A multi-metal composite catalyst for hydrodeoxygenation of biomass oil

Abstract

The application discloses a preparation method of a multi-metal composite catalyst for biomass oil hydrodeoxygenation, which comprises the following steps: taking a metal oxyacid salt as raw material, and preparing a metal oxide by using a hydrothermal method; taking the metal oxide as a carrier, loading metal chloride on the surface of the metal oxide by using an impregnation method, and then performing sulfidation to obtain a metal oxide loaded metal sulfide composite material; finally, loading metal nitrate on the surface of the composite material by using the impregnation method, and performing reduction and passivation to obtain the multi-metal composite catalyst. The preparation process of the catalyst is simple, the obtained catalyst has good biomass oil hydrodeoxygenation activity and stability, and the application provides a new design idea and an industrial application direction for developing a high-efficiency stable, low-cost multi-metal composite hydrodeoxygenation catalyst.

Description

Technical Field

[0001] This invention belongs to the field of biomass oil hydrodeoxygenation catalytic technology, specifically relating to a preparation method and application of a biomass oil hydrodeoxygenation multi-metal composite catalyst. Background Technology

[0002] With economic development, the demand for fuels and chemical products is constantly increasing, leading to increasingly serious problems such as greenhouse gas emissions and energy shortages. Therefore, developing and utilizing green and renewable new energy sources is key to solving these problems. Biomass, as a carrier for storing solar energy in the form of chemical energy, occupies an important position in the global energy structure as a new type of green and renewable resource. It has been extensively researched and developed and has good application prospects. However, its low calorific value and high viscosity limit its large-scale application.

[0003] In existing technologies, reducing the oxygen content in biomass oil through hydrodeoxygenation to improve oil quality is a crucial means of converting biomass derivatives into liquid fuels. Despite significant efforts and progress by researchers, the design and construction of highly efficient hydrodeoxygenation catalysts remain a core challenge in biomass oil catalytic conversion technology. Commonly used catalysts, such as those with sulfides, carbides, and phosphides as active components, exhibit high initial activity for biomass oil hydrodeoxygenation. However, these components are difficult to remove further after reacting with oxygen, leading to a gradual loss of the active phase on the catalyst surface. As the reaction progresses, the catalyst activity significantly decreases. Furthermore, noble metal catalysts and transition metal catalysts such as nickel and cobalt often experience side reactions such as excessive hydrogenation of aromatic rings, carbon-oxygen bond decomposition, and carbon-carbon bond hydrogenolysis during the hydrodeoxygenation of biomass-based oxygen-containing compounds. These reactions require high hydrogen pressure and high temperature, resulting in harsh conditions, high hydrogen and energy consumption, and low atom utilization. Oxyphilic metal oxides such as molybdenum and iron exhibit strong interactions with oxygen atoms and excellent carbon-oxygen bond activation properties, but their poor hydrogenation performance limits their application in hydrodeoxygenation reactions. Therefore, developing a low-cost, stable, and highly effective biomass oil hydrodeoxygenation catalyst holds significant promise for future applications. Summary of the Invention

[0004] This invention addresses the problems of poor stability, high cost, and cumbersome synthesis routes in existing hydrodeoxygenation catalysts by providing a novel, highly efficient, and multifunctional multimetallic composite catalyst preparation method. This method is simple, can be scaled up, and the resulting catalyst exhibits good activity and stability in the hydrodeoxygenation of biomass oil.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing a multi-metal composite catalyst for hydrodeoxygenation of biomass oil, comprising the following steps: 1) The metal oxide support was prepared by dissolving the metal oxo acid salt in water and then carrying out a hydrothermal reaction, followed by pH adjustment, centrifugation and washing, drying and calcination in air atmosphere. 2) The metal chloride salt was dissolved in water and then added to the metal oxide support prepared in step 1). The mixture was stirred overnight at room temperature, then the solvent was removed by rotary evaporation and dried to constant weight. After that, it was placed in a tube furnace for sulfidation to obtain a metal oxide-supported metal sulfide composite material. 3) The metal oxide-supported metal sulfide composite material obtained in step 2) is added to an aqueous solution of metal nitrate, stirred overnight at room temperature, then the solvent is removed by rotary evaporation, and then dried to constant weight. After that, it is placed in a tube furnace for reduction, and after cooling to room temperature, it is directly passivated in a tube furnace to obtain the multi-metal composite catalyst.

[0006] Further, the metal oxophosphate in step 1) includes ZrOCl·8H2O and (NH4)6Mo7O. 24 ·4H2O、(NH4)6W7O 24 One or more of ·6H2O and Ti(OC4H9)4.

[0007] Furthermore, in step 1), the concentration of the solution obtained by dissolving the metal oxophosphate in water is 0.01~1 mol / L.

[0008] Furthermore, the hydrothermal reaction in step 1) is carried out at a temperature of 60~240 ℃ for a time of 3~48 h.

[0009] Further, after the hydrothermal reaction in step 1), the pH is adjusted to 8-10.

[0010] Furthermore, the centrifugal washing speed in step 1) is 6000-12000 r / min.

[0011] Furthermore, in step 1), the drying process uses a forced-air drying oven with a drying temperature of 100~150 ℃ and a drying time of 6~24 h.

[0012] Further, the roasting temperature in step 1) is 110~900 ℃ and the time is 1~12 h.

[0013] Further, the metal chloride salt in step 2) includes one or more of MoCl5, WCl5, CoCl2, and NiCl2.

[0014] Furthermore, in step 2), the amount of metal chloride salt used is calculated based on the mass of the metal contained therein being 0-50% of the mass of the metal oxide carrier.

[0015] Furthermore, the temperature of the rotary evaporation in step 2) is 80~150 ℃.

[0016] Furthermore, the drying in step 2) is carried out in a forced-air drying oven with a drying temperature of 100~150 ℃ and a drying time of 6~24 h.

[0017] Further, the vulcanization in step 2) is carried out in a mixed gas atmosphere of 5% H2S / 10% H2 / 85% N2, and heat-treated at 180~450℃ for 1~12 h.

[0018] Further, the metal nitrate mentioned in step 3) includes one or more of Co(NO3)2, Ni(NO3)2, Pd(NO3)2, Pt(NO3)2, and Ru(NO)(NO3)3.

[0019] Furthermore, in step 3), the amount of metal nitrate is converted to a metal molar ratio of 0 to 5 with that of the metal sulfide in the composite material.

[0020] Furthermore, the temperature of the rotary evaporation in step 3) is 80~150 ℃.

[0021] Furthermore, the drying in step 3) is carried out in a vacuum drying oven with a drying temperature of 70~120 ℃ and a drying time of 6~24 h.

[0022] Further, the reduction in step 3) is carried out in a mixed gas atmosphere of 10% H2 / 90% Ar at 150~800 °C for 1~10 h.

[0023] Further, the passivation in step 3) is performed in a mixed gas atmosphere of 2% O2 / 98% N2 for 6 to 24 hours.

[0024] The obtained multi-metal composite catalyst can be used for the hydrodeoxygenation of biomass oils such as lignin pyrolysis oil, biomass pyrolysis oil, biomass-based oxygenated compounds, and bio-oils.

[0025] Furthermore, in the reaction, the mass ratio of the multi-metal composite catalyst to the biomass oil used is 1-20%.

[0026] Furthermore, in the reaction, the hydrogen pressure is 0~20 MPa, the reaction temperature is 120~450 ℃, the reaction time is 1~24 h, and the hydrogen-to-oil ratio is 0~2000.

[0027] The technical solution of the present invention has the following advantages: (1) The preparation method of the multi-metal composite catalyst proposed in this invention can highly disperse the active components on the surface of the support. Through the strong interaction between metals, metal sulfides and metal oxides, the activity and stability of the catalyst are greatly improved. This solves the problems of poor stability and complex synthesis process of existing multi-metal composite catalysts, and provides a new design idea for developing efficient, high-stability and low-cost multi-metal composite catalysts.

[0028] (2) The multi-metal composite catalyst prepared by this invention can achieve deep deoxygenation of different biomass oils. Specifically, the multi-metal composite catalyst prepared by this invention can selectively cleave the carbon-oxygen bonds of alcohol hydroxyl groups, phenolic hydroxyl groups, fatty acids, fatty acid esters, and glycerol esters, etc., and its deoxygenation rate for biomass oils can reach more than 99%, with a target product selectivity of more than 90%. In addition, the structure of this multi-metal composite catalyst is highly designable and can be widely applied to the hydrodeoxygenation process of different biomass oils. Attached Figure Description

[0029] Figure 1 The catalyst Co / MoS obtained in Example 1 2-x SEM image of ZrO2.

[0030] Figure 2 The catalyst Co / MoS obtained in Example 1 2-x XRD pattern of ZrO2. Detailed Implementation

[0031] A method for preparing a multi-metal composite catalyst for hydrodeoxygenation of biomass oil, comprising the following steps: 1) Dissolve the metal oxoacid salt in a certain amount of deionized water to obtain a solution with a concentration of 0.01~1 mol / L. Then transfer it to a reaction vessel and hydrothermally react at 60~240 ℃ for 3~48 h. Adjust the pH to 8~10, centrifuge and wash at 6000-12000 r / min, and place it in a forced-air drying oven to dry at 100~150 ℃ for 6~24 h. After grinding, calcine in a muffle furnace at 110~900 ℃ for 1~12 h in an air atmosphere to obtain the metal oxide support. 2) The metal chloride salt was fully dissolved in deionized water, and then the prepared metal oxide support was added. The mixture was stirred overnight at room temperature, and the solvent was removed by rotary evaporation at 80~150 °C. The mixture was then transferred to a forced-air drying oven and dried at 100~150 °C for 6~24 h to constant weight. The mixture was then placed in a tube furnace and a mixed gas of 5% H2S / 10% H2 / 85% N2 was introduced. The mixture was then sulfided at 180~450 °C for 1~12 h to obtain the metal oxide supported metal sulfide composite material. 3) The metal nitrate was fully dissolved in deionized water, and then the prepared metal oxide-supported metal sulfide composite material was added. The mixture was stirred overnight at room temperature, and the solvent was removed by rotary evaporation at 80-150 °C. The mixture was then transferred to a vacuum drying oven and dried at 70-120 °C for 6-24 h until constant weight was achieved. The mixture was then placed in a tube furnace and a mixed gas of 10% H2 / 90% Ar was introduced. The mixture was reduced at 150-800 °C for 1-10 h. After that, the temperature was lowered to room temperature and a mixed gas of 2% O2 / 98% N2 was introduced for passivation for 6-24 h to obtain a multi-metal composite catalyst.

[0032] Wherein, the metal oxophosphate in step 1) includes ZrOCl·8H2O and (NH4)6Mo7O 24 ·4H2O、(NH4)6W7O 24 One or more of ·6H2O and Ti(OC4H9)4.

[0033] Step 2) The metal chloride salt includes one or more of MoCl5, WCl5, CoCl2, and NiCl2. Its dosage is calculated based on the mass of the metal contained therein being 0-50% of the mass of the metal oxide carrier.

[0034] Step 3) The metal nitrates mentioned include one or more of Co(NO3)2, Ni(NO3)2, Pd(NO3)2, Pt(NO3)2, and Ru(NO)(NO3)3.

[0035] To make the content of this invention easier to understand, the technical solution of this invention will be further described below with reference to specific embodiments, but this invention is not limited thereto.

[0036] The present invention will be described in detail below through specific embodiments.

[0037] Example 1: A multi-metal composite catalyst Co / MoS 2-x The preparation of ZrO2 involves the following steps: (1) Weigh 14.0 g of ZrOCl·8H2O, add deionized water to make up to 100 mL, stir evenly to obtain a 0.4 mol / L zirconium oxychloride aqueous solution; take 60 mL into a hydrothermal reactor, hydrothermally react at 150 ℃ for 6 h, cool to room temperature, adjust pH to 8.2 with ammonia water, centrifuge and wash at 5000 r / min in a centrifuge, and put it into a forced-air drying oven to dry at 110 ℃ for 12 h; grind the dried sample and place it in a muffle furnace to calcine at 350 ℃ for 4 h to obtain ZrO2 support; (2) Weigh 1.4 g of MoCl5 and dissolve it completely in 50 mL of deionized water. Add 5.0 g of ZrO2 support and stir overnight at room temperature. Then transfer it to a rotary evaporator at 90 °C to remove the solvent. Dry it in a 110 °C oven for 12 h until constant weight. Then place the obtained sample in a tube furnace and pass a mixed gas of 5% H2S / 10% H2 / 85% N2 through it. Sulfide it at 320 °C for 4 h to obtain MoS. 2-x -ZrO2 composite material; (3) Weigh 0.14 g of Co(NO3)2 and dissolve it completely in 50 mL of deionized water, then add 2.0 g of MoS2. 2-x The ZrO2 composite material was stirred overnight at room temperature, and the solvent was removed by rotary evaporation at 90 °C. After cooling to room temperature, it was transferred to an 80 °C vacuum drying oven and dried for 12 h to constant weight. The dried sample was then placed in a tube furnace, and a mixture of 10% H2 / 90% Ar gas was introduced. Reduction was carried out at 320 °C for 4 h. After cooling to room temperature, a mixture of 2% O2 / 98% N2 gas was continued to be introduced into the tube furnace, and passivation was carried out at room temperature for 4 h to obtain the target catalyst Co / MoS2. 2-x -ZrO2, with a Mo loading of 10% and a Co / Mo molar ratio of 1 / 3.

[0038] The prepared catalyst Co / MoS 2-x -ZrO2 is used for the selective deoxygenation of p-methylphenol, specifically by weighing 0.5g of Co / MoS2. 2-x ZrO2, 0.8 g of p-methylphenol, and 26 g of decahydronaphthalene were added to a 100 mL high-pressure reactor, sealed, and high-purity H2 was introduced to purge air from the reactor. The reactor was pressurized to 3 MPa and heated to 320 °C at a rate of 5 °C / min, and reacted for 5 h. After the reactor cooled to room temperature, the reaction solution was filtered and completely dissolved in methanol. Qualitative and quantitative analysis was performed using gas chromatography-mass spectrometry.

[0039] The results showed that Co / MoS 2-x The deoxygenation degree of p-methylphenol treated with ZrO2 was 99%, and the selectivity of the main product toluene was 96.0%.

[0040] Example 2: A multi-metal composite catalyst Co / MoS 2-x The preparation of ZrO2 involves the following steps: (1) Weigh 14.0 g of ZrOCl·8H2O, add deionized water to make up to 100 mL, stir evenly to obtain a 0.4 mol / L zirconium oxychloride aqueous solution; take 60 mL into a hydrothermal reactor, hydrothermally react at 150 ℃ for 6 h, cool to room temperature, adjust pH to 8.2 with ammonia water, centrifuge and wash at 5000 r / min in a centrifuge, and put it into a forced-air drying oven to dry at 110 ℃ for 12 h; grind the dried sample and place it in a muffle furnace to calcine at 350 ℃ for 4 h to obtain ZrO2 support; (2) Weigh 2.8 g of MoCl5 and dissolve it completely in 50 mL of deionized water. Add 5.0 g of ZrO2 support and stir overnight at room temperature. Then transfer it to a 90 ℃ rotary evaporator to remove the solvent, and dry it in a 110 ℃ forced-air drying oven for 12 h until constant weight. Then place the obtained sample in a tube furnace, introduce a mixed gas of 5% H2S / 10% H2 / 85% N2, and sulfide it at 320 ℃ for 4 h to obtain MoS. 2-x -ZrO2 composite material; (3) Weigh 0.14 g of Co(NO3)2 and dissolve it completely in 50 mL of deionized water, then add 2.0 g of MoS2. 2-x The ZrO2 composite material was stirred overnight at room temperature, and the solvent was removed by rotary evaporation at 90 °C. After cooling to room temperature, it was transferred to an 80 °C vacuum drying oven and dried for 12 h to constant weight. The dried sample was then placed in a tube furnace, and a mixture of 10% H2 / 90% Ar gas was introduced. Reduction was carried out at 320 °C for 4 h. After cooling to room temperature, a mixture of 2% O2 / 98% N2 gas was continued to be introduced into the tube furnace, and passivation was carried out at room temperature for 4 h to obtain the target catalyst Co / MoS2. 2-x -ZrO2, with a Mo loading of 20% and a Co / Mo molar ratio of 1 / 3.

[0041] The prepared catalyst Co / MoS 2-x -ZrO2 is used for the selective deoxygenation of p-methylphenol, specifically by weighing 0.5g of Co / MoS2. 2-x ZrO2, 0.8 g of p-methylphenol, and 26 g of decahydronaphthalene were added to a 100 mL high-pressure reactor, sealed, and high-purity H2 was introduced to purge air from the reactor. The reactor was pressurized to 3 MPa and heated to 320 °C at a rate of 5 °C / min, and reacted for 5 h. After the reactor cooled to room temperature, the reaction solution was filtered and completely dissolved in methanol. Qualitative and quantitative analysis was performed using gas chromatography-mass spectrometry.

[0042] The results showed that Co / MoS 2-x The deoxygenation rate of p-methylphenol treated with ZrO2 was 98.5%, and the selectivity of the main product toluene was 92.5%.

[0043] Example 3: A multi-metal composite catalyst Co / MoS 2-x The preparation of ZrO2 involves the following steps: (1) Weigh 14 g of ZrOCl·8H2O, add deionized water to 100 mL, stir evenly to obtain a 0.4 mol / L zirconium oxychloride aqueous solution; take 60 mL to a hydrothermal reactor, hydrothermally react at 150 ℃ for 6 h, cool to room temperature, adjust pH to 8.2 with ammonia, centrifuge and wash at 5000 r / min in a centrifuge, and dry in a 110 ℃ forced-air drying oven for 12 h; grind the dried sample and place it in a muffle furnace, calcine at 350 ℃ for 4 h to obtain ZrO2 support; (2) Weigh 1.4 g of MoCl5 and dissolve it completely in 50 mL of deionized water. Add 5 g of ZrO2 support and stir overnight at room temperature. Then, remove the solvent in a rotary evaporator at 90 °C and dry it in a 110 °C oven for 12 h until constant weight. Then, place the dried sample in a tube furnace and pass a mixed gas of 5% H2S / 10% H2 / 85% N2 through it. Sulfide it at 320 °C for 4 h to obtain MoS2. 2-x -ZrO2 intermediate; (3) Weigh 0.76 g of Co(NO3)2 and dissolve it completely in 50 mL of deionized water, then add 2 g of MoS2. 2-x The ZrO2 intermediate was stirred overnight at room temperature, and the solvent was removed by rotary evaporation at 90 °C. After cooling to room temperature, the sample was transferred to a vacuum drying oven at 80 °C and dried for 12 h to constant weight. The dried sample was then placed in a tube furnace, and a mixture of 10% H2 / 90% Ar gas was introduced. Reduction was carried out at 320 °C for 4 h. After cooling to room temperature, a mixture of 2% O2 / 98% N2 gas was continued to be introduced into the tube furnace, and passivation was carried out at room temperature for 12 h to obtain the target catalyst Co / MoS2. 2-x -ZrO2, with a Mo loading of 10% and a Co / Mo molar ratio of 1 / 0.5.

[0044] The prepared catalyst Co / MoS 2-x -ZrO2 is used for the selective deoxygenation of p-methylphenol, specifically by weighing 0.5g of Co / MoS2. 2-x ZrO2, 0.8 g of p-methylphenol, and 26 g of decahydronaphthalene were added to a 100 mL high-pressure reactor, sealed, and purged with high-purity H2 five times. The reactor was then pressurized to 3 MPa and heated to 320 °C at a rate of 5 °C / min for 5 h. After the reaction, the reactor was allowed to cool to room temperature. The reaction solution was then filtered and completely dissolved in methanol. Qualitative and quantitative analysis was performed using gas chromatography-mass spectrometry.

[0045] The results showed that Co / MoS 2-x The deoxygenation rate of p-methylphenol treated with ZrO2 was 78.9%, and the selectivity of the main product toluene was 54.5%.

[0046] Example 4: A multi-metal composite catalyst Co / MoS 2-x The preparation of ZrO2 involves the following steps: (1) Weigh 14 g of ZrOCl·8H2O, add deionized water to 100 mL, stir evenly to obtain a 0.4 mol / L zirconium oxychloride aqueous solution; take 60 mL to a hydrothermal reactor, hydrothermally react at 150 ℃ for 6 h, cool to room temperature, adjust pH to 8.2 with ammonia, centrifuge and wash at 5000 r / min, and dry in a 110 ℃ forced-air drying oven for 12 h; grind the dried sample and place it in a muffle furnace, calcine at 350 ℃ for 5 h to obtain ZrO2 support; (2) Weigh 1.4 g of MoCl5 and dissolve it completely in 50 mL of deionized water. Add 5 g of ZrO2 support and stir overnight at room temperature. Then, place the sample in a 90 ℃ rotary evaporator to remove the solvent, and then transfer it to a 110 ℃ forced-air drying oven to dry for 12 h until constant weight. After that, place the dried sample in a tube furnace and pass a mixed gas of 5% H2S / 10% H2 / 85% N2 through it. Sulfide it at 200 ℃ for 4 h to obtain MoS. 2-x -ZrO2 intermediate; (3) Weigh 0.14 g of Co(NO3)2 and dissolve it completely in 50 mL of deionized water, then add 2 g of MoS2. 2-x The ZrO2 intermediate was stirred overnight at room temperature, then the solvent was removed by rotary evaporation in a 90 °C rotary evaporator. After cooling to room temperature, the sample was dried in an 80 °C vacuum drying oven for 12 h to constant weight. The dried sample was then placed in a tube furnace, and a mixture of 10% H2 / 90% Ar gas was introduced. Reduction was carried out at 320 °C for 4 h. After cooling to room temperature, a mixture of 2% O2 / 98% N2 gas was introduced into the tube furnace, and passivation was carried out at room temperature for 12 h to obtain the target catalyst Co / MoS2. 2-x -ZrO2, with a Mo loading of 10% and a Co / Mo molar ratio of 1 / 3.

[0047] The prepared catalyst Co / MoS 2-x -ZrO2 is used for the selective deoxygenation of p-methylphenol, specifically by weighing 0.5g of Co / MoS2. 2-xZrO2, 0.8 g of p-methylphenol, and 26 g of decahydronaphthalene were added to a 100 mL high-pressure reactor, sealed, and high-purity H2 was introduced to purge air from the reactor. The reactor was pressurized to 3 MPa and heated to 320 °C at a rate of 5 °C / min for 5 h. After the reaction, the reactor was allowed to cool to room temperature, the reaction solution was filtered and completely dissolved in methanol, and qualitative and quantitative analysis was performed using gas chromatography-mass spectrometry.

[0048] The results showed that Co / MoS 2-x The deoxygenation rate of p-methylphenol treated with ZrO2 was 48%, and the selectivity of the main product toluene was 65%.

[0049] Example 5: A multi-metal composite catalyst Co / MoS 2-x The preparation of ZrO2 involves the following steps: (1) Weigh 14 g of ZrOCl·8H2O, add deionized water to 100 mL, stir evenly to obtain a 0.4 mol / L zirconium oxychloride aqueous solution; take 60 mL to a hydrothermal reactor, hydrothermally react at 150 ℃ for 6 h, cool to room temperature, adjust pH to 8.2 with ammonia, centrifuge and wash at 5000 r / min in a centrifuge, and place in a forced-air drying oven to dry at 110 ℃ for 12 h; grind the dried sample and place it in a muffle furnace to calcine at 350 ℃ for 4 h to obtain ZrO2 support; (2) Weigh 1.4 g of MoCl5 and dissolve it completely in 50 mL of deionized water. Add 5 g of ZrO2 support and stir overnight at room temperature. Then, place the sample in a 90 ℃ rotary evaporator to remove the solvent, and then transfer it to a 110 ℃ forced-air drying oven to dry for 12 h until constant weight. After that, place the dried sample in a tube furnace and pass a mixed gas of 5% H2S / 10% H2 / 85% N2 through it. Sulfide it at 320 ℃ for 4 h to obtain MoS. 2-x -ZrO2 intermediate; (3) Weigh 0.14 g of Co(NO3)2 and dissolve it completely in 50 mL of deionized water, then add 2 g of MoS2. 2-x The ZrO2 intermediate was stirred overnight at room temperature, then the solvent was removed by rotary evaporation in a 90 °C rotary evaporator. After cooling to room temperature, the sample was dried in an 80 °C vacuum drying oven for 12 h to constant weight. The dried sample was then placed in a tube furnace, and a mixture of 10% H2 / 90% Ar gas was introduced. Reduction was carried out at 550 °C for 4 h. After cooling to room temperature, a mixture of 2% O2 / 98% N2 gas was introduced into the tube furnace, and passivation was carried out at room temperature for 4 h to obtain the target catalyst Co / MoS2. 2-x -ZrO2, with a Mo loading of 10% and a Co / Mo molar ratio of 1 / 3.

[0050] The prepared catalyst Co / MoS 2-x -ZrO2 is used for the selective deoxygenation of p-methylphenol, specifically by weighing 0.5g of Co / MoS2. 2-x ZrO2, 0.8 g of p-methylphenol, and 26 g of decahydronaphthalene were added to a 100 mL high-pressure reactor, sealed, and high-purity H2 was introduced to purge air from the reactor. The reactor was pressurized to 3 MPa and heated to 320 °C at a rate of 5 °C / min for 5 h. After the reaction, the reactor was allowed to cool to room temperature, the reaction solution was filtered and completely dissolved in methanol, and qualitative and quantitative analysis was performed using gas chromatography-mass spectrometry.

[0051] The results showed that Co / MoS 2-x The deoxygenation rate of p-methylphenol treated with ZrO2 was 91.9%, and the selectivity of the main product toluene was 91.5%.

[0052] Example 6: A multi-metal composite catalyst Pt / MoS 2-x The preparation of ZrO2 involves the following steps: (1) Weigh 14 g of ZrOCl·8H2O, add deionized water to 100 mL, stir evenly to obtain a 0.4 mol / L zirconium oxychloride aqueous solution; take 60 mL to a hydrothermal reactor, hydrothermally react at 150 ℃ for 6 h, cool to room temperature, adjust pH to 8.2 with ammonia, centrifuge and wash at 5000 r / min in a centrifuge, and dry in a 110 ℃ forced-air drying oven for 12 h; grind the dried sample and place it in a muffle furnace, calcine at 350 ℃ for 4 h to obtain ZrO2 support; (2) Weigh 1.4 g of MoCl5 and dissolve it completely in 50 mL of deionized water. Add 5 g of ZrO2 support and stir overnight at room temperature. Then, evaporate the sample to dryness in a rotary evaporator at 90 °C. Transfer the sample to a drying oven at 110 °C and dry for 12 h to constant weight. Then, place the dried sample in a tube furnace and pass a mixed gas of 5% H2S / 10% H2 / 85% N2 through it. Sulfide the sample at 320 °C for 4 h to obtain MoS2. 2-x -ZrO2 intermediate; (3) Weigh 0.22 g of Pt(NO3)2 and dissolve it completely in 50 mL of deionized water, then add 2 g of MoS2. 2-xThe ZrO2 intermediate was stirred overnight at room temperature, then the solvent was removed by rotary evaporation in a 90 °C rotary evaporator. After cooling to room temperature, the sample was dried in an 80 °C vacuum drying oven for 12 h to constant weight. The dried sample was then placed in a tube furnace, and a mixture of 10% H2 / 90% Ar gas was introduced. Reduction was carried out at 320 °C for 4 h. After cooling to room temperature, a mixture of 2% O2 / 98% N2 gas was introduced into the tube furnace, and passivation was carried out at room temperature for 4 h to obtain the target catalyst Pt / MoS2. 2-x -ZrO2, with a Mo loading of 10% and a Pt / Mo molar ratio of 1 / 3.

[0053] The prepared catalyst Pt / MoS 2-x -ZrO2 is used for the selective deoxygenation of p-methylphenol, specifically by weighing 0.5g of Pt / MoS2. 2-x ZrO2, 0.8 g of p-methylphenol, and 26 g of decahydronaphthalene were added to a 100 mL high-pressure reactor, sealed, and high-purity H2 was introduced to purge air from the reactor. The reactor was pressurized to 3 MPa and heated to 320 °C at a rate of 5 °C / min for 5 h. After the reaction, the reactor was allowed to cool to room temperature, the reaction solution was filtered and completely dissolved in methanol, and qualitative and quantitative analysis was performed using gas chromatography-mass spectrometry.

[0054] The results show that Pt / MoS 2-x The deoxygenation rate of p-methylphenol treated with ZrO2 was 99%, and the selectivity of the main product toluene was 79.4%.

[0055] Example 7: A multi-metal composite catalyst Co / NiMoS x The preparation of ZrO2 involves the following steps: (1) Weigh 14 g of ZrOCl·8H2O, add deionized water to 100 mL, stir evenly to obtain a 0.4 mol / L zirconium oxychloride aqueous solution; take 60 mL to a hydrothermal reactor, hydrothermally react at 150 ℃ for 6 h, cool to room temperature, adjust pH to 8.2 with ammonia, centrifuge and wash at 5000 r / min in a centrifuge, and place in a forced-air drying oven to dry at 110 ℃ for 12 h; grind the dried sample and place it in a muffle furnace to calcine at 350 ℃ for 4 h to obtain ZrO2 support; (2) Weigh 0.11 g of NiCl2 and 1.19 g of MoCl5 respectively, dissolve them completely in 50 mL of deionized water, add 5 g of ZrO2 support, and stir overnight at room temperature; then place them in a 90 ℃ rotary evaporator to remove the solvent, and then transfer them to a 110 ℃ forced-air drying oven to dry for 12 h to constant weight. After that, place the dried sample in a tube furnace, introduce a mixed gas of 5% H2S / 10% H2 / 85% N2, and sulfide it at 320 ℃ for 4 h to obtain NiMoS x -ZrO2 intermediate; (3) Weigh 0.13 g of Co(NO3)2 and dissolve it completely in 50 mL of deionized water, then add 2 g of NiMoS x The ZrO2 intermediate was stirred overnight at room temperature, then the solvent was removed by rotary evaporation in a 90 °C rotary evaporator. After cooling to room temperature, the sample was dried in an 80 °C vacuum drying oven for 12 h to constant weight. The dried sample was then placed in a tube furnace, and a mixture of 10% H2 / 90% Ar gas was introduced. Reduction was carried out at 320 °C for 4 h. After cooling to room temperature, a mixture of 2% O2 / 98% N2 gas was continued to be introduced into the tube furnace, and passivation was carried out at room temperature for 4 h to obtain the target catalyst Co / NiMoS2. x -ZrO2, wherein the Mo loading is 10%, the molar ratio of Co / NiMo is 1 / 3, and the molar ratio of Ni / Mo is 1 / 5.

[0056] The prepared catalyst Co / NiMoS x -ZrO2 is used for the selective deoxygenation of p-methylphenol, specifically by weighing 0.5g of Co / NiMoS2. x ZrO2, 0.8 g of p-methylphenol, and 26 g of decahydronaphthalene were added to a 100 mL high-pressure reactor, sealed, and high-purity H2 was introduced to purge air from the reactor. The reactor was pressurized to 3 MPa and heated to 320 °C at a rate of 5 °C / min for 5 h. After the reaction, the reactor was allowed to cool to room temperature, the reaction solution was filtered and completely dissolved in methanol, and qualitative and quantitative analysis was performed using gas chromatography-mass spectrometry.

[0057] The results show that Co / NiMoS x -ZrO2 has a deoxygenation rate of 99% for methylphenol and a selectivity of 86.7% for the main product toluene.

[0058] Example 8: A multi-metal composite catalyst Co-MoS 2-x The preparation of / ZrO2-TiO2 involves the following steps: (1) Weigh 7.2 g of ZrOCl·8H2O and 7.5 g of (Ti(OC4H9)4 respectively, add deionized water to 100 mL, stir evenly to obtain a 0.4 mol / L mixed aqueous solution of zirconium oxychloride and tetrabutyl titanate; take 60 mL into a hydrothermal reactor, hydrothermally react at 150 ℃ for 6 h, cool to room temperature, adjust pH to 8.2 with ammonia water, centrifuge and wash at 5000 r / min in a centrifuge, and place in a forced-air drying oven to dry at 110 ℃ for 12 h; grind the dried sample and place it in a muffle furnace, calcin at 350 ℃ for 4 h to obtain ZrO2-TiO2 support; (2) Weigh 1.4 g of MoCl5 and dissolve it completely in 50 mL of deionized water. Add 5 g of ZrO2-TiO2 support and stir overnight at room temperature. Then, evaporate the sample to dryness in a rotary evaporator at 90 ℃. Transfer the sample to a drying oven at 110 ℃ and dry it for 12 h until constant weight. Then, place the dried sample in a tube furnace and pass a mixed gas of 5% H2S / 10% H2 / 85% N2 through it. Sulfide the sample at 320 ℃ for 4 h to obtain MoS. 2-x / ZrO2-TiO2 intermediate; (3) Weigh 0.14 g of Co(NO3)2 and dissolve it completely in 50 mL of deionized water, then add 2 g of MoS2. 2-x The ZrO2-TiO2 intermediate was stirred overnight at room temperature, then the solvent was removed by rotary evaporation in a 90 ℃ rotary evaporator. After cooling to room temperature, the sample was dried in an 80 ℃ vacuum drying oven for 12 h to constant weight. The dried sample was then placed in a tube furnace, and a mixture of 10% H2 / 90% Ar gas was introduced. Reduction was carried out at 320 ℃ for 4 h. After cooling to room temperature, a mixture of 2% O2 / 98% N2 gas was continued to be introduced into the tube furnace, and passivation was carried out at room temperature for 4 h to obtain the target catalyst Co-MoS2. 2-x / ZrO2-TiO2, wherein the Mo loading is 10%, the molar ratio of Co / Mo is 1 / 3, and the molar ratio of Zr / Ti is 1 / 1.

[0059] The prepared catalyst Co-MoS 2-x / ZrO2-TiO2 is used for the selective deoxygenation of p-methylphenol, specifically by weighing 0.5 g of Co-MoS2. 2-x ZrO2-TiO2, 0.8 g of p-methylphenol, and 26 g of decahydronaphthalene were added to a 100 mL high-pressure reactor, sealed, and high-purity H2 was introduced to purge air from the reactor. The reactor was pressurized to 3 MPa and heated to 320 °C at a rate of 5 °C / min for 5 h. After the reaction, the reactor was allowed to cool to room temperature, the reaction solution was filtered and completely dissolved in methanol, and qualitative and quantitative analysis was performed using gas chromatography-mass spectrometry.

[0060] The results showed that Co-MoS 2-x The deoxygenation rate of ZrO2-TiO2 for p-methylphenol was 98.4%, and the selectivity for the main product toluene was 75.2%.

[0061] Example 9: A multi-metal composite catalyst CoNi / MoS 2-x The preparation of ZrO2 involves the following steps: (1) Weigh 14 g of ZrOCl·8H2O, add deionized water to 100 mL, stir evenly to obtain a 0.4 mol / L zirconium oxychloride aqueous solution; take 60 mL to a hydrothermal reactor, hydrothermally react at 150 ℃ for 6 h, cool to room temperature, adjust pH to 8.2 with ammonia, centrifuge and wash at 5000 r / min in a centrifuge, and place in a forced-air drying oven to dry at 110 ℃ for 12 h; grind the dried sample and place it in a muffle furnace to calcine at 350 ℃ for 4 h to obtain ZrO2 support; (2) Weigh 1.4 g of MoCl5 and dissolve it completely in 50 mL of deionized water. Add 5 g of ZrO2 support and stir overnight at room temperature. Then, evaporate the sample to dryness in a rotary evaporator at 90 °C. Transfer the sample to a drying oven at 110 °C and dry for 12 h to constant weight. Then, place the dried sample in a tube furnace and pass a mixed gas of 5% H2S / 10% H2 / 85% N2 through it. Sulfide the sample at 320 °C for 4 h to obtain MoS2. 2-x -ZrO2 intermediate; (3) Weigh out 0.06 g of Co(NO3)2 and 0.06 g of Ni(NO3)2 respectively, dissolve them completely in 50 mL of deionized water, and add 2 g of MoS2. 2-x The ZrO2 intermediate was stirred overnight at room temperature, then the solvent was removed by rotary evaporation in a 90 °C rotary evaporator. After cooling to room temperature, the sample was dried in an 80 °C vacuum drying oven for 12 h to constant weight. The dried sample was then placed in a tube furnace, and a mixture of 10% H2 / 90% Ar gas was introduced. Reduction was carried out at 320 °C for 4 h. After cooling to room temperature, a mixture of 2% O2 / 98% N2 gas was continued to be introduced into the tube furnace, and passivation was carried out at room temperature for 4 h to obtain the target catalyst CoNi / MoS2. 2-x -ZrO2, wherein the Mo loading is 10%, the molar ratio of Co / Ni is 1 / 1, and the molar ratio of CoNi / Mo is 1 / 3.

[0062] The prepared catalyst CoNi / MoS 2-x -ZrO2 is used for selective deoxidation of lignin pyrolysis oil, specifically by weighing 0.5 g of CoNi / MoS. 2-xZrO2, 0.8 g of lignin pyrolysis oil, and 26 g of decahydronaphthalene were added to a 100 mL high-pressure reactor, sealed, and high-purity H2 was introduced to purge air from the reactor. The reactor was pressurized to 3 MPa and heated to 360 °C at a rate of 5 °C / min for 10 h. After the reaction, the reactor was allowed to cool to room temperature, the reaction solution was filtered and completely dissolved in methanol to obtain the liquid product. The liquid product was qualitatively and quantitatively analyzed using gas chromatography-mass spectrometry, gas chromatography-flame ionization detector, and elemental analysis.

[0063] The results show that CoNi / MoS 2-x - The deoxidation rate of lignin pyrolysis oil treated with ZrO2 was 97.5%.

[0064] Example 10: The catalyst Co / MoS prepared in Example 1 2-x -ZrO2 is used for selective deoxygenation of waste oils, specifically by weighing 0.5 g of Co·MoS2. 2-x ZrO2, 1.8 g of waste oil, and 26 g of decahydronaphthalene were added to a 100 mL high-pressure reactor, sealed, and high-purity H2 was introduced to purge air from the reactor. The reactor was pressurized to 3 MPa and heated to 320 °C at a rate of 5 °C / min for 5 h. After the reaction, the reactor was allowed to cool to room temperature. The reaction solution was then filtered and completely dissolved in methanol. Qualitative and quantitative analyses were performed using gas chromatography-mass spectrometry and elemental analysis.

[0065] The results showed that Co / MoS 2-x The deoxygenation rate of waste oil treated with ZrO2 was 92.6%, and the selectivity for alkanes was 83.6%.

[0066] Example 11: The catalyst Co / MoS prepared in Example 1 2-x -ZrO2 is used for the selective deoxygenation of tridecanoic acid glycerides, specifically by weighing 0.5 g of Co / MoS2. 2-x ZrO2, 4.2 g of tridecanoic acid glyceride, and 26 g of decahydronaphthalene were added to a 100 mL high-pressure reactor, sealed, and high-purity H2 was introduced to purge air from the reactor. The reactor was pressurized to 3 MPa and heated to 320 °C at a rate of 5 °C / min for 5 h. After the reaction, the reactor was allowed to cool to room temperature, the reaction solution was filtered and completely dissolved in methanol. Qualitative and quantitative analysis was performed using gas chromatography-mass spectrometry and elemental analysis.

[0067] The results showed that Co / MoS 2-x The deoxygenation rate of tridecanoic acid glyceride treated with ZrO2 was 89.7%, and the selectivity of the main product decadecane was 88.2%.

[0068] As can be seen from the above, the catalyst prepared by the present invention has high activity for hydrodeoxygenation of biomass oil, can realize hydrodeoxygenation of biomass oil under mild conditions, and the deoxygenation rate can be close to 100%, and the yield of the main product can be as high as 90% or more.

[0069] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.

Claims

1. A method for preparing a multi-metal composite catalyst for the hydrodeoxygenation of biomass oil, characterized in that, Includes the following steps: 1) ZrOCl2·8H2O was dissolved in water and subjected to a hydrothermal reaction. After pH adjustment, centrifugation and washing, drying and calcination in air atmosphere were carried out to obtain a metal oxide support. 2) The metal chloride salt was dissolved in water and then added to the metal oxide support prepared in step 1). The mixture was stirred overnight at room temperature, then the solvent was removed by rotary evaporation and dried to constant weight. After that, it was placed in a tube furnace for sulfidation to obtain a metal oxide-supported metal sulfide composite material. 3) The metal oxide-supported metal sulfide composite material obtained in step 2) is added to an aqueous solution of metal nitrate, stirred overnight at room temperature, then the solvent is removed by rotary evaporation, dried to constant weight, and then reduced in a tube furnace. After cooling to room temperature, passivation is carried out directly in a tube furnace to obtain the multi-metal composite catalyst. Step 2) The metal chloride salt is MoCl5; the sulfidation is carried out in a mixed gas atmosphere of 5% H2S / 10% H2 / 85% N2, and heat treatment is performed at 180~450 ℃ for 1~12 h. Step 3) The metal nitrate is Co(NO3)2 or Pt(NO3)2; the reduction is carried out in a mixed gas atmosphere of 10% H2 / 90% Ar at 320~550 ℃ for 1~10 h; the passivation is carried out in a mixed gas atmosphere of 2% O2 / 98% N2 for 6~24 h.

2. The method for preparing a multi-metal composite catalyst for hydrodeoxygenation of biomass oil according to claim 1, characterized in that, Step 1) The concentration of ZrOCl2·8H2O dissolved in water is 0.4~1 mol / L; the temperature of the hydrothermal reaction is 150~240 ℃ and the time is 3~48 h; the pH is adjusted to 8~10 after the hydrothermal reaction; the calcination temperature is 350~900 ℃ and the time is 1~12 h.

3. The method for preparing a multi-metal composite catalyst for hydrodeoxygenation of biomass oil according to claim 1, characterized in that, Step 2) The amount of metal chloride salt used is calculated based on the mass of the metal contained therein accounting for 0 to 50% of the mass of the metal oxide carrier, and the amount used is not 0.

4. The method for preparing a multi-metal composite catalyst for hydrodeoxygenation of biomass oil according to claim 1, characterized in that, The amount of metal nitrate used in step 3) is calculated based on a metal molar ratio of 0 to 5 with that of the metal sulfide in the composite material, and the amount used is not 0.

5. The application of a multi-metal composite catalyst prepared by the method described in claim 1 in the hydrodeoxygenation reaction of biomass oil.

6. The application according to claim 5, characterized in that, The biomass oil includes one or both of biomass pyrolysis oil and bio-oil.

7. The application according to claim 5, characterized in that, In the reaction, the mass ratio of the multi-metal composite catalyst to the biomass oil used is 1~20%; the reaction hydrogen pressure is 0~20 MPa and not 0; the reaction temperature is 120~450 ℃; the reaction time is 1~24 h; and the hydrogen-to-oil ratio is 0~2000 and not 0.

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