CN117960220A - Catalyst for selectively reducing nitroaromatic compounds and application thereof - Google Patents
Catalyst for selectively reducing nitroaromatic compounds and application thereof Download PDFInfo
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- CN117960220A CN117960220A CN202211331983.8A CN202211331983A CN117960220A CN 117960220 A CN117960220 A CN 117960220A CN 202211331983 A CN202211331983 A CN 202211331983A CN 117960220 A CN117960220 A CN 117960220A
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- catalyst
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- nitrogen
- nitroaromatic compounds
- mesoporous carbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 150000001875 compounds Chemical class 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 7
- -1 aromatic amine compounds Chemical class 0.000 claims abstract description 6
- 239000002923 metal particle Substances 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000000935 solvent evaporation Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 5
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 239000007806 chemical reaction intermediate Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 11
- 239000012498 ultrapure water Substances 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000004982 aromatic amines Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ZYMCBJWUWHHVRX-UHFFFAOYSA-N (4-nitrophenyl)-phenylmethanone Chemical compound C1=CC([N+](=O)[O-])=CC=C1C(=O)C1=CC=CC=C1 ZYMCBJWUWHHVRX-UHFFFAOYSA-N 0.000 description 2
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 2
- SYZVQXIUVGKCBJ-UHFFFAOYSA-N 1-ethenyl-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(C=C)=C1 SYZVQXIUVGKCBJ-UHFFFAOYSA-N 0.000 description 2
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 2
- SCCCFNJTCDSLCY-UHFFFAOYSA-N 1-iodo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(I)C=C1 SCCCFNJTCDSLCY-UHFFFAOYSA-N 0.000 description 2
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 2
- NKJIFDNZPGLLSH-UHFFFAOYSA-N 4-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C=C1 NKJIFDNZPGLLSH-UHFFFAOYSA-N 0.000 description 2
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- IHIJFQRUYCEKCZ-UHFFFAOYSA-N n-methyl-4-nitrobenzenesulfonamide Chemical compound CNS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 IHIJFQRUYCEKCZ-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- RBKHNGHPZZZJCI-UHFFFAOYSA-N (4-aminophenyl)-phenylmethanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC=C1 RBKHNGHPZZZJCI-UHFFFAOYSA-N 0.000 description 1
- IFSSSYDVRQSDSG-UHFFFAOYSA-N 3-ethenylaniline Chemical compound NC1=CC=CC(C=C)=C1 IFSSSYDVRQSDSG-UHFFFAOYSA-N 0.000 description 1
- YBAZINRZQSAIAY-UHFFFAOYSA-N 4-aminobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1 YBAZINRZQSAIAY-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 description 1
- VLVCDUSVTXIWGW-UHFFFAOYSA-N 4-iodoaniline Chemical compound NC1=CC=C(I)C=C1 VLVCDUSVTXIWGW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for selectively reducing nitroaromatic compounds and application thereof. The invention adopts nitrogen-doped mesoporous carbon material loaded ruthenium metal as a heterogeneous catalyst to catalyze the reduction of nitroaromatic compounds to obtain aromatic amine compounds. The method has wide substrate application range, has remarkable reduction effect on important pharmaceutical reaction intermediate molecules, can reach 99 percent of yield, can carry out reaction under the condition of mild temperature and hydrogen pressure, can recycle heterogeneous catalyst, is easy to recycle, and has green and environment-friendly reaction process. The catalyst prepared by the invention has high specific surface area and large pore volume, ordered mesoporous pore canal and ultra-small metal particle size, and can be repeatedly used for more than five times without obvious activity attenuation.
Description
Technical Field
The invention belongs to the field of heterogeneous catalysis organic synthesis, and particularly relates to a method for selectively reducing nitroaromatic compounds by using a nitrogen-doped mesoporous carbon material supported ruthenium metal catalyst.
Background
In the field of organic synthesis, amine compounds are important intermediates for the production of other compounds. Therefore, the hydrogenation of nitroaromatics to obtain functionalized aromatic amines is of great importance in the dye and pharmaceutical industries, especially nitroaromatics with certain unsaturated functionalities. Traditional methods for synthesizing aromatic amine compounds comprise reduction methods such as metal, electrolysis and hydrazine hydrate, but the methods have high energy consumption, high corrosion resistance requirement on equipment and serious environmental pollution, and have been gradually replaced by catalytic hydrogenation. In catalytic hydrogenation, homogeneous catalysts have a high chemical selectivity, but usually require additional ligands or additives, which are difficult to separate from the reaction system after the end of the reaction, and the metal components used are difficult to recover. And compared with a homogeneous catalyst, the heterogeneous catalyst has the advantages of easy separation and recycling, and has higher economic value.
At present, a heterogeneous catalyst with high activity, high selectivity, good cycle stability and mild reaction conditions is not available.
Disclosure of Invention
Aiming at the technical problems, the invention provides a catalyst for selectively reducing nitroaromatic compounds and application thereof. According to the invention, the nitrogen-doped mesoporous carbon-supported ruthenium metal material is used as a heterogeneous catalyst, so that the selective reduction of the nitroaromatic compound containing unsaturated groups can be realized under mild conditions, the aromatic amine is obtained, and the reaction has the characteristics of high conversion rate, high selectivity and good cycle stability, and is expected to become a feasible way of industrial catalysis.
The technical scheme provided by the invention is as follows:
in a first aspect, the invention provides a method for preparing a nitrogen-doped mesoporous carbon supported ruthenium metal catalyst, comprising the following steps:
(1) Mixing and dispersing ruthenium chloride aqueous solution, tryptophan and mesoporous silica template SBA-15-OH with silicon hydroxyl on the surface of a pore canal in an ethanol-water mixed solvent, and uniformly stirring;
(2) The preparation method comprises the steps of solvent evaporation, heating and roasting, removing the template agent SBA-15-OH, washing, drying and grinding.
Further, in the step (1), the dosage ratio of ruthenium chloride, tryptophan and SBA-15-OH is 0.05-0.2mmol, 0.8-3.2g and 1-2g.
Further, in the step (2), the temperature-raising roasting is performed in an argon atmosphere, and the roasting temperature is 500-900 ℃.
In a second aspect, the invention provides a nitrogen-doped mesoporous carbon supported ruthenium metal catalyst prepared by the method in the first aspect.
Further, in the catalyst, the size of ruthenium metal particles is below 5nm, and the mass fraction is 0.1-20wt%. Preferably, the mass fraction is 1-5wt%.
In a third aspect, the present invention provides the use of the catalyst of the second aspect for the selective reduction of nitroaromatic compounds, comprising the steps of:
(1) Uniformly stirring and mixing the nitrogen-doped mesoporous carbon supported ruthenium metal catalyst, nitroaromatic compounds and a solvent;
(2) Placing the mixture into a high-pressure reaction kettle, filling hydrogen, and magnetically stirring the mixture at room temperature or under heating to perform a reaction;
(3) And (3) recovering the reaction product to obtain the arylamine compound.
Further, in the step (1), the molar ratio of the metal ruthenium atom to the nitroaromatic compound in the nitrogen-doped mesoporous carbon supported ruthenium metal catalyst is 0.01-10:100, and the dosage ratio of the nitroaromatic compound to the solvent is 1g:10-200mL.
Further, in the step (1), the nitroaromatic compound is a substituent of nitrobenzene, and the substituent contains at least one electron withdrawing group or at least one electron donating group; the electron withdrawing group comprises-C.ident.N, -C=O, -Cl, -Br, -I, -F, -c=c-, said electron donating group comprising-CH 3,–NH3,–O–CH3.
Still further, the substituents include-Cl, -Br, -I, -F, -C=CH 2, -C≡N, C1-C2 alkyl, C1-C2 alkoxy, -COR 1,–R2C≡N,–SO2R3,R1 is selected from hydrogen, phenyl, C1-C2 alkyl or amino, R 2 is selected from phenyl or C1-C2 alkyl, R 3 is selected from C1-C2 alkyl substituted amino. Preferably, the substituents are selected from the group consisting of-Cl, -Br, -I, -F, -c=ch 2,–CH3,–COH,–COPh,–O–CH3,–C≡N,–CH2 c≡n or-SO 2NHCH3.
In the step (1), the solvent is one or more of water, ethanol, methanol, tetrahydrofuran, ethyl acetate, dichloromethane, acetonitrile and cyclohexane.
Further, in the step (1), the reaction temperature is 0-200 ℃, the reaction pressure is 0.01-10MPa, and the reaction time is 0.01-200 hours. Preferably, the reaction pressure is 0.1-5MPa and the reaction time is 0.1-20 hours.
In the step (3), after the reaction is finished, the reaction liquid is filtered, extracted and simply purified to obtain an aromatic amine product.
In the step (3), after the reaction is finished, the catalyst is washed, centrifuged and dried for recycling.
The invention has the beneficial effects that:
1) The heterogeneous nitrogen doped mesoporous carbon supported ruthenium metal catalyst is synthesized by a one-pot method, the synthesis process is simple, the operation is simple and convenient, the industrialized mass production can be realized, and meanwhile, the material has a regular and ordered mesoporous structure and a high specific surface area.
2) The method for selectively reducing nitroaromatic compounds provided by the invention can realize the selective reduction of nitroaromatic compounds containing unsaturated groups into aromatic amine under mild conditions, and can also selectively reduce nitro to target amino products for an important intermediate 4-nitro-N-methylbenzenesulfonamide in pharmaceutical reaction, thereby achieving high conversion rate, high selectivity and good cycle stability, and being expected to become a feasible way of industrial catalysis.
3) The catalyst prepared by the invention has high specific surface area and large pore volume, ordered mesoporous pore canal and ultra-small metal particle size, and can be repeatedly used for more than five times without obvious activity attenuation.
Drawings
FIG. 1 is an X-ray diffraction pattern of the nitrogen-doped mesoporous carbon supported ruthenium metal catalyst prepared in example 1.
FIG. 2 is a transmission electron microscope image of the nitrogen-doped mesoporous carbon supported ruthenium metal catalyst prepared in example 1.
Detailed Description
The invention provides a method for selectively reducing nitroaromatic compounds and a catalyst thereof, and the invention is described in detail below for the purpose, technical scheme and effect of the invention to be clearer and clearer. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The preparation method of the nitrogen-doped mesoporous carbon supported ruthenium metal catalyst comprises the following steps:
0.8-3.2g tryptophan is dissolved in 20mL ethanol and 20mL ultrapure water, heated and stirred at 50-70 ℃ until the tryptophan is completely dissolved, 0.5-2mL ruthenium chloride aqueous solution with the concentration of 0.1mol/L and 1-2g SBA-15-OH template agent are added into the solution, the solution is stirred for 3 hours, the solvent is evaporated, and the solution is transferred into an oven with the temperature of 50-70 ℃ for drying for 12-24 hours. And (3) pyrolyzing the sample at a high temperature of 500-900 ℃ in an argon atmosphere in a tube furnace, wherein the heating rate is 1-10 ℃/min, cooling to room temperature, removing the SBA-15-OH template agent by using a sodium hydroxide solution, and carrying out suction filtration, water washing and freeze drying to obtain the nitrogen-doped mesoporous carbon supported ruthenium metal catalyst material. The size of the ruthenium metal particles is below 5nm, the mass fraction is 1-5wt%, the specific surface area is 760m 2/g, and the pore volume is 0.80cm 3/g.
FIG. 1 is an X-ray diffraction pattern of the prepared nitrogen-doped mesoporous carbon supported ruthenium metal catalyst. As can be seen from the graph, the prepared nitrogen-doped mesoporous carbon supported ruthenium metal catalyst has no obvious metal ruthenium diffraction peak, which indicates that the metal ruthenium is uniformly distributed on the carrier, and the particle size is small.
Fig. 2 is a transmission electron microscope image of the prepared nitrogen-doped mesoporous carbon-supported ruthenium metal catalyst. The graph shows that the prepared nitrogen-doped mesoporous carbon supported ruthenium metal catalyst completely replicates the mesoporous morphology of the template SBA-15-OH, ruthenium metal is uniformly distributed in mesoporous channels, and the particle size is about 2 nm.
Application example 1
10Mg of the catalyst prepared in example 1, 0.2mmol of p-chloronitrobenzene and 1mL of ultrapure water were charged into a reaction tube, placed in a high-pressure reaction vessel, and 10bar of hydrogen was charged thereinto, and repeated six times to completely discharge air, and finally 10bar of hydrogen was charged thereinto, and reacted at 25℃for 10 hours. After the reaction, the mixture was filtered and extracted with ethyl acetate, and the p-chloronitrobenzene conversion and the p-chloroaniline selectivity were both 99% calculated by gas chromatography.
Application example 2
10Mg of the catalyst prepared in example 1, 0.2mmol of p-fluoronitrobenzene and 1mL of ultrapure water were charged into a reaction tube, placed in a high-pressure reaction vessel, and 10bar of hydrogen was charged thereinto, and repeated six times to completely discharge air, and finally 10bar of hydrogen was charged thereinto, and reacted at 25℃for 10 hours. After the reaction, the mixture is filtered, extracted by ethyl acetate, and the conversion rate of p-fluoronitrobenzene and the selectivity of p-fluoroaniline are calculated to reach 99% by using gas chromatography.
Application example 3
10Mg of the catalyst prepared in example 1, 0.2mmol of p-bromonitrobenzene and 1mL of ultrapure water were charged into a reaction tube, placed in a high-pressure reaction vessel, and 10bar of hydrogen was charged thereinto, and repeated six times to completely discharge air, and finally 10bar of hydrogen was charged thereinto, and reacted at 25℃for 10 hours. After the reaction, the mixture is filtered, extracted by ethyl acetate, and the conversion rate of p-bromonitrobenzene and the selectivity of p-bromoaniline are calculated to reach 99% by using gas chromatography.
Application example 4
10Mg of the catalyst prepared in example 1, 0.2mmol of p-iodonitrobenzene and 1mL of ultrapure water were charged into a reaction tube, placed in a high-pressure reaction vessel, and 10bar of hydrogen was charged thereinto, and repeated six times to completely discharge air, and finally 10bar of hydrogen was charged thereinto, and reacted at 25℃for 10 hours. After the reaction, the mixture is filtered, extracted by ethyl acetate, and the conversion rate of p-iodonitrobenzene and the selectivity of p-iodoaniline are calculated to reach 99% by using gas chromatography.
Application example 5
10Mg of the catalyst prepared in example 1, 0.2mmol of p-methylnitrobenzene and 1mL of ultrapure water were charged into a reaction tube, placed in a high-pressure reaction vessel, and 10bar of hydrogen was charged thereinto, and repeated six times to completely discharge air, and finally 10bar of hydrogen was charged thereinto, and reacted at 25℃for 10 hours. After the reaction, the mixture was filtered and extracted with ethyl acetate, and the p-methylnitrobenzene conversion and the p-methylaniline selectivity were both 99% calculated by gas chromatography.
Application example 6
10Mg of the catalyst prepared in example 1, 0.2mmol of 3-nitrostyrene and 1mL of ultra pure water were charged into a reaction tube, placed in a high-pressure reaction vessel, and 10bar of hydrogen was charged thereinto, and repeated six times to completely discharge air, and finally 10bar of hydrogen was charged thereinto, and reacted at 25℃for 10 hours. After the reaction, the mixture was filtered and extracted with ethyl acetate, and the 3-nitrostyrene conversion and the 3-vinylaniline selectivity were both 99% as calculated by gas chromatography.
Application example 7
10Mg of the catalyst prepared in example 1, 0.2mmol of 4-nitrobenzophenone and 1mL of ultrapure water were charged into a reaction tube, placed in a high-pressure reaction vessel, 10bar of hydrogen was charged thereinto, and repeated six times to completely discharge air, and finally 10bar of hydrogen was charged thereinto, and reacted at 25℃for 10 hours. After the reaction, the mixture is filtered and extracted by ethyl acetate, and the conversion rate of the 4-nitrobenzophenone and the selectivity of the 4-aminobenzophenone are both up to 99% by using gas chromatography.
Application example 8
10Mg of the catalyst prepared in example 1, 0.2mmol of p-nitroanisole and 1mL of ultrapure water were charged into a reaction tube, placed in a high-pressure reaction vessel, and 10bar of hydrogen was charged thereinto, and repeated six times to completely discharge air, and finally 10bar of hydrogen was charged thereinto, and reacted at 25℃for 10 hours. Filtering after the reaction is finished, extracting by using ethyl acetate, and calculating the conversion rate of the p-nitroanisole and the selectivity of the p-aminoanisole to 99% by using gas chromatography.
Application example 9
10Mg of the catalyst prepared in example 1, 0.2mmol of p-nitrobenzonitrile and 1mL of ultrapure water were charged into a reaction tube, placed in a high-pressure reaction vessel, and 10bar of hydrogen was charged thereinto, and repeated six times to completely discharge air, and finally 10bar of hydrogen was charged thereinto, and reacted at 25℃for 20 hours. After the reaction, the mixture was filtered and extracted with ethyl acetate, and the conversion of p-nitrobenzonitrile and the selectivity of p-aminobenzonitrile were both 99% as calculated by gas chromatography.
Application example 10
10Mg of the catalyst prepared in example 1, 0.2mmol of 4-nitro-N-methylbenzenesulfonamide and 1mL of ultrapure water were charged into a reaction tube, placed in a high-pressure reaction vessel, 10bar of hydrogen was charged thereinto, and repeated six times to completely discharge air, and finally 10bar of hydrogen was charged thereinto to react at 25℃for 20 hours. After the reaction, the mixture is filtered and extracted by ethyl acetate, and the conversion rate of 4-nitro-N-methyl phenyl methane sulfonamide and the selectivity of 4-amino-N-methyl phenyl methane sulfonamide are both up to 99% by using gas chromatography.
The present invention is not limited to the above-mentioned embodiments, but any modifications, equivalents, improvements and modifications within the scope of the invention will be apparent to those skilled in the art.
Claims (10)
1. A preparation method of a nitrogen-doped mesoporous carbon supported ruthenium metal catalyst is characterized by comprising the following steps of: the method comprises the following steps:
(1) Mixing and dispersing ruthenium chloride aqueous solution, tryptophan and mesoporous silica template SBA-15-OH with silicon hydroxyl on the surface of a pore canal in an ethanol-water mixed solvent, and uniformly stirring;
(2) The preparation method comprises the steps of solvent evaporation, heating and roasting, removing the template agent SBA-15-OH, washing, drying and grinding.
2. The method of manufacturing according to claim 1, characterized in that: in the step (1), the dosage ratio of ruthenium chloride, tryptophan and SBA-15-OH is 0.05-0.2mmol, 0.8-3.2g and 1-2g.
3. The method of manufacturing according to claim 1, characterized in that: in the step (2), the temperature-rising roasting is performed in an argon atmosphere, and the roasting temperature is 500-900 ℃.
4. A nitrogen-doped mesoporous carbon supported ruthenium metal catalyst is characterized in that: a method according to any one of claims 1 to 3.
5. The catalyst of claim 4, wherein: in the catalyst, the size of ruthenium metal particles is below 5nm, and the mass fraction is 0.1-20wt%.
6. Use of the catalyst according to claim 4 or 5 for the selective reduction of nitroaromatic compounds, characterized in that it comprises the following steps:
(1) Uniformly stirring and mixing the nitrogen-doped mesoporous carbon supported ruthenium metal catalyst, nitroaromatic compounds and a solvent;
(2) Placing the mixture into a high-pressure reaction kettle, filling hydrogen, and magnetically stirring the mixture at room temperature or under heating to perform a reaction;
(3) And (3) recovering the reaction product to obtain the arylamine compound.
7. The use according to claim 6, characterized in that: in the step (1), the molar ratio of metal ruthenium atoms to nitroaromatic compounds in the nitrogen-doped mesoporous carbon supported ruthenium metal catalyst is 0.01-10:100, and the dosage ratio of nitroaromatic compounds to solvents is 1g:10-200mL.
8. The use according to claim 6, characterized in that: in the step (1), the nitroaromatic compound is a substituent of nitrobenzene, wherein the substituent contains at least one electron withdrawing group or at least one electron donating group; said electron withdrawing group comprising-C≡N, -C=O, -Cl, -Br, -I, -F and-c=c-, said electron donating groups comprising-CH 3,–NH2,–O–CH3.
9. The use according to claim 6, characterized in that: in the step (1), the solvent is one or more than two of water, ethanol, methanol, tetrahydrofuran, ethyl acetate, dichloromethane, acetonitrile and cyclohexane.
10. The use according to claim 6, characterized in that: in the step (1), the reaction temperature is 0-200 ℃, the reaction pressure is 0.01-10MPa, and the reaction time is 0.01-200 hours.
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