Supported catalyst taking bimetallic sulfide as carrier and application thereof

Abstract

The invention discloses a supported metal catalyst taking bimetallic sulfide as a carrier and application of the supported metal catalyst in hydrodeoxygenation reaction of biomass oil. A metal ion liquid is used as a precursor, a molybdenum-containing bimetallic sulfide carrier skeleton is constructed through vulcanization, and solvothermal loading and tubular furnace reduction treatment are combined to prepare the catalyst which is stable in structure, tight in interface coupling and remarkable in surface hydrophobicity. Wherein the strong interaction and electronic structure synergy between the bimetallic sulfide carrier and the loaded metal can effectively regulate and control the electronic property of the active site, and significantly improve the hydrodeoxygenation activity, product selectivity and inactivation resistance of the catalyst, so that the catalyst shows high conversion efficiency and long service life in the hydrodeoxygenation reaction of biomass oil; and a new thought is provided for controllable preparation and large-scale application of the low-cost and high-performance catalyst.

Description

Technical Field

[0001] This invention belongs to the field of biomass oil hydrodeoxygenation catalysis technology, specifically a hydrophobic catalyst that uses a bimetallic sulfide as a support and achieves highly dispersed loading of active metals, which exhibits excellent deoxygenation efficiency, product selectivity and stability in the biomass oil hydrodeoxygenation reaction. Background Technology

[0002] In the fields of renewable energy and green chemistry, biomass oil is considered one of the important raw materials to replace fossil resources. However, biomass oil usually contains a large amount of oxygen-containing compounds, resulting in poor thermal stability and strong corrosiveness, making it difficult to use directly as fuel or chemical feedstock. Hydrodeoxygenation (HDO) is a key process for reducing the oxygen content of biomass oil and improving its quality, and an efficient and stable catalyst system is the core for realizing the industrial application of this process.

[0003] Existing hydrodeoxygenation catalysts mostly employ oxide supports to support metal or single-metal sulfide catalyst systems. These catalysts generally suffer from problems such as unreasonable distribution of active sites, low metal utilization, and susceptibility to deactivation due to water and polar oxides generated during the reaction. Especially in high-moisture, high-polarity reaction environments, traditional hydrophilic supports struggle to maintain long-term stable operation of the catalyst.

[0004] In recent years, bimetallic sulfide materials (such as CoMoS, NiMoS, or WMoS) have been considered ideal functional materials for hydrodeoxygenation due to their advantages in electronic structure and active site configuration. However, existing studies mostly use them directly as active phases, failing to fully utilize their stabilizing, dispersing, and synergistic effects as supports for added metals. Furthermore, methods for constructing supported metal catalysts using bimetallic sulfides as supports still suffer from complex processes, difficulty in controlling synergistic effects, and insufficient hydrophobicity, hindering their further industrial applications. Therefore, there is an urgent need to develop a high-performance catalyst system using bimetallic sulfides as supports and achieving multi-metal synergistic effects through metal loading to meet the requirements of high activity, high stability, and environmental adaptability in biomass oil hydrodeoxygenation reactions. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a supported metal catalyst with bimetallic sulfide as the carrier, which exhibits high conversion efficiency and long service life in the hydrodeoxygenation reaction of biomass oil. This provides a new technical route for the efficient hydrodeoxygenation of biomass oil and is of great significance for promoting the high-value utilization of renewable resources and green chemical processes.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: A supported catalyst using a bimetallic sulfide as a carrier is prepared by the following steps: 1) Ionic liquid, sulfur powder and decahydronaphthalene are mixed in a reaction vessel to carry out a sulfidation reaction. After the reaction, the mixture is cooled to room temperature, centrifuged, washed and vacuum dried to constant weight to obtain a bimetallic sulfide. 2) The metal ionic liquid, decahydronaphthalene and the bimetallic sulfide obtained in step 1) are mixed in a reactor for doping reaction. After the reaction, the mixture is cooled to room temperature, centrifuged, washed and vacuum dried to constant weight, and then placed in a tube furnace for reduction to obtain the supported catalyst.

[0007] Further, the ionic liquid mentioned in step 1) 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 in a molar ratio of (5-50):1.

[0008] Furthermore, 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, the copper-based ionic liquid is [N 8881 ]2CuCl4.

[0009] Furthermore, the amount of sulfur powder used in step 1) is calculated based on a molar ratio of S to the total number of metal atoms in the ionic liquid of 1 to 20.

[0010] Furthermore, 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.

[0011] Further, the metal ionic liquid mentioned in step 2) is [N 8881 ]2CoCl4、[N 8881 FeCl4, [N 8881 ]2NiCl4、[N 8881 ]2CuCl4、[N 8881 ]2ZnCl4、[N 8881 One or more of 2WO4.

[0012] Furthermore, in step 2), the amount of metal ionic liquid used is calculated based on a molar ratio of 0 to 3 between the metal atoms it contains and the total metal atoms in the bimetallic sulfide.

[0013] Furthermore, the doping reaction described in step 2) is carried out under normal pressure and N2 atmosphere, with a reaction temperature of 250~450 ℃ and a reaction time of 0~36 h.

[0014] Furthermore, the reduction described in step 2) is carried out in a mixed gas atmosphere of 10% H2 / 90% Ar, at a reaction temperature of 150~800 ℃, and for a reaction time of 1~10 h.

[0015] Furthermore, the centrifugation speed in steps 1) and 2) is 5000~120000 r / min.

[0016] Furthermore, the vacuum drying temperature described in steps 1) and 2) is 80~150 ℃.

[0017] The supported catalyst with bimetallic sulfide as the carrier can be used in the hydrodeoxygenation reaction of one or more biomass oils, including lignin pyrolysis oil, biomass pyrolysis oil, biomass-based oxygenated compounds, and bio-oils.

[0018] Furthermore, in the reaction, the mass ratio of the supported catalyst with bimetallic sulfide as the carrier to the biomass oil used 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-to-oil ratio is 0~2000.

[0019] 1) This invention constructs a catalyst system with multi-metal synergistic effect and hydrophobic properties by loading metal active components onto the surface of bimetallic sulfide supports such as CoMoS, NiMoS, WMoS or CuMoS.

[0020] This invention uses ionic liquids as supported metal precursors. Leveraging their excellent dispersibility and structural tunability, multiple metal species can be highly uniformly co-dispersed on the surface of a bimetallic sulfide support, effectively suppressing impurity phase formation and metal agglomeration. Compared to monometallic supported catalysts, the multimetallic supported system exhibits stronger interactions between different metals and between the supported metal and the bimetallic sulfide support. This facilitates the construction of low-coordination active site structures with significant synergistic effects, resulting in significant advantages in catalyst structural stability, resistance to deactivation, and lifespan, ultimately leading to a substantial improvement in overall catalytic efficiency.

[0021] Meanwhile, ionic liquids, as oil-soluble metal precursors, naturally endow the resulting multi-metal supported catalysts with excellent hydrophobic properties. The hydrophobicity of the catalyst effectively repels water molecules in the reaction system, reducing the competitive adsorption of water on active sites, further enhancing the synergistic effect between the multi-metal and bimetallic sulfide supports, and improving catalytic activity and operational stability. Furthermore, the hydrophobic surface facilitates the enrichment and mass transfer of organic components from biomass oil on the catalyst surface, reducing reaction energy consumption and catalyst preparation costs, achieving high-purity, high-yield target products, and thus significantly increasing the economic added value of biomass oil.

[0022] 2) This invention prepares structurally stable bimetallic sulfide supports using different metal ionic liquids as precursors; subsequently, a solvothermal technique is employed to load and highly disperse the target metal active component on the support surface, followed by reduction treatment to obtain a supported metal catalyst using bimetallic sulfide as the support. This method facilitates the formation of a tight interfacial coupling structure between the supported metal and the bimetallic sulfide support, thereby achieving synergistic regulation of electronic structure and active sites. This not only ensures the high activity of the catalyst but also significantly improves its stability and selectivity for the target product in the HDO reaction of biomass oil.

[0023] 3) The hydrophobic catalyst prepared by this invention, using bimetallic sulfide as a support, exhibits excellent deep deoxygenation capability and reaction adaptability in the hydrodeoxygenation reactions of various biomass oils. Benefiting from the synergistic regulatory effect between the bimetallic sulfide support and the multimetal-supported active component, the catalyst structure possesses high designability and versatility. It can be controlled and optimized according to the compositional characteristics of different biomass oil feedstocks, and can be widely applied to the hydrodeoxygenation processes of various biomass oils, demonstrating good industrial scale-up potential and application prospects. Detailed Implementation

[0024] A supported catalyst using a bimetallic sulfide as a carrier is prepared by the following steps: 1) 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, along with sulfur powder and decahydronaphthalene, are added to a reaction vessel and subjected to sulfidation reaction at 180~360 ℃ and hydrogen pressure of 0~8 MPa for 0~36 h. After cooling to room temperature, the mixture is centrifuged and washed at 5000~120000 r / min and then vacuum dried at 80~150 ℃ to constant weight to obtain bimetallic sulfide. 2) The metal ionic liquid, decahydronaphthalene, and the bimetallic sulfide obtained in step 1) are added to a reactor and reacted at 250-450 °C for 0-36 h under normal pressure and N2 atmosphere. After cooling to room temperature, the mixture is centrifuged and washed at 5000-120000 r / min, and then vacuum dried at 80-150 °C to constant weight. The mixture is then placed in a tube furnace and reduced at 150-800 °C for 1-10 h in a mixed gas atmosphere of 10% H2 / 90% Ar to obtain the supported catalyst.

[0025] Among them, the molybdenum-based ionic liquid mentioned in step 1) 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, the copper-based ionic liquid is [N 8881]2CuCl4, wherein the molar ratio of molybdenum-based ionic liquid to other ionic liquids is 5-50:1. The amount of sulfur powder used is calculated based on a molar ratio of S to the total metal atoms in the ionic liquid of 1-20.

[0026] The metal ionic liquid mentioned in step 2) is [N 8881 ]2CoCl4、[N 8881 FeCl4, [N 8881 ]2NiCl4、[N 8881 ]2CuCl4、[N 8881 ]2ZnCl4、[N 8881 One or more of the following are used: 2WO4, and the amount used is calculated based on a molar ratio of the metal atoms contained to the total metal atoms in the bimetallic sulfide of 0 to 3.

[0027] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0028] The present invention will be described in detail below through specific embodiments.

[0029] Example 1: Preparation of Fe / NiMoS catalyst (1) Preparation of NiMoS support Weigh 1.9205 g of ionic liquid [N 8881 ]2MoO4, 0.1004 g ionic liquid [N 8881 2NiCl4, 30 g decahydronaphthalene, and 0.3405 g sulfur powder were sequentially added to a 100 mL high-pressure reactor. After sealing, high-purity hydrogen gas was introduced to replace the air inside the reactor, and the pressure was increased to 4 MPa. Under stirring, the reactor was heated to 280 °C at a rate of 5 °C / min and reacted for 24 h. After the reaction was completed, the reactor was allowed to cool naturally to room temperature. The reaction solution was then transferred to a centrifuge and washed by centrifugation at 5000 r / min. The separated solid product was placed in a vacuum drying oven and dried to constant weight at 80 °C to obtain Ni1Mo. 20 S 40 Carrier.

[0030] (2) Preparation of Fe / NiMoS catalyst Weigh 0.1852 g of ionic liquid [N 8881 FeCl4, 15 g decahydronaphthalene, and 0.1056 g of the Ni1Mo prepared above 20 S 40The support was added to a 25 mL high-pressure reactor, sealed, and high-purity nitrogen was introduced to replace the air inside the reactor. The reactor was then heated to 320 °C at a rate of 5 °C / min under a nitrogen protective atmosphere at atmospheric pressure for 5 h. After the reaction, the mixture was allowed to cool naturally to room temperature. The reaction solution was centrifuged and washed at 5000 r / min to obtain a solid product. The obtained solid product was then vacuum dried at 80 °C to constant weight. Subsequently, the dried sample was placed in a tube furnace and reduced at 400 °C for 2 h under a mixed atmosphere of 10% H₂ / 90% Ar to finally obtain the target catalyst Fe / NiMoS, where the molar ratio of metal atoms in Fe / (Ni+Mo) was 0.48.

[0031] Example 2 Preparation of Fe / CoMoS catalyst (1) Preparation of CoMoS support Weigh 1.9205 g of ionic liquid [N 8881 ]2MoO4, 0.1004 g ionic liquid [N 8881 2CoCl4, 30 g of decahydronaphthalene, and 0.3405 g of sulfur powder were sequentially added to a 100 mL high-pressure reactor. After sealing, high-purity hydrogen gas was introduced to replace the air inside the reactor, and the pressure was increased to 4 MPa. Under stirring, the reactor was heated to 280 °C at a rate of 5 °C / min and reacted for 24 h. After the reaction was completed, the reactor was allowed to cool naturally to room temperature. The reaction solution was then transferred to a centrifuge and washed by centrifugation at 5000 r / min. The separated solid product was placed in a vacuum drying oven and dried at 80 °C to constant weight to obtain Co1Mo. 20 S 40 Carrier.

[0032] (2) Preparation of Fe / CoMoS catalyst Weigh 0.1852 g of ionic liquid [N 8881 FeCl4, 15 g decahydronaphthalene, and 0.1056 g of the Co1Mo prepared above 20 S 40 The support was added to a 25 mL high-pressure reactor, sealed, and high-purity nitrogen was introduced to replace the air inside the reactor. The reactor was then heated to 320 °C at a rate of 5 °C / min under a nitrogen protective atmosphere at atmospheric pressure for 5 h. After the reaction, the mixture was allowed to cool naturally to room temperature. The reaction solution was centrifuged and washed at 5000 r / min to obtain a solid product. The obtained solid product was then vacuum dried at 80 °C to constant weight. Subsequently, the dried sample was placed in a tube furnace and reduced at 350 °C for 2 h under a mixed atmosphere of 10% H₂ / 90% Ar to finally obtain the target catalyst Fe / CoMoS, where the molar ratio of Fe / (Co+Mo) was 0.48.

[0033] Example 3 Preparation of Fe / CuMoS catalyst (1) Preparation of CuMoS support Weigh 1.9205 g of ionic liquid [N 8881 ]2MoO4, 0.1009 g ionic liquid [N 8881 2CuCl4, 30 g decahydronaphthalene, and 0.3405 g sulfur powder were sequentially added to a 100 mL high-pressure reactor. After sealing, high-purity hydrogen gas was introduced to replace the air inside the reactor, and the pressure was increased to 4 MPa. Under stirring, the reactor was heated to 280 °C at a rate of 5 °C / min and reacted for 24 h. After the reaction was completed, the reactor was allowed to cool naturally to room temperature. The reaction solution was then transferred to a centrifuge and washed by centrifugation at 5000 r / min. The separated solid product was placed in a vacuum drying oven and dried at 80 °C to constant weight to obtain Cu1Mo. 20 S 40 Carrier.

[0034] (2) Preparation of Fe / CuMoS catalyst Weigh 0.1852 g of ionic liquid [N 8881 FeCl4, 15 g decahydronaphthalene, and 0.1056 g of the Cu1Mo prepared above 20 S 40 The support was added to a 25 mL high-pressure reactor, sealed, and high-purity nitrogen was introduced to replace the air inside the reactor. The reactor was then heated to 320 °C at a rate of 5 °C / min under a nitrogen protective atmosphere at atmospheric pressure for 5 h. After the reaction, the mixture was allowed to cool naturally to room temperature. The reaction solution was centrifuged and washed at 5000 r / min to obtain a solid product. The obtained solid product was then vacuum dried at 80 °C to constant weight. Subsequently, the dried sample was placed in a tube furnace and reduced at 400 °C for 3 h under a mixed atmosphere of 10% H₂ / 90% Ar to finally obtain the target catalyst Fe / CuMoS, where the molar ratio of Fe / (Cu+Mo) was 0.48.

[0035] Example 4: Preparation of Fe / WMoS catalyst (1) Preparation of WMoS support Weigh 1.9205 g of ionic liquid [N 8881 ]2MoO4, 0.1138 g ionic liquid [N 88812WCl4, 30 g of decahydronaphthalene, and 0.3405 g of sulfur powder were sequentially added to a 100 mL high-pressure reactor. After sealing, high-purity hydrogen gas was introduced to replace the air inside the reactor, and the pressure was increased to 4 MPa. Under stirring, the reactor was heated to 280 °C at a rate of 5 °C / min and reacted for 24 h. After the reaction was completed, the reactor was allowed to cool naturally to room temperature. The reaction solution was then transferred to a centrifuge and washed by centrifugation at 5000 r / min. The separated solid product was placed in a vacuum drying oven and dried to constant weight at 80 °C to obtain W1Mo. 20 S 40 Carrier.

[0036] (2) Preparation of Fe / WMoS catalyst Weigh 0.1852 g of ionic liquid [N 8881 FeCl4, 15 g decahydronaphthalene, and 0.1056 g of the W1Mo prepared above 20 S 40 The support was added to a 25 mL high-pressure reactor, sealed, and high-purity nitrogen was introduced to replace the air inside the reactor. The reactor was then heated to 320 °C at a rate of 5 °C / min under a nitrogen protective atmosphere at atmospheric pressure for 5 h. After the reaction, the mixture was allowed to cool naturally to room temperature. The reaction solution was centrifuged and washed at 5000 r / min to obtain a solid product. The obtained solid product was then vacuum dried at 80 °C to constant weight. Subsequently, the dried sample was placed in a tube furnace and reduced at 300 °C for 4 h under a mixed atmosphere of 10% H2 / 90% Ar to finally obtain the target catalyst Fe / WMoS, where the molar ratio of metal atoms of Fe / (W+Mo) was 0.50.

[0037] Comparative Example 1: Preparation of Fe / MoS2 catalyst (1) Preparation of MoS2 support Weigh 1.9205 g of ionic liquid [N 8881 2MoO4, 30 g decahydronaphthalene, and 0.3405 g sulfur powder were sequentially added to a 100 mL high-pressure reactor. After sealing, high-purity hydrogen was introduced to replace the air inside the reactor, and the pressure was increased to 4 MPa. Under stirring, the reactor was heated to 280 °C at a rate of 5 °C / min and reacted for 24 h. After the reaction was completed, the reactor was allowed to cool naturally to room temperature. The reaction solution was then transferred to a centrifuge and washed by centrifugation at 5000 r / min. The separated solid product was placed in a vacuum drying oven and dried to constant weight at 80 °C to obtain the MoS2 support.

[0038] (2) Preparation of Fe / MoS2 catalyst Weigh 0.1858 g of ionic liquid [N 8881FeCl4, 15 g of decahydronaphthalene, and 0.1056 g of the prepared MoS2 support were added to a 25 mL high-pressure reactor. After sealing, high-purity nitrogen was introduced to replace the air inside the reactor, and a normal nitrogen atmosphere was maintained. The reactor was heated to 320 °C at a rate of 5 °C / min and reacted for 5 h. After the reaction, the mixture was allowed to cool naturally to room temperature, centrifuged, washed, and vacuum dried at 80 °C for 12 h. The dried sample was then placed in a tube furnace and reduced at 400 °C for 2 h under a mixed atmosphere of 10% H2 / 90% Ar to obtain the target catalyst Fe / MoS2 catalyst, wherein the molar ratio of Fe / Mo was 0.50.

[0039] Comparative Example 2: Preparation of Co / MoS2 catalyst (1) Preparation of MoS2 support The preparation method of the MoS2 support is the same as that of Comparative Example 1.

[0040] (2) Preparation of Co / MoS2 catalyst Weigh 0.1858 g of ionic liquid [N 8881 CoCl4, 15 g of decahydronaphthalene, and 0.1056 g of the prepared MoS2 support were added to a 25 mL high-pressure reactor. After sealing, high-purity nitrogen was introduced to replace the air inside the reactor, and the nitrogen atmosphere was maintained at atmospheric pressure. The reactor was heated to 320 °C at a rate of 5 °C / min and reacted for 5 h. After the reaction, the reactor was allowed to cool naturally to room temperature, centrifuged, washed, and vacuum dried at 80 °C for 12 h. The dried sample was then placed in a tube furnace and reduced at 350 °C for 2 h under a mixed atmosphere of 10% H2 / 90% Ar to obtain the target catalyst, Co / MoS2 catalyst, in which the molar ratio of Co / Mo was 0.50.

[0041] Comparative Example 3: Preparation of Fe / CoMoS Catalyst (1) Preparation of MoS2 support The preparation method of the MoS2 support is the same as that of Comparative Example 1.

[0042] (2) Preparation of CoS2 support Weigh 1.8765 g of ionic liquid [N 8881 2CoCl4, 30 g decahydronaphthalene, and 0.3405 g sulfur powder were sequentially added to a 100 mL high-pressure reactor. After sealing, high-purity hydrogen was introduced to replace the air inside the reactor, and the pressure was increased to 4 MPa. Under stirring, the reactor was heated to 280 °C at a rate of 5 °C / min and reacted for 24 h. After the reaction was completed, the reactor was allowed to cool naturally to room temperature. The reaction solution was then transferred to a centrifuge and washed by centrifugation at 5000 r / min. The separated solid product was placed in a vacuum drying oven and dried to constant weight at 80 °C to obtain the CoS2 support.

[0043] (3) Preparation of Fe / CoMoS catalyst Weigh 0.1752 g of ionic liquid [N 8881 FeCl4, 15 g of decahydronaphthalene, 0.1 g of the previously prepared MoS2, and 0.0038 g of CoS2 were added to a 25 mL high-pressure reactor. After sealing, high-purity nitrogen was introduced to replace the air inside the reactor, and a normal nitrogen atmosphere was maintained. The reactor was heated to 320 °C at a rate of 5 °C / min and reacted for 5 h. After the reaction, the reactor was allowed to cool naturally to room temperature, centrifuged, washed, and vacuum dried at 80 °C for 12 h. The dried sample was then placed in a tube furnace and reduced at 400 °C for 2 h under a mixed atmosphere of 10% H2 / 90% Ar to finally obtain the target catalyst Fe / CoMoS2 catalyst, in which the molar ratio of metal atoms of Fe / (Mo+Co) was 0.47.

[0044] Performance testing of catalyst in the selective deoxygenation reaction of methyl myristate Weigh 0.0081 g of the catalyst prepared above and 1.845 g of methyl myristate, add them to a 10 mL high-pressure reactor, seal the reactor, purge the air inside with high-purity hydrogen, and pressurize to 4 MPa. Then, under stirring, heat to 280 °C at a rate of 5 °C / min and react for 5 h. After the reaction is complete, allow it to cool naturally to room temperature, filter the reaction solution, and dissolve the filter residue thoroughly in methanol. Then, perform qualitative and quantitative analysis using gas chromatography-mass spectrometry (GC-MS).

[0045] Table 1

[0046] The results above show that the iron-based catalyst prepared with bimetallic sulfide as support exhibits significantly better catalytic activity than the catalyst prepared with monometallic sulfide support in the hydrodeoxygenation reaction of methyl tetradecanoate. There are also significant performance differences among different bimetallic supports. Among them, the Fe / CoMoS catalyst prepared with CoMoS as support shows the best catalytic performance, and it can achieve complete conversion and highly selective hydrodeoxygenation of methyl tetradecanoate under mild reaction conditions (280℃, 4 MPa H2).

[0047] Meanwhile, a comparison of the results of Comparative Example 3 and Example 2 shows that the preparation method of the CoMoS support has a decisive influence on the structure of the active phase of the catalyst and its performance in the hydrogenation reaction of methyl tetradecanoate. Compared with physically mixing MoS2 and CoS2, the one-step co-precipitation of the ionic liquid precursor in a high-pressure hydrogen atmosphere not only achieves atomic-level uniform doping of Co, Mo, and S, which is beneficial to the formation of a highly active CoMoS solid solution phase, but also the constructed coordination unsaturated sites have optimized electronic structure and hydrogen activation ability. In the hydrogenation deoxygenation process of methyl tetradecanoate, this CoMoS active phase can effectively promote the adsorption activation of fatty acid methyl esters and the selective breaking of CO bonds, inhibit the occurrence of excessive hydrogenation cracking side reactions, thereby significantly improving the degree of deoxygenation and the selectivity of alkane formation.

[0048] The above results show that CoMoS has significant advantages in stabilizing active metal species, promoting reactant activation, inhibiting side reactions such as decarboxylation / decarbonylation, and improving overall reaction efficiency. It is a bimetallic sulfide support material with great application potential. The one-step co-precipitation method for preparing CoMoS support is one of the key factors for achieving high deoxidation degree and high selectivity in the hydrogenation reaction of methyl tetradecanoate.

[0049] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A supported catalyst using a bimetallic sulfide as a carrier, characterized in that, Its preparation method includes the following steps: 1) Ionic liquid, sulfur powder and decahydronaphthalene are mixed and subjected to sulfidation reaction. After the reaction, the mixture is cooled to room temperature, washed by centrifugation and dried under vacuum to obtain bimetallic sulfide. 2) The metal ionic liquid, decahydronaphthalene and the bimetallic sulfide obtained in step 1) are mixed and subjected to a doping reaction. After the reaction, the mixture is cooled to room temperature, centrifuged, washed and vacuum dried, and then placed in a tube furnace for reduction to obtain the supported catalyst.

2. The method for preparing a supported catalyst using a bimetallic sulfide as a carrier according to claim 1, characterized in that, The ionic liquid mentioned in step 1) is a mixture of molybdenum-based ionic liquid and any one of cobalt-based, tungsten-based, nickel-based, or copper-based ionic liquids in a molar ratio of (5-50):1; wherein 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, the copper-based ionic liquid is [N 8881 ]2CuCl4.

3. The supported catalyst using a bimetallic sulfide as a carrier according to claim 1, characterized in that, The amount of sulfur powder used in step 1) is calculated based on the molar ratio of S to the total metal atoms in the ionic liquid being 1 to 20.

4. The supported catalyst using a bimetallic sulfide as a carrier according to claim 1, characterized in that, 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. The supported catalyst using a bimetallic sulfide as a carrier according to claim 1, characterized in that, The metal ionic liquid mentioned in step 2) is [N 8881 ]2CoCl4、[N 8881 FeCl4, [N 8881 ]2NiCl4、[N 8881 ]2CuCl4、[N 8881 ]2ZnCl4、[N 8881 One or more of 2WO4; the amount used is calculated based on a molar ratio of the metal atoms contained to the total metal atoms in the bimetallic sulfide of 0 to 3.

6. A supported catalyst using a bimetallic sulfide as a carrier according to claim 1, characterized in that, The doping reaction described in step 2) is carried out under normal pressure and N2 atmosphere, with a reaction temperature of 250~450 ℃ and a reaction time of 0~36 h.

7. A supported catalyst using a bimetallic sulfide as a carrier according to claim 1, characterized in that, The reduction described in step 2) is carried out in a mixed gas atmosphere of 10% H2 / 90% Ar, at a reaction temperature of 150~800 ℃, and for a reaction time of 1~10 h.

8. The application of a supported catalyst with a bimetallic sulfide as described in claim 1 in the hydrodeoxygenation reaction of biomass oil.

9. The application according to claim 8, characterized in that, The biomass oil includes one or more of the following: lignin pyrolysis oil, biomass pyrolysis oil, biomass-based oxygenated compounds, and bio-oils.

10. The application according to claim 8, characterized in that, In the reaction, the mass ratio of the supported catalyst with bimetallic sulfide as the carrier to the biomass oil used 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-to-oil ratio is 0~2000.

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