A catalyst for preparing furfuryl alcohol by hydrogenation of furfural, a preparation method thereof and application thereof in preparing furfuryl alcohol by hydrogenation of furfural

Abstract

The present application provides a kind of catalyst for preparing furfuryl alcohol by furfural hydrogenation, its preparation method and its application in preparing furfuryl alcohol by furfural hydrogenation.The preparation method of the present application comprises the following steps: under stirring condition, water is added to aluminum isopropyl alcohol;After stirring reaction, filtration, washing, drying, then high temperature calcination is obtained to obtain alumina;Alumina is immersed in copper nitrate solution, impregnation is stirred, dried, calcined reduction to obtain catalyst.The catalyst of the present application is Cu-Al catalyst, the preparation method of catalyst is simple, green and environmentally friendly, and the cost is low;The obtained catalyst is applied to the preparation of furfuryl alcohol by furfural hydrogenation, so that the reaction can be carried out at lower reaction temperature and lower reaction pressure, and furfuryl alcohol can be prepared with high conversion rate and high selectivity, the conversion rate of furfural can reach 100%, and the selectivity of furfuryl alcohol can reach 100%.

Description

Technical Field

[0001] This invention specifically relates to a catalyst for the hydrogenation of furfural to furfuryl alcohol, its preparation method, and its application in the hydrogenation of furfural to furfuryl alcohol, belonging to the fields of catalyst preparation and furfuryl alcohol production. Background Technology

[0002] The increasing depletion of fossil fuels and stringent environmental protection requirements have prompted the comprehensive utilization of renewable biomass resources. Furfural, primarily derived from abundant biomass, readily undergoes catalytic hydrogenation due to its reactive aldehyde group and furan ring, producing various products such as furfuryl alcohol. Furfuryl alcohol is an important chemical raw material, mainly used in the production of various properties of furan resins, furfuryl urea-formaldehyde resins, phenolic resins, and other resins, as well as functional materials such as plastics, pigments, fibers, and pharmaceuticals. With the continuous development of industries such as machinery, construction, automobiles, and pharmaceuticals, market demand is expanding. Therefore, finding a method for the efficient and selective hydrogenation of furfural to prepare furfuryl alcohol is of great significance.

[0003] Currently, the industrial production of furfural to furfuryl alcohol in my country mainly relies on liquid-phase catalytic hydrogenation, using Cu-Cr catalysts at a reaction temperature of 180℃ and a pressure of 7-10 MPa. The required catalysts are primarily imported. This method involves high reaction temperatures and pressures, demanding reaction conditions, and high costs. Therefore, there is an urgent need to develop a catalyst and method that can achieve efficient production of furfuryl alcohol from furfural under mild reaction conditions.

[0004] Chinese patent document CN107952444A discloses a Cu-Cr-Zr catalyst and a method for preparing furfuryl alcohol by hydrogenation of furfural. This method uses a Cu-Cr-Zr catalyst at 200℃ and 7.5 MPa hydrogen pressure to prepare furfuryl alcohol, achieving a furfural conversion rate of 100% and a furfuryl alcohol selectivity >99%. Chinese patent document CN110871085A discloses a Cu-Cr-Al catalyst and a method for preparing furfuryl alcohol by hydrogenation of furfural. This method uses a Cu-Cr-Al catalyst at 170–240℃ and 6.0–8.0 MPa hydrogen pressure to prepare furfuryl alcohol, achieving a furfural conversion rate >98% and a furfuryl alcohol selectivity >95%. The above methods involve high reaction temperatures and pressures, increasing costs; the catalysts used contain Cr, which is harmful to the environment, thus limiting their application; further improvements are needed in furfural conversion and furfuryl alcohol selectivity.

[0005] Chinese patent document CN110734416A discloses a Ni-based catalyst and a method for preparing furfuryl alcohol by hydrogenation of furfural. This method uses a Ni-based catalyst to prepare furfuryl alcohol at 160–170°C and under 2.5–3 MPa hydrogen conditions, achieving a furfural conversion rate of 100% and a furfuryl alcohol selectivity >93%. While the reaction conditions are relatively mild, the reaction temperature remains high, and the furfuryl alcohol selectivity needs further improvement.

[0006] Therefore, there is an urgent need to develop a highly efficient catalyst suitable for the selective hydrogenation of furfural to furfuryl alcohol, so as to prepare furfuryl alcohol with high conversion and high selectivity at lower reaction temperatures and lower reaction pressures. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a catalyst for the hydrogenation of furfural to furfuryl alcohol, its preparation method, and its application in the hydrogenation of furfural to furfuryl alcohol. The catalyst of this invention is a Cu-Al catalyst, and its preparation method is simple, environmentally friendly, and low-cost. When applied to the hydrogenation of furfural to furfuryl alcohol, the resulting catalyst enables the reaction to achieve high conversion and high selectivity of furfuryl alcohol at relatively low reaction temperatures and pressures, with furfural conversion reaching 100% and furfuryl alcohol selectivity reaching 100%.

[0008] The technical solution of the present invention is as follows:

[0009] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol includes the following steps:

[0010] (1) Water was added to aluminum isopropoxide under stirring conditions; after stirring and reaction, the mixture was filtered, washed, dried, and then calcined at high temperature to obtain aluminum oxide.

[0011] (2) The catalyst is obtained by immersing alumina in copper nitrate solution, stirring and impregnating, drying and calcining.

[0012] According to a preferred embodiment of the present invention, in step (1), the temperature of the water is 60-100°C; the temperature of the aluminum isopropoxide is 20-100°C; the aluminum isopropoxide is a solid; boiling water is rapidly added to the solid aluminum isopropoxide to carry out the reaction. Preferably, the temperature of the water is 90-100°C; the temperature of the aluminum isopropoxide is 20-100°C. Most preferably, the temperature of the water is 100°C; the temperature of the aluminum isopropoxide is 100°C.

[0013] According to a preferred embodiment of the present invention, in step (1), the mass ratio of aluminum isopropoxide to boiling water is 1:2-16, preferably 3:16.

[0014] According to a preferred embodiment of the present invention, in step (1), the stirring reaction temperature is 60-100°C, and the stirring reaction time is 2-8 hours. More preferably, the stirring reaction temperature is 90-100°C. Most preferably, the stirring reaction temperature is 100°C.

[0015] According to a preferred embodiment of the present invention, in step (1), the high-temperature calcination temperature is 300-700℃, the high-temperature calcination time is 1-3h, and the high-temperature calcination atmosphere is air. Preferably, the high-temperature calcination temperature is 400-700℃. Most preferably, the high-temperature calcination temperature is 400℃.

[0016] According to a preferred embodiment of the present invention, in step (2), the copper nitrate solution is a methanol solution of copper nitrate or an aqueous solution of copper nitrate; the mass concentration of the copper nitrate solution is 0.001-0.1 g / mL. Preferably, the copper nitrate solution is a methanol solution of copper nitrate.

[0017] According to a preferred embodiment of the present invention, in step (2), the mass of copper in copper nitrate is 5%-40% of the mass of aluminum oxide. Preferably, the mass of copper in copper nitrate is 10%-30% of the mass of aluminum oxide.

[0018] According to a preferred embodiment of the present invention, in step (2), the stirring and impregnation temperature is room temperature, and the stirring and impregnation time is 5-10 hours.

[0019] According to a preferred embodiment of the present invention, in step (2), the calcination reduction method is as follows: calcination at 300–700°C for 2–6 hours in an air atmosphere; followed by reduction at 200–500°C for 1–4 hours in a reducing atmosphere. Preferably, the calcination reduction method is as follows: calcination at 400°C for 2 hours in an air atmosphere; followed by reduction at 300–400°C for 2 hours in a reducing atmosphere.

[0020] Preferably, the reducing atmosphere is one of hydrogen, a mixture of hydrogen and argon, a mixture of hydrogen and nitrogen, or a mixture of hydrogen and helium.

[0021] A catalyst for the hydrogenation of furfural to furfuryl alcohol is prepared by the above method.

[0022] According to a preferred embodiment of the present invention, the catalyst is an alumina-supported copper element; the copper loading in the catalyst is 5-40 wt%. Preferably, the copper loading in the catalyst is 10 wt%-30 wt%.

[0023] The aforementioned catalyst is used in the hydrogenation of furfural to prepare furfuryl alcohol.

[0024] According to a preferred embodiment of the present invention, the application method includes the steps of: thoroughly mixing furfural, catalyst, and solvent, and reacting them under hydrogen conditions of 0.5–3 MPa and at 80–120 °C to obtain furfuryl alcohol.

[0025] Preferably, the solvent is one of isopropanol, water or ethanol; the mass ratio of furfural to solvent volume is 10-70 mg / mL.

[0026] Preferably, the mass of the catalyst is 5-30% of the mass of furfural.

[0027] Preferably, the reaction temperature is 90–120°C, the reaction time is 2–12 h, and the hydrogen pressure is 1–3 MPa.

[0028] The technical features and beneficial effects of this invention are as follows:

[0029] 1. This invention employs a specific preparation method to obtain small-particle-size, highly active alumina through rapid hydrolysis and calcination. Copper nitrate is then impregnated onto the alumina surface, followed by calcination and reduction to obtain the catalyst. The catalyst preparation method of this invention is simple, environmentally friendly, and cost-effective. The specific preparation method of this invention yields alumina with a specific microstructure, which allows copper ions to be better and more fully adsorbed onto the alumina surface and to exert complex interactions during the calcination and reduction process, ultimately producing the Cu-Al₂O₃ catalyst of this invention.

[0030] 2. In the preparation process of alumina in this invention, the hydrolysis temperature of aluminum isopropoxide and the amount of water are crucial. Both factors are used to control the hydrolysis rate. A slow hydrolysis rate will cause alumina grains to grow, resulting in a decrease in the activity of the resulting catalyst in the hydrogenation of furfural. By controlling the hydrolysis temperature of aluminum isopropoxide and the amount of water, rapid hydrolysis is achieved, generating small-grained, highly active alumina that exposes more surface defects, allowing for better loading of copper, promoting furfural adsorption and activation, and improving the hydrogenation activity of furfural.

[0031] 3. In the catalyst preparation method of this invention, the temperature of water, the temperature of aluminum isopropoxide, the hydrolysis reaction temperature, the mass ratio of aluminum isopropoxide to water, the calcination temperature, the copper loading in the catalyst, the reduction temperature and atmosphere, and the type of solvent used in the copper nitrate solution all have a certain influence on the catalytic performance of the obtained catalyst. Inappropriate conditions will lead to a decrease in catalytic activity. Furthermore, using different methods to prepare the alumina support will also reduce the catalytic performance of the obtained catalyst. The catalyst preparation method of this invention, as a whole, requires the combined action of all steps and conditions to achieve the excellent effects of this invention.

[0032] 4. The catalyst of this invention is applied to the catalytic hydrogenation of furfural to prepare furfuryl alcohol. The reaction temperature, pressure, and feedstock dosage all have a certain impact on the conversion rate and selectivity; unsuitable conditions will lead to a decrease in both conversion rate and selectivity. The application method of this invention, as a whole, requires the combined action of all steps and conditions to achieve its excellent effects.

[0033] 5. The catalyst of this invention, when applied to the catalytic hydrogenation of furfural to prepare furfuryl alcohol, can significantly reduce the reaction temperature and hydrogen pressure, thereby increasing the yield of furfuryl alcohol. This results in a reaction exhibiting high low-temperature reactivity, enabling the preparation of furfuryl alcohol with high conversion and high selectivity at lower reaction temperatures and pressures. The conversion rate of furfural can reach 100%, the selectivity of furfuryl alcohol can reach 100%, and the yield and purity of furfuryl alcohol can reach 100%, which is beneficial for industrial application. Attached Figure Description

[0034] Figure 1This is a scanning electron microscope image of the alumina Al-1 prepared in Example 1. Detailed Implementation

[0035] The present invention will be further described below with reference to embodiments. However, the present invention is not limited to these embodiments.

[0036] Unless otherwise specified, all reagents or materials used in the examples are commercially available; and all methods used are existing methods unless otherwise specified.

[0037] Example 1

[0038] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol includes the following steps:

[0039] (1) Preparation of aluminum oxide Al-1:

[0040] Under stirring conditions, boiling water at 100°C was rapidly added to solid aluminum isopropoxide at 100°C, with a mass ratio of aluminum isopropoxide to boiling water of 3:16. After complete addition, the mixture was stirred continuously at 100°C for 4 hours, then filtered, washed, dried, and calcined in air at 400°C for 2 hours to obtain alumina, denoted as Al-1.

[0041] The scanning electron microscope image of the prepared alumina Al-1 is shown below. Figure 1 As shown.

[0042] (2) Prepare a 10wt% copper-supported catalyst.

[0043] 0.58 g of copper nitrate was dissolved in 70 mL of methanol to prepare a solution, and 2 g of alumina (Al₁₀) was added. The solution was stirred and impregnated at room temperature for 8 h. The solution was then dried to obtain a solid sample. This solid sample was calcined at 400 °C for 2 h in air, and then reduced at 400 °C for 2 h under hydrogen / argon atmosphere (40 / 40 mL / min) to obtain the catalyst.

[0044] Example 2

[0045] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol is described in Example 1, except that: in step (2), the reduction temperature is 200°C; other steps and conditions are the same as in Example 1.

[0046] Example 3

[0047] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol is described in Example 1, except that: in step (2), the reduction temperature is 300°C; other steps and conditions are the same as in Example 1.

[0048] Example 4

[0049] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol is described in Example 1, except that: in step (2), the reduction temperature is 500℃; other steps and conditions are the same as in Example 1.

[0050] Example 5

[0051] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol is described in Example 1, except that: in step (1), the calcination temperature is 300°C; other steps and conditions are the same as in Example 1.

[0052] Example 6

[0053] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol is described in Example 1, except that: in step (1), the calcination temperature is 500°C; other steps and conditions are the same as in Example 1.

[0054] Example 7

[0055] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol is described in Example 1, except that: in step (1), the calcination temperature is 700°C; other steps and conditions are the same as in Example 1.

[0056] Example 8

[0057] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol includes the following steps:

[0058] (1) Preparation of aluminum oxide Al-2:

[0059] Under stirring conditions, water at 90°C was rapidly added to aluminum isopropoxide solid at 90°C, with a mass ratio of aluminum isopropoxide to water of 3:16. After complete addition, the mixture was stirred continuously at 90°C for 4 hours, then filtered, washed, dried, and calcined in air at 400°C for 2 hours to obtain alumina, denoted as Al-2.

[0060] (2) Preparation of 10wt% copper-supported catalyst. The preparation method is the same as in Example 1.

[0061] Example 9

[0062] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol includes the following steps:

[0063] (1) Preparation of aluminum oxide Al-3:

[0064] Under stirring conditions, water at 80°C was rapidly added to aluminum isopropoxide solid at 80°C, with a mass ratio of aluminum isopropoxide to water of 3:16. After complete addition, the mixture was stirred continuously at 80°C for 4 hours, then filtered, washed, dried, and calcined in air at 400°C for 2 hours to obtain alumina, denoted as Al-3.

[0065] (2) Preparation of 10wt% copper-supported catalyst. The preparation method is the same as in Example 1.

[0066] Example 10

[0067] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol includes the following steps:

[0068] (1) Preparation of aluminum oxide Al-4:

[0069] Under stirring conditions, water at 60°C was rapidly added to aluminum isopropoxide solid at 60°C, with a mass ratio of aluminum isopropoxide to water of 3:16. After complete addition, the mixture was stirred continuously at 60°C for 4 hours, then filtered, washed, dried, and calcined in air at 400°C for 2 hours to obtain alumina, denoted as Al-4.

[0070] (2) Preparation of 10wt% copper-supported catalyst. The preparation method is the same as in Example 1.

[0071] Example 11

[0072] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol includes the following steps:

[0073] (1) Preparation of aluminum oxide Al-5:

[0074] Under stirring conditions, boiling water at 100°C was rapidly added to solid aluminum isopropoxide at room temperature, with a mass ratio of aluminum isopropoxide to water of 3:16. After complete addition, the mixture was stirred continuously at 100°C for 4 hours, then filtered, washed, dried, and calcined in air at 400°C for 2 hours to obtain alumina, denoted as Al-5.

[0075] (2) Preparation of 10wt% copper-supported catalyst. The preparation method is the same as in Example 1.

[0076] Example 12

[0077] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol includes the following steps:

[0078] (1) Preparation of aluminum oxide Al-6:

[0079] Under stirring conditions, boiling water at 100°C was rapidly added to solid aluminum isopropoxide at 100°C, with a mass ratio of aluminum isopropoxide to water of 1:16. After complete addition, the mixture was stirred continuously at 100°C for 4 hours, then filtered, washed, dried, and calcined in air at 400°C for 2 hours to obtain alumina, denoted as Al-6.

[0080] (2) Preparation of 10wt% copper-supported catalyst. The preparation method is the same as in Example 1.

[0081] Example 13

[0082] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol includes the following steps:

[0083] (1) The preparation of aluminum oxide Al-1 is the same as in Example 1;

[0084] (2) Prepare a 30wt% copper-supported catalyst.

[0085] 1.77 g of copper nitrate was dissolved in 70 mL of methanol to prepare a solution, and 2 g of alumina (Al₁₀) was added. The solution was stirred and impregnated at room temperature for 8 h. The solution was then dried to obtain a solid sample. This solid sample was calcined at 400 °C for 2 h in air, and then reduced at 400 °C for 2 h under hydrogen / argon atmosphere (40 / 40 mL / min) to obtain the catalyst.

[0086] Example 14

[0087] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol includes the following steps:

[0088] (1) The preparation of aluminum oxide Al-1 is the same as in Example 1;

[0089] (2) Prepare a 5wt% copper-supported catalyst.

[0090] 0.3 g of copper nitrate was dissolved in 70 mL of methanol to prepare a solution, and 2 g of alumina (Al₁₀) was added. The solution was stirred and impregnated at room temperature for 8 h. The solution was then dried to obtain a solid sample. This solid sample was calcined at 400 °C for 2 h in air, and then reduced at 400 °C for 2 h under hydrogen / argon atmosphere (40 / 40 mL / min) to obtain the catalyst.

[0091] Example 15

[0092] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol is as described in Example 1, except that in step (2), methanol is replaced with water; the other steps and conditions are the same as in Example 1.

[0093] Example 16

[0094] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol is described in Example 1, except that in step (2), the reducing atmosphere is hydrogen / nitrogen (40 / 40 mL / min); other steps and conditions are the same as in Example 1.

[0095] Example 17

[0096] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol is as described in Example 1, except that in step (2), the reducing atmosphere is hydrogen (80 mL / min); the other steps and conditions are the same as in Example 1.

[0097] Comparative Example 1

[0098] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol includes the following steps:

[0099] (1) Preparation of aluminum oxide Al-7:

[0100] Pour 80g of water into a round-bottom beaker and heat it in a water bath at 60℃. Add 15g of aluminum isopropoxide (solid) to the round-bottom flask and stir magnetically for 4 hours. Filter, wash, and dry the mixture. Then calcine it in air at 400℃ for 2 hours to obtain aluminum oxide, denoted as Al-7.

[0101] (2) Preparation of 10wt% copper-supported catalyst. The preparation method is the same as in Example 1.

[0102] Comparative Example 2

[0103] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol includes the following steps:

[0104] (1) Preparation of aluminum oxide Al-8:

[0105] 50g of aluminum isopropoxide and 100ml of isopropanol were placed in a round-bottom flask and heated to 80°C. The mixture was stirred until the aluminum isopropoxide dissolved. A mixture of 10g of water and 30g of isopropanol was added to the round-bottom flask. The mixture was stirred at 80°C for 2 hours to hydrolyze the solution. The solution was then filtered, washed, and dried. Finally, it was calcined in air at 400°C for 2 hours to obtain aluminum oxide, denoted as Al-8.

[0106] (2) Preparation of 10wt% copper-supported catalyst. The preparation method is the same as in Example 1.

[0107] Comparative Example 3

[0108] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol includes the following steps:

[0109] (1) Preparation of alumina Al-9:

[0110] Carbon separation method: Carbon dioxide is passed into a 2 mol / L sodium aluminate aqueous solution at 60℃ with a flow rate of 40 ml / min. The carbon separation reaction is carried out with stirring, and the reaction is stopped when the pH reaches 12. Subsequently, the mixture is aged in a constant temperature water bath at 80℃ for 4 hours, filtered, washed, and dried. Then, it is calcined in air at 400℃ for 2 hours to obtain alumina, denoted as Al-9.

[0111] (2) Preparation of 10wt% copper-supported catalyst. The preparation method is the same as in Example 1.

[0112] Comparative Example 4

[0113] A method for preparing a catalyst for the hydrogenation of furfural to furfuryl alcohol includes the following steps:

[0114] (1) Preparation of alumina Al-10:

[0115] Neutralization method: Glacial acetic acid is added dropwise to a 2 mol / L sodium aluminate aqueous solution to neutralize the solution until the pH is close to neutral. Then, a 2 mol / L sodium aluminate solution is slowly added dropwise to the solution, and the mixture is stirred at room temperature for 6 hours. The solution is then filtered, washed, and dried, and finally calcined in air at 400°C for 2 hours to obtain alumina, denoted as Al-10.

[0116] (2) Preparation of 10wt% copper-supported catalyst. The preparation method is the same as in Example 1.

[0117] Application Example 1

[0118] The catalysts prepared in Examples 1, 8-12, and Comparative Examples 1-2 were applied to the hydrogenation of furfural to prepare furfuryl alcohol, and the application methods are as follows:

[0119] 100 mg of catalyst, 500 mg of furfural, and 30 mL of isopropanol were added to a batch reactor and mixed thoroughly. The mixture was then reacted at 90 °C for 3 h under 1 MPa hydrogen atmosphere to obtain furfuryl alcohol. The reaction solution was filtered and its composition was determined by gas chromatography.

[0120] The conversion rate and selectivity test results are shown in Table 1.

[0121] Table 1 Results of the catalytic reaction

[0122]

[0123]

[0124] As shown in Table 1, the catalyst prepared by Al-1 has the highest activity, and the catalyst prepared by the specific method of this invention has better performance than other methods.

[0125] Application Example 2

[0126] The catalyst prepared in Example 1 was used to prepare furfural alcohol by hydrogenation. The application method was the same as described in Application Example 1, except that the reaction temperatures were 80, 100, 110 and 120 °C respectively; other steps and conditions were the same as in Application Example 1.

[0127] The test results are shown in Table 2.

[0128] Table 2. Results of catalytic reactions at different reaction temperatures.

[0129]

[0130] Application Example 3

[0131] The catalyst prepared in Example 1 was used to prepare furfural alcohol by hydrogenation. The application method was the same as described in Application Example 1, except that the hydrogen pressure was 0.5, 2, and 3 MPa respectively; other steps and conditions were the same as in Application Example 1.

[0132] The test results are shown in Table 3.

[0133] Table 3. Catalytic reaction results under different reaction pressures

[0134]

[0135] Application Example 4

[0136] The catalysts prepared in Examples 1-4 were applied to the hydrogenation of furfural to prepare furfuryl alcohol, and the application methods are as follows:

[0137] 100 mg of catalyst, 500 mg of furfural, and 30 mL of isopropanol were added to a batch reactor and mixed thoroughly. The mixture was then reacted at 100 °C for 3 h under 1 MPa hydrogen atmosphere to obtain furfuryl alcohol. The reaction solution was filtered and its composition was determined by gas chromatography.

[0138] The conversion rate and selectivity test results are shown in Table 4.

[0139] Table 4. Results of catalytic reactions at different reduction temperatures

[0140]

[0141] Application Example 5

[0142] The catalysts prepared in Examples 1 and 5-7 were applied to the hydrogenation of furfural to prepare furfuryl alcohol, and the application method is as follows:

[0143] 100 mg of catalyst, 500 mg of furfural, and 30 mL of isopropanol were added to a batch reactor and mixed thoroughly. The mixture was then reacted at 100 °C for 3 h under 1 MPa hydrogen atmosphere to obtain furfuryl alcohol. The reaction solution was filtered and its composition was determined by gas chromatography.

[0144] The conversion rate and selectivity test results are shown in Table 5.

[0145] Table 5. Catalytic reaction results at different alumina calcination temperatures.

[0146]

[0147] Application Example 6

[0148] The catalysts prepared in Examples 1, 16-17, and Comparative Examples 3-4 were applied to the hydrogenation of furfural to prepare furfuryl alcohol, and the application methods are as follows:

[0149] 100 mg of catalyst, 500 mg of furfural, and 30 mL of isopropanol were added to a batch reactor and mixed thoroughly. The mixture was then reacted at 100 °C for 3 h under 1 MPa hydrogen atmosphere to obtain furfuryl alcohol. The reaction solution was filtered and its composition was determined by gas chromatography.

[0150] The conversion rate and selectivity test results are shown in Table 6.

[0151] Table 6. Catalytic reaction results of catalysts obtained under different preparation conditions

[0152]

[0153] Application Example 7

[0154] The catalysts prepared in Examples 1 and 13-15 were applied to the hydrogenation of furfural to prepare furfuryl alcohol, and the application method is as follows:

[0155] 100 mg of catalyst, 500 mg of furfural, and 30 mL of isopropanol were added to a batch reactor and mixed thoroughly. The mixture was then reacted at 90 °C for 3 h under 1 MPa hydrogen atmosphere to obtain furfuryl alcohol. The reaction solution was filtered and its composition was determined by gas chromatography.

[0156] The conversion rate and selectivity test results are shown in Table 7.

[0157] Table 7 Catalytic reaction results of catalysts obtained under different preparation conditions

[0158]

[0159] Application Example 8

[0160] The catalyst prepared in Example 1 was applied to the hydrogenation of furfural to prepare furfuryl alcohol, and the application method is as follows:

[0161] 100 mg of catalyst, 2000 mg of furfural, and 30 mL of isopropanol were added to a batch reactor and mixed thoroughly. The mixture was then reacted at 100 °C for 12 h under 1 MPa hydrogen atmosphere to obtain furfuryl alcohol. The reaction solution was filtered and its composition was determined by gas chromatography.

[0162] Furfural conversion rate 100%, furfuryl alcohol selectivity 100%.

[0163] Application Example 9

[0164] The catalyst prepared in Example 1 was applied to the hydrogenation of furfural to prepare furfuryl alcohol, and the application method is as follows:

[0165] 100 mg of catalyst, 2000 mg of furfural, and 30 mL of isopropanol were added to a batch reactor and mixed thoroughly. The mixture was then reacted at 90 °C for 3 h under 1 MPa hydrogen atmosphere to obtain furfuryl alcohol. The reaction solution was filtered and its composition was determined by gas chromatography.

[0166] The furfural conversion rate was 11%, and the furfuryl alcohol selectivity was 100%.

[0167] Application Example 10

[0168] The catalyst prepared in Example 1 was applied to the hydrogenation of furfural to prepare furfuryl alcohol, and the application method is as follows:

[0169] 100 mg of catalyst, 500 mg of furfural, and 30 mL of isopropanol were added to a batch reactor and mixed thoroughly. The mixture was then reacted at 90 °C for 5 h under 1 MPa hydrogen atmosphere to obtain furfuryl alcohol. The reaction solution was filtered and its composition was determined by gas chromatography.

[0170] Furfural conversion rate 100%, furfuryl alcohol selectivity 100%.

[0171] Application Example 11

[0172] The catalyst prepared in Example 1 was applied to the hydrogenation of furfural to prepare furfuryl alcohol, and the application method is as follows:

[0173] 100 mg of catalyst, 500 mg of furfural, and 30 mL of isopropanol were added to a batch reactor and mixed thoroughly. The mixture was then reacted at 90 °C for 6 h under 1 MPa hydrogen atmosphere to obtain furfuryl alcohol. The reaction solution was filtered and its composition was determined by gas chromatography.

[0174] Furfural conversion rate 100%, furfuryl alcohol selectivity 100%.

Claims

1. An application of a catalyst for the hydrogenation of furfural to prepare furfuryl alcohol, characterized in that, The method for preparing furfuryl alcohol by hydrogenation of furfural includes the following steps: thoroughly mixing furfural, catalyst, and solvent, and reacting under 1 MPa hydrogen atmosphere at 90–120 °C to obtain furfuryl alcohol. The solvent is isopropanol; the mass-to-volume ratio of furfural to solvent is 10-70 mg / mL; the mass of the catalyst is 20% of the mass of furfural; the reaction time is 3-6 h; the catalyst is copper supported on an alumina carrier; the copper loading in the catalyst is 10 wt%-30 wt%. The method for preparing the catalyst for the hydrogenation of furfural to furfuryl alcohol includes the following steps: (1) Add water to aluminum isopropoxide under stirring conditions; After stirring and reacting, filtering, washing, drying, and then calcining at high temperature, alumina is obtained. The temperature of the water was 100℃; the temperature of the aluminum isopropoxide was 100℃; the aluminum isopropoxide was a solid; boiling water was rapidly added to the solid aluminum isopropoxide to carry out the reaction; the mass ratio of aluminum isopropoxide to boiling water was 3:16; the stirring reaction temperature was 100℃; the high-temperature calcination temperature was 400℃; the high-temperature calcination time was 2h; and the high-temperature calcination atmosphere was air. (2) The catalyst is obtained by immersing aluminum oxide in copper nitrate solution, stirring, drying, calcining and reducing; the copper nitrate solution is a methanol solution of copper nitrate; the mass of copper element in copper nitrate is 10%-30% of the mass of aluminum oxide; the calcination and reduction method is as follows: calcination at 400℃ for 2h in air atmosphere; then reduction at 300-400℃ for 2h in reducing atmosphere; the reducing atmosphere is a mixed atmosphere of hydrogen and nitrogen.

2. The application of the catalyst for the hydrogenation of furfural to furfuryl alcohol according to claim 1, characterized in that, Step (2) includes one or more of the following conditions: i. The mass concentration of the copper nitrate solution is 0.001-0.1 g / mL; ii. The stirring and impregnation temperature is room temperature, and the stirring and impregnation time is 5-10 hours.

Images