that utilizes microwave to produce in autoclave or golden palladium composite Nano colloid, induction gold platinum or gold palladium bimetal nano particles modifiy, modified bimetal nano particles is deposited on carbon support, obtains the carbon supported Au-Pt or Au-Pd catalyst with high electrocatalytic active.When chemistry coreduction, add polyvinylpyrrolidone and cook protective agent.
Chinese patent CN102895970A(organic aerogel load P d compound prepares method and the Pd/C catalyst of Pd/C catalyst) with organic aerogel for carbon matrix precursor and catalyst carrier, water solublity Pd compound is catalyst activity component source, utilize equi-volume impregnating, be prepared from by dip loading, ageing, high temperature cabonization, hydrogen gas reduction step.The method needs 600 DEG C of high temperature above carbonizations, and condition is harsher, and energy consumption is high.
Chinese patent CN102916201A(palladium on carbon nanocatalyst and preparation method thereof) adopt liquid phase reactor method two-step oxidation modified carbon support and by liquid complexing coreduction approach, Pd uniform particle is dispersed in the surface of above-mentioned high-area carbon.Chelating agent used is disodiumedetate, sodium citrate, 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 chelating agent cladding activity phase that the method uses, makes catalysis activity reduce.
Chinese patent CN102872861A(mono-kind utilizes the method that ethanol reduction prepares Technique of Nano Pd eelctro-catalyst) utilize the reduction of ethanol and cosolvent effect by Palladous chloride. (PdCl2) it is reduced to Metal Palladium (Pd) nanoparticle, first prepare ethanol water；Then by PdCl2A kind of in powder and protective agent sodium lauryl sulphate, polyvinylpyrrolidone, cetyl trimethylammonium bromide adds to alcoholic solution, logical protection gas N2Or Ar and at 60-80 DEG C stir 1-3h, make palladium cation generation reduction reaction obtain Pd nano particle；It is centrifugally separating to obtain black precipitate after completion of the reaction, dry after using ethanol, washing with acetone, obtain Technique of Nano Pd eelctro-catalyst.
Chinese patent CN102784642A(load type double-metal alloy catalyst and its production and use) described catalyst is with ceria for carrier, with Metal Palladium and silver for active component.By two step synthesis, impregnated in silver salt solution by ceria, after dipping balance, evaporate solvent, air calcination, then by gained sample double-steeping after palladium salt solution, dipping balance, evaporate solvent, calcine in air, obtain palladium-silver bimetallic catalyst precursor, then through H during use2High-temperature activation.The method needs to carry out high-temperature process, makes activity that agglomeration to occur mutually, and the dispersibility of activity phase is poor.
Chinese patent CN1026009900A(Load-type gold-palladium bimetallic catalyst and preparation method thereof) magnesium oxide carrier is immersed in the impregnation liquid being made up of gold chloride and Palladous chloride., after reaching dipping balance, then with the metal ion of the reducing plant extract absorption such as Cacumen Platycladi, Folium Celtis Sinensis, Folium Nelumbinis.Then filtration washing dries, and obtains Load-type gold-palladium bimetallic catalyst then through calcination activation.
Chinese patent CN102544531A(Pd/TiO2/ C composite nano-catalyst and its preparation method and application) by the nano-TiO of pretreated VulcanXC-72 activated carbon powder and water heat transfer2Powder is sufficiently mixed, and adding concentration is the glycol water of 25%, and strong stirring obtains activated carbon and TiO2The mixed solution of the carrier of composition；Palladium chloride solution and stabilizer trisodium citrate, then to drip excessive sodium borohydride be reducing agent, after reaction 3h, is washed to noresidue chloride ion after sucking filtration, at vacuum drying, final Pd/TiO2/ C composite nano-catalyst.
Chinese patent CN103055852A(is used for high dispersive palladium/carbon nano-tube catalyst and the preparation method of anthraquinone hydrogenation) Palladous chloride. hydrochloric acid solution is joined in carbon nano tube suspension, the pH to 9-12 of suspension is regulated with aqueous slkali, palladium ion is precipitated, add excessive reductant formaldehyde (or sodium formate, glucose), at 40-60 DEG C, carry out reduction reaction, to obtain palladium/carbon nano-tube catalyst through filtering, wash and drying.
The various improved methods that above-mentioned patent is previously mentioned, are primarily intended to the content and dispersive property that to improve nanometer metal palladium crystallite.It is true that in existing preparation method, the control of Metal Palladium content of crystallite is less desirable, dispersive property is not high.In liquid-phase reduction process; the size of palladium crystallite is controlled by adding protective agent; remove in protectant process at high-temperature oxydation, there is the migration of palladium crystallite in various degree and grow up, and the reduction of Pd ion is required for realizing by adding excessive reductant.
Ketohexamethylene is to have multiduty industrial chemicals perhaps, mainly for the preparation of synthetic fibers nylon 6 and nylon66 fiber, also acts as the important intermediate of the fine chemicals such as medicine, coating, dyestuff.Phenol hydrogenation is the important approach preparing Ketohexamethylene.Owing to general catalyst is active low in a mild condition, and Ketohexamethylene is easily hydrogenated with by-products such as generating Hexalin further, and selectivity is not high.Even if such as temperature is more than 100 DEG C at 120-160 DEG C, pressure 2-10MPa under severe conditions, higher conversion (> 80% to be reached) when realize the high selectivity (> 95% of Ketohexamethylene) remain a catalysis difficult problem with challenge.Therefore, in a mild condition, directly selecting property of phenol Hydrogenation is still a challenge for Ketohexamethylene.Efficiently, highly selective synthesizing cyclohexanone is always up a challenge difficult problem.
Summary of the invention
It is an object of the invention 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, including:
1) with nano-TiO2The activated carbon of modifying and decorating is complex carrier；
2) with Pd nano-particle for active component；
Wherein, described active component and the TiO on described complex carrier2There is the strong interaction of metal and carrier, form PdTiO2Structure, is thusly-formed the structure PdTiO of described catalyst2/ activated carbon.
In a preferred embodiment of the present invention, described nano-TiO2Modified activated carbon outer surface and the TiO of inner surfaces of pores formation it is carried on single or multiple lift dispersity2/ AC(activated carbon) complex carrier.
In a preferred embodiment of the present invention, the particle diameter of described nano-particle is 1-10nm, it is preferable that 1-5nm, described TiO2Particle diameter be 1-20nm.
In a preferred embodiment of the present invention, TiO2The activated carbon of modifying and decorating is the TiO of complex carrier2Mass content account for the 1-15% of described complex carrier gross mass, it is preferable that 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, it is preferable that 0.5%-3.0%.
In a preferred embodiment of the present invention, described activated carbon is preferably cocoanut active charcoal.
The final structure of the catalyst of the present invention is PdTiO2/AC。
The preparation method that the invention provides a kind of described palladium-carbon catalyst, including:
I) with salpeter solution, activated carbon will be modified process and obtain modified active Carbon Materials；
Ii) by TiO2It is carried on step i) the modified active Carbon Materials obtained, obtains TiO2/ activated carbon composite carrier material；
Iii) by step ii) TiO that obtains2/ activated carbon composite carrier material is distributed in the solution containing Pd to stir every light, then filter under irradiation under ultraviolet ray, dry obtain described PdTiO2/ activated carbon.
In a preferred embodiment of the present invention, described by TiO2The step being carried on step i) the modified active Carbon Materials obtained includes:
Modified active Carbon Materials, containing Ti solution, is scattered in described containing, in Ti solution, regulating pH value to 2-4, and carry out sonic oscillation so that entering containing Ti solution in the duct of described modified active Carbon Materials, then stand plastic, finally calcining obtains described TiO by preparation2/ activated carbon composite carrier material.
In present invention further optimization embodiment, the compound method of described titaniferous solution is:
A) the alcoholic solution A of butyl titanate is prepared；
B) the mixed solution B of preparation water and dehydrated alcohol；
C) when stirring, solution B is added dropwise in solution A, forms mixed solution C, namely obtain described containing Ti solution.
Described mixed solution C is be generally sol-gel state.
Concrete, the preparation method of the catalyst of the present invention includes:
1) carrier active carbon (AC) pretreatment
Being placed in the salpeter solution of variable concentrations by scrubbed, to boil 2～3 times cocoanut active charcoal, be heated to reflux 4h in 60～70 DEG C of water-baths, deionized water wash filters, to solution ph in neutrality, dry at 80 DEG C, obtains through HNO3The absorbent charcoal material of solution modification.
2) complex carrier TiO2The preparation of/AC
Sol-gel process load TiO2: the alcoholic solution A of preparation butyl titanate；The mixed solution B of preparation water and dehydrated alcohol；When stirring, solution B is added dropwise in solution A, forms sol-gel shape solution C, namely obtain described containing Ti solution.Modified active Carbon Materials step 1) obtained is distributed in mixed solution C, enriching HNO3Adjust pH to 3, stir 5～10min, then sonic oscillation 10min makes colloidal sol enter in AC duct, stops stirring and is settled into gel, dry at 80 DEG C, calcine 2h at 500 DEG C, obtain TiO2/ 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: take step 2) prepare TiO2/ AC composite carrier dispersed with stirring is in deionized water, add methanol, dark place stirring 5-15min, adding a certain amount of chlorine Asia palladium acid solution, concentrated hydrochloric acid adjusts pH to 3～5, and 0.1-1h is quickly stirred in dark place, it is subsequently placed under ultraviolet light and radiates 5～6h, washing, filtration in neutrality, vacuum drying at 50-90 DEG C, obtain PdTiO to filtrate2/ AC catalyst.
Present invention also offers the application in catalytic hydrogenation reaction, catalytic dehydrogenating reaction, catalytic oxidation and carbon carbon coupling reaction of a kind of described palladium-carbon catalyst.Especially described palladium-carbon catalyst at phenol selectivity Hydrogenation for the application in Ketohexamethylene.
Compared with existing palladium-carbon catalyst technology of preparing, the method have the advantages that employing photocatalysis direct-reduction process prepares nano-noble metal catalyst PdTiO2/AC。
1, the method utilizes photo catalytic reduction principle that palladium cation Restore All can be made for corresponding simple substance, as long as and light application time long enough the load factor of palladium just can be made close even up to completely；
2, operating procedure rambunctious is eliminated, it is not necessary to high-temperature calcination, it is possible to avoid Pd nano particle reunite under the high temperature conditions or sinter；
3, need not any reducing agent reduction, it is not required that surfactant etc. protect, eliminate high-temperature oxydation remove protective agent cause palladium, golden nanometer particle reunion grow up；
4, there is the strong interaction of metal and carrier between nanometer metal palladium and titanium dioxide, be firmly combined with, change the electronic state of Technique of Nano Pd, the migration of restriction Pd nano particle and reunion；
5, the palladium crystallite particle diameter of nano Pd catalyst only has 1-10nm, and even 1-5nm is evenly distributed, and good dispersion, catalytic performance is good；
6, preparation condition is gentle, it is easy to operation and control granular size；
7, preparation technology is simple；With H2The nano-noble metal catalyst PdTiO of preparation is investigated for reducing agent2The 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 PdTiO of embodiment 1 preparation2The XRD figure of/AC.
Fig. 3 is the nano Pd catalyst PdTiO of embodiment 2 preparation2The XRD figure of/AC.
Detailed description of the invention
Describing embodiments of the present invention in detail below with reference to drawings and Examples, to the present invention, how application technology means solve technical problem whereby, and the process that realizes reaching technique effect can fully understand and implement according to this.As long as it should be noted that do not constitute conflict, each embodiment in the present invention and each feature in each embodiment can be combined with each other, and the technical scheme formed is all within protection scope of the present invention.
Embodiment 1
1) Activated Carbon Pretreatment: scrubbed, to boil 2～3 times cocoanut active charcoal is placed in the salpeter solution that mass fraction is 10.94%, it is heated to reflux 4h in～60 DEG C of water-baths, deionized water filters, washing is neutrality to pH, at 110 DEG C, dry 12h, obtains the modified activated carbon through oxidation processes；
2) sol-gel process load TiO2: preparation solution A and solution B, when magnetic agitation, B is dropwise slowly added in solution A, forms mixed solution C colloidal sol, 12.03g modified activated carbon step 1) obtained is distributed in solution C, enriching HNO3(66-68 mass %) adjusts pH to 3, stirs 5～10min, then sonic oscillation 10min makes colloidal sol enter in AC duct, stops stirring and is settled into gel, and dry 12h at 80 DEG C calcines 2h, obtains TiO at 500 DEG C2Carrying capacity is the composite carrier TiO of 9.95%2/AC.Wherein, solution A: 5.664g(～6ml) butyl titanate is scattered in the dehydrated alcohol of 25ml；Solution B: 1ml ultra-pure water is scattered in the dehydrated alcohol of 15ml
3) photo catalytic reduction load P d: take step 2) prepare TiO2/ AC composite carrier 5.316g, dispersed with stirring is in 300ml ultra-pure water, add the methanol of 10ml, dark place stirring 10min, add the chlorine Asia palladium acid solution that 2.458ml palladium content is 20g/L, pH to 3～5 is adjusted with the concentrated hydrochloric acid of mass concentration 37%, 1h is quickly stirred in dark place, is subsequently placed under the ultraviolet light of 15w and radiates 5h, filters, washs to filtrate in neutrality, at 90 DEG C, vacuum drying 12h, obtains PdTiO2/ AC catalyst, the mass fraction 0.916% of palladium.
As described in Figure 1, the monocrystalline peak of Pa is clearly as seen from Figure 1 the XRD figure of the catalyst that the present embodiment obtains, it is seen that the load Pa crystal grain of monocrystalline on this catalyst.
Embodiment 2
By sol-gel process by TiO2Load on modified activated carbon, obtain complex carrier TiO2/AC.Metal Palladium is loaded to complex carrier TiO by the method for recycling photo catalytic reduction2On/AC, obtain PdTiO through subsequent filter, washing, dry run2/AC。
Specific implementation process is with embodiment 1, the difference is that HNO3Concentration is 11.13%, complex carrier TiO2TiO in/AC2Mass content is 9.89%, catalyst PdTiO2In/AC, the mass content of palladium is 0.5%.
As described in Figure 2, the monocrystalline peak of Pa is clearly as seen from Figure 2 the XRD figure of the catalyst that the present embodiment obtains, it is seen that the load Pa crystal grain of monocrystalline on this catalyst.
Embodiment 3
With embodiment 1, the difference is that complex carrier TiO2TiO in/AC2Mass content is 15%, catalyst PdTiO2In/AC, Pd content is 0.5 mass %.
Embodiment 4
With embodiment 1, the difference is that complex carrier TiO2TiO in/AC2Content is 20 mass %, catalyst PdTiO2In/AC, Pd content is 0.5 mass %.
Embodiment 5
With embodiment 1, the difference is that concentration of nitric acid is 15 mass %, complex carrier TiO2TiO in/AC2Mass content is 20%, catalyst PdTiO2In/AC, Pd mass content is 0.5%.
Embodiment 6
The nano Pd catalyst of preparation in above-described embodiment 1～5 is used for catalysis of phenol selective hydrogenation and prepares Ketohexamethylene reaction.Reaction carries out in 300mL autoclave, is sequentially added into catalyst 0.5～4g, 40mL hexamethylene (or dichloromethane) and 0.1～1g phenol, passes into H2Air 5～8 times in displacement still, high-speed stirred at 800 rpm, when temperature in the kettle rises to temperature required 80～100 DEG C of experiment, pass into H2Make pressure maintain 1.0MPa, react 2～6h.After reaction terminates, in still, reactant liquor at room temperature cools down, and the Hexalin in product, cyclohexanone content Agilent6890N gas chromatograph adopt internal standard method to be analyzed with chlorobenzene for internal standard substance.
Embodiment 7
With embodiment 6, adding catalyst 4g, the phenol 0.8g of embodiment 1 preparation, reaction temperature 100 DEG C, solvent is dichloromethane, and the response time is 2h, and phenol conversion is 73.0%, and Ketohexamethylene selectivity is 95.7%.
Embodiment 8
With embodiment 6, adding catalyst 4g, the phenol 0.8g of embodiment 1 preparation, reaction temperature 100 DEG C, solvent is dichloromethane, and the response time is 6h, and phenol conversion is 76.4%, and Ketohexamethylene selectivity is 94.9%.
Embodiment 9
With embodiment 6, adding catalyst 4g, the phenol 0.8g of embodiment 1 preparation, reaction temperature 100 DEG C, solvent is hexamethylene, and the response time is 2h, and phenol conversion is 84.5%, and Ketohexamethylene selectivity is 83.7%.
Embodiment 10
With embodiment 6, adding catalyst 4g, the phenol 0.8g of embodiment 2 preparation, reaction temperature 100 DEG C, solvent is dichloromethane, and the response time is 6h, and phenol conversion is 52.7%, and Ketohexamethylene selectivity is 92.0%.
Embodiment 11
With embodiment 1, the difference is that concentration of nitric acid is 10 mass %, complex carrier TiO2TiO in/AC2Content is 10%, catalyst PdTiO2The Pd content added in/AC is 2 mass %.
With embodiment 6, the difference is that reaction carries out in 50mL autoclave, add the catalyst 0.24g of above-mentioned preparation, phenol 0.35g, reaction temperature 80 DEG C, solvent is dichloromethane, response time is 2h, and phenol conversion is more than 99%, and Ketohexamethylene selectivity is 98.9%.
Embodiment 12
With embodiment 1, the difference is that concentration of nitric acid is 10 mass %, complex carrier TiO2TiO in/AC2Content is 10%, catalyst PdTiO2The Pd content added in/AC is 2 mass %.
With embodiment 6, the difference is that reaction carries out in 50mL autoclave, add the catalyst 0.24g of above-mentioned preparation, phenol 0.35g, reaction temperature 90 DEG C, solvent is dichloromethane, response time is 2h, and phenol conversion is 99.9%, and Ketohexamethylene selectivity is 90.89%.
Embodiment 13
With embodiment 1, the difference is that concentration of nitric acid is 10 mass %, complex carrier TiO2TiO in/AC2Content is 10%, catalyst PdTiO2The Pd content added in/AC is 2 mass %.
With embodiment 6, the difference is that reaction carries out in 50mL autoclave, add the catalyst 0.24g of above-mentioned preparation, phenol 0.35g, reaction temperature 100 DEG C, solvent is dichloromethane, response time is 2h, and phenol conversion is 99.9%, and Ketohexamethylene selectivity is 87.8%.
Claims (2)
1. palladium-carbon catalyst is at phenol selectivity Hydrogenation for the application in Ketohexamethylene, and wherein, described palladium-carbon catalyst is prepared by following steps:
I) with salpeter solution, activated carbon is modified process and obtains modified active Carbon Materials；
Ii) by TiO2It is carried on the step i) absorbent charcoal material obtained, obtains TiO2/ activated carbon composite carrier material；
Iii) by step ii) TiO that obtains2/ activated carbon composite carrier material is distributed in the solution containing Pd to stir every light, then filter under irradiation under ultraviolet ray, dry obtain described PdTiO2/ activated carbon；
In step ii) in, described by TiO2The step being carried on the step i) absorbent charcoal material obtained includes: preparation is containing Ti solution, absorbent charcoal material is scattered in described containing in Ti solution, regulate pH value to 2-4, and carry out sonic oscillation, make in the duct containing the Ti solution described absorbent charcoal material of entrance, then standing plastic, finally calcining obtains described TiO2/ activated carbon composite carrier material.
2. application according to claim 1, it is characterised in that the compound method of described titaniferous solution is:
A) the alcoholic solution A of butyl titanate is prepared；
B) the mixed solution B of preparation water and dehydrated alcohol；
C) when stirring, solution B is added dropwise in solution A, forms mixed solution C, namely obtain described containing Ti solution.
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