A method for synthesizing bio-based glutaronitrile from furfural

Abstract

The application is a method for synthesizing bio-based glutaronitrile from furfural. The amide is prepared by reacting furfural with hydroxylamine to prepare furfuryl cyanide and further hydrating it. The method first selectively hydrolyzes the ring of furanamide to obtain 5-hydroxyvaleramide, then uses acetonitrile as a dehydrating agent and Pd / SiO2 as a catalyst to realize the dehydration of 5-hydroxyvaleramide to generate 5-hydroxyvaleronitrile, and finally realizes the generation of glutaronitrile through a fixed-bed ammoniation reaction. The application develops a new process for synthesizing glutaronitrile with the characteristics of primary raw materials, green safety and sustainability, and has important practical and theoretical value.

Description

Technical Field

[0001] The invention belongs to the field of chemical raw material synthesis, and particularly relates to a method for preparing glutaronitrile from biomass raw materials. Background Art

[0002] Glutaronitrile is an important raw material for the production of pentamethylenediamine. Pentamethylenediamine is mainly used in the production of nylon 56 and pentamethylene diisocyanate (PDI) in the synthesis of high molecular weight polymers such as polyamide and polyurethane. Nylon 56 has a unique odd-even structure, with NH and C=O in the macromolecular chain in a dislocated state. It has good mechanical properties, hygroscopicity, thermal stability, flame retardancy, dyeing properties, wear resistance and softness, and is mainly used in textiles, engineering plastics and filter membranes (Synthetic Fibers, 2019, 48(12):53; RSC Advances, 2021, 11(39):23922-23942); PDI is a new type of aliphatic diisocyanate. Due to its similar structure and chemical properties to HDI and its higher carbon content, it has the potential to replace HDI in downstream products. It is mainly used in the manufacture of yellowing-resistant polyurethane coatings, inks and artificial leather (Critical Reviews in Environmental Science and Technology, 2022, 52(2):157-202). In addition, pentamethylenediamine is also widely used in agriculture and medicine.

[0003] Currently, the main methods for preparing pentamethylenediamine are biotransformation and chemical synthesis. The biotransformation method (Chinese Journal of Process Engineering, 2023, 23(7):958-971) is the mainstream technology for producing pentamethylenediamine. This method uses lysine as the raw material and produces pentamethylenediamine in one step through the action of decarboxylase. However, it is not easy to produce on a large scale, and the separation of the product and the post-treatment of the waste liquid of the biofermentation method are difficult;

[0004] Researchers have studied chemical synthesis methods, which essentially involve synthesizing the nitrile precursor of an amine and then hydrogenating the nitrile to obtain the amine. A patent (US Patent 2,409,086[P]. 1946-10-8) reports the preparation of cyano-containing aldehyde compounds from aliphatic aldehydes and acrylonitrile catalyzed by sodium hydroxide or sodium cyanide. However, side reactions such as self-polymerization and condensation of the reactants occur, resulting in large amounts of dinitrile and acetal compounds as byproducts, resulting in low yields of the target product. Liu Zechao et al. (CN 113698300 B, 2023-07-14) reported that acrylonitrile reacted with acetaldehyde in the presence of N,N-dihydroxyethyl-1,4-pentanediamine to produce 5-formylvaleronitrile, which was then reacted with ammonia and hydrogen to obtain a high yield of pentamethylenediamine. Zhang Wenzhen et al. (CN 115073318 B, 2023-03-03) reported a carbon dioxide-promoted method for synthesizing glutaronitrile and other polycondensation monomer precursors from acetonitrile and acrylonitrile. Li Chong et al. (Petrochemical Industry, 2010, 39(5): 524-527) used an amorphous nickel catalyst to carry out catalytic hydrogenation of glutaronitrile to produce pentamethylenediamine, with a pentamethylenediamine yield of 66.8%. Gilles Laval et al. (Cheminform, 2003, 2003(29):542-546) reported a process for preparing pentamethylenediamine by hydrogenating 5-aminovaleronitrile using NaBH4 as a hydrogen source under the catalysis of nickel chloride hexahydrate. This method has high selectivity for pentamethylenediamine, but the conversion rate is low, with a product yield of only 79%. Zhang Jianmei et al. (CN 111454172 B, 2023-04-28) reported a method for preparing glutaramide from dimethyl glutarate and aqueous ammonia, and then obtaining glutaronitrile in the presence of a dehydrating agent. Chen Enzhi et al. (CN 219631290U, 2023.09.05) reported a system for producing glutaronitrile from glutaric acid and ammonia.

[0005] In summary, bioconversion methods for producing pentamethylenediamine face challenges in large-scale production, while biofermentation methods present difficulties in product separation and wastewater post-treatment. While chemical synthesis methods for producing pentamethylenediamine (nitrile) offer scaled production and ease of product separation, they still face challenges such as unsustainable raw material availability, high raw material costs, and severe environmental pollution, making sustainable development impossible. Summary of the Invention

[0006] The present invention addresses the limitations of current technologies by providing a method for synthesizing bio-based glutaronitrile from furfural. This method first produces 5-hydroxyvaleramide through selective hydrogenolysis of furfural, followed by dehydration of 5-hydroxyvaleramide to 5-hydroxyvaleronitrile using acetonitrile as a dehydrating agent and Pd / SiO2 as a catalyst. Finally, glutaronitrile is obtained through a fixed-bed amination reaction. This method develops a new, low-cost, sustainable process for synthesizing glutaronitrile using primary raw materials. The process is environmentally friendly, safe, and sustainable, and has significant practical and theoretical value.

[0007] The present invention is achieved through the following technical solutions:

[0008] A method for synthesizing bio-based glutaronitrile from furfural, the method comprising the following steps:

[0009] (1) Furfural hydrogenolysis ring opening to produce 5-hydroxyvaleramide:

[0010] Furfural, water, and a supported bimetallic catalyst are added to a reactor, which is sealed and stirred at 40-180° C. for 0.1-6 hours in a 0.1-4 MPa hydrogen atmosphere to obtain 5-hydroxyvaleramide, tetrahydrofuran furfural, and 2-hydroxyvaleramide.

[0011] The furfural concentration in the reactor is 0.1 to 1 mol / L, and the mass ratio of the supported bimetallic catalyst to furfural is 0.1 to 1:1.

[0012] The supported bimetallic catalyst is composed of Pt, transition metal and carrier; the loading amount of active metal Pt is 1% to 10%;

[0013] The transition metal is Mo, Mn, Co or Re;

[0014] The transition metal loading is 0.1% to 1%;

[0015] The carrier is activated carbon, silicon dioxide, zirconium oxide, magnesium oxide, aluminum oxide, cerium oxide, hydrotalcite or titanium dioxide;

[0016] (2) Dehydration of 5-hydroxyvaleramide to 5-hydroxyvaleronitrile:

[0017] 5-hydroxyvaleramide, water, acetonitrile, and a supported metal catalyst are added to a reactor, stirred and reacted at 40-120° C. for 0.1-6 hours to obtain 5-hydroxyvaleronitrile;

[0018] In the reactor, the concentration of 5-hydroxyvaleramide is 0.1 to 1 mol / L, the mass ratio of the supported metal catalyst to 5-hydroxyvaleramide is 0.1 to 1:1; the volume ratio of acetonitrile to water is 1:0.8 to 1.2;

[0019] The Pd loading amount of the supported metal catalyst is 0.2% to 10%; the carrier is SiO2 or ZSM-5;

[0020] (3) Amination of 5-hydroxyvaleronitrile to glutaronitrile:

[0021] 5-Hydroxyvaleronitrile solution, ammonia and nitrogen are introduced into a fixed bed reactor at 220-350° C. and loaded with a supported Ni-M / Al 2 O 3 catalyst to obtain glutaronitrile;

[0022] The mass space velocity (WHSV) of the 5-hydroxyvaleronitrile solution is 6 to 20 ml / (gcat*h), and the molar ratio of 5-hydroxyvaleronitrile: ammonia: nitrogen is 1:5:1.

[0023] The concentration of the 5-hydroxyvaleronitrile solution is 0.01 to 0.5 mol / L; the solvent is tetrahydrofuran, 1,4-dioxane or acetonitrile;

[0024] The preferred reaction temperature is 240-290° C.; the mass space velocity (WHSV) is 6-10 ml / (gcat*h); and the catalyst is reduced at 500-700° C. for 0.5-2.0 h before the reaction.

[0025] Among them, in the supported Ni-M / Al2O3 catalyst, the loading amount of Ni is 2% to 10%, and the loading amount of M is 1% to 10%; the carrier is γ-Al2O3; M = Fe, Co, Cu or Zn; the dehydrogenation catalyst is M; and the amination catalyst is Ni.

[0026] The particle size of the supported Ni-M / Al2O3 catalyst is 20-40 meshes.

[0027] The essential features of the present invention are:

[0028] The present invention uses biomass furfural as the initial raw material, undergoes furfural hydrogenolysis ring-opening reaction, 5-hydroxyvaleramide dehydration reaction, and 5-hydroxyvaleronitrile amination reaction, and ultimately obtains the target product, bio-based glutaronitrile. Its characteristics are: (1) it uses renewable biomass furfural as the raw material, which is sustainable; (2) the reaction conditions are mild, there is no pollutant emission, and it is green and inherently safe; (3) it combines the advantages of biotransformation and chemical synthesis. The overall process route for synthesizing glutaronitrile from furfural is as follows:

[0029]

[0030] The beneficial effects of the present invention are:

[0031] The present invention uses biomass as raw material instead of traditional petrochemical raw materials to open up a new route for producing glutaronitrile. It is a new process for synthesizing glutaronitrile at low cost, which has the characteristics of primary raw materials, green safety and sustainability. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the embodiments of the present invention, the drawings of the embodiments are briefly introduced below.

[0033] Figure 1 : hydrogen spectrum of furfural prepared in Example 1;

[0034] Figure 2 : The carbon spectrum of furfural prepared in Example 1;

[0035] Figure 3 : Hydrogen spectrum of 5-hydroxyvaleramide prepared in Example 1;

[0036] Figure 4 : 5-hydroxyvaleramide carbon spectrum prepared in Example 1;

[0037] Figure 5 : Hydrogen spectrum of 5-hydroxyvaleronitrile prepared in Example 5;

[0038] Figure 6 : 5-hydroxyvaleronitrile carbon spectrum prepared in Example 5;

[0039] Figure 7 : Hydrogen spectrum of glutaronitrile prepared in Example 7;

[0040] Figure 8 : Carbon spectrum of glutaronitrile prepared in Example 7; DETAILED DESCRIPTION

[0041] The present invention provides a method for preparing glutaronitrile from biomass raw materials, which mainly comprises the following steps:

[0042] (1) Furfural hydrogenolysis ring-opening reaction to produce 5-hydroxyvaleramide

[0043]

[0044] This step utilizes a supported catalyst to inhibit the formation of 2-hydroxyvaleramide (by preferentially cleaving the CO bond of the furan ring linked to the amide group) and promote the formation of 5-hydroxyvaleramide. Under the reaction system of the present invention, the raw material conversion rate is close to 100%, and the yield of 5-hydroxyfuramide is over 42%.

[0045] In conclusion, the method of the present invention has a feasible technical solution, a simple production process, low operation difficulty, and good application prospects.

[0046] The preparation method of the catalyst comprises the following steps:

[0047] The catalyst was prepared by the incipient wetness impregnation method. Weigh 0.5g of cerium oxide, take an appropriate amount of MnCl2·4H2O aqueous solution, evenly impregnate it on CeO2, ultrasonicate for 30min, impregnate for 12h, and dry it at 120℃ overnight. Then take an appropriate amount of H2PtCl6·6H2O and evenly impregnate it on Mn / CeO2, ultrasonicate for 30min, impregnate for 12h, and dry it at 120℃ overnight. The obtained solid was calcined in a muffle furnace at 500℃ for 3h with a heating rate of 5℃ / min (the content of Pt is 5wt% and the content of Mn is 2%). Before use, place the catalyst in a tube furnace and reduce it at 300℃ (nitrogen 80ml / min, hydrogen 80ml / min) for 2h. 5%Pt-2%Mn / CeO2 was obtained. (2) Dehydration of 5-hydroxyvaleramide to 5-hydroxyvaleronitrile

[0048]

[0049] This step uses 5-hydroxyvaleramide as a raw material, supported Pd / SiO2 as a catalyst, and acetonitrile as a dehydrating agent to produce 5-hydroxyvaleronitrile by dehydration in the coexistence of water and acetonitrile. The production process is simple, the operation is easy, the raw material conversion rate is close to 100%, and the yield of 5-hydroxyvaleronitrile is 86.1%.

[0050] The preparation method of the catalyst comprises the following steps:

[0051] The catalyst was prepared by the equal volume impregnation method. 0.0504 g of PdCl2 was weighed and dissolved in 4 ml of 0.05 mol / L dilute hydrochloric acid. After fully dissolved, it was ultrasonicated for 5 minutes to prepare an impregnation solution. Subsequently, 2 g of SiO2 was weighed and added to the impregnation solution. After stirring with a glass rod and ultrasonicated for 30 minutes, the catalyst was allowed to stand for 12 hours and then placed in a 120°C drying oven for 12 hours. It was then calcined at 400°C for 3 hours to obtain 0.9% Pd / SiO2. (3) Amination of 5-hydroxyvaleronitrile to glutaronitrile

[0052]

[0053] This step aims to develop a dehydrogenation amination catalyst with high selectivity and good stability, which can be used to synthesize fatty nitriles from fatty alcohols and ammonia in the absence of hydrogen, so as to be suitable for industrial application.

[0054] The preparation method of the catalyst comprises the following steps:

[0055] The Ni-M / Al2O3 catalyst (M) was prepared using a deposition-precipitation (DP) method with a loading of 6 wt%. The metal precursors included Ni(NO3)2·6H2O, Cu(NO3)2·3H2O, Co(NO3)2·6H2O, and Fe(NO3)3·9H2O. The DP method involves dropping an aqueous urea solution into a vigorously stirred γ-Al2O3 and metal precursor aqueous solution in a glass beaker. The molar ratio of Ni to M (Ni-M / Al2O3) was set to 1. The mixture was tightly sealed with plastic film and heated with stirring on a thermostilicate. The mixture was maintained at 70°C for 10 h (Cu and Ni-Cu) or at 90°C for 5 h (Ni, Ni-Co, and Ni-Fe). Note that for Cu-containing catalysts, the temperature should not exceed 70°C because dehydration of the precipitated Cu(OH)2 can form aggregated CuO. The molar ratio of urea to total metal was set to ≥100 (Cu, Ni-Cu, Ni-Fe, Ni-Co). After deposition, the colorless supernatant was removed, and the resulting solid was washed three times with deionized water (DI) and then dried under reduced pressure. The resulting powder was calcined at 500°C for 1 h and then reduced at 400°C (Cu / Al2O3) or 600°C (Ni / Al2O3 and Ni-M / Al2O3) under a flow rate of 50 mL / min H2 for 1 h.

[0056] The furfural is prepared from furfural as a raw material, including the reaction of furfural and hydroxylamine to produce furonitrile (Chemical Industry and Engineering Journal, 2023, 74(09): 3708-3715) and the hydration of furonitrile to produce furfural (Ind. Eng. Chem. Res. 2019, 58, 17319-17324).

[0057] Example 1

[0058] The substrate furfural, the catalyst 5% Pt-1% Re / CeO2 (mass ratio), and 15 mL of water were added to a 50 mL reactor. The resulting reaction solution had a furfural concentration of 0.5 mol / L. The reaction mixture was sealed and filled with hydrogen at a pressure of 1 MPa. The stirring rate was 1000 rpm, the mass ratio of 5% Pt-1% Re / CeO2 to furfural was 0.7:1, the reaction temperature was 160°C, and the reaction time was 0.5 h. The reaction product was filtered through a 0.22 micron organic filter membrane, and the raw materials and products were quantitatively analyzed using a 2489 high-performance liquid chromatography UV / Vis detector Waters e2695 separation module. Experimental results showed that under the above reaction conditions, the furfural conversion rate was 100%, and the yield of 5-hydroxyvaleramide was 32%.

[0059] Attachment Figure 1 H NMR spectrum and attached Figure 2 The NMR C spectrum is the raw material furfural, attached Figure 3 H NMR spectrum and attached Figure 4The target substance can be confirmed to be 5-hydroxyvaleramide by nuclear magnetic resonance spectroscopy.

[0060] Example 2

[0061] The substrate furfural, the catalyst 5% Pt-2% Co / CeO2 (mass ratio), and 15 mL of water were added to a 50 mL reactor. The resulting reaction solution had a furfural concentration of 0.5 mol / L. The reaction mixture was sealed and filled with hydrogen at a pressure of 0.5 MPa. The stirring rate was 1000 rpm, the mass ratio of 5% Pt-2% Co / CeO2 to furfural was 0.7:1, the reaction temperature was 160°C, and the reaction time was 0.5 h. The reaction product was filtered through a 0.22 micron organic filter membrane, and the raw materials and products were quantitatively analyzed using a 2489 high-performance liquid chromatography UV / visible detector Waters e2695 separation module. Experimental results showed that under the above reaction conditions, the furfural conversion rate was 100%, and the yield of 5-hydroxyvaleramide was 40%.

[0062] Example 3

[0063] The substrate furfural, the catalyst 5% Pt-2% Mn / CeO2 (mass ratio), and 15 mL of water were added to a 50 mL reactor. The resulting reaction solution had a furfural concentration of 0.5 mol / L. The reaction mixture was sealed and filled with hydrogen at a pressure of 0.5 MPa. The stirring rate was 1000 rpm, the mass ratio of 5% Pt-2% Mn / CeO2 to furfural was 0.5:1, the reaction temperature was 160°C, and the reaction time was 0.5 h. The reaction product was filtered through a 0.22 μm organic filter membrane and quantitatively analyzed using a 2489 HPLC UV / Vis detector with a Waters e2695 separation module. Experimental results showed that under the above reaction conditions, the furfural conversion rate was 100%, and the yield of 5-hydroxyvaleramide was 42%.

[0064] Example 4

[0065] The substrate furfural, the catalyst 5% Pt-1% Mo / CeO2 (mass ratio), and 15 mL of water were added to a 50 mL reactor. The resulting reaction solution had a furfural concentration of 0.5 mol / L. The reactor was sealed and filled with hydrogen at a pressure of 2 MPa. The stirring rate was 1000 rpm, the mass ratio of 5% Pt-1% Mo / CeO2 to furfural was 0.6:1, the reaction temperature was 160°C, and the reaction time was 0.5 h. The reaction product was filtered through a 0.22 micron organic filter membrane, and the raw materials and products were quantitatively analyzed using a 2489 high-performance liquid chromatography UV / visible detector Waters e2695 separation module. Experimental results showed that under the above reaction conditions, the furfural conversion rate was 100%, and the yield of 5-hydroxyvaleramide was 36%.

[0066] Example 5

[0067] 5-Hydroxyvaleramide (0.2g) was added to acetonitrile (10ml) and water (10ml), and then placed in a three-necked flask and stirred to fully dissolve 5-hydroxyvaleramide (5-hydroxyvaleramide concentration was 0.17mol / L), and then 0.2g of catalyst (0.9% Pd / SiO2) was added. The reaction was then stopped in a water bath at 60°C for 4h, cooled to room temperature, and the reaction solution was centrifuged and the supernatant was taken for chromatographic analysis. The product yield was determined by the internal standard method, and the internal standard was biphenyl. The raw material conversion rate was 100%. According to the quantitative calculation based on the internal standard method, the product yield was 86.1%. Figure 3 、 4 The NMR hydrogen spectrum and carbon spectrum of the raw material 5-hydroxyvaleramide; Figure 5 , 6 is the H NMR spectrum and C NMR spectrum of the product 5-hydroxyvaleronitrile.

[0068] Example 6

[0069] 5-Hydroxyvaleramide (0.2 g) was added to acetonitrile (10 ml) and water (10 ml). The mixture was then placed in a three-necked flask and stirred to fully dissolve the 5-hydroxyvaleramide (5-hydroxyvaleramide concentration was 0.17 mol / L). 0.2 g of catalyst (5% Pd / SiO2) was then added. The reaction was then stopped in a 60°C water bath for 6 h. The mixture was cooled to room temperature, centrifuged, and the supernatant analyzed by chromatography. The product yield was determined by the internal standard method using biphenyl as the internal standard. The raw material conversion was 100%. Quantitative calculation using the internal standard method yielded a product yield of 94.1%.

[0070] Example 7

[0071] 5-Hydroxyvaleronitrile (5 g) was dissolved in 1,4-dioxane (500 ml) (the concentration of the 5-hydroxyvaleronitrile solution was 0.1 mol / L). 1 g of the prepared catalyst (6% Ni-6% Cu / Al2O3 by mass) was pressed into pellets, crushed, and screened to obtain particles of 20-40 mesh. The resulting catalyst was placed in a fixed-bed reactor with an inner diameter of 6 mm. Activity was evaluated under the following conditions: a reaction temperature of 300°C, a reaction pressure of atmospheric pressure, a 5-hydroxyvaleronitrile: ammonia: nitrogen ratio of 1:5:1 (molar), and a mass space velocity (WHSV) of 5-hydroxyvaleronitrile solution of 6 ml / (gcat*h). The results were as follows: a 5-hydroxyvaleronitrile conversion of 96% and a glutaronitrile yield of 61.0%. Figure 5 、 6 The NMR hydrogen spectrum and carbon spectrum of the raw material 5-hydroxyvaleronitrile; Figure 7 , 8 is the H NMR spectrum and C NMR spectrum of the product glutaronitrile.

[0072] Example 8

[0073] 5-Hydroxyvaleronitrile (5 g) was dissolved in 1,4-dioxane (500 ml) (the concentration of the 5-hydroxyvaleronitrile solution was 0.1 mol / L). 1 gram of the prepared catalyst (6% Ni-2% Co / Al2O3 by mass) was pressed into tablets and then crushed to screen out particles of 20-40 mesh. The resulting catalyst was placed in a fixed-bed reactor with an inner diameter of 6 mm. Activity was evaluated under the following conditions: a reaction temperature of 310°C, a reaction pressure of normal pressure, a 5-hydroxyvaleronitrile:ammonia:nitrogen ratio of 1:5:1 (molar), and a mass space velocity (WHSV) of the 5-hydroxyvaleronitrile solution of 6 ml / (gcat*h). The results were as follows: a 5-hydroxyvaleronitrile conversion of 93% and a glutaronitrile yield of 52.0%.

[0074] Example 9

[0075] 5-Hydroxyvaleronitrile (5 g) was dissolved in tetrahydrofuran (500 ml) (the concentration of the 5-hydroxyvaleronitrile solution was 0.1 mol / L). 1 gram of the prepared catalyst, 6% Ni-4% Fe / Al O (mass ratio), was pelletized and then crushed to screen out particles of 20-40 mesh. The resulting catalyst was placed in a fixed-bed reactor with an inner diameter of 6 mm. Activity was evaluated under the conditions of a reaction temperature of 290° C., a reaction pressure of normal pressure, 5-hydroxyvaleronitrile:ammonia:nitrogen = 1:5:1 (molar), and a mass space velocity (WHSV) of the 5-hydroxyvaleronitrile solution = 6 ml / (gcat*h). The results were as follows: a 5-hydroxyvaleronitrile conversion of 62% and a glutaronitrile yield of 36.0%.

[0076] Example 10

[0077] 5-Hydroxyvaleronitrile (5 g) was dissolved in acetonitrile (500 ml) (the concentration of the 5-hydroxyvaleronitrile solution was 0.1 mol / L). 1 gram of the prepared catalyst (6% Ni / Al2O3 by mass) was pressed into tablets and then crushed to screen out 20-40 mesh particles. The resulting catalyst was placed in a fixed-bed reactor with an inner diameter of 6 mm. Activity was evaluated under the following conditions: a reaction temperature of 300°C, a reaction pressure of normal pressure, a 5-hydroxyvaleronitrile:ammonia:nitrogen ratio of 1:5:1 (molar), and a mass space velocity (WHSV) of the 5-hydroxyvaleronitrile solution of 6 ml / (gcat*h). The results were as follows: a 5-hydroxyvaleronitrile conversion of 76% and a glutaronitrile yield of 36.0%.

[0078] Matters not covered by the present invention are known technologies.

Claims

1. A method for synthesizing bio-based glutaronitrile from furfural, characterized in that the method comprises the following steps: (1) Furfural hydrogenolysis ring opening to produce 5-hydroxyvaleramide: Furfural, water, and a supported bimetallic catalyst are added to a reactor, which is sealed and stirred at 40-180° C. for 0.1-6 hours in a 0.1-4 MPa hydrogen atmosphere to obtain 5-hydroxyvaleramide, tetrahydrofuran furfural, and 2-hydroxyvaleramide. The furfural concentration in the reactor is 0.1 to 1 mol / L, and the mass ratio of the supported bimetallic catalyst to furfural is 0.1 to 1:

1. The supported bimetallic catalyst is composed of Pt, a transition metal and a carrier; the loading amount of the active metal Pt is 1% to 10%; the loading amount of the transition metal is 0.1% to 1%; The transition metal is Mo, Mn, Co or Re; The carrier is cerium oxide; (2) Dehydration of 5-hydroxyvaleramide to 5-hydroxyvaleronitrile: 5-hydroxyvaleramide, water, acetonitrile, and a supported metal catalyst are added to a reactor, stirred and reacted at 40-120° C. for 0.1-6 hours to obtain 5-hydroxyvaleronitrile; In the reactor, the concentration of 5-hydroxyvaleramide is 0.1 to 1 mol / L, the mass ratio of the supported metal catalyst to 5-hydroxyvaleramide is 0.1 to 1:1; the volume ratio of acetonitrile to water is 1:0.8 to 1.2; The Pd loading amount of the supported metal catalyst is 0.2% to 10%; the carrier is SiO2 or ZSM-5; (3) Amination of 5-hydroxyvaleronitrile to glutaronitrile: 5-Hydroxyvaleronitrile solution, ammonia and nitrogen are introduced into a fixed bed reactor at 220-350° C. and loaded with a supported Ni-M / Al 2 O 3 catalyst to obtain glutaronitrile; The mass space velocity (WHSV) of the 5-hydroxyvaleronitrile solution is 6-20 ml / (gcat*h), and the molar ratio of 5-hydroxyvaleronitrile: ammonia: nitrogen is 1:5:

1. The concentration of the 5-hydroxyvaleronitrile solution is 0.01 to 0.5 mol / L; the solvent is tetrahydrofuran, 1,4-dioxane or acetonitrile; Wherein, in the supported Ni-M / Al2O3 catalyst, the loading amount of Ni is 2%~10%, the loading amount of M is 1%~10%; the carrier is γ-Al2O3; M = Fe, Co, Cu or Zn.

2. The method for synthesizing bio-based glutaronitrile from furfural as claimed in claim 1, characterized in that In step (3), the reaction temperature is 240-290°C; the mass space velocity (WHSV) is 6-10 ml / (gcat*h); and the catalyst is reduced at 500-700°C for 0.5-2.0h before the reaction.

3. The method for synthesizing bio-based glutaronitrile from furfural as claimed in claim 1, characterized in that The particle size of the supported Ni-M / Al2O3 catalyst described in step (3) is 20-40 mesh.

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