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CN-122006805-A - Supported catalyst with bimetallic sulfide as carrier and application thereof

CN122006805ACN 122006805 ACN122006805 ACN 122006805ACN-122006805-A

Abstract

The invention discloses a supported metal catalyst taking bimetallic sulfide as a carrier and application thereof in hydrodeoxygenation reaction of biomass oil. The catalyst is prepared by taking metal ion liquid as a precursor, constructing a molybdenum-containing bimetallic sulfide carrier skeleton through vulcanization, and combining solvothermal load and tubular furnace reduction treatment. The strong interaction and the electronic structure synergy between the bimetallic sulfide carrier and the supported metal can effectively regulate and control the electronic property of the active site, and obviously improve the hydrodeoxygenation activity, the product selectivity and the deactivation resistance of the catalyst, so that the catalyst shows high conversion efficiency and long service life in the hydrodeoxygenation reaction of biomass oil, and provides a new idea for the controllable preparation and the large-scale application of the catalyst with low cost and high performance.

Inventors

  • HUANG KUAN
  • WANG ZISHI
  • JIANG LILONG
  • CAO YANNING
  • MA YONGDE
  • CAI ZHENPING
  • ZHANG HONGWEI

Assignees

  • 福州大学

Dates

Publication Date
20260512
Application Date
20260403

Claims (10)

  1. 1. The preparation method of the supported catalyst taking the bimetallic sulfide as the carrier is characterized by comprising the following steps: 1) Mixing ionic liquid, sulfur powder and decalin for vulcanization reaction, cooling to room temperature after the reaction, and carrying out centrifugal washing and vacuum drying to obtain a bimetallic sulfide; 2) Mixing metal ion liquid, decalin and the bimetallic sulfide prepared in the step 1) for doping reaction, cooling to room temperature after the reaction, centrifugally washing, drying in vacuum, and then placing in a tube furnace for reduction to prepare the supported catalyst.
  2. 2. The preparation method of the supported catalyst taking the bimetallic sulfide as the carrier of claim 1, wherein in the step 1), the ionic liquid is a mixture of molybdenum-based ionic liquid and any one of cobalt-based ionic liquid, tungsten-based ionic liquid, nickel-based ionic liquid or copper-based ionic liquid according to a molar ratio (5-50): 1, wherein the molybdenum-based ionic liquid is [ N 8881 ] 2 MoO 4 ], the cobalt-based ionic liquid is [ N 8881 ] 2 CoCl 4 ], the tungsten-based ionic liquid is [ N 8881 ] 2 WO 4 ], the nickel-based ionic liquid is [ N 8881 ] 2 NiCl 4 , and the copper-based ionic liquid is [ N 8881 ] 2 CuCl 4 .
  3. 3. The supported catalyst using a bimetallic sulfide as a carrier according to claim 1, wherein the amount of sulfur powder used in the step 1) is converted to a molar ratio of S to total metal atoms in the ionic liquid of 1 to 20.
  4. 4. The supported catalyst using a bimetallic sulfide as a carrier according to claim 1, wherein the temperature of the sulfidation reaction in step 1) is 180-360 ℃, the time is 0-36 h, and the hydrogen pressure is 0-8 MPa.
  5. 5. The supported catalyst using a bimetallic sulfide as a carrier according to claim 1, wherein in the step 2), the metal ionic liquid is one or more of [N 8881 ] 2 CoCl 4 、[N 8881 ]FeCl 4 、[N 8881 ] 2 NiCl 4 、[N 8881 ] 2 CuCl 4 、[N 8881 ] 2 ZnCl 4 、[N 8881 ] 2 WO 4 , and the amount is converted according to the molar ratio of the metal atoms to the total metal atoms in the bimetallic sulfide of 0-3.
  6. 6. The supported catalyst using a bimetallic sulfide as a carrier according to claim 1, wherein the doping reaction in step 2) is performed under normal pressure and N 2 atmosphere, the reaction temperature is 250-450 ℃, and the reaction time is 0-36 h.
  7. 7. The supported catalyst with a bimetallic sulfide as a carrier according to claim 1, wherein the reduction in step 2) is performed in a mixed gas atmosphere of 10% h 2 /90% ar, the reaction temperature is 150-800 ℃ and the reaction time is 1-10 h.
  8. 8. Use of the supported bimetallic sulfide-supported catalyst of claim 1 in hydrodeoxygenation reactions of biomass oils.
  9. 9. The use of claim 8, wherein the biomass oil comprises one or more of lignin pyrolysis oil, biomass-based oxygenates, biolipid.
  10. 10. The use according to claim 8, wherein in the reaction, the mass ratio of the supported catalyst using the bimetallic sulfide as a carrier to the biomass oil is 1-20%, the reaction hydrogen pressure is 0-10 MPa, the reaction temperature is 30-400 ℃, the reaction time is 0-36 h, and the hydrogen-oil ratio is 0-2000.

Description

Supported catalyst with bimetallic sulfide as carrier and application thereof Technical Field The invention belongs to the technical field of hydrodeoxygenation catalysis of biomass oil, and particularly relates to a hydrophobic catalyst which takes bimetallic sulfide as a carrier and realizes high dispersion and loading of active metal, wherein the hydrophobic catalyst has excellent deoxidation efficiency, product selectivity and stability in a hydrodeoxygenation reaction of biomass oil. Background In the renewable energy and green chemistry fields, biomass oil is considered as one of the important raw materials to replace fossil resources. However, biomass oil generally contains a large amount of oxygen-containing compounds, which results in poor thermal stability and strong corrosiveness, and is difficult to be directly used as fuel or chemical raw material. Hydrodeoxygenation (HDO) is a key process for reducing the oxygen content and improving the quality of biomass oil, and a high-efficiency and stable catalyst system is a core for realizing industrial application of the process. The existing hydrodeoxygenation catalyst adopts an oxide carrier to load metal or a single metal sulfide catalyst system. The catalyst has the common problems of unreasonable active site distribution, low metal utilization rate, easy deactivation caused by the influence of water and polar oxide generated in the reaction process, and the like in the reaction process. Particularly under the high-moisture and high-polarity reaction environment, the traditional hydrophilic carrier is difficult to keep the long-term stable operation of the catalyst. In recent years, bimetallic sulfide materials (such as CoMoS, niMoS, or WMoS) have been considered ideal hydrodeoxygenation functional materials because of their advantages in electronic structure and active site configuration. However, most of the prior researches use the active phase as an active phase directly, and the stabilizing, dispersing and synergistic regulating and controlling effects of the active phase serving as a carrier on externally added metals are not fully exerted. Meanwhile, the preparation method for constructing the supported metal catalyst by taking the bimetallic sulfide as a carrier still has the problems of complex process, difficult regulation and control of the synergistic effect, insufficient hydrophobic performance and the like, and further industrial application of the supported metal catalyst is restricted. Therefore, there is a need to develop a high-performance catalyst system which uses a bimetallic sulfide as a carrier and realizes a multi-metal synergistic effect through a supported metal so as to meet the requirements of the hydrodeoxygenation reaction of biomass oil on high activity, high stability and environmental adaptability. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a supported metal catalyst taking bimetallic sulfide as a carrier, which has high conversion efficiency and long service life in the hydrodeoxygenation reaction of biomass oil, provides a new technical path for the efficient hydrodeoxygenation of biomass oil, and has important significance for promoting the high-valued utilization of renewable resources and the green chemical process. In order to achieve the above purpose, the invention adopts the following technical scheme: The preparation method of the supported catalyst taking the bimetallic sulfide as the carrier comprises the following steps: 1) Mixing ionic liquid, sulfur powder and decalin in a reaction kettle for vulcanization reaction, cooling to room temperature after the reaction, and performing centrifugal washing and vacuum drying to constant weight to obtain a bimetallic sulfide; 2) Mixing metal ion liquid, decalin and the bimetallic sulfide prepared in the step 1) in a reaction kettle for doping reaction, cooling to room temperature after the reaction, centrifugally washing, drying in vacuum to constant weight, and then placing in a tubular furnace for reduction to prepare the supported catalyst. Further, the ionic liquid in the step 1) is a mixture composed of molybdenum-based ionic liquid and any one of cobalt-based ionic liquid, tungsten-based ionic liquid, nickel-based ionic liquid or copper-based ionic liquid according to the molar ratio of (5-50): 1. Further, the molybdenum-based ionic liquid is [ N 8881]2MoO4 ], the cobalt-based ionic liquid is [ N 8881]2CoCl4 ], the tungsten-based ionic liquid is [ N 8881]2WO4 ], the nickel-based ionic liquid is [ N 8881]2NiCl4 ], and the copper-based ionic liquid is [ N 8881]2CuCl4. Further, the amount of the sulfur powder in the step 1) is converted according to the molar ratio of S to the total metal atoms in the ionic liquid being 1-20. Further, the temperature of the vulcanization reaction in the step 1) is 180-360 ℃, the time is 0-36 h, and the hydrogen pressure is 0-8 MPa. Further, in step 2), the metal ion liquid is one or