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CN-117427635-B - Metal nano-particles loaded by reductive carrier and application thereof in preparation of azo aromatic hydrocarbon

CN117427635BCN 117427635 BCN117427635 BCN 117427635BCN-117427635-B

Abstract

A metal nano particle loaded by a reducing carrier and an application thereof in preparing azoic arene relate to the field of catalytic hydrogenation of nitroarene, the metal nano particle loaded by the reducing carrier is dispersed into an alcohol solvent containing a bidentate amine auxiliary agent, the nitroarene is added, hydrogen is introduced to remove air in a reaction vessel, hydrogen with the pressure of 0.1-0.6MPa is kept, catalytic hydrogenation reaction is carried out at the temperature of below 5 ℃, after the hydrogenation reaction is finished, air is introduced into the reaction vessel to carry out oxidation reaction to obtain azoxybenzene (I), Wherein R is selected from hydrogen, alkyl, halogen, alkoxy, hydroxy, amino or acyl.

Inventors

  • WU QINGYUAN
  • LIU SHENGJIE
  • CHEN JIE
  • ZHENG NANFENG

Assignees

  • 嘉庚创新实验室

Dates

Publication Date
20260508
Application Date
20230925

Claims (14)

  1. 1. Use of a metal nanoparticle catalyst supported by a reducing carrier in the preparation of azobenzene oxide or diphenyl hydrazine or azobenzene, wherein the metal comprises one or more of Pt, pd, ni, ir, ru and Rh, the particle size of the metal nanoparticle is less than 5 nm, the reducing carrier comprises one or more of SnO 2 、Fe 2 O 3 、Fe 3 O 4 、FeO、Co 3 O 4 、TiO 2 、MnO 2 、CuO、ZnO、Ga 2 O 3 、In 2 O 3 and GeO 2 , the content of the metal nanoparticle in the catalyst is 0.5-10 wt% and the content of the reducing carrier is 90-99.5 wt% based on the total mass of the catalyst.
  2. 2. The use according to claim 1, wherein the content of metal nanoparticles in the catalyst is 0.5-5.0 wt%.
  3. 3. A method for selectively preparing azoxybenzene by nitroarene is characterized by comprising the steps of dispersing metal nano particles loaded by a reducing carrier in the application according to claim 1 or 2 into an organic solvent containing a bidentate amine auxiliary agent, adding nitroarene, introducing hydrogen to remove air in a reaction container, keeping hydrogen of 0.1-0.6 MPa ℃ for catalytic hydrogenation reaction at a temperature below 5 ℃, introducing air into the reaction container for oxidation reaction after the hydrogenation reaction is completed to obtain azoxybenzene (I), (I), Wherein each R is independently selected from hydrogen, alkyl, halogen, alkoxy, hydroxy, amino, or acyl.
  4. 4. A method according to claim 3, wherein the bidentate amine adjuvant is selected from one or more of ethylenediamine, propylenediamine, butylenediamine, pentylene diamine and hexylenediamine.
  5. 5. A method according to claim 3, wherein the proportion of the bidentate amine adjuvant to the total volume of the organic solvent is from 40% to 100%.
  6. 6. A method according to claim 3, wherein the organic solvent is selected from one or more of ethanol, methanol, cyclohexanol, isopropanol, cyclohexane, tetrahydrofuran, dioxane, dimethyl sulfoxide and chloroform.
  7. 7. A method for preparing diphenyl hydrazine is characterized by comprising the steps of dispersing metal nano particles loaded by a reducing carrier in the application according to claim 1 or 2 into an organic solvent containing a bidentate amine auxiliary agent, adding nitroarene, introducing hydrogen to remove air in a reaction container, keeping hydrogen of 0.1-0.6 MPa, carrying out catalytic hydrogenation reaction at a temperature below 5 ℃, introducing air into the reaction container after the hydrogenation reaction is finished to carry out oxidation reaction to obtain azobenzene (I) oxide, introducing hydrogen of 0.1-0.6 MPa, carrying out catalytic hydrogenation reaction, and obtaining diphenyl hydrazine (II) after the hydrogenation reaction is finished; (II), Wherein each R is independently selected from hydrogen, alkyl, halogen, alkoxy, hydroxy, amino, or acyl.
  8. 8. The method of claim 7, wherein the bidentate amine adjuvant is selected from one or more of ethylenediamine, propylenediamine, butylenediamine, pentylene diamine, and hexylenediamine.
  9. 9. The method of claim 7, wherein the proportion of the bidentate amine adjuvant to the total volume of the organic solvent is 40% to 100%.
  10. 10. The method of claim 7, wherein the organic solvent is selected from one or more of ethanol, methanol, cyclohexanol, isopropanol, cyclohexane, tetrahydrofuran, dioxane, dimethyl sulfoxide, and chloroform.
  11. 11. A process for preparing azobenzene includes such steps as dispersing the metallic nanoparticles carried by reductive carrier in the application of claim 1 or 2 in organic solvent containing bidentate amine assistant, adding nitroarene, introducing hydrogen to remove air from reaction container, holding hydrogen at 0.1-0.6 MPa deg.C, catalytic hydrogenation, introducing air to reaction container for oxidizing reaction to obtain azobenzene (I), introducing hydrogen at 0.1-0.6 MPa, catalytic hydrogenation to obtain diphenyl hydrazine (II), and introducing air to reaction container for oxidizing diphenyl hydrazine (II) to obtain azobenzene (III) (III), Wherein each R is independently selected from hydrogen, alkyl, halogen, alkoxy, hydroxy, amino, or acyl.
  12. 12. The method of claim 11, wherein the bidentate amine adjuvant is selected from one or more of ethylenediamine, propylenediamine, butylenediamine, pentylene diamine, and hexylenediamine.
  13. 13. The method of claim 11, wherein the proportion of the bidentate amine adjuvant to the total volume of the organic solvent is 40% to 100%.
  14. 14. The method of claim 11, wherein the organic solvent is selected from one or more of ethanol, methanol, cyclohexanol, isopropanol, cyclohexane, tetrahydrofuran, dioxane, dimethyl sulfoxide, and chloroform.

Description

Metal nano-particles loaded by reductive carrier and application thereof in preparation of azo aromatic hydrocarbon Technical Field The invention relates to the field of catalytic hydrogenation of nitroaromatics, in particular to a metal nanoparticle loaded by a reductive carrier and application thereof in preparation of azo aromatics. Background Catalysis is a key discipline of sustainable development that allows chemical conversions to be performed at lower temperatures while reducing or even avoiding the formation of byproducts. It is therefore very important to prepare catalysts which are more active, in particular more selective. Selectivity is critical for chemical transformations, especially when one chemical reaction involves multiple reactive groups, and only a specific one needs to be transformed while other transformations are avoided. The reactions include direct, condensation and disproportionation routes, many of which contain a number of products, and in addition, the presence of one or more substituents on the aromatic ring, such as c= C, C ≡ C, C = O, C = N, C ≡n and C-X (halogen), etc., with high selectivity to "recognize" and convert the nitro group, thus obtaining functionalized nitrosamines, hydroxylamines and amines is very challenging. Meanwhile, the design and synthesis of a novel catalyst with high catalytic selectivity also have great application value. Azobenzene oxide, diphenyl hydrazine and azobenzene are important intermediates necessary for the production of many fine and large scale chemicals, such as dyes, pharmaceuticals and agrochemicals. According to literature reports (CHEMCATCHEM, 2009,1,210-221; chem. Rev.,2019,119,2611-2680), the current catalyst can better realize the catalysis of the deep hydrogenation of nitroaromatics to prepare corresponding amines, but the high-selectivity obtaining of azoxybenzene, diphenyl hydrazine and azobenzene is still a scientific and technical problem which afflicts the scientific community for many years. Heterogeneous noble metal catalysts are known to continuously activate H 2 at low temperatures and to achieve rapid hydrogenation of unsaturated groups, generally exhibiting high activity. However, such catalysts are not recognized for the target group, resulting in very low selectivity. On the other hand, stoichiometric reducing agents such as Na 2S2O4, fe, sn or Zn, while selectively hydrogenating polyunsaturated compounds, are low cost and easy to handle, they have the fatal disadvantage that large amounts of solid waste are formed during the reaction, are environmentally unfriendly and difficult to sustain (Science, 2006,313,332-334). It is clearly the best choice if their disadvantages can be avoided and advantages integrated. Disclosure of Invention In one aspect, a catalyst is provided for the selective catalytic hydrogenation of nitrobenzene, and in another aspect, a process for the selective preparation of azobenzene oxide, hydrazobenzene, and azobenzene from nitrobenzene is provided. The technical scheme of the invention is as follows: In a first aspect, there is provided a reduced support supported metal nanoparticle catalyst, the metal comprising one or more of Pt, pd, ni, ir, ru and Rh, the metal nanoparticles having a particle size of less than 5nm, the reducible support comprising one or more of SnO2,Fe2O3、Fe3O4、FeO、Co3O4、TiO2、MnO2、CuO、ZnO、Ga2O3、In2O3 or GeO 2, the metal nanoparticles being present in the catalyst in an amount of about 0.5 to about 10wt% and the reduced support being present in an amount of about 90 to about 99.5wt% based on the total mass of the catalyst. In some embodiments, the metal nanoparticles are present in the catalyst in an amount of about 0.5 wt% to about 5.0wt%; In a second aspect, a method for selectively preparing azoxybenzene by nitrobenzene is provided, the metal nano particles loaded by the reductive carrier of the first aspect of the invention are dispersed into an organic solvent containing a bidentate amine auxiliary agent, nitroarene is added, hydrogen is introduced to remove air in a reaction vessel, hydrogen with the pressure of 0.1-0.6MPa is maintained, catalytic hydrogenation reaction is carried out at the temperature of below 5 ℃, after the hydrogenation reaction is completed, air is introduced into the reaction vessel to carry out oxidation reaction to obtain azoxybenzene (I), Wherein R is selected from hydrogen, alkyl, halogen, alkoxy, hydroxy, amino or acyl. In a third aspect, a method for preparing diphenyl hydrazine is provided, metal nano particles loaded by a reducing carrier are dispersed in an organic solvent containing a bidentate amine auxiliary agent, nitroarene is added, hydrogen is introduced to remove air in a reaction vessel, hydrogen with the pressure of 0.1-0.6MPa is kept, catalytic hydrogenation reaction is carried out at the temperature of below 5 ℃, air is introduced into the reaction vessel after the hydrogenation reaction is finished to carry out oxidation