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CN-122006764-A - Ni/MoC catalyst and preparation method and application thereof

CN122006764ACN 122006764 ACN122006764 ACN 122006764ACN-122006764-A

Abstract

The invention discloses a Ni/MoC catalyst and a preparation method and application thereof. The catalyst takes metal carbide as a carrier and transition metal as a active auxiliary agent. The catalyst prepared by the invention skillfully constructs a high-efficiency, economical and environment-friendly hydrogen storage-hydrogenation circulating system, successfully solves a series of pain points of high-pressure danger, high noble metal catalyst cost, difficult selective control and the like faced by the traditional ANT hydrogenation process, and provides a brand-new path with industrialized potential for the green synthesis of sym-OHA and related fine chemicals.

Inventors

  • YANG YING
  • MA HAORUI
  • LIU HE
  • GUO AIJUN
  • ZHANG JIAYI
  • ZHANG ZHENG
  • ZHANG YUNYI
  • JIN XIAOHAN
  • LI YARU
  • ZHANG XIAOQI
  • Guo Jinzhuang

Assignees

  • 中国石油大学(华东)

Dates

Publication Date
20260512
Application Date
20260331

Claims (10)

  1. 1. A Ni/MoC catalyst characterized by comprising a metal carbide support, and a transition metal as a catalyst active component supported on the metal carbide support; the metal in the metal carbide is Mo; the metal in the transition metal is at least one selected from Ni, cu, co, fe.
  2. 2. The Ni/MoC catalyst of claim 1 wherein the molar ratio of transition metal to metal in the metal carbide support is 2.5-10:100.
  3. 3. The preparation method of the Ni/MoC catalyst is characterized by comprising the following steps: Step 1, preparing a catalyst precursor, namely dissolving transition metal salt A for preparing a catalyst active component and B for preparing a carrier into deionized water according to the corresponding metal molar ratio, continuously stirring to uniformly mix the transition metal salt A and the B, and performing rotary evaporation at 80+/-5 ℃ to obtain a co-crystallization mixture serving as the catalyst precursor; Step 2, oxidizing the catalyst precursor, namely calcining the catalyst precursor prepared in the step 1 at a single-step heating rate of 5+/-0.5 ℃ per minute at 450-550 ℃ under an air atmosphere for 3-5 h to obtain a metal oxide intermediate; And 3, reducing/carbonizing to obtain the catalyst, namely reducing and carbonizing the metal oxide intermediate prepared in the step 2 by using a tubular furnace in a methane/hydrogen atmosphere of 19-21 vol% in a two-stage heating program, wherein the heating program is that the temperature is increased to 300+/-30 ℃ at a heating rate of 5+/-0.5 ℃ per minute, and then the temperature is increased to the final temperature from 300+/-30 ℃ at a heating rate of 1+/-0.1 ℃ per minute, and the temperature is kept to be 1.5-2.5 h.
  4. 4. The method for preparing a Ni/MoC catalyst according to claim 3, wherein in the step 1, the molar ratio of the transition metal salt hydrate A to the carrier B is 2.5-10:100.
  5. 5. A method of preparing a Ni/MoC catalyst according to claim 3 wherein in step 1 the transition metal salt is selected from the nitrate hydrate form of Ni, cu, co, fe; The B used for preparing the metal carbide carrier is an ammonium salt compound of Mo.
  6. 6. The method for preparing Ni/MoC catalyst according to claim 3, wherein the transition metal salt A in the step 1 is selected from Ni(NO 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O、Co(NO 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 O; The B used for preparing the carrier is selected from (NH 4 ) 6 Mo 7 O 24 ·4H 2 O).
  7. 7. The method for preparing a Ni/MoC catalyst according to claim 3, wherein the final temperature of reduction/carbonization of the metal oxide intermediate in the step 3 is 500-900 ℃.
  8. 8. Use of the Ni/MoC catalyst of claim 1 to catalyze ANT hydrogenation reactions.
  9. 9. The application of the ANT hydrogenation to prepare sym-OHA based on the Ni/MoC catalyst is characterized by comprising the following steps of adding the ANT and the Ni/MoC catalyst as claimed in claim 1 into a high-pressure reaction kettle, adding deionized water and methanol into the reaction kettle as hydrogen sources, and introducing N 2 into the reaction kettle for boosting pressure to perform reaction.
  10. 10. The use of Ni/MoC catalyst based ANT hydrogenation for the preparation of sym-OHA according to claim 9, wherein the pressure of N 2 in the autoclave is 0.5-5 MPa, the reaction temperature is 200-400 ℃, and the reaction time is 1-10 h.

Description

Ni/MoC catalyst and preparation method and application thereof Technical Field The invention belongs to the technical field of catalyst preparation, and particularly relates to a Ni/MoC catalyst, and a preparation method and application thereof. Background The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art. Symmetrical octahydroanthracene (sym-OHA) is used as a 'molecular platform' with highly symmetrical structure, and has important value in leading-edge scientific research and functional material development. sym-OHA is a key precursor and a structural unit for constructing high-performance organic semiconductor materials, particularly acene derivatives, and the molecule has high carrier mobility and excellent solution processability and is widely applied to the fields of Organic Field Effect Transistors (OFETs), organic solar cells (OPVs), organic Light Emitting Diodes (OLEDs) and the like. In addition, a quinone compound can be derived by oxidation of sym-OHA, and the quinone compound has application potential in organic electrode material systems such as lithium/sodium ion batteries and the like by virtue of symmetrical frameworks and reversible redox characteristics. Therefore, the synthesis of sym-OHA not only relates to the molecule itself, but also serves as a 'seed' of a functional material, and has profound significance for promoting the development of multiple fields. Sym-OHA is mainly derived from anthracene molecule (ANT) hydrogenation, and its hydrogenation products also include Dihydroanthracene (DHA), tetrahydroanthracene (THA), asymmetric octahydroanthracene (cis/trans-OHA), and perhydro anthracene (PHA) (shown in the following figures). The ANT itself has a stable aromatic conjugated structure, the hydrogenation process of which needs to overcome the kinetic and thermodynamic energy barriers of the aromatic ring step by step, and the reaction conditions are harsh. In addition, the ANT hydrogenation products have similar structures, similar polarities and close boiling points, and are difficult to separate sym-OHA from the product, and the energy consumption is huge, so that the improvement of the content of sym-OHA in the product by adjusting the catalytic conditions is a more economic and reasonable way, and the catalyst is required to be higher. The traditional ANT hydrogenation process is mostly carried out under the high-temperature high-pressure high-risk hydrogen environment by depending on noble metal catalysts (such as Pt, pd, ru and the like), and has the problems of high cost, easy coking or sulfur poisoning deactivation and the like, so that the application of the catalyst is limited. The non-noble metal catalyst (such as Ni, co, etc.) has lower cost, but is easy to generate perhydrogenation products in the hydrogenation process or induce side reactions such as aromatic ring cracking, etc., so that the selectivity of the target product sym-OHA is not ideal. In recent years, supercritical methanol becomes an ideal medium for heterogeneous catalytic reaction due to its unique physicochemical properties (such as low viscosity, high diffusion coefficient and adjustable polarity), and can generate active hydrogen in situ by reforming reaction with water, and can effectively dissolve polycyclic aromatic hydrocarbon substrates and relieve carbon deposition on the surface of the catalyst. Therefore, the polarity and mass transfer behavior of the reaction system can be further regulated and controlled by constructing a supercritical methanol-mediated water ANT in-situ hydrogenation system (Supercritical methanol-MEDIATED WATER, SMW), and the generation and transfer of hydrogen species are promoted to realize the directional conversion of ANT. Transition metal carbides such as beta-Mo 2 C exhibit the potential to replace noble metals in methanol liquid phase reforming and ANT hydrogenation reactions due to their electronic structure and excellent thermal stability. However, the uneven acid-base distribution on the surface of the beta-Mo 2 C material easily leads to low ANT hydrogenation degree. In summary, in the prior art, the activity of the catalyst and sym-OHA selectivity are difficult to be compatible, and the cooperative regulation and control mechanism of the reaction medium on the mass transfer and hydrogen transfer processes is not clear. The development of a catalyst with high selectivity and high activity is still a problem to be solved in the art of ANT hydrogenation. Disclosure of Invention Aiming at the defects existing in the prior art, the invention aims to provide a Ni/MoC catalyst, and a preparation method and application thereof. The invention provides a catalyst for preparing sym-OHA by in-situ hydrogenation of water ANT mediated by supercritical methanol, a preparation method thereof and application thereof to the field of practice. The catalyst takes metal carbide as a carrier an