CN103724174B - A kind of method preparing pimelinketone - Google Patents
A kind of method preparing pimelinketone Download PDFInfo
- Publication number
- CN103724174B CN103724174B CN201310721645.XA CN201310721645A CN103724174B CN 103724174 B CN103724174 B CN 103724174B CN 201310721645 A CN201310721645 A CN 201310721645A CN 103724174 B CN103724174 B CN 103724174B
- Authority
- CN
- China
- Prior art keywords
- tio
- porous material
- reaction
- catalyst
- catalyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/006—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenation of aromatic hydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/40—Constitutive chemical elements of heterogeneous catalysts of Group IV (IVA or IVB) of the Periodic Table
- B01J2523/47—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/82—Metals of the platinum group
- B01J2523/824—Palladium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of method preparing pimelinketone, comprising: adopt palladium catalyst PdTiO
2/ porous material is that raw material carries out a step selective catalysis hydrogenation reaction to prepare pimelinketone with phenol; The consumption of catalyzer accounts for the 0.1-40% of phenol quality.Described PdTiO
2/ porous material catalyzer comprises: 1) with nano-TiO
2the porous material of modifying and decorating is complex carrier; 2) with Pd nano particle for active ingredient; Wherein, the TiO on described active ingredient and described complex carrier
2there is the strong interaction of metal and carrier, form PdTiO
2structure, so forms the structure PdTiO of described catalyzer
2/ porous material.
Description
Technical field
The present invention relates to organic chemical industry field, be specifically related to a kind of method preparing pimelinketone, particularly relate to a kind of Pyrogentisinic Acid and carry out selective hydrogenation and prepare method in pimelinketone.
Background technology
Pimelinketone has multiduty industrial chemicals perhaps, mainly for the preparation of synthon nylon 6 and nylon66 fiber, also can be used as the important intermediate of the fine chemicals such as medicine, coating, dyestuff.Phenol hydrogenation prepares the important approach of of pimelinketone.Because general catalyzer is active low in a mild condition, and the easy hydrogenation further of pimelinketone generates the by products such as hexalin, and selectivity is not high.Even if such as temperature is greater than 100 DEG C at 120-160 DEG C, pressure 2-10MPa under severe conditions, the highly selective (>95%) realizing pimelinketone under reaching the condition of higher conversion (>80%) remains the catalysis difficult problem that has challenge.Therefore, in a mild condition, the direct selective hydrogenation of phenol is prepared pimelinketone and is still a challenge.Efficiently, highly selective synthesizing cyclohexanone is a challenge difficult problem always.
Chinese patent CN1519052A(load P d hydrogenation catalyst and preparation method thereof, uses the method for the preparing cyclohexanone from phenol of this catalyzer) utilize conventional pickling process to prepare Pd/SiO
2catalyzer.By the carrier S iO that dry gel method synthesizes
2be immersed in PdCl
2in solution, in 100 DEG C of dryings, in 200 DEG C of N
2middle insulation 2-4 hour.Then at the H of 400 DEG C
2middle reduction 4-6 hour.The method needs pyroprocessing, and palladium crystallite particle diameter is restive, and the dispersiveness on carrier is bad, and catalytic effect is unstable, and needs higher catalytic temperature.
In addition, loaded nano noble metal catalyst has good Hydrogenation, at the shortening of all kinds of unsaturated organic compounds of the industries such as petrochemical complex, pharmacy, dyestuff, agricultural chemicals.Nano Pd catalyst, as a kind of hydrogenation catalyst of excellent property, is usually used in the selective hydrogenation of eneyne hydrocarbon, nitro, nitroso-group, ketone, aldehyde etc., chemical industry occupies extremely important status.It is generally acknowledged, the loaded nano palladium catalyst of excellent property structurally should have following characteristics: 1) active component palladium microcrystal grain wants little of nano level, and content wants high, and surface exposure atom wants many; 2) carrier specific surface area is large, and active ingredient is at carrier surface good dispersity.
The character of catalyzer is except depending on composition and content, and also closely related with the preparation method of catalyzer and processing condition etc., same raw material, identical composition and content, during preparation method's difference, the activity and selectivity of catalyzer may have very large difference.Palladium-carbon catalyst will 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 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 presoma is carried on carrier by the method for flooding or deposit by palladium salt, is forming palladium oxide crystallite, then at H through high-temperature calcination
2hightemperature gas-phase reduction is carried out in atmosphere.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 being added with in carrier and protectant liquid phase environment; through peroxyformic acid, formaldehyde, glucose, sodium formiate, sodium borohydride, metaphosphoric acid sodium dihydrogen, hydrazine hydrate; the reductive action of the reductive agents such as polyvalent alcohol, is carried on metal simple-substance palladium on carrier.The method is by adding protective material (polymkeric substance; tensio-active agent) control the granular size of palladium particle; but need carry out deactivated catalyst through subsequent high temperature oxidising process removing protective material, this process can make palladium crystallite generation agglomeration, reduces in the dispersiveness of carrier surface.
Some exemplary that the existing patent about preparing in nano Pd catalyst is mentioned, but still have respective problem or weak point:
Chinese patent CN102125838A(mono-kind prepares highly selective Pd/TiO
2the method of-C hydrogenation catalyst) by repeatedly pH swing method, palladium ion is deposited to TiO
2on-C powder, then carry out reduction treatment by the one in formaldehyde, formic acid, hydrazine hydrate, glucose, sodium formiate, sodium borohydride, paraformaldehyde or its combination, more after filtration, washing, dry Pd/TiO
2-C catalyst.This invention need consume a large amount of alkali lye and reductive 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 Virahol, then quadrol is added, Trisodium Citrate, ammoniacal liquor, the complexing agents such as ethylenediamine tetraacetic acid (EDTA), stirring is kept to make complexing agent and Pd ion after being warming up to 40 ~ 80 DEG C, the abundant complexing of Pt ion, regulate pH value to 7 ~ 11 of mixed solution, add high-area carbon, sonic oscillation also adds strong mixing, make Pd and Pt active substance dispersed at carbon surface, obtained raw material charcoal slurry, pass into rare gas element, removing dissolved oxygen wherein, dropwise add sodium borohydride, dimethylamino borine, the reductive agents such as xitix, abundant reduction Pd, Pt, filter, washing, carbon-supported nano Pd-Pt alloy catalyst is obtained after drying.The complexing agent that the method adds can the active phase of Pd, Pt of coated reduction, makes catalyst activity reduction.
Chinese patent CN102463352A(mono-kind synthesizes the hexahedral method of bimetallic Pd-Au core-shell) utilize two-step approach in aqueous phase, synthesize Pd-Au core-shell structure copolymer hexahedron.First with H
2pdCl
4for palladium source, xitix is reductive agent, with hexadecyl brometo de amonio for stablizer synthesizes hexahedral Pd seed, then by crystal epitaxy method, with HAuCl
4for Au source, xitix is reductive agent, is stablizer, has synthesized bimetallic Pd-Au core-shell hexahedron in aqueous phase with cetyl pyridinium bromide.The method adds protective material, and purposes is restricted.
Chinese patent CN102476051A(precious metal/TiO
2-C catalyst and preparation method thereof) by TiO
2-C complex carrier impregnated in containing in the precious metal salt solutions such as palladium salt, ruthenium salt, obtain catalyst precursor, again through 100 DEG C of dry 2h, reduce with any one in reductive agent formaldehyde, formic acid, hydrazine hydrate, paraformaldehyde, glucose, sodium formiate, sodium borohydride or hydrogen or its combination again, obtain precious metal/TiO
2-C catalyst.The bad dispersibility of active phase prepared by the method, nano-sized crystal content is low.
The Catalysts and its preparation method that Chinese patent CN102513100A(mono-kind is activated carbon supported and application) in catalyzer take gac as carrier, the bimetallic catalyst being active ingredient with platinum and palladium.Preparation method: the gac through salpeter solution immersion treatment be impregnated in H
2pdCl
4the aqueous solution and H
2ptCl
64 ~ 8h in the aqueous solution, dipping terminates rear alkali lye and regulates reaction solution pH=9, filters, filter cake is washed to neutrality, the filter cake of acquisition add hydrazine hydrate reduction agent in l0 ~ 50 DEG C reaction l ~ 5h, after filtration, washing, after drying, obtained activated carbon supported catalyzer.The shortcoming of the method is active ingredient bad dispersibility on carrier, and grain diameter is restive.
Chinese patent CN102806105A(load type gold palladium catalyst and Synthesis and applications thereof) using ion exchange resin as carrier, resin is used successively acid, neutralizing treatment process, then itself and golden metallic palladium precursor water solution are carried out ion-exchange, reduce with reductive agents such as ammonia borine, sodium borohydride, vitamins Cs again, after drying, obtain catalyzer.The carrier used in the method is expensive, and the scope of application is restricted.
Chinese patent CN102553582A(mono-kind prepares the method that carbon carries golden platinum or golden palladium bimetallic catalyst) the golden platinum of the high temperature high pressure process that utilizes microwave to produce in autoclave chemistry co-reducing process synthesis or golden palladium composite Nano colloid, induce golden platinum or the modification of golden palladium bimetal nano particles, the bimetal nano particles of modification is being deposited on carbon support, and the carbon obtaining having high electrocatalytic active carries golden platinum or golden palladium catalyst.When chemical coreduction, add polyvinylpyrrolidone and cook protective material.
Chinese patent CN102895970A(organic aerogel load P d compound prepares method and the Pd/C catalyzer of Pd/C catalyzer) be carbon matrix precursor and support of the catalyst with organic aerogel, water-soluble 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 more than 600 DEG C 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 reaction method two-step oxidation modified carbon support and by liquid complexing coreduction approach, Pd uniform particle be dispersed in the surface of above-mentioned high-area carbon.Complexing agent used is disodium ethylene diamine tetraacetate, Trisodium Citrate, cyclohexanediaminetetraacetic acid salt, methyl ethyl diketone or sodium tartrate, and reductive agent used is sodium borohydride, ethylene glycol, citric acid or formic acid.The coated active phase of complexing agent that the method uses, makes catalytic activity reduce.
The method that Chinese patent CN102872861A(mono-kind utilizes ethanol reduction to prepare Technique of Nano Pd eelctro-catalyst) utilize the reductive action of ethanol and solubility promoter effect by Palladous chloride (PdCl
2) be reduced to palladium metal (Pd) nanoparticle, first configure aqueous ethanolic solution; Then by PdCl
2one in powder and protective material sodium lauryl sulphate, polyvinylpyrrolidone, cetyl trimethylammonium bromide is added in ethanolic soln, logical protection gas N
2or Ar stir 1-3h at 60-80 DEG C, make palladium positively charged ion generation reduction reaction obtain Pd nano particle; Centrifugation obtains black precipitate after completion of the reaction, dry after using ethanol, washing with acetone, obtains Technique of Nano Pd eelctro-catalyst.
Chinese patent CN102784642A(load type double-metal alloy catalyst and its production and use) described catalyzer take cerium dioxide as carrier, with palladium metal and silver for active ingredient.By two step synthesis, impregnated in silver salt solution by cerium dioxide, after dipping balance, evaporating solvent, air calcination, then by gained sample double-steeping in palladium salts solution, after dipping balance, evaporating solvent, calcine in air, obtain palladium-silver bimetallic catalyst precursor, again through H during use
2high-temperature activation.The method needs to carry out pyroprocessing, makes activity mutually agglomeration occur, 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 steeping fluid be made up of hydrochloro-auric acid and Palladous chloride, after reaching dipping balance, then with the metal ion of the reducing plant extract absorption such as Leafy twigs of Oriental Arborvitae, Leaf of Chinese Hackberry, lotus leaf.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 the nano-TiO of pretreated VulcanXC-72 activity charcoal powder and water heat transfer
2powder fully mixes, and adds the aqueous glycol solution that concentration is 25%, strong stirring, obtains gac and TiO
2the mixing solutions of the carrier of composition; Palladium chloride solution and stablizer trisodium citrate, then to drip excessive sodium borohydride be reductive 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 used for high dispersive palladium/carbon nano-tube catalyst and the preparation method of anthraquinone hydrogenation) Palladous chloride hydrochloric acid soln is joined in carbon nano tube suspension, the pH to 9-12 of suspension is regulated with alkaline solution, palladium ion is precipitated, add excessive reductant formaldehyde (or sodium formiate, glucose) again, reduction reaction is carried out, after filtration, washing and dry palladium/carbon nano-tube catalyst at 40-60 DEG C.
What above-mentioned patent was mentioned variously improves one's methods, and object mainly will improve content and the dispersing property of nanometer metal palladium crystallite.In fact, in existing preparation method, the control of palladium metal content of crystallite is not very desirable, and dispersing property is not high.In liquid-phase reduction process; the size of palladium crystallite is controlled by adding protective material; remove in protectant process at high temperature oxidation, there is 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.
Summary of the invention
The object of the present invention is to provide a kind of method preparing pimelinketone of highly selective, it comprises the hydrogenation catalyst using a kind of excellent performance, its dispersing property is good, and especially Pyrogentisinic Acid's selective hydrogenation has fine catalytic performance, overcomes above-mentioned deficiency of the prior art.
The invention provides a kind of method preparing pimelinketone, comprising:
Adopt palladium catalyst PdTiO
2/ porous material is that raw material carries out a step selective catalysis hydrogenation reaction to prepare pimelinketone with phenol; The consumption of catalyzer accounts for the 0.1-40% of phenol quality, preferred 0.1-10%.
In a preferred embodiment of the present invention, described PdTiO
2/ porous material catalyzer comprises:
1) with nano-TiO
2the porous material of modifying and decorating is complex carrier;
2) with Pd nano particle for active ingredient;
Wherein, the TiO on described active ingredient and described complex carrier
2there is the strong interaction of metal and carrier, form PdTiO
2structure, so forms the structure PdTiO of described catalyzer
2/ porous material.
In a preferred embodiment of the present invention, described porous material includes but not limited to gac, carbonaceous molecular sieve, SiO
2, MCM-22 molecular sieve, the porous material such as MCM-41 molecular sieve.
In a preferred embodiment of the present invention, described gac is preferably cocoanut active charcoal.
In further preferred implementation of the present invention, the nano particle of at least one metal that described catalyzer also comprises in other transition metal except Pd is active ingredient;
Wherein, the TiO on described active ingredient and described complex carrier
2there is the strong interaction of metal and carrier, form Pd-MTiO
2structure, so forms the structure Pd-MTiO of described catalyzer
2/ porous material composite carried catalyst, at least one during wherein M is selected from except Pd transition metal.
In a preferred embodiment of the present invention, described M is selected from least one in Au, Pt, Ir, Fe, Co, Ni and Mn.
In a preferred embodiment of the present invention, the nano-TiO on described catalyzer
2the TiO of described porous material outside surface and inner surfaces of pores formation is carried on single or multiple lift dispersion state
2/ porous material complex carrier.
In a preferred embodiment of the present invention, the particle diameter of the nano particle in described catalyzer is 1-10nm, preferred 1-5nm, described TiO
2particle diameter be 1-20nm.
In a preferred embodiment of the present invention, the mass content of described active ingredient accounts for the 0.6-10% of catalyzer total mass, preferred 0.6-1.8%.
In a preferred embodiment of the present invention, the temperature of reaction of described selective catalysis hydrogenation reaction is 50-120 DEG C, and the reaction times is 1-6 hour, and reaction pressure is 0.5-2.0MPa, preferred 0.8-1.5MPa.
In a preferred embodiment of the present invention, also comprise methylene dichloride in described reaction as reaction solvent, wherein the mass ratio of phenol and described methylene dichloride is 1:1-60.
In a preferred embodiment of the present invention, described method also comprises and described selective catalysis hydrogenation reaction being coupled with film percolation filtering separation method; Technique of Nano Pd Pd/carbon catalyst PdTiO
2/ porous material particle is 1-30mm, and film percolation filtering separation pressure is 0.15-0.8MPa.
Comprise in the method for film percolation filtering separation described in the further preferred implementation of the present invention: use the solid particulate in inorganic metal membrane filter appts filtration reaction product, the catalyst solid particle residue thing that the pore size of described inorganic metal membrane filter appts can stop particle diameter minimum passes through, and the interception capacity that the percolation of described inorganic metal membrane filter appts filters is 100%, flux is every square metre of 600-2500 liter per hour.
In the further preferred implementation of the present invention, the micro-pore diameter of described inorganic metal film is 0.5-10 micron.
Present invention also offers a kind of preparation method of described metal catalyst, comprising:
I) with salpeter solution, modification is carried out to porous material and obtain modified porous material;
Ii) by TiO
2be carried on step I) on the modified porous material that obtains, obtain TiO
2/ porous material composite carrier;
Iii) by step I i) TiO that obtains
2/ porous material composite carrier is distributed in the solution containing Pd and stirs every light, and then under UV-irradiation, filtration, drying obtain described PdTiO
2/ porous material; Or by step I i) TiO that obtains
2/ porous material composite carrier is distributed in the solution containing Pd and stirs every light, and then under UV-irradiation, filtration, drying obtain described PdTiO
2/ porous material, then by described PdTiO
2/ porous material is distributed in the solution containing M and stirs every light, and then under UV-irradiation, filtration, drying obtain described Pd-MTiO
2/ porous material; Or by step I i) TiO that obtains
2/ porous material composite carrier is distributed in the solution containing Pd and M and stirs every light, and then under UV-irradiation, filtration, drying obtain described Pd-MTiO
2/ porous material; Wherein, described M is selected from least one in Au, Pt, Ir, Fe, Co, Ni and Mn.
In a preferred embodiment of the present invention, described by TiO
2being carried on step I) step of modified porous material that obtains comprises:
Configuration is containing Ti solution, and modified porous dispersion of materials contained in Ti solution in described, adjust ph to 2-4, and carries out sonic oscillation, makes to enter in the duct of described modified porous material containing Ti solution, then leaves standstill plastic, and finally calcining obtains described TiO
2/ porous material composite carrier.
In present invention further optimization embodiment, the compound method of described titaniferous solution is:
A) the ethanolic soln A of butyl (tetra) titanate is configured;
B) the mixing solutions B of water and dehydrated alcohol is configured;
C) under the condition stirred, solution B is dropwise joined in solution A, form mixed solution C, namely obtain described containing Ti solution.In the present invention, described mixed solution C is general in sol-gel state.
Concrete, be wherein gac with porous material, as an example, the preparation method of catalyzer of the present invention comprise:
1) carrier active carbon (AC) pre-treatment
Cocoanut active charcoal through washing, boiling 2 ~ 3 times is placed in the salpeter solution of different concns, reflux 4h in 60 ~ 70 DEG C of water-baths, deionized water wash filters, to solution ph in neutral, dry at 80 DEG C, obtains through HNO
3the absorbent charcoal material of solution modification.
2) complex carrier TiO
2the preparation of/AC
Sol-gel method load TiO
2: the ethanolic soln A of configuration butyl (tetra) titanate; The mixing solutions B of configuration water and dehydrated alcohol; Under the condition stirred, solution B is dropwise joined in solution A, form sol-gel shape solution C, namely 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 makes colloidal sol enter in AC duct, stop stirring being settled into gel, dry at 80 DEG C, calcine 2h at 500 DEG C, 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-Au: get step 2) obtained TiO
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 again, concentrated hydrochloric acid adjusts pH to 3 ~ 5, dark place rapid stirring 0.1-1h, then radiation 5 ~ 6h under UV-light is placed in, wash, be filtered to filtrate in neutral, dry at 20-100 DEG C, obtain PdTiO
2/ AC catalyzer.
By PdTiO obtained above
2the chlorauric acid solution that/AC is 3 ~ 5 at pH irradiates 5 ~ 6h again through UV-light, filters, washs to neutral, dry at ~ 100 DEG C, obtains Pd-AuTiO
2/ AC nanometer bi-metal catalyst.
Present invention also offers a kind of described catalyzer at phenol selectivity Hydrogenation for the application in pimelinketone.
Compared with existing catalyst preparation technology, the present invention has following beneficial effect: adopt photochemical catalysis direct-reduction process to prepare nano-noble metal catalyst Pd-MTiO
2/ porous material.
1, the method utilizes photo catalytic reduction principle can make the simple substance that the positively charged ion Restore All of the transition metal such as gold, palladium, platinum is correspondence, as long as and light application time sufficiently long just can make the load factor of described metal close to even reaching complete;
2, eliminate operating procedure rambunctious, do not need high-temperature calcination, palladium, golden nanometer particle can be avoided to reunite under the high temperature conditions or sinter;
3, without any need for reductive agent reduction, also do not need the protections such as tensio-active agent, eliminate high temperature oxidation remove protective material 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, in conjunction with firmly, 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 2-10nm, is evenly distributed, good dispersity, 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 the nano-noble metal catalyst PdTiO of preparation investigated by reductive agent
2the catalytic performance of/AC catalysis of phenol selective hydrogenation, nano Pd catalyst catalytic performance prepared by the method is good, good stability.
Compared with the production method of existing pimelinketone, method of the present invention has following characteristics and beneficial effect thereof:
1, high-activity nano palladium carbon catalyst is adopted to be that raw material one step selective catalysis hydrogenation reaction prepares pimelinketone and hexalin, mild condition, work simplification with phenol;
2, be that raw material one step selective catalysis hydrogenation reaction can prepare pimelinketone and hexalin with phenol, pimelinketone selectivity is high, can reach more than 95%;
3, utilize phenol selective catalysis hydrogenation reaction system pressure to realize membrane filtration lock out operation, save energy, work simplification.Adopt macrobead Technique of Nano Pd Pd/carbon catalyst, its grain graininess is 1-30mm; Can by the complete filtering separation of inorganic metal membrane filter appts out.Its advantage is save energy and non-wastewater discharge.
4, eliminate the process procedure of phenol shortening prior art polystep reaction, except the feature except 1 and advantage, significantly can also shorten the production cycle.
Accompanying drawing explanation
Fig. 1 is nano Pd catalyst PdTiO
2/ AC selective catalysis hydrogenation reaction and membrane filtration separation coupling technique prepare pimelinketone and hexalin schematic flow sheet.
Fig. 2 is nano Pd catalyst PdTiO prepared by embodiment 1
2the schematic flow sheet of/AC.
Fig. 3 is nano Pd catalyst PdTiO prepared by embodiment 12
2the XRD figure of/AC.
Fig. 4 is nano Pd catalyst PdTiO prepared by embodiment 13
2the XRD figure of/AC.
Embodiment
Describe embodiments of the present invention in detail below with reference to drawings and Examples, to the present invention, how utilisation technology means solve technical problem whereby, and the implementation procedure 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 be combined with each other, and the technical scheme formed is all within protection scope of the present invention.
Embodiment 1
1) gac (AC) pre-treatment: the cocoanut active charcoal through washing, boiling 2 ~ 3 times is placed in the salpeter solution that massfraction is 10.94%, reflux 4h in ~ 60 DEG C of water-baths, deionized water filters, wash to pH in neutral, dry 12h at 110 DEG C, obtains the modified activated carbon through oxide treatment;
2) sol-gel method load TiO
2: configuration solution A and solution B, under the condition of magnetic agitation, dropwise slowly join B in solution A, and form mixed solution C colloidal sol, 12.03g modified activated carbon step 1) obtained is distributed in solution C, enriching HNO
3(66-68 quality %) adjusts pH to 3, stir 5 ~ 10min, then sonic oscillation 10min makes colloidal sol enter in AC duct, and stop stirring being settled into gel, dry 12h at 80 DEG C, calcines 2h at 500 DEG C, obtain TiO
2carrying capacity is the composite carrier TiO of 9.95%
2/ AC.Wherein, solution A: 5.664g(~ 6ml) butyl (tetra) titanate is scattered in the dehydrated alcohol of 25ml; Solution B: 1ml ultrapure water is scattered in the dehydrated alcohol of 15ml
3) photo catalytic reduction load P d: get step 2) obtained TiO
2/ AC composite carrier 5.316g, dispersed with stirring is in 300ml ultrapure water, add the methyl alcohol of 10ml, 10min is stirred in dark place, then adds the sub-palladium acid solution of chlorine that 2.458ml palladium content is 20g/L, concentrated hydrochloric acid with 37% adjusts pH to 3 ~ 5, dark place rapid stirring 1h, is then placed in radiation 5h under the UV-light of 15w, filters, washs to filtrate in neutral, at 90 DEG C, dry 12h, obtains PdTiO
2/ AC catalyzer, the massfraction 0.916% of palladium.
4) photo catalytic reduction load Au: get the PdTiO that step 3) is obtained
2/ AC catalyzer TiO
2/ AC composite carrier 5.316g, dispersed with stirring is in 300ml ultrapure water, add the methyl alcohol of 10ml, 10min is stirred in dark place, then the chlorauric acid solution 2.21ml hydrochloro-auric acid content adding preparation is 20g/L, concentrated hydrochloric acid with 37% adjusts pH to 3 ~ 5, dark place rapid stirring 1h, is then placed in radiation 5h under the UV-light of 15w, filters, washs to filtrate in neutral, at 90 DEG C, vacuum-drying 12h, obtains Au-PdTiO
2/ AC catalyzer, the massfraction of palladium is the massfraction of 0.916%, Au is 0.9%.
Embodiment 2
By sol-gel method by TiO
2load on the gac of modification, obtain complex carrier TiO
2/ AC.Palladium metal is loaded to complex carrier TiO by the method for recycling photo catalytic reduction
2on/AC, obtain PdTiO through subsequent filter, washing, drying process
2/ AC.
Specific implementation process with embodiment 1, unlike HNO
3concentration is 11.13 quality %, complex carrier TiO
2tiO in/AC
2content is 9.89 quality %, catalyst P dTiO
2in/AC, the content of palladium is 0.5 quality %.
4) photo catalytic reduction load Au: get the PdTiO that step 3) is obtained
2/ AC catalyzer TiO
2/ AC composite carrier 5.316g, dispersed with stirring is in 300ml ultrapure water, add the methyl alcohol of 10ml, 10min is stirred in dark place, then the chlorauric acid solution 2.21ml hydrochloro-auric acid content adding preparation is 20g/L, pH to 3 ~ 5 are adjusted with the concentrated hydrochloric acid that content is 37 quality %, dark place rapid stirring 1h, is then placed in radiation 5h under the UV-light of 15w, filters, washs to filtrate in neutral, at 90 DEG C, vacuum-drying 12h, obtains Au-PdTiO
2/ AC catalyzer, the massfraction of the massfraction 0.5%, Au of palladium is 0.9%.
Embodiment 3
With embodiment 1, unlike complex carrier TiO
2tiO in/AC
2mass content is 15%, catalyst P dTiO
2in/AC, Pd mass content is 0.916%.
4) photo catalytic reduction load Au: get the PdTiO that step 3) is obtained
2/ AC catalyzer TiO
2/ AC composite carrier 5.316g, dispersed with stirring is in 300ml ultrapure water, add the methyl alcohol of 10ml, 10min is stirred in dark place, then the chlorauric acid solution 1.21ml hydrochloro-auric acid content adding preparation is 20g/L, concentrated hydrochloric acid with 37% adjusts pH to 3 ~ 5, dark place rapid stirring 1h, is then placed in radiation 5h under the UV-light of 15w, filters, washs to filtrate in neutral, at 90 DEG C, dry 12h, obtains Au-PdTiO
2/ AC catalyzer, the massfraction of the massfraction 0.916%, Au of palladium is 0.5%.
Embodiment 4
The nano Pd catalyst of preparation in above-described embodiment 1 is used for catalysis of phenol selective hydrogenation and prepares pimelinketone reaction.Reaction is carried out in 300mL autoclave, adds catalyzer 4g, 40mL solvent hexanaphthene and 0.8g phenol successively, passes into H
2air 5 ~ 8 times in displacement still, high-speed stirring at 800 rpm, when temperature in the kettle rises to temperature required 80 ~ 100 DEG C of experiment, passes into H
2pressure is made to maintain 1.0MPa, reaction 2h.After reaction terminates, in still, reaction solution at room temperature cools, and the hexalin in product, cyclohexanone content Agilent6890N gas chromatograph adopt marker method to be that internal standard substance is analyzed with chlorobenzene.Phenol conversion is 73.0%, and pimelinketone selectivity is 95.7%.
Embodiment 5
With embodiment 6, add catalyzer 4g prepared by embodiment 1, phenol 0.8g, temperature of reaction 100 DEG C, solvent is methylene dichloride, and the reaction times is 6h, and phenol conversion is 76.4%, and pimelinketone selectivity is 94.9%.
Embodiment 6
With embodiment 6, add catalyzer 4g prepared by embodiment 1, phenol 0.8g, temperature of reaction 100 DEG C, solvent is acetone, and the reaction times is 2h, and phenol conversion is 84.5%, and pimelinketone selectivity is 83.7%.
Embodiment 7
With embodiment 6, add catalyzer 4g prepared by embodiment 2, phenol 0.8g, temperature of reaction 100 DEG C, solvent is methylene dichloride, and the reaction times is 6h, and phenol conversion is 52.7%, and pimelinketone selectivity is 92.0%.
Embodiment 8
With embodiment 6, add catalyzer 4g prepared by embodiment 1, phenol 0.8g, temperature of reaction 100 DEG C, solvent is methylene dichloride, and the reaction times is 6h, and phenol conversion is 91.5%, and pimelinketone selectivity is 94.9%.
Embodiment 9
With embodiment 6, add nanometer bi-metal catalyst catalyzer 4g prepared by embodiment 1, phenol 0.8g, temperature of reaction 100 DEG C, solvent is methylene dichloride, and the reaction times is 2h, and phenol conversion is 88.6%, and pimelinketone selectivity is 95.7%.
Embodiment 10
With embodiment 6, add nanometer bi-metal catalyst 4g prepared by embodiment 1, phenol 0.8g, temperature of reaction 100 DEG C, solvent is methylene dichloride, and the reaction times is 6h, and phenol conversion is 96.4%, and pimelinketone selectivity is 94.9%.
Embodiment 11
With embodiment 6, add nanometer bi-metal catalyst catalyzer 4g prepared by embodiment 1, phenol 0.8g, temperature of reaction 100 DEG C, solvent is methylene dichloride, and the reaction times is 2h, and phenol conversion is 87.0%, and pimelinketone selectivity is 95.7%.
Embodiment 12
1) Activated Carbon Pretreatment: the cocoanut active charcoal through washing, boiling 2 ~ 3 times is placed in the salpeter solution that massfraction is 10.94%, reflux 4h in ~ 60 DEG C of water-baths, deionized water filters, wash to pH in neutral, dry 12h at 110 DEG C, obtains the modified activated carbon through oxide treatment;
2) sol-gel method load TiO
2: configuration solution A and solution B, under the condition of magnetic agitation, dropwise slowly join B in solution A, and form mixed solution C colloidal sol, 12.03g modified activated carbon step 1) obtained is distributed in solution C, enriching HNO
3(66-68 quality %) adjusts pH to 3, stir 5 ~ 10min, then sonic oscillation 10min makes colloidal sol enter in AC duct, and stop stirring being settled into gel, dry 12h at 80 DEG C, calcines 2h at 500 DEG C, obtain TiO
2carrying capacity is the composite carrier TiO of 9.95%
2/ AC.Wherein, solution A: 5.664g(~ 6ml) butyl (tetra) titanate is scattered in the dehydrated alcohol of 25ml; Solution B: 1ml ultrapure water is scattered in the dehydrated alcohol of 15ml
3) photo catalytic reduction load P d: get step 2) obtained TiO
2/ AC composite carrier 5.316g, dispersed with stirring is in 300ml ultrapure water, add the methyl alcohol of 10ml, 10min is stirred in dark place, then adds the sub-palladium acid solution of chlorine that 2.458ml palladium content is 20g/L, pH to 3 ~ 5 are adjusted with the concentrated hydrochloric acid of mass concentration 37%, dark place rapid stirring 1h, is then placed in radiation 5h under the UV-light of 15w, filters, washs to filtrate in neutral, at 90 DEG C, vacuum-drying 12h, obtains PdTiO
2/ AC catalyzer, the massfraction 0.916% of palladium.
As described in Figure 3, the monocrystalline peak of Pa clearly as seen from Figure 1 the XRD figure of the catalyzer that the present embodiment obtains, as seen the load Pa crystal grain of monocrystalline on this catalyzer.
Embodiment 13
By sol-gel method by TiO
2load on the gac of modification, obtain complex carrier TiO
2/ AC.Palladium metal is loaded to complex carrier TiO by the method for recycling photo catalytic reduction
2on/AC, obtain PdTiO through subsequent filter, washing, drying process
2/ AC.
Specific implementation process with embodiment 12, unlike HNO
3concentration is 11.13%, complex carrier TiO
2tiO in/AC
2mass content is 9.89%, catalyst P dTiO
2in/AC, the mass content of palladium is 0.5%.
As described in Figure 4, the monocrystalline peak of Pa clearly as seen from Figure 2 the XRD figure of the catalyzer that the present embodiment obtains, as seen the load Pa crystal grain of monocrystalline on this catalyzer.
Embodiment 14
With embodiment 12, unlike complex carrier TiO
2tiO in/AC
2mass content is 15%, catalyst P dTiO
2in/AC, Pd content is 0.5 quality %.
Embodiment 15
With embodiment 12, unlike complex carrier TiO
2tiO in/AC
2content is 20 quality %, catalyst P dTiO
2in/AC, Pd content is 0.5 quality %.
Embodiment 16
With embodiment 12, be 15 quality % unlike concentration of nitric acid, complex carrier TiO
2tiO in/AC
2mass content is 20%, and in catalyst P dTiO2/AC, Pd mass content is 0.5%.
Embodiment 17
The nano Pd catalyst of preparation in above-described embodiment 12 ~ 16 is used for catalysis of phenol selective hydrogenation and prepares pimelinketone reaction.Reaction is carried out in 300mL autoclave, add catalyzer 0.5 ~ 4g, 40mL hexanaphthene (or methylene dichloride) and 0.1 ~ 1g phenol successively, pass into H2 and to replace in still air 5 ~ 8 times, high-speed stirring at 800 rpm, when temperature in the kettle rises to temperature required 80 ~ 100 DEG C of experiment, passing into H2 makes pressure maintain 1.0MPa, reaction 2 ~ 6h.After reaction terminates, in still, reaction solution at room temperature cools, and the hexalin in product, cyclohexanone content Agilent6890N gas chromatograph adopt marker method to be that internal standard substance is analyzed with chlorobenzene.
Embodiment 18
With embodiment 17, add catalyzer 4g prepared by embodiment 1, phenol 0.8g, temperature of reaction 100 DEG C, solvent is methylene dichloride, and the reaction times is 2h, and phenol conversion is 73.0%, and pimelinketone selectivity is 95.7%.
Embodiment 19
With embodiment 17, add catalyzer 4g prepared by embodiment 1, phenol 0.8g, temperature of reaction 100 DEG C, solvent is methylene dichloride, and the reaction times is 6h, and phenol conversion is 76.4%, and pimelinketone selectivity is 94.9%.
Embodiment 20
With embodiment 17, add catalyzer 4g prepared by embodiment 1, phenol 0.8g, temperature of reaction 100 DEG C, solvent is hexanaphthene, and the reaction times is 2h, and phenol conversion is 84.5%, and pimelinketone selectivity is 83.7%.
Embodiment 21
With embodiment 17, add catalyzer 4g prepared by embodiment 2, phenol 0.8g, temperature of reaction 100 DEG C, solvent is methylene dichloride, and the reaction times is 6h, and phenol conversion is 52.7%, and pimelinketone selectivity is 92.0%.
Embodiment 22
With embodiment 12, be 10 quality % unlike concentration of nitric acid, complex carrier TiO
2tiO in/AC
2content is 10%, catalyst P dTiO
2the Pd content added in/AC is 2 quality %.
With embodiment 17, carry out in 50mL autoclave unlike reaction, add the catalyzer 0.24g of above-mentioned preparation, phenol 0.35g, temperature of reaction 80 DEG C, solvent is methylene dichloride, reaction times is 2h, and phenol conversion is more than 99%, and pimelinketone selectivity is 98.9%.
Embodiment 23
With embodiment 12, be 10 quality % unlike concentration of nitric acid, complex carrier TiO
2tiO in/AC
2content is 10%, catalyst P dTiO
2the Pd content added in/AC is 2 quality %.
With embodiment 17, carry out in 50mL autoclave unlike reaction, add the catalyzer 0.24g of above-mentioned preparation, phenol 0.35g, temperature of reaction 90 DEG C, solvent is methylene dichloride, reaction times is 2h, and phenol conversion is 99.9%, and pimelinketone selectivity is 90.89%.
Embodiment 24
With embodiment 12, be 10 quality % unlike concentration of nitric acid, complex carrier TiO
2tiO in/AC
2content is 10%, catalyst P dTiO
2the Pd content added in/AC is 2 quality %.
With embodiment 17, carry out in 50mL autoclave unlike reaction, add the catalyzer 0.24g of above-mentioned preparation, phenol 0.35g, temperature of reaction 100 DEG C, solvent is methylene dichloride, reaction times is 2h, and phenol conversion is 99.9%, and pimelinketone selectivity is 87.8%.
Embodiment 25
Liquid-solid mixture after embodiment 17-24 catalysis selective catalysis hydrogenation reaction is through inorganic metal membrane filter appts, selective catalysis hydrogenation reaction system pressure is utilized to carry out the pressure reduction of membrane filtration lock out operation needs, by certain pressure reduction 0.15MPa-0.35MPa, percolation filter operation is carried out to the liquid-solid mixture in inorganic metal membrane filter appts, catalyst solid particle is separated from the liquid-solid mixture after selective catalysis hydrogenation reaction.
Percolation filter operation temperature is at 60-90 degree Celsius; Adopt the membrane pore size 0.5-1um of inorganic metal membrane filtration; Catalyzed reaction uses catalyzer to be granularity 1-20mm Technique of Nano Pd Pd/carbon catalyst; The catalyst solid particle residue thing that the pore size of inorganic metal film can stop grain graininess minimum passes through, and the interception capacity that inorganic metal film percolation filters is 100%; Carry out percolation filter operation at certain pressure reduction 0.15MPa-0.35MPa, the flux that its membrane filtration is separated can reach every square metre of 600-2500 liter per hour.
By selective catalysis hydrogenation process and membrane filtration sepn process coupling integration in a closed system, special sequence of control is set, automatic control can be realized.
Wherein, selective catalysis hydrogenation reaction and membrane filtration separation coupling are integrated in a closed system, coordinate specific routine, realize automatically controlling.Can level of automation be improved, reduce the labour intensity of operator.
Claims (8)
1. prepare a method for pimelinketone, it is characterized in that: adopt catalyst P d-Au/TiO
2-porous material, be that raw material carries out a step selective catalysis hydrogenation reaction to prepare pimelinketone with phenol, the consumption of catalyzer accounts for the 0.1-40% of phenol quality;
Described catalyst P d-Au/TiO
2-porous material comprises:
1) with nano-TiO
2the porous material of modifying and decorating is complex carrier;
2) with the nano particle of Pd nano particle and Au for active ingredient;
Wherein, the TiO on described active ingredient and described complex carrier
2there is the strong interaction of metal and carrier, form Pd-Au/TiO
2structure, so forms the structure Pd-Au/TiO of described catalyzer
2the catalyzer of-porous material complex carrier structure.
2. method according to claim 1, is characterized in that, described nano-TiO
2the TiO of described porous material outside surface and inner surfaces of pores formation is carried on single or multiple lift dispersion state
2-porous material complex carrier.
3. method according to claim 1, is characterized in that, the particle diameter of described nano particle is 1-10nm, described TiO
2particle diameter be 1-20nm.
4. the method according to any one of claim 1-3, is characterized in that, the preparation method of described catalyzer is:
I) with salpeter solution, modification is carried out to porous material and obtain modified porous material;
Ii) by TiO
2be carried on step I) on the modified porous material that obtains, obtain TiO
2-porous material composite carrier;
Iii) by step I i) TiO that obtains
2-porous material composite carrier is distributed in the solution containing Pd and stirs every light, and then under UV-irradiation, filtration, drying obtain described Pd/TiO
2-porous material, then by described Pd/TiO
2-porous material is distributed in the solution containing Au and stirs every light, and then under UV-irradiation, filtration, drying obtain described Pd-Au/TiO
2-porous material; Or by step I i) TiO that obtains
2-porous material composite carrier is distributed in the solution containing Pd and Au and stirs every light, and then under UV-irradiation, filtration, drying obtain described Pd-Au/TiO
2-porous material.
5. the method according to any one of claim 1-3, is characterized in that, the temperature of reaction of described selective catalysis hydrogenation reaction is 50-120 DEG C, and the reaction times is 1-6 hour, and reaction pressure is 0.5-2.0MPa.
6. the method according to any one of claim 1-3, is characterized in that, using methylene dichloride as reaction solvent in described reaction, wherein the mass ratio of phenol and described methylene dichloride is 1:1-60.
7. the method according to any one of claim 1-3, is characterized in that, described selective catalysis hydrogenation reaction is coupled with film percolation filtering separation method; Catalyst P d-Au/TiO
2the particle of-porous material is 1-30mm, and film percolation filtering separation pressure is 0.15-0.8MPa.
8. method according to claim 7, it is characterized in that, described film percolation filtering separation method is: use the solid particulate in inorganic metal membrane filter appts filtration reaction product, the catalyst solid particle residue thing that the pore size of described inorganic metal membrane filter appts can stop particle diameter minimum passes through, and the interception capacity that the percolation of described inorganic metal membrane filter appts filters is 100%, flux is every square metre of 600-2500 liter per hour; The micro-pore diameter of described inorganic metal film is 0.5-10 micron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310721645.XA CN103724174B (en) | 2013-12-24 | 2013-12-24 | A kind of method preparing pimelinketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310721645.XA CN103724174B (en) | 2013-12-24 | 2013-12-24 | A kind of method preparing pimelinketone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103724174A CN103724174A (en) | 2014-04-16 |
| CN103724174B true CN103724174B (en) | 2016-03-30 |
Family
ID=50448511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310721645.XA Active CN103724174B (en) | 2013-12-24 | 2013-12-24 | A kind of method preparing pimelinketone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103724174B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672069B (en) * | 2015-01-21 | 2016-08-24 | 中国科学院兰州化学物理研究所 | A kind of Ketohexamethylene or the preparation method of substituted cyclohexanone |
| CN105413681B (en) * | 2015-12-10 | 2017-12-26 | 沈阳化工研究院有限公司 | A kind of p methoxy phenol hydrogenation catalyst and preparation method thereof and hydrogenation reaction |
| CN110247069A (en) * | 2016-05-26 | 2019-09-17 | 昆明理工大学 | Carbon carries MnPd nanocatalyst and preparation method thereof |
| CN106423161B (en) * | 2016-10-10 | 2019-07-02 | 湘潭大学 | A kind of preparation method and catalyst of hydrogenation catalyst |
| CN108570667A (en) * | 2017-03-14 | 2018-09-25 | 中国科学技术大学 | A kind of preparation method of metal film, reactor and preparation method thereof and compound |
| CN108380195B (en) * | 2018-03-26 | 2020-12-11 | 上海师范大学 | Preparation method and application of molecular oxygen activation catalyst constructed based on surface oxygen defects |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101709027A (en) * | 2009-11-27 | 2010-05-19 | 中国科学院化学研究所 | Method and special catalyst for preparing cyclohexanone in one step by phenol hydrogenation |
| CN102125838A (en) * | 2011-01-12 | 2011-07-20 | 中国石油化工股份有限公司 | Method for preparing high-selectivity Pd/TiO2-C hydrogenation catalyst |
| CN103007978A (en) * | 2012-12-28 | 2013-04-03 | 湘潭大学 | Nanometer metal catalyst as well as preparation method and application thereof |
-
2013
- 2013-12-24 CN CN201310721645.XA patent/CN103724174B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101709027A (en) * | 2009-11-27 | 2010-05-19 | 中国科学院化学研究所 | Method and special catalyst for preparing cyclohexanone in one step by phenol hydrogenation |
| CN102125838A (en) * | 2011-01-12 | 2011-07-20 | 中国石油化工股份有限公司 | Method for preparing high-selectivity Pd/TiO2-C hydrogenation catalyst |
| CN103007978A (en) * | 2012-12-28 | 2013-04-03 | 湘潭大学 | Nanometer metal catalyst as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103724174A (en) | 2014-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103691431B (en) | A kind of palladium-carbon catalyst and preparation method and application | |
| CN103724174B (en) | A kind of method preparing pimelinketone | |
| US11772076B2 (en) | Preparation method of nitrogen-doped hierarchical-porous carbon-loaded nanometer Pd catalyst and product and application thereof | |
| CN102513104B (en) | Preparation method of benzaldehydes compound and novel double-metal catalyst loaded by mesoporous carbon for preparation method | |
| CN102553579B (en) | Preparation method of high-dispersity supported nano metal catalyst | |
| CN109718806B (en) | Noble metal monoatomic catalyst and preparation method and application thereof | |
| CN103691434B (en) | A kind of metallic catalyst and preparation method and application | |
| CN106423161B (en) | A kind of preparation method and catalyst of hydrogenation catalyst | |
| CN104646025B (en) | A kind of preparation method of hollow Pt/Ni alloys and graphene aerogel composite | |
| CN104307515B (en) | A kind of Au-Pd/ graphen catalyst and its preparation method and application | |
| CN105665027B (en) | The preparation method of high-dispersion loading type metal nano catalyst | |
| CN106984320A (en) | A kind of high-dispersion loading type metallic catalyst and preparation method thereof | |
| CN105642311A (en) | Carbon-based non-noble metal @ noble metal core-shell nano catalyst and preparation method thereof by taking MOFs (Metal-Organic Framework) as template | |
| CN109482177A (en) | A kind of nano-noble metal catalyst preparation method | |
| CN104857955A (en) | Method for preparing a noble metal nano catalyst | |
| CN104549263B (en) | A kind of Pd/ niobic acid nanometer sheet catalyst and its preparation method and application | |
| CN107694563A (en) | Palladium carbon catalyst and its preparation method and application | |
| CN102909034B (en) | Preparation of supported gold-nickel alloy nanocatalyst | |
| CN112871167A (en) | MOFs (metal-organic frameworks) -packaged ultrafine alloy nanoparticles as well as preparation method and application thereof | |
| CN106881089B (en) | A kind of preparation method of controllable graphene-supported cheap IB-VIIIB race duplex metal nano granule composite material | |
| CN109046379A (en) | A kind of perovskite composite oxides load platinum catalyst and its preparation and application | |
| CN109621949B (en) | Magnesium-aluminum hydrotalcite supported superfine nano palladium catalyst and preparation method thereof | |
| CN113600181A (en) | Preparation method of nano palladium supported catalyst | |
| CN106622229B (en) | The preparation method and phenol selectivity of hydrogenation catalyst add the method for hydrogen preparing cyclohexanone | |
| CN107442160B (en) | A kind of preparation method of anti-sintering loading type Pd base catalysis material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |