Catalyst for preparing furfuryl amine through furfural hydrogenation amination and preparation method thereof

Abstract

The invention relates to the technical field of catalysts, in particular to a catalyst for preparing furfuryl amine through furfural hydrogenation amination and a preparation method of the catalyst, and the catalyst comprises the following raw materials in parts by weight: 63-71 parts of a carrier, 14-24 parts of an auxiliary agent and 2-3 parts of an additive; the method for preparing the furfuryl amine catalyst through furfural hydrogenation amination comprises the following steps: step 1, preparing an auxiliary agent, wherein the auxiliary agent comprises the following raw materials: a porous material, a doping material, a composite material and magnesium powder; 2, preparing a carrier, wherein the raw materials of the carrier comprise gamma-aluminum oxide, tetrabutyl titanate and urea; step 3, loading a carrier to prepare a loaded carrier; and 4, finally preparing to obtain the catalyst for preparing furfuryl amine through furfural hydrogenation amination. According to the invention, the high activity, high selectivity and strong stability of the catalyst are realized by accurately regulating and controlling the ruthenium-cobalt bimetallic ratio, the titanium-aluminum composite carrier structure and the composite additive system.

Description

Technical Field

[0001] The invention relates to the technical field of catalysts, in particular to a catalyst for preparing furfural amine by hydrogenation of furfural and a preparation method thereof. Background Art

[0002] Furfural is an important organic chemical intermediate with wide applications in medicine, pesticides, dyes and other fields. Furfural hydrogenation amination is an important process route for the preparation of furfural. The performance of the catalyst in this reaction directly affects the reaction efficiency, product selectivity and industrial production cost.

[0003] Current furfural hydroamination catalysts for furfural amine lack an effective mechanism for immobilizing the active components, making it difficult to maintain high activity while ensuring long-term operational stability. This leads to rapid performance degradation and difficulty in regeneration during continuous reactions, making them unable to meet the stringent requirements of modern green chemical production for high catalyst efficiency and stability. Based on this, the present invention provides a furfural hydroamination catalyst for furfural amine and a method for its preparation. Summary of the Invention

[0004] The present invention aims to provide a catalyst for preparing furfural amine by hydrogenating amination of furfural and a preparation method thereof. The catalyst for preparing furfural amine by hydrogenating amination of furfural prepared by the present invention solves the problems of uneven dispersion of active components of traditional catalysts, high energy consumption at high temperatures, susceptibility to ammonia poisoning, and poor stability, and can effectively meet the stringent requirements of green chemical production for high efficiency and stability of catalysts.

[0005] To achieve the above object, the present invention provides the following technical solution: a method for preparing a catalyst for furfural hydrogenation amination, comprising the following raw materials in parts by weight: 63-71 parts of a carrier, 14-24 parts of an auxiliary agent, and 2-3 parts of an additive; The catalyst for furfural hydrogenation amination to furfural amine is prepared by the following method: Step 1: Preparation of additives. The raw materials of the additives include porous materials, doping materials, composite materials, and magnesium powder; Step 2: Carrier preparation, the raw materials of the carrier include γ-alumina, tetrabutyl titanate, and urea; Step 3: Carrier loading, to obtain a loaded carrier; Step 4: Final preparation, to obtain the furfural hydrogenation amination catalyst to furfural amine.

[0006] Preferably, the additive is selected from sesbania powder.

[0007] Preferably, the preparation method of the auxiliary agent comprises the following steps: weighing porous material, doping material, and composite material as needed and adding them into a mixer, setting the speed to 20-30 rpm and mixing for 50-60 minutes, then adding magnesium powder and continuing to mix for 30 minutes to obtain a premix, adding the premix into an atmosphere furnace, introducing ammonia, heating to 930-980°C at 4-5°C / min and keeping warm for 2-3 hours, and crushing and grinding the obtained product and passing it through a 100-150 mesh sieve to obtain the auxiliary agent, wherein the mass ratio of the porous material, doping material, composite material, and magnesium powder is (4-6): (2-4): (1-3): (0.5-1).

[0008] Preferably, the preparation method of the porous material is as follows: nano-silica and urea are added to a ball mill in a mass ratio of 1:3, the speed is set to 350-450 rpm, and the ball mill is transferred to a tube furnace after 50-60 minutes. Nitrogen is introduced and the temperature is increased to 650-750°C at 5°C / min and then kept warm for 100-120 minutes. The obtained product is crushed and passed through a 200 mesh sieve to obtain a porous material, wherein the nitrogen flow rate is 50 ml / min.

[0009] Preferably, the preparation method of the doping material is as follows: sucrose and urea are dissolved in deionized water in a mass ratio of 2:3, the resulting product is added to a high-pressure reactor, the speed is set to 250-300 rpm, the temperature is raised to 175-180°C, and the reaction is carried out for 2-3 hours. The resulting product is filtered to obtain a filter cake, which is added to a tubular furnace, and the temperature is raised to 780-820°C at 8-10°C / min under a nitrogen atmosphere, and calcined for 180-200 minutes. The resulting product is ball-milled and sieved through a 300-350 mesh sieve to obtain a doping material, wherein the mass of sucrose is 12-14% of the mass of deionized water.

[0010] Preferably, the preparation method of the composite material is as follows: mixing cyanide and cerium nitrate in a mass ratio of 1:1 and adding them to deionized water, stirring in a 60-65°C water bath until completely dissolved, then adding citric acid, and continuing to stir until a clear state to obtain a mixed solution, transferring the mixed solution to a constant temperature magnetic stirrer, setting the temperature to 78-82°C and the speed to 450-550rpm, stirring until the viscosity reaches 900-1100Pa·s to obtain a gel, transferring it to a muffle furnace, heating it to 600°C at 3-4°C / min and keeping it warm for 120-150min, and crushing the obtained product to a particle size of 5-10μm, which is the composite material, wherein the mass of cyanide is 9-11% of the mass of deionized water, and the mass ratio of cyanide to citric acid is 1:(2-3).

[0011] Preferably, the specific method for preparing the carrier is: adding γ-alumina, tetrabutyl titanate, and urea to a reactor, adding ammonia water dropwise to adjust the pH to 8.3-8.7, setting the rotation speed to 180-220 rpm and the temperature to 78-82°C, treating for 100-130 minutes, transferring the resulting product to a rotary kiln, calcining at 590-610°C for 200-250 minutes to obtain a first coarse material, and grinding the first coarse material by a ball mill to a specific surface area of ​​220-240 m2 / g to obtain a carrier.

[0012] Preferably, the mass ratio of γ-alumina, tetrabutyl titanate, and urea is (48-52): (4-6): (8-10).

[0013] Preferably, the carrier loading method includes the following steps: Step 1: Mix ruthenium trichloride and cobalt nitrate in a molar ratio of 1.8:1, add deionized water, and stir to dissolve to obtain an impregnation solution, wherein the total mass of ruthenium trichloride and cobalt nitrate is 2.5-3.5% of the mass of the carrier, and the solid content of the impregnation solution is 20-25%; Step 2: Add the carrier to the impregnation tank, pour in the impregnation liquid and perform ultrasonic treatment at 40kHz for 50-60min. Transfer the obtained product to an oven, set the temperature at 105-115℃ and dry it for 200-240min to obtain the loaded carrier.

[0014] Preferably, the specific method of the final preparation comprises the following steps: S1: Add the auxiliary agent, carrier and additive into the mixer, set the speed to 40-50 rpm, and mix for 40-50 minutes to obtain a mixture; S2: Add the mixed material into a tablet press and produce granules with a particle size of 5-6 mm under a pressure of 15 MPa; S3: The pellets are loaded into a fixed-bed reactor, and after hydrogen is introduced, the temperature is increased to 350-400°C at a heating rate of 2-3°C / min, and then the temperature is maintained at a constant temperature for 175-185 minutes. The obtained product is cooled to room temperature under nitrogen protection to obtain a furfural hydrogenation amination catalyst for furfural amine.

[0015] Compared with the prior art, the present invention has the following beneficial effects: The present invention discloses a preparation method of a catalyst for preparing furfural by hydrogenation amination of furfural. By precisely controlling the ratio of a ruthenium-cobalt bimetallic, a titanium-aluminum composite support structure, and a composite auxiliary agent system, the high activity, high selectivity, and strong stability of the catalyst are achieved. By leveraging the synergistic effect of active components in a specific ratio, the mass transfer advantages of a multi-level porous support, and the construction of a nitrogen-resistant environment, the catalyst solves the problems of uneven dispersion of active components, high energy consumption at high temperatures, susceptibility to ammonia poisoning, and poor stability in traditional catalysts. The catalyst is suitable for green synthesis processes in the field of biomass conversion and provides an efficient, stable, and environmentally friendly catalytic solution for the amination reactions of other aldehyde-containing compounds, thereby promoting energy conservation and sustainable development in related chemical production. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 The invention proposes a flow chart of a furfural hydrogenation amination catalyst to produce furfural amine and a preparation method thereof. DETAILED DESCRIPTION

[0017] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0018] In order to enable those skilled in the art to better understand the solution of the present application, the technical solution in the embodiments of the present application will be clearly and completely described below in conjunction with the accompanying drawings.

[0019] Example 1

[0020] The preparation method of a catalyst for preparing furfural by hydrogenation amination of furfural comprises the following raw materials in parts by weight: 63 parts of a carrier, 14 parts of an auxiliary agent, and 2 parts of an additive; The catalyst for furfural hydrogenation amination to furfural amine is prepared by the following method: Step 1: Preparation of additives. The raw materials of the additives include porous materials, doping materials, composite materials, and magnesium powder; Step 2: Carrier preparation, the raw materials of the carrier include γ-alumina, tetrabutyl titanate, and urea; Step 3: Carrier loading, to obtain a loaded carrier; Step 4: Final preparation, to obtain a catalyst for furfural hydrogenation amination to furfural amine.

[0021] Wherein, the additive is selected from sesbania powder.

[0022] Among them, the preparation method of the auxiliary agent includes the following steps: weighing porous material, doping material, and composite material as needed and adding them into a mixer, setting the speed to 20 rpm and mixing for 50 minutes, then adding magnesium powder, and continuing to mix for 30 minutes to obtain a premix, adding the premix into an atmosphere furnace, introducing ammonia, heating to 930°C at 4°C / min and keeping warm for 2 hours, and the resulting product is crushed and ground and then passed through a 100-mesh sieve to obtain an auxiliary agent, wherein the mass ratio of porous material, doping material, composite material, and magnesium powder is 4:2:1:0.5.

[0023] The preparation method of the porous material is as follows: nano-silica and urea are added to a ball mill in a mass ratio of 1:3, the speed is set to 350 rpm, and after ball milling for 50 minutes, the ball mill is transferred to a tube furnace, nitrogen is introduced, and the temperature is increased to 650°C at 5°C / min and then kept warm for 100 minutes. The obtained product is crushed and passed through a 200-mesh sieve to obtain a porous material, wherein the nitrogen flow rate is 50 ml / min.

[0024] Among them, the preparation method of the doping material is as follows: sucrose and urea are dissolved in deionized water in a mass ratio of 2:3, the resulting product is added to a high-pressure reactor, the speed is set to 250 rpm, the temperature is raised to 175°C, and the reaction is carried out for 2 hours. The resulting product is filtered to obtain a filter cake, which is added to a tubular furnace, and the temperature is raised to 780°C at 8°C / min under a nitrogen atmosphere, and calcined for 180 minutes. The resulting product is ball-milled and passed through a 300-mesh sieve to obtain a doping material, wherein the mass of sucrose is 12% of the mass of deionized water.

[0025] The preparation method of the composite material is as follows: mixing cyanide and cerium nitrate in a mass ratio of 1:1, adding the mixture to deionized water, stirring in a 60°C water bath until completely dissolved, then adding citric acid, and continuing to stir until a clear state is obtained to obtain a mixed solution, transferring the mixed solution to a constant temperature magnetic stirrer, setting the temperature to 78°C and the speed to 450rpm, stirring until the viscosity reaches 900Pa·s to obtain a gel, transferring the mixture to a muffle furnace, heating to 600°C at 3°C / min and keeping warm for 120min, and crushing the obtained product to a particle size of 5μm, which is the composite material, wherein the mass of cyanide is 9% of the mass of deionized water, and the mass ratio of cyanide to citric acid is 1:2.

[0026] Among them, the specific method for preparing the carrier is: add γ-alumina, tetrabutyl titanate, and urea to the reactor, add ammonia water to adjust the pH to 8.3, set the speed to 180 rpm and the temperature to 78°C, and treat for 100 minutes. The resulting product is transferred to a rotary kiln and calcined at 590°C for 200 minutes to obtain a first coarse material. The first coarse material is ground by a ball mill to a specific surface area of ​​220 m2 / g to obtain a carrier.

[0027] Among them, the mass ratio of γ-alumina, tetrabutyl titanate and urea is 48:4:8.

[0028] The carrier loading method includes the following steps: Step 1: Mix ruthenium trichloride and cobalt nitrate in a molar ratio of 1.8:1, add deionized water, and stir to dissolve to obtain an impregnation solution, wherein the total mass of ruthenium trichloride and cobalt nitrate is 2.5% of the carrier mass, and the solid content of the impregnation solution is 20%; Step 2: Add the carrier to the impregnation tank, pour in the impregnation liquid and perform ultrasonic treatment at 40kHz for 50 minutes. Transfer the obtained product to an oven, set the temperature to 105℃ and dry it for 200 minutes to obtain the loaded carrier.

[0029] The final preparation method includes the following steps: S1: Add the auxiliary agent, carrier and additive into the mixer, set the speed to 40 rpm, and mix for 40 minutes to obtain a mixture; S2: Add the mixed material into a tablet press and produce granules with a particle size of 5 mm under a pressure of 15 MPa; S3: The pellets were loaded into a fixed-bed reactor, and after hydrogen was introduced, the temperature was increased to 350°C at a heating rate of 2°C / min and then kept at a constant temperature for 175 min. The obtained product was cooled to room temperature under nitrogen protection to obtain a furfural hydrogenation amination catalyst for furfural amine.

[0030] Example 2

[0031] A method for preparing a catalyst for preparing furfural by hydrogenation amination of furfural comprises the following raw materials in parts by weight: 67 parts of a carrier, 19 parts of an auxiliary agent, and 2.5 parts of an additive; The catalyst for furfural hydrogenation amination to furfural amine is prepared by the following method: Step 1: Preparation of additives. The raw materials of the additives include porous materials, doping materials, composite materials, and magnesium powder; Step 2: Carrier preparation, the raw materials of the carrier include γ-alumina, tetrabutyl titanate, and urea; Step 3: Carrier loading, to obtain a loaded carrier; Step 4: Final preparation, to obtain a catalyst for furfural hydrogenation amination to furfural amine.

[0032] Wherein, the additive is selected from sesbania powder.

[0033] The preparation method of the auxiliary agent includes the following steps: weighing porous material, doping material, and composite material as needed and adding them into a mixer, setting the speed to 25 rpm and mixing for 55 minutes, then adding magnesium powder and continuing to mix for 30 minutes to obtain a premix, adding the premix into an atmosphere furnace, introducing ammonia, heating to 950°C at 4.5°C / min and keeping warm for 2.5 hours, and the obtained product is crushed and ground and then passed through a 125-mesh sieve to obtain an auxiliary agent, wherein the mass ratio of the porous material, doping material, composite material, and magnesium powder is 5:3:2:0.8.

[0034] The preparation method of the porous material is as follows: nano-silica and urea are added to a ball mill in a mass ratio of 1:3, the speed is set to 400 rpm, and after ball milling for 55 minutes, the mixture is transferred to a tube furnace, nitrogen is introduced, and the temperature is increased to 700°C at 5°C / min and then kept warm for 110 minutes. The obtained product is crushed and passed through a 200-mesh sieve to obtain a porous material, wherein the nitrogen flow rate is 50 ml / min.

[0035] Among them, the preparation method of the doping material is as follows: sucrose and urea are dissolved in deionized water in a mass ratio of 2:3, the resulting product is added to a high-pressure reactor, the speed is set to 280 rpm, the temperature is raised to 178°C, and the reaction is carried out for 2.5 hours. The resulting product is filtered to obtain a filter cake, which is added to a tubular furnace, and the temperature is raised to 800°C at 9°C / min under a nitrogen atmosphere, and calcined for 190 minutes. The resulting product is ball-milled and passed through a 320-mesh sieve to obtain a doping material, wherein the mass of sucrose is 13% of the mass of deionized water.

[0036] The preparation method of the composite material is as follows: mixing cyanide and cerium nitrate in a mass ratio of 1:1 and adding the mixture to deionized water, stirring in a 63°C water bath until completely dissolved, then adding citric acid, and continuing to stir until a clear state is obtained to obtain a mixed solution, transferring the mixed solution to a constant temperature magnetic stirrer, setting the temperature to 80°C and the speed to 500 rpm, stirring until the viscosity reaches 1000 Pa·s to obtain a gel, transferring it to a muffle furnace, heating it to 600°C at 3.5°C / min and keeping it warm for 135 minutes, and crushing the obtained product to a particle size of 8μm, which is the composite material, wherein the mass of cyanide is 10% of the mass of deionized water, and the mass ratio of cyanide to citric acid is 1:2.5.

[0037] Among them, the specific method for preparing the carrier is: adding γ-alumina, tetrabutyl titanate, and urea to a reactor, adding ammonia water to adjust the pH to 80.5, setting the speed to 200 rpm and the temperature to 80°C, and treating for 115 minutes. The resulting product is transferred to a rotary kiln and calcined at 600°C for 220 minutes to obtain a first coarse material. The first coarse material is ground in a ball mill to a specific surface area of ​​230 m2 / g to obtain a carrier.

[0038] Among them, the mass ratio of γ-alumina, tetrabutyl titanate and urea is 50:5:9.

[0039] The carrier loading method includes the following steps: Step 1: Mix ruthenium trichloride and cobalt nitrate in a molar ratio of 1.8:1, add deionized water, and stir to dissolve to obtain an impregnation solution, wherein the total mass of ruthenium trichloride and cobalt nitrate is 3% of the mass of the carrier, and the solid content of the impregnation solution is 22%; Step 2: Add the carrier to the impregnation tank, pour in the impregnation liquid and ultrasonically treat at 40kHz for 55min. Transfer the obtained product to an oven and set the temperature to 108℃ for drying for 220min to obtain the loaded carrier.

[0040] The final preparation method includes the following steps: S1: Add the auxiliary agent, carrier and additive into the mixer, set the speed to 45 rpm, and mix for 45 minutes to obtain a mixture; S2: The mixture was added to a tablet press and granules with a particle size of 5.5 mm were obtained under a pressure of 15 MPa; S3: The pellets were loaded into a fixed-bed reactor, and after hydrogen was introduced, the temperature was increased to 380°C at a heating rate of 2.5°C / min, and then the temperature was maintained at a constant temperature for 180 min. The obtained product was cooled to room temperature under nitrogen protection to obtain a furfural hydrogenation amination catalyst for furfural amine.

[0041] Example 3

[0042] The preparation method of a catalyst for preparing furfural by hydrogenation amination of furfural comprises the following raw materials in parts by weight: 71 parts of a carrier, 24 parts of an auxiliary agent, and 3 parts of an additive; The catalyst for furfural hydrogenation amination to furfural amine is prepared by the following method: Step 1: Preparation of additives. The raw materials of the additives include porous materials, doping materials, composite materials, and magnesium powder; Step 2: Carrier preparation, the raw materials of the carrier include γ-alumina, tetrabutyl titanate, and urea; Step 3: Carrier loading, to obtain a loaded carrier; Step 4: Final preparation, to obtain a catalyst for furfural hydrogenation amination to furfural amine.

[0043] Wherein, the additive is selected from sesbania powder.

[0044] The preparation method of the auxiliary agent includes the following steps: weighing porous material, doping material, and composite material as needed and adding them into a mixer, setting the speed to 30 rpm and mixing for 60 minutes, then adding magnesium powder and continuing to mix for 30 minutes to obtain a premix, adding the premix into an atmosphere furnace, introducing ammonia, heating to 980°C at 5°C / min and keeping warm for 3 hours, and the obtained product is crushed and ground and then passed through a 150-mesh sieve to obtain an auxiliary agent, wherein the mass ratio of the porous material, doping material, composite material, and magnesium powder is 6:4:3:1.

[0045] Among them, the preparation method of the porous material is: add nano-silica and urea into a ball mill in a mass ratio of 1:3, set the speed to 450 rpm, ball mill for 60 minutes, transfer to a tube furnace, introduce nitrogen, and heat to 750°C at 5°C / min and then keep warm for 120 minutes. The obtained product is crushed and passed through a 200-mesh sieve to obtain a porous material, wherein the nitrogen flow rate is 50 ml / min.

[0046] Among them, the preparation method of the doping material is as follows: sucrose and urea are dissolved in deionized water in a mass ratio of 2:3, the resulting product is added to a high-pressure reactor, the speed is set to 300 rpm, the temperature is raised to 180°C, and the reaction is carried out for 3 hours. The resulting product is filtered to obtain a filter cake, which is added to a tubular furnace, and the temperature is raised to 820°C at 10°C / min under a nitrogen atmosphere, and calcined for 200 minutes. The resulting product is ball-milled and passed through a 350-mesh sieve to obtain a doping material, wherein the mass of sucrose is 14% of the mass of deionized water.

[0047] The preparation method of the composite material is as follows: mixing cyanide and cerium nitrate in a mass ratio of 1:1, adding the mixture to deionized water, stirring in a 65°C water bath until completely dissolved, then adding citric acid, and continuing to stir until clear to obtain a mixed solution, transferring the mixed solution to a constant temperature magnetic stirrer, setting the temperature to 82°C and the speed to 550 rpm, stirring until the viscosity reaches 1100 Pa·s to obtain a gel, transferring the mixture to a muffle furnace, heating to 600°C at 4°C / min and keeping warm for 150 minutes, and crushing the obtained product to a particle size of 10 μm, which is the composite material, wherein the mass of cyanide is 11% of the mass of deionized water, and the mass ratio of cyanide to citric acid is 1:3.

[0048] Among them, the specific method for preparing the carrier is: add γ-alumina, tetrabutyl titanate, and urea to the reactor, add ammonia water to adjust the pH to 8.7, set the speed to 220 rpm and the temperature to 82°C, and treat for 130 minutes. The resulting product is transferred to a rotary kiln and calcined at 610°C for 250 minutes to obtain a first coarse material. The first coarse material is ground by a ball mill to a specific surface area of ​​240 m2 / g to obtain a carrier.

[0049] Among them, the mass ratio of γ-alumina, tetrabutyl titanate and urea is 52:6:10.

[0050] The carrier loading method includes the following steps: Step 1: Mix ruthenium trichloride and cobalt nitrate in a molar ratio of 1.8:1, add deionized water, and stir to dissolve to obtain an impregnation solution, wherein the total mass of ruthenium trichloride and cobalt nitrate is 3.5% of the carrier mass, and the solid content of the impregnation solution is 25%; Step 2: Add the carrier to the impregnation tank, pour in the impregnation liquid and ultrasonically treat at 40kHz for 60min. Transfer the obtained product to an oven and set the temperature at 115℃ to dry for 240min to obtain the loaded carrier.

[0051] The final preparation method includes the following steps: S1: Add the auxiliary agent, carrier and additive into the mixer, set the speed to 50 rpm, and mix for 50 minutes to obtain a mixture; S2: The mixture was added to a tablet press and granules with a particle size of 6 mm were obtained under a pressure of 15 MPa; S3: The pellets were loaded into a fixed-bed reactor, and after hydrogen was introduced, the temperature was increased to 400°C at a heating rate of 3°C / min and then maintained at a constant temperature for 185 min. The obtained product was cooled to room temperature under nitrogen protection to obtain a furfural hydrogenation amination catalyst for furfural amine.

[0052] Comparative Example 1: This comparative example differs from Example 1 in that the auxiliary agent preparation does not contain a composite material.

[0053] Comparative Example 2: This comparative example differs from Example 1 in that when the carrier is loaded, the molar ratio of ruthenium trichloride to cobalt nitrate is changed to 1:1.

[0054] Comparative Example 3: This comparative example differs from Example 1 in that ultrasonic treatment is omitted during carrier loading, and only mechanical stirring and impregnation are used.

[0055] Comparative Example 4: This comparative example differs from Example 1 in that tetrabutyl titanate is not contained in the carrier preparation.

[0056] Test method: A fixed-bed reactor was used with a catalyst loading of 5g. The raw materials were a furfural-ammonia mixture (furfural:ammonia molar ratio of 1:3), and hydrogen was used as the reducing gas (furfural:hydrogen molar ratio of 1:5). The reaction temperature was 150°C, the pressure was 2MPa, and the liquid space velocity was 1h⁻¹. The reaction was continued for 6h. The furfural conversion rate, furfurylamine selectivity, and stability were tested. Furfural conversion rate: (initial furfural amount - unreacted furfural amount) / initial furfural amount × 100%; Furfurylamine selectivity: the amount of furfurylamine generated / the amount of furfural converted × 100%; Stability: After 5 consecutive cycles, the ratio of the conversion rate of the 5th reaction to the conversion rate of the first reaction × 100%.

[0057] The test data of Examples 1-3 and Comparative Examples 1-4 are recorded in the following table:

[0058] By comparing the data in the table, it can be seen that the furfural conversion rate, furfurylamine selectivity and stability in Examples 1-3 are relatively close; Comparative analysis of Comparative Example 1 and Examples 1-3 shows that in Comparative Example 1, the furfural conversion rate decreased by about 12%, the furfural amine selectivity decreased by about 12%, and the stability decreased by about 28%. The reason is that the lanthanum and cerium rare earth elements in the composite material can form oxygen vacancies, promote the adsorption and activation of reaction intermediates, and inhibit the formation of carbon deposits. In the absence of the composite material, the number of active sites is reduced, the carbon deposition rate is accelerated, and the performance is significantly reduced; Comparative analysis of Comparative Example 2 and Examples 1-3 shows that the furfural conversion rate decreased by about 8%, and the furfural amine selectivity decreased by about 7%. This is because a Ru-Co molar ratio of 1.8:1 can form an optimal synergistic effect (Ru activates hydrogen and Co promotes C=N bond cleavage). When the ratio is changed to 1:1, the bimetallic synergistic effect is weakened, the active site matching degree decreases, and the reaction efficiency is reduced; Comparative analysis of Comparative Example 3 and Examples 1-3 shows that the furfural conversion rate decreased by about 6%, and the furfural amine selectivity decreased by about 9%. This is because ultrasonic treatment promotes the penetration of active components into the support pores through the cavitation effect, thereby improving the dispersion. The decreased dispersion leads to the agglomeration of active sites, a decrease in the effective specific surface area, and an increase in side reactions (such as excessive hydrogenation of furfural to produce furfuryl alcohol). Comparative analysis of Comparative Example 4 and Examples 1-3 shows that the performance of Comparative Example 4 degrades most significantly. This is because the TiO formed by the hydrolysis of tetrabutyl titanate forms a composite support with γ-alumina, which can improve thermal stability and surface acidity uniformity. When only γ-alumina is used, the support is prone to phase transformation during high-temperature reactions, resulting in pore collapse, sintering of active components, and a sharp decrease in stability.

[0059] Therefore, this catalyst exhibits excellent low-temperature hydrogenation activity by precisely controlling the ratio of active components and the carrier structure. The core lies in the 1.8:1 Ru-Co bimetallic synergy. Ru efficiently activates hydrogen, and Co promotes the selective breaking of the C=N bond. Combined with the high specific surface area (220-240 m2 / g) and multi-level pores (3-10 nm) of the titanium-aluminum composite carrier, the furfural hydrogenation amination reaction can be carried out efficiently at a lower temperature. Compared with traditional catalysts that require high temperatures (above 200°C) to drive the reaction, this catalyst can achieve a furfural conversion rate of 96% and a conversion rate of 92% at 150°C. The catalyst achieves excellent furfural selectivity and significantly reduces energy consumption. Furthermore, the nitrogen-tolerant environment created by the dopant and composite effectively mitigates ammonia poisoning of active sites, ensuring reaction stability. This characteristic is perfectly suited for green synthesis processes in biomass conversion, reducing side reactions and energy consumption caused by high temperatures, in line with low-carbon and environmentally friendly concepts, and providing a sustainable solution for the efficient conversion of biomass derivatives such as furfural. Furthermore, the dopant in this catalyst weakens ammonia adsorption by adjusting its electronic structure, the through-pores of the porous material accelerate ammonia diffusion, and the stable framework formed by the nitridation of magnesium powder inhibits coverage of active components by nitrogen species. After five cycles, the stability reaches 88%, significantly higher than that of conventional catalysts. This nitrogen-tolerant property not only ensures long-term stable operation of the furfural hydroamination reaction but also lays the foundation for its expansion into the amination of other aldehyde-containing compounds. For example, in the amination of benzaldehyde and formaldehyde, it effectively resists interference from nitrogen-containing species in the reaction system, maintaining high selectivity. Furthermore, the use of green additives such as sesbania powder in the preparation process further reduces environmental impact, providing a highly efficient, stable, and environmentally friendly catalytic option for the amination of aldehyde compounds in various fields.

[0060] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0061] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to the specific embodiments described. Obviously, many modifications and variations are possible based on the content of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. The preparation method of furfural hydrogenation amination furfurylamine catalyst is characterized in that, The composition comprises the following raw materials in parts by weight: 63-71 parts of a carrier, 14-24 parts of an auxiliary agent, and 2-3 parts of an additive; The catalyst for furfural hydrogenation amination to furfural amine is prepared by the following method: Step 1: Preparation of additives. The raw materials of the additives include porous materials, doping materials, composite materials, and magnesium powder; Step 2: Carrier preparation, the raw materials of the carrier include γ-alumina, tetrabutyl titanate, and urea; Step 3: Carrier loading, to obtain a loaded carrier; Step 4: Final preparation, to obtain the furfural hydrogenation amination catalyst to furfural amine.

2. the preparation method of furfural hydrogenation amination furfurylamine catalyst according to claim 1, wherein the additive is selected from sesbania powder.

3. The preparation method of furfural hydrogenation amination furfurylamine catalyst according to claim 1, wherein The preparation method of the additive comprises the following steps: weighing porous material, doping material and composite material as required and adding them into a mixer, setting the rotation speed to 20-30 rpm and mixing for 50-60 minutes, then adding magnesium powder and continuing to mix for 30 minutes to obtain a premix, adding the premix into an atmosphere furnace, introducing ammonia, heating to 930-980°C at a rate of 4-5°C / min and maintaining the temperature for 2-3 hours, and crushing and grinding the obtained product and passing it through a 100-150 mesh sieve to obtain the additive, wherein the mass ratio of the porous material, doping material, composite material and magnesium powder is (4-6): (2-4): (1-3): (0.5-1).

4. the preparation method of furfural hydrogenation amination furfurylamine catalyst according to claim 1, is characterized in that, The porous material is prepared by adding nano-silica and urea in a mass ratio of 1:3 into a ball mill, setting the rotation speed to 350-450 rpm, ball milling for 50-60 minutes, transferring the mixture to a tube furnace, introducing nitrogen, heating the mixture to 650-750° C. at a rate of 5° C. / min, and then maintaining the temperature for 100-120 minutes. The obtained product is crushed and passed through a 200-mesh sieve to obtain the porous material, wherein the nitrogen flow rate is 50 ml / min.

5. The preparation method of furfural hydrogenation amination furfurylamine catalyst according to claim 1, wherein The preparation method of the doping material comprises: dissolving sucrose and urea in deionized water in a mass ratio of 2:3, adding the resulting product into a high-pressure reactor, setting the speed to 250-300 rpm, heating to 175-180° C., reacting for 2-3 hours, filtering the resulting product to obtain a filter cake, adding the filter cake into a tubular furnace, heating to 780-820° C. at 8-10° C. / min under a nitrogen atmosphere, roasting for 180-200 minutes, and ball-milling the resulting product and passing it through a 300-350 mesh sieve to obtain the doping material, wherein the mass of sucrose is 12-14% of the mass of deionized water.

6. The method for preparing a furfural catalyst by hydrogenating amination of furfural according to claim 1, wherein The preparation method of the composite material comprises the following steps: mixing cyanide nitrate and cerium nitrate in a mass ratio of 1:1, adding the mixture to deionized water, stirring the mixture in a 60-65°C water bath until completely dissolved, adding citric acid, and continuing to stir the mixture until it becomes clear to obtain a mixed solution, transferring the mixed solution to a constant temperature magnetic stirrer, setting the temperature to 78-82°C and the rotation speed to 450-550 rpm, stirring the mixture until the viscosity reaches 900-1100 Pa·s, and obtaining a gel, transferring the mixture to a muffle furnace, heating the mixture to 600°C at a rate of 3-4°C / min and maintaining the temperature for 120-150 min, and crushing the obtained product to a particle size of 5-10 μm, thereby obtaining the composite material, wherein the mass of cyanide nitrate is 9-11% of the mass of deionized water, and the mass ratio of cyanide nitrate to citric acid is 1:(2-3).

7. The method for preparing a furfural catalyst by hydrogenating amination of furfural according to claim 1, wherein The specific method for preparing the carrier is as follows: γ-alumina, tetrabutyl titanate and urea are added to a reactor, ammonia water is added dropwise to adjust the pH to 8.3-8.7, the rotation speed is set to 180-220 rpm and the temperature is set to 78-82°C, and the treatment is carried out for 100-130 minutes. The obtained product is transferred to a rotary kiln and calcined at 590-610°C for 200-250 minutes to obtain a first coarse material. The first coarse material is ground in a ball mill to a specific surface area of ​​220-240 m2 / g to obtain a carrier.

8. The method for preparing a furfural catalyst by hydrogenating amination of furfural according to claim 7, wherein The mass ratio of γ-alumina, tetrabutyl titanate and urea is (48-52): (4-6): (8-10).

9. The method for preparing a furfural catalyst by hydrogenating amination of furfural according to claim 1, wherein The specific method of carrier loading includes the following steps: Step 1: Mix ruthenium trichloride and cobalt nitrate in a molar ratio of 1.8:1, add deionized water, and stir to dissolve to obtain an impregnation solution, wherein the total mass of ruthenium trichloride and cobalt nitrate is 2.5-3.5% of the mass of the carrier, and the solid content of the impregnation solution is 20-25%; Step 2: Add the carrier to the impregnation tank, pour in the impregnation liquid and perform ultrasonic treatment at 40kHz for 50-60min. Transfer the obtained product to an oven, set the temperature at 105-115℃ and dry it for 200-240min to obtain the loaded carrier.

10. The method for preparing a furfural hydrogenation amination catalyst according to claim 1, wherein: The specific method of final preparation comprises the following steps: S1: Add the auxiliary agent, carrier and additive into the mixer, set the speed to 40-50 rpm, and mix for 40-50 minutes to obtain a mixture; S2: Add the mixed material into a tablet press and produce granules with a particle size of 5-6 mm under a pressure of 15 MPa; S3: The pellets are loaded into a fixed-bed reactor, and after hydrogen is introduced, the temperature is increased to 350-400°C at a heating rate of 2-3°C / min, and then the temperature is maintained at a constant temperature for 175-185 minutes. The obtained product is cooled to room temperature under nitrogen protection to obtain a furfural hydrogenation amination catalyst for furfural amine.

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