CN110152661A - A kind of nitrobenzene compounds hydrogenation synthesis amino benzenes compounds nanometer Au-CeO2(cube) catalyst - Google Patents
A kind of nitrobenzene compounds hydrogenation synthesis amino benzenes compounds nanometer Au-CeO2(cube) catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 25
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 22
- 150000001448 anilines Chemical class 0.000 title abstract description 4
- 150000005181 nitrobenzenes Chemical class 0.000 title description 6
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 title description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001298 alcohols Chemical class 0.000 claims abstract 2
- 229910000510 noble metal Inorganic materials 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000001556 precipitation Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- WYUHTVDGHDRPDW-UHFFFAOYSA-N 3-hydroxy-N-phenyl-4-phenyldiazenylnaphthalene-2-carboxamide Chemical compound C1(=CC=CC=C1)N=NC1=C(C(=CC2=CC=CC=C12)C(=O)NC1=CC=CC=C1)O WYUHTVDGHDRPDW-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 239000006079 antiknock agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- FFEVHTMMGXLTCX-UHFFFAOYSA-N iron nitrobenzene Chemical compound [Fe].[N+](=O)([O-])C1=CC=CC=C1 FFEVHTMMGXLTCX-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RFKJHQXSLBUONF-UHFFFAOYSA-N methyl blue free acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=NC=2C=CC(=CC=2)S(O)(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S(O)(=O)=O)=CC=2)C=C1 RFKJHQXSLBUONF-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical fields of organic chemistry and catalytic chemistry using nitrobenzene matters as raw material, using alcohols as solvent, using hydrogen as hydrogen source, in the presence of a catalyst, it carries out hydrogenation reaction and generates phenyl amines product, it is using nanocube ceria as carrier that the catalyst forms substantially, and active component is the noble metals such as Au, and preparation method is using deposition-precipitation method that Au is immobilized to nanocube CeO2On.It is an advantage of the invention that prepared catalyst p-nitrophenyl hydrogenation activity is good, reaction condition is mild, in 120 DEG C and 2MPa H2Under the conditions of, reacting 2h, nitrobenzene conversion rate and aniline selectively all reach 99.9% or more, meanwhile, catalyst has good reusability.
Description
Technical field
The invention belongs to the technical fields of organic chemistry and catalytic chemistry, are related to a kind of for nitrobenzene hydrogenation synthesis benzene
Catalyst of amine substance and preparation method thereof.
Background technique
Aniline is one of most important intermediate in dye industry, can be used for manufacturing acid ink blue in dye industry
Deng；Have in terms of organic pigment for manufacturing bronze red etc..Dyestuff nigrosine is used in printing and dyeing industry；It is used in pesticide industry
In many agrochemicals of production；It is the important source material of rubber chemicals, also can be used as the raw material of medical sulfa drug, while is also production
The intermediate of fragrance, plastics, varnish, film etc.；And it can be used as the stabilizer in explosive, the anti-knock agent in gasoline and be used as molten
Agent；It is other to be also used as manufacture hydroquinone, 2-phenylindone etc..The synthetic method of aniline mainly has nitrobenzene iron powder reducing
Method, Benzene Chloride amination method, Catalytic Hydrogenation of Nitrobenzene reduction method and phenol ammonolysis process.Iron powder reducing method is most ancient method, should
Method falls behind, and aniline yield rate is low, and pollution is more serious, which is gradually eliminated.Benzene Chloride amination method higher cost.Catalysis adds
Hydrogen method is the reducing agent that the direct compound for using hydrogen or capable of decomposing generation hydrogen adds hydrogen as nitro compound.At present with
Hydrogen adds hydrogen to be current industrial more commonly used method as reducing agent progress nitro compound.
Document (He Daiping, department of chemistry, tsinghua university, 2006 (31)) is prepared for Au-ZrO by deposition-precipitation method2It urges
Agent, in 1MPa H2Under the conditions of 150 DEG C, 2h, conversion ratio 91.8% are reacted, the load capacity of Au is 4%.Document (Song
China, Chemistry and Chemical Engineering College, the such as Dong Haixin Northeast Petroleum University, 2012) pass through research Pt-TiO2Catalyst is to adjacent chlorine nitre
Discovery, carrier TiO are reacted in the influence of base benzene hydrogenation under conditions of normal pressure, 80 DEG C2Crystal form to the catalytic activity shadow of catalyst
Sound is larger, with Detitanium-ore-type TiO2It is apparently higher than for the catalyst choice hydrogenation activity of carrier with rutile TiO2For carrier
Catalyst.Document (Wen Xia, Hunan Normal University, 2015,17-23) is by loading Au catalysis to titania nanotube
Nitrobenzene hydrogenation the study found that 90 DEG C, 0.3MPa, reaction 1h under conditions of, with hydro-thermal reaction for 24 hours through 400 DEG C roast
The titania nanotube burnt is the catalyst of carrier preparation when being catalyzed nitrobenzene hydrogenation, and conversion ratio can achieve
79.28%.Document (Cao Liu, Hunan Normal University, 2014,14-21), using the titanium dioxide of different crystal type as load
Body is prepared for three kinds of different catalyst Au-TiO by deposition-precipitation method2.Wherein Au-TiO2Type-A catalyst is in H2 pressure
It is 90 DEG C for 0.4MPa, reaction temperature, mixing speed is to react 4h under the reaction condition of 500rpm, and the conversion ratio of nitrobenzene reaches
To 99% or more.And after the catalyst circulation uses 3 times, the conversion ratio of nitrobenzene falls below 91.7% from 99.75%.To sum up
It is described, due to Au base catalyst hydrogenation of chloronitrobenzene conversion ratio be not very high, catalyst thermal stability and reusability also
It is not good enough.Nanocube CeO prepared by the present invention2Immobilized Au base catalyst shows high reaction speed under mild conditions
Rate and reusability is good.It is because of carrier nanocube CeO2Structure, acid-base property and oxidation-reduction quality this is catalyzed to Au
The activity and selectivity of reaction has an impact.Wherein, nanocube CeO2Oxide with oxidation-reduction quality has as carrier
Conducive to the Preferential adsorption of nitro in nitrobenzene compounds, thus with high nitro hydrogenation selectivity.With redox
The nanocube CeO of property2It realizes in active site for carrier (for example, the edge of deficient sites, crystal face and Au/corner position
Point) on nitro Preferential adsorption, to hinder the absorption and non-selective hydrogenation of other groups.Further, since defect
In the presence of the electronics transfer from defective locations to metal d with enhancing can further adjust H2Activation and dissociation.
It is a discovery of the invention that the nanocube ceria with (100) crystal face is carrier loaded nanogold, due to its spy
Different crystal face, suitable acid-base property and suitable oxygen defect position has very high using hydrogen as the nitrobenzene compounds of hydrogen source
Hydrogenation activity and phenyl amines selectivity of product.
Summary of the invention
The purpose of the present invention is to provide a kind of for that can accelerate the efficient catalytic of reaction rate under relatively mild conditions
The nanocube CeO of hydrogenation of chloronitrobenzene2Immobilized Au base catalyst and preparation method thereof.
A kind of technical solution of the present invention: nanocube CeO for nitrobenzene matters hydrogenation reaction2Immobilized Au base
Catalyst and preparation method thereof, the catalyst is by nano Ce O2It is formed with Au, Au is active component.Preparation method is using heavy
The product precipitation method are immobilized to nano Ce O by Au2On.Specific preparation process is as follows:
(1) Ce (NO for being 0.1 ~ 5mol/L by concentration3)3•6H2O solution and 5 ~ 50mL concentration are 0.1 ~ 10mol/L NaOH solution
It is sufficiently mixed, is transferred in water heating kettle and is handled at 100 ~ 200 DEG C after mixing evenly, sufficiently washed after being then centrifuged for water and ethyl alcohol
Make the aobvious alkalinity of solution, be then dried overnight at 80 ~ 200 DEG C, obtaining yellow powder is precursor carrier.
(2) obtained solid in (1) is weighed 0.1 ~ 10g to be distributed in 50 ~ 150mL water, 2 ~ 30g urine is then added
The chlorauric acid solution that concentration is 0.01 ~ 10mol/L is added dropwise in element thereto dropwise after stirring at 50 ~ 180 DEG C, after
Continue 1 ~ 15h of aging at 50 ~ 180 DEG C, centrifugation gained precipitating is sufficiently washed through water can no longer detect chloride ion into supernatant
In the presence of being then dried overnight at 50 ~ 200 DEG C, obtain catalyst.
(3) catalyst made from (2) be can be used for into nitrobenzene compounds and adds hydrogen aniline category matter, in which: with mole
Than for 1:85 ~ 1:170 nitrobenzene and alcohol be raw material and solvent, hydrogenation reaction is carried out in the presence of a catalyst, to sample after reaction
Product are centrifuged, and aniline category matter is obtained: it is characterized in that, catalyst and raw material are packed into autoclave reactor, reaction temperature
Degree be 20 ~ 200 DEG C, Hydrogen Vapor Pressure be 0.1 ~ 15MPa, the reaction time be 0.5 ~ for 24 hours.
It is an advantage of the current invention that operating condition is mild, the reaction time is short, and catalyst performance is good, and catalyst is easy to react
System separation, entire reaction system are easy to implement, and for the high conversion rate of nitrobenzene up to 99% or more, the selectivity of aniline is also up to 99%
More than, and there is good reusability, it is suitable for industrial applications.
Specific embodiment
The present invention is further illustrated below by specific embodiment,
Embodiment 1
(1) hydro-thermal method prepares different-shape carrier nano Ce O2
Ce (the NO of 0.4mol/L3)3•6H2The concentration of O solution (5ml, cerous nitrate 0.868g) and 35mL are 0.1 ~ 6mol/L
NaOH solution is sufficiently mixed, and is transferred in water heating kettle after stirring 30min and is handled for 24 hours at 180 DEG C, abundant with water and ethyl alcohol after centrifugation
Washing makes the aobvious alkalinity of solution, is then dried overnight at 105 DEG C, and obtaining yellow powder is precursor carrier.Then using 800 DEG C of roastings
4h。
(2) deposition-precipitation method prepares solid catalyst Au-CeO2
By the nano Ce O of 1g different-shape2Then support dispersion is added 6g urea, is sufficiently stirred under 80 degree into 94mL water
The chlorauric acid solution (0.5mL is added dropwise when being 1wt% in load capacity) that concentration is 0.1mol/L is added dropwise after uniformly thereto dropwise, continues
The aging 4h at 80 DEG C, centrifugation gained precipitating sufficiently wash into supernatant the presence that can no longer detect chloride ion through water, then
It is dried overnight at 105 DEG C, roasts 4h at 200 DEG C after dry.Obtain catalyst 1.
Embodiment 2
With embodiment 1, but nanocube CeO2Maturing temperature be 600 DEG C, Au-CeO2- cube(cube) roasting
The catalyst 2 that temperature is 200 DEG C.
Embodiment 3
With embodiment 1, but nanocube CeO2Maturing temperature be 400 DEG C, Au-CeO2- cube(cube) roasting
The catalyst 3 that temperature is 200 DEG C.
Embodiment 4
With embodiment 1, but nanocube CeO2Maturing temperature be 200 DEG C, Au-CeO2- cube(cube) roasting
The catalyst 4 that temperature is 200 DEG C.
Embodiment 5
With embodiment 1, but nanocube CeO2Maturing temperature be 200 DEG C, Au-CeO2- cube(cube) roasting
The catalyst 5 that temperature is 600 DEG C.
Embodiment 6
With embodiment 1, but nanocube CeO2Maturing temperature be 200 DEG C, Au-CeO2- cube(cube) roasting
The catalyst 6 that temperature is 400 DEG C.
Embodiment 7
With embodiment 1, but nanocube CeO2Maturing temperature be 200 DEG C, Au-CeO2- cube(cube) roasting
The catalyst 7 that temperature is 200 DEG C.
Embodiment 8
With catalyst prepared by embodiment 1-7, Catalytic Hydrogenation of Nitrobenzene reaction is carried out.
Catalytic Hydrogenation of Nitrobenzene reaction carries out in 100ml autoclave, and 0. 1 g are accurately weighed in autoclave and are urged
Agent, 1mmol nitrobenzene, 1mmol normal octane and 10mL dehydrated alcohol lead to hydrogen 5 times or more after sealing repeatedly as solvent, will
Hydrogen Vapor Pressure is adjusted to 2. 0 MPa.It places it in magnetic agitation oil bath pan, the heating reaction 2h at 120 DEG C.It is extracted out after cooling
Solution in kettle is centrifuged to obtain product.
Reaction product uses chromatographic, and normal octane is internal standard, catalyst 1-4 catalytic performance such as table 1, catalyst
Performance such as table 2.
The hydrogenation of chloronitrobenzene catalytic performance of 1 catalyst 1-4 of table
| Entry | catalyst | Conv. (%) | Sel. (%) |
| 1 | Embodiment 1 | 4.0 | 38.47 |
| 2 | Embodiment 2 | 9.08 | 79.8 |
| 3 | Embodiment 3 | 99.3 | 99.6 |
| 4 | Embodiment 4 | 87.5 | 99.8 |
Preferred vector nanocube CeO as can be seen from Table 12Maturing temperature be 400 DEG C.
The hydrogenation of chloronitrobenzene catalytic performance of 2 catalyst 5-7 of table
| Entry | catalyst | Conv. (%) | Sel. (%) |
| 1 | Embodiment 5 | 0.7 | 99.5 |
| 2 | Embodiment 6 | 63.3 | 90.7 |
| 3 | Embodiment 7 | 87.5 | 99.8 |
Preferred catalyst Au-CeO as can be seen from Table 22- cube(cube) maturing temperature be 200 DEG C.
Embodiment 9
Changing the reaction time in embodiment 8 is 1h, and identical (catalyst recycled every time is wanted for other reaction conditions and embodiment 8
200 DEG C of roasting 4h), sample calculates the conversion ratio of nitrobenzene and the selectivity of aniline into chromatography after reaction terminates, and ties
Fruit is as shown in table 3.
The Repeatability of 3 catalyst 3 of table
| Entry | Reaction cycles | Conv. (%) | Sel. (%) |
| 1 | 1 | 50.9 | 94.5 |
| 2 | 2 | 69.4 | 99.6 |
| 3 | 3 | 61.5 | 93.8 |
Catalyst Au-CeO as can be seen from Table 32- cube-400-200 is highly stable, and conversion ratio and the basic holding of selectivity are not
Become.
In conclusion experiments have shown that, preferred catalyst is Au-CeO2The maturing temperature of-cube-400-200(carrier is
400 DEG C, the maturing temperature of catalyst is 200 DEG C), and it is very stable, it can be recycled for multiple times.
Embodiment 10
Comparative example 1-2
Au-CeO is respectively adopted2- poly(CeO2For nanometer polyhedral) and Au-CeO2- rod(CeO2For nanometer rods) catalysis nitro
Benzene hydrogenation, catalyst amount 1mmol, and reaction time are 2h, in other conditions and the identical feelings of embodiment 8
Under condition, carries out hydrogenation reaction and be contrasted a 1-2 investigation reaction result.
The nitrobenzene hydrogenation result of 4 comparative example of table
| Comparative example | catalyst | Conv. (%) | Sel. (%) |
| 1 | Au-CeO2-poly | 88.0 | 75.6 |
| 2 | Au-CeO2-rod | 90.9 | 89.1 |
The catalyst nitrobenzene hydrogenation of different-shape is used in comparative example 1-2.To sum up, it can be seen that the choosing of cube
Selecting property and conversion ratio are higher, have all reached 99% or more, and since nanocube ceria has (100) crystal face, special
Different crystal face, suitable acid-base property and suitable oxygen defect position is more advantageous to nitrobenzene compounds and generates aniline category matter.
The present invention is not limited to embodiment of above, can make various changes and variants according to the present invention, without departing from this
The spirit of invention, should belong to the scope of the present invention.
Claims (4)
1. a kind of nanocube CeO for nitrobenzene hydrogenation2Immobilized Au base catalyst, it is characterized in that the base of catalyst
This group becomes nanocube CeO2And Au, nanocube CeO2For carrier, Au is active component.
2. catalyst according to claim 1, it is characterised in that the metal oxide for supported noble metals Au, Pt is to receive
Rice cube CeO2。
3. catalyst according to claim 1, which is characterized in that be for the nitrobenzene and alcohol of 1:85 ~ 1:170 with molar ratio
Raw material and solvent carry out hydrogenation reaction in the presence of a catalyst, are centrifuged to sample after reaction, obtain aniline category matter: its
It being characterized in that, catalyst and raw material are packed into autoclave reactor, and reaction temperature is 20 ~ 200 DEG C, Hydrogen Vapor Pressure is 0.1 ~
15MPa, the reaction time be 0.5 ~ reacted down for 24 hours, the catalyst be with different temperatures roast nanocube
CeO2For carrier, Au being supported on carrier and roast obtained catalyst using different temperature, dosage is 0.5 ~
20g, Au content are 1wt% ~ 10wt%..
4. solvent alcohols used in nitrobenzene hydrogenation described in accordance with the claim 3 can be the alcohol such as ethyl alcohol, methanol, propyl alcohol
Substance.
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| CN113209977A (en) * | 2021-04-02 | 2021-08-06 | 北京理工大学 | Preparation method and application of hydrogenation catalyst with tannic acid as stabilizer |
| CN116603523A (en) * | 2023-05-23 | 2023-08-18 | 中国科学院大连化学物理研究所 | Preparation and application of Pt-based catalyst supported by modified cerium oxide carrier |
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