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CN-122006777-A - Palladium monoatomic-ruthenium cluster double-active-site hydrogenation catalyst, and preparation method and application thereof

CN122006777ACN 122006777 ACN122006777 ACN 122006777ACN-122006777-A

Abstract

The invention relates to a palladium single atom-ruthenium cluster double-active site hydrogenation catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps of (1) mixing a palladium active component precursor and ruthenium active component precursor mixed salt solution with a defect-rich boron nitride carrier to obtain an intermediate mixture; and (2) mixing the intermediate mixture obtained in the step (1) with a reducing agent, and performing low-temperature reduction treatment to obtain the palladium monoatomic-ruthenium cluster double-active-site hydrogenation catalyst, wherein the defect-rich boron nitride carrier is prepared by adopting a modifying agent, and the modifying agent comprises a Zn-containing group compound. The catalyst prepared by the invention can realize high-efficiency hydrogenation of nitroaromatic hydrocarbon under mild conditions, has excellent catalytic activity and stability under working conditions, and has good industrial application potential.

Inventors

  • WANG LIGUO
  • HAN ZIQIANG
  • LI HUIQUAN
  • ZHANG JIAJUN
  • CAO YAN

Assignees

  • 中国科学院过程工程研究所

Dates

Publication Date
20260512
Application Date
20260225

Claims (10)

  1. 1. A method for preparing a palladium monoatomic-ruthenium cluster double-active-site hydrogenation catalyst, which is characterized by comprising the following steps: (1) Mixing a palladium active component precursor and a ruthenium active component precursor mixed salt solution with a defect-rich boron nitride carrier to obtain an intermediate mixture; (2) Mixing the intermediate mixture obtained in the step (1) with a reducing agent, and carrying out low-temperature reduction treatment to obtain the palladium monoatomic-ruthenium cluster double-active-site hydrogenation catalyst; The defect-rich boron nitride carrier is prepared by adopting a modifier, wherein the modifier comprises a Zn-based compound.
  2. 2. The method of claim 1, wherein the method of preparing the defect-rich boron nitride carrier of step (1) comprises: Mixing a nitrogen source, a boron source and a modifier, and roasting to obtain the defective boron nitride carrier.
  3. 3. The method according to claim 2, wherein the Zn-based compound comprises any one or a combination of at least two of zinc hydroxide, zinc oxide, zinc chloride, zinc sulfate, basic zinc carbonate, or zinc acetate; the nitrogen source comprises any one or a combination of at least two of ammonia, urea, ethylenediamine, aniline and naphthylamine, and the boron source comprises boric acid.
  4. 4. The preparation method according to claim 2, wherein the mass ratio of the nitrogen source, the boron source and the modifier is (10-50): 10-50): 1; The method for mixing the nitrogen source, the boron source and the modifier comprises heating and stirring; The temperature of heating and stirring is 30-80 ℃, and the time of heating and stirring is 2-4 hours; The temperature of the roasting treatment is 800-1000 ℃ and the time is 5-20h.
  5. 5. The method of claim 1, wherein the palladium active component precursor of step (1) comprises any one or a combination of at least two of [Pd(NH 3 ) 4 ](NO 3 ) 2 、[Pd(NH 3 )] 4 SO 4 、(NH 4 ) 2 PdCl 6 、K 2 PdCl 4 、Na 2 PdCl 4 、Pd(Ac) 2 、Pd(OAc) 2 、PdCl 2 、Pd(NO 3 ) 2 ; The ruthenium active component precursor comprises any one or a combination of at least two of RuCl 3 ·nH 2 O、Ru 2 Cl 4 (CO) 6 、RuI 3 、K 2 RuCl or (NH) 4 RuCl 6 .
  6. 6. The method according to claim 1, wherein the molar ratio of the total content of the palladium active component precursor and the ruthenium active component precursor in step (1) to the defective boron nitride rich carrier is (0.01 to 0.05): 1; the mixing method in the step (1) comprises ultrasonic auxiliary impregnation, wherein the ultrasonic time of the ultrasonic auxiliary impregnation is 1-5h.
  7. 7. The method of claim 1, wherein the reducing agent of step (2) comprises sodium borohydride; The molar ratio of the reducing agent to the total content of the palladium active component precursor and the ruthenium active component precursor is 20-80:1; the temperature of the low-temperature reduction treatment in the step (2) is 10-30 ℃; the time of the low-temperature reduction treatment in the step (2) is 30-120min; The low-temperature reduction treatment in the step (2) is performed in an oxygen-free atmosphere, and the gas used in the oxygen-free atmosphere comprises any one or a combination of at least two of nitrogen, hydrogen and argon.
  8. 8. A palladium monoatomic-ruthenium cluster double-active site hydrogenation catalyst, characterized in that the palladium monoatomic-ruthenium cluster double-active site hydrogenation catalyst is prepared by the preparation method according to any one of claims 1 to 7.
  9. 9. Use of the hydrogenation catalyst according to claim 8 for the hydrogenation of nitroaromatics to prepare alicyclic amines.
  10. 10. The method according to claim 9, wherein the method comprises the step of hydrogenating nitroaromatics in a hydrogen atmosphere using the hydrogenation catalyst; the mass of the hydrogenation catalyst is 1-25wt% of the mass of nitroarene; the temperature of the nitroarene hydrogenation is 50-100 ℃; The initial pressure of the nitroarene hydrogenation is 1-3MPa; The reaction time of the nitroarene hydrogenation is 60-180min; The nitroarene hydrogenation is carried out in a solvent medium; the solvent comprises any one or a combination of at least two of tetrahydrofuran, methanol, isopropanol, ethanol, cyclohexane, cyclohexylamine, N-butanol, toluene, N-methylpyrrolidone and tert-butanol.

Description

Palladium monoatomic-ruthenium cluster double-active-site hydrogenation catalyst, and preparation method and application thereof Technical Field The invention relates to the technical field of catalyst preparation, in particular to a palladium single atom-ruthenium cluster double-active-site hydrogenation catalyst, a preparation method and application thereof. Background In recent years, the application of alicyclic amine in key core fields such as wind power, microelectronics industry, rocket propellant and the like is rapidly growing. Among them, cyclohexylamine is the most representative alicyclic amine, and can be used for preparing chemicals such as cyclohexanol, cyclohexanone, caprolactam, acetate fiber and nylon, and for synthesizing artificial sweeteners (sodium sulfamate and calcium sulfamate), metal corrosion inhibitors, rubber vulcanization additives, dyes, plasticizers, natural product extractants, and the like. Meanwhile, the solvent can be used in the industrial fields of resin, paint, fat, paraffin oil and the like. The alicyclic amine is mainly characterized by amino and cyclic-ring radical, so its construction is a key link for alicyclic amine synthesis, for example, amino can be obtained by catalytic ammoniation or nitro hydrogenation, and cycloalkyl can be obtained by aromatic ring or cycloolefin hydrogenation. The nitroarene catalytic hydrogenation method is a mainstream technology for producing alicyclic amine at present. The fixed bed gas phase catalytic hydrogenation has better maturity and stability, the catalyst and the product do not need to be separated, the equipment cost is lower, but the disadvantage is that the catalyst is easy to deactivate in the reaction process, the catalyst needs to be frequently replaced, and side reactions easily occur when the catalyst is locally overheated. The liquid phase hydrogenation process of nitroarene has lower temperature than gas phase hydrogenation, high production capacity and less side products, and the hydrogenation catalyst plays the core role. Therefore, the development of the catalyst with high efficiency and good selectivity has important significance for the process for producing alicyclic amine by hydrogenating nitroaromatic hydrocarbon. CN120132885A discloses a preparation method of a platinum monoatomic-platinum cluster double-site catalyst of boron nitride confinement, which comprises the steps of mixing urea, boric acid and carbon nanotubes, carrying out grinding treatment, placing the ground mixture in an ammonia-argon mixed atmosphere environment for first pyrolysis to obtain powder, adding the powder into a boric acid solution, heating and stirring to obtain a boron nitride carrier rich in defects, washing and drying the carrier, immersing the carrier into a platinum salt aqueous solution, carrying out ultrasonic dispersion, carrying out drying treatment by adopting a vacuum freeze-drying method, and finally carrying out second pyrolysis on a dried sample in the ammonia-argon mixed atmosphere. CN114653371A discloses a preparation method of an atomic-level dispersed metal catalyst supported by high-defect boron nitride, which comprises the steps of mixing urea, boric acid and carbon nano tubes, grinding, reacting at 800-1100 ℃ in an ammonia-argon mixed atmosphere, mixing the obtained powder with a boric acid solution, heating, washing with water to obtain a composite material rich in the defect boron nitride, mixing the composite material rich in the defect boron nitride with a metal salt solution, carrying out ultrasonic treatment, freeze-drying, and finally carrying out heat treatment at 650-850 ℃ in the ammonia-argon mixed atmosphere to obtain the atomic-level dispersed metal catalyst supported by the high-defect boron nitride. In view of the above, there is still room for improvement in the design of active components, preparation process and reaction conditions of the existing catalysts. Therefore, development of a novel catalyst which is efficient, simple and convenient to prepare, mild in reaction condition and good in stability is needed to promote industrial application of the technology for preparing alicyclic amine by hydrogenating nitroaromatic hydrocarbon. Disclosure of Invention In order to solve the technical problems, the invention provides a palladium single atom-ruthenium cluster double-active-site hydrogenation catalyst, and a preparation method and application thereof. The palladium single atom-ruthenium cluster double-active site hydrogenation catalyst has the advantages of simple preparation method, high dispersibility of active components, improved catalytic activity, realization of high-efficiency cyclohexylamine synthesis under mild conditions, and remarkable improvement of yield. To achieve the purpose, the invention adopts the following technical scheme: in a first aspect, the present invention provides a method for preparing a palladium monoatomic-ruthenium cluster double active site hydrogenation