Supported catalyst for preparing furfuryl alcohol through liquid-phase hydrogenation of furfural as well as preparation method and application of supported catalyst

Abstract

The invention provides a supported catalyst for preparing furfuryl alcohol by liquid-phase hydrogenation of furfural as well as a preparation method and application of the supported catalyst. The catalyst is formed by loading copper metal nanoparticles on the surface of an Al2O3 carrier or a composite Al2O3 carrier, wherein the composite Al2O3 carrier is ZrO2 (at) Al2O3, CeO2 (at) Al2O3 or TiO2 (at) Al2O3. The catalyst disclosed by the invention is simple in preparation process, environment-friendly and non-toxic, and has the characteristics of excellent catalytic activity and recyclability. Under the conditions of low temperature and pressure, high conversion rate and high selectivity preparation of furfuryl alcohol from furfural can be realized, and the method has a good industrial application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of furfuryl alcohol production and catalysis, and specifically relates to a supported catalyst for preparing furfuryl alcohol by liquid-phase hydrogenation of furfural, and a preparation method and application thereof. Background Art

[0002] The depletion of fossil fuel resources and the worsening of environmental problems are becoming global concerns. In recent years, the utilization of biomass has received widespread attention in the field of sustainable and green chemistry, and lignocellulosic biomass is one of them. Furfural is a potential biofuel and chemical platform that can be obtained by acid-catalyzed hydrolysis and dehydration of pentoses, which are derived from hemicellulose in lignocellulosic biomass; at the same time, the multiple functional groups in furfural make it active in generating a variety of derivatives through hydrogenation, oxidation, hydrogenolysis or decarbonylation reactions, such as furfuryl alcohol, maleic anhydride, 2-methylfuran, tetrahydrofuroyl, furan, etc. Furfural derivatives are widely used in medicine, pesticides, synthetic plastics and other fields, and are considered to be one of the most promising raw materials for the sustainable production of fuels and chemicals in the 21st century.

[0003] Furfuryl alcohol is one of the most common products in the hydrogenation of furfural. About 65% of the furfural produced each year in the world is converted into furfuryl alcohol. Furfuryl alcohol can be further converted into biofuel molecules, resins, synthetic fibers and some fine chemical products, such as vitamin C, lysine, etc. At present, furfuryl alcohol is mainly used in the production of resins, which have excellent chemical stability, heat resistance and mechanical strength, and show good corrosion resistance and solvent resistance. Therefore, the research on the selective hydrogenation of furfural to prepare furfuryl alcohol has received widespread attention from academia and industry. However, there are still some bottlenecks that hinder the industrial application of these reactions.

[0004] Chinese patent document CN107952444A discloses a catalyst in which copper oxide is dispersed on chromium trioxide by ball milling, which can be used to catalyze the hydrogenation of furfural to prepare furfuryl alcohol. The catalyst reacts at a reaction temperature of 180-200°C and a pressure of 5-8 MPaH 2 , achieving efficient hydrogenation of furfural to produce furfuryl alcohol. The harsh reaction conditions of the catalyst mean high requirements for reaction equipment and increased industrial costs, and also increase the danger of operation. In addition, the chromium trioxide used contains chromium elements that are harmful to the environment, which is not conducive to environmental protection.

[0005] Chinese patent document CN115974820A discloses the catalyst Pt / @FeO X / SBA-15 catalyzes the hydrogenation of furfural to furfuryl alcohol, and can achieve 100% conversion rate and 100% selectivity of furfural at 60°C for 3 hours; Patent CN116673022A loads Pt on montmorillonite, and can also convert furfural into furfuryl alcohol under mild conditions. However, the preparation process of this catalyst requires the use of precious metals such as Pt, resulting in high costs, which limits its promotion in industrial applications.

[0006] Chinese patent document CN109529912A discloses a Cu / @CeO 2 / SBA-15 catalyst. The catalyst is prepared by coating CeO on the surface of SBA-15 molecular sieve. 2 The film layer was loaded with Cu by impregnation. At 120℃ and 1MPa H 2 Under the same conditions, the catalyst can achieve a furfural conversion rate of 97.9% and a furfuryl alcohol selectivity of 97.4%. Despite the excellent performance, the reaction conditions are high, and there is still room for further improvement in catalytic activity and selectivity. Summary of the invention

[0007] In view of the deficiencies of the prior art, the present invention provides a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural, and a preparation method and application thereof. The catalyst has a simple preparation process, is environmentally friendly and non-toxic, has excellent catalytic activity and can be recycled. Under relatively low temperature and pressure conditions, high conversion rate of furfural and high selectivity for preparing furfuryl alcohol can be achieved, and the catalyst has good industrial application prospects.

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

[0009] A supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural, the catalyst being Al 2 O 3 Support or composite Al 2 O 3 The surface of the carrier is loaded with copper metal nanoparticles; wherein the composite Al 2 O 3 The carrier is ZrO 2 @Al 2 O 3 、CeO 2 @Al 2 O 3 or TiO 2 @Al 2 O 3 .

[0010] According to the preferred embodiment of the present invention, the composite Al 2 O 3 In the carrier, ZrO 2 、CeO 2 or TiO 2 The mass is Al2 O 3 The mass content of the copper element in the catalyst is 1wt%-15wt%; the mass content of the copper element in the catalyst is 5%-20%.

[0011] According to the preferred embodiment of the present invention, Al 2 O 3 Support or composite Al 2 O 3 The specific surface area of ​​the carrier is 300-450m 2 / g, the particle size of copper metal nanoparticles is 4.2nm-10nm. The particle size of copper metal nanoparticles is as low as 4.2nm, ensuring excellent dispersibility and catalytic performance.

[0012] The method for preparing the supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural comprises the steps of:

[0013] (1) Add zirconium nitrate, cerium nitrate or tetrabutyl titanate to the isopropanol solution of aluminum isopropoxide, mix thoroughly, add the hydrolyzate, react, centrifuge, dry, and calcine to obtain a composite Al 2 O 3 Carrier;

[0014] Alternatively, the isopropanol solution of aluminum isopropoxide and the hydrolyzate are mixed evenly, reacted, and then centrifuged, dried, and calcined to obtain Al 2 O 3 Carrier;

[0015] (2) Composite Al 2 O 3 Support or Al 2 O 3 The carrier is immersed in a copper nitrate solution, and after reaction, solid-liquid separation, drying, calcination and reduction, a supported catalyst for preparing furfuryl alcohol by liquid-phase hydrogenation of furfural is obtained.

[0016] Preferably according to the present invention, in step (1), the concentration of the isopropanol solution of aluminum isopropoxide is 1-30 g:100 mL.

[0017] Preferably, according to the present invention, in step (1), the method for preparing the isopropanol solution of aluminum isopropoxide comprises the steps of: adding aluminum isopropoxide to isopropanol, stirring at 40-90° C. for 1-3 hours, to obtain the isopropanol solution of aluminum isopropoxide.

[0018] According to the preferred embodiment of the present invention, in step (1), the amount of zirconium nitrate, cerium nitrate or tetrabutyl titanate is such that the composite Al 2 O 3 ZrO in carrier 2 、CeO 2 or TiO 2 The mass is Al 2 O3 1wt%-15wt% of mass.

[0019] Preferably, in step (1), the pH of the hydrolyzate is 3-12, preferably 7-12, and most preferably 10; the hydrolyzate consists of water, isopropanol and a pH adjuster, wherein the pH adjuster is 20-30% by mass of ammonia water or 0.1-2% by mass of a nitric acid aqueous solution; in the hydrolyzate, the mass ratio of water to isopropanol is 1:1-7; the molar ratio of aluminum isopropoxide to water in the hydrolyzate is 1:2-15; and the hydrolyzate addition rate is 0.2-50 mL / min.

[0020] Preferably according to the present invention, in step (1), the reaction temperature is 40-90° C., the reaction time is 1-12 h, and the reaction is carried out under stirring conditions.

[0021] Preferably according to the present invention, in step (1), the drying temperature is 40-90° C. and the drying time is 1-12 h.

[0022] According to the preferred embodiment of the present invention, in step (1), the calcination temperature is 400-700°C, the calcination time is 1-3 hours, and the calcination atmosphere is air. The calcination temperature is preferably 500-700°C, and most preferably 600°C.

[0023] Preferably, according to the present invention, in step (2), the copper nitrate solution is a methanol solution of copper nitrate or an aqueous solution of copper nitrate; and the mass concentration of the copper nitrate solution is 0.01-1 g / mL.

[0024] Preferably, according to the present invention, in step (2), the mass of copper nitrate is such that the mass content of copper element in the catalyst is 5%-20%.

[0025] Preferably according to the present invention, in step (2), the reaction temperature is room temperature, the reaction time is 2-12 hours, and the reaction is carried out under stirring conditions.

[0026] According to the preferred embodiment of the present invention, in step (2), the calcination reduction conditions are: reduction at 200-500°C for 1-4h under hydrogen atmosphere. The preferred reduction temperature is 300-500°C, and most preferably 400°C.

[0027] The supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural is used in preparing furfuryl alcohol by hydrogenation of furfural.

[0028] According to a preferred embodiment of the present invention, the method for preparing furfuryl alcohol by hydrogenating furfural is as follows: furfural, a solvent and a catalyst are fully mixed, and furfuryl alcohol is obtained by hydrogenation reaction.

[0029] Preferably, the solvent is isopropanol; the mass ratio of furfural to the solvent is 1:20-50.

[0030] Preferably, the mass ratio of catalyst to furfural is 1:4-20.

[0031] Preferably, the hydrogenation reaction conditions are as follows: hydrogen pressure 0.5-2MPa, temperature 80-120°C, reaction time 1-8h, stirring at 600-1000rpm. Preferably, the hydrogen pressure is 1-1.5MPa and the temperature is 90-95°C.

[0032] The technical features and beneficial effects of the present invention are as follows:

[0033] 1. The catalyst preparation method of the present invention is simple and low in cost. Compared with the catalyst containing toxic and harmful heavy metals such as Cr used in the industrial catalytic conversion of furfural to furfuryl alcohol in the prior art, the catalyst prepared by the present invention is non-toxic, reduces the harm to people in the industrial production environment, and is green, safe and environmentally friendly.

[0034] 2. The present invention provides a catalyst, which is composed of an alumina or composite alumina carrier and copper metal particles loaded thereon. In the hydrolysis process of aluminum isopropoxide, metal salts are added as catalyst aids, and the hydrolysis conditions in the hydrolysis process are adjusted to obtain pseudo-boehmite with better conditions, and then the roasting temperature is adjusted to obtain a catalyst with a large specific surface area of ​​300-450m 2 / g of metal oxide modified alumina carrier. In the present invention, a non-precious metal copper material is used as a catalyst to catalyze the hydrogenation of furfural to furfuryl alcohol, which is low in price and the catalyst can be recycled. The preparation method of alumina or composite alumina carrier is simple, and does not require the use of protective agents such as templates and surfactants. Copper metal particles are loaded on the alumina carrier by an impregnation method to synthesize a catalyst with good dispersibility and high activity. Compared with other catalysts using alumina and copper metal, this catalyst can achieve higher activity.

[0035] 3. In the carrier preparation method of the present invention, during the hydrolysis of aluminum isopropoxide, the pH of the hydrolyzate is an important parameter that affects the performance of pseudo-boehmite and the final alumina material. Appropriate pH helps to control key properties such as the hydrolysis rate, precursor structure, and specific surface area and pore structure of the final alumina, while inappropriate pH may lead to insufficient hydrolysis, particle agglomeration or pore structure collapse, affecting the application performance of the material. Introducing zirconium nitrate, cerium nitrate or tetrabutyl titanate during the hydrolysis of aluminum isopropoxide and calcining to prepare a composite alumina carrier can effectively improve its pore structure, specific surface area, thermal stability, acid-base properties and metal dispersibility. The synergistic effect of different doping components enables the carrier to exhibit more excellent performance in catalytic applications, providing a more adjustable design strategy for the preparation of supported metal catalysts.

[0036] 4. The present invention improves the catalytic activity of the catalyst by changing the pH of the hydrolyzate and calcining, changing the surface acid properties and specific surface area of ​​the carrier, promoting the adsorption of furfural molecules and hydrogen, and thus improving the reaction activity. The particle size of the active metal Cu in the catalyst of the present invention is less than 10nm, and the catalyst activity is high. The catalyst of the present invention can work at 80°C, reducing the risk factor. Furfuryl alcohol can be prepared with high conversion rate and high selectivity under the conditions of reaction temperature of 90°C and 1MPa, 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 conducive to industrial application. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 : Al obtained in Examples 1, 14, 18, and 22 2 O 3 , 10ZrO 2 @Al 2 O 3 , 10CeO 2 @Al 2 O 3 and 10TiO 2 @Al 2 O 3 BET chart;

[0038] Figure 2 : Example 22 10Cu / 10TiO 2 @Al 2 O 3 TEM image of. DETAILED DESCRIPTION

[0039] The present invention will be further described below in conjunction with the embodiments, but the present invention is not limited by these embodiments.

[0040] The reagents and materials used in the examples are commercially available unless otherwise specified; the methods used are existing methods unless otherwise specified.

[0041] Example 1

[0042] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural comprises the following steps:

[0043] (1) Aluminum isopropoxide is added to isopropanol in a ratio of 100 mL:10 g. Stir at 80°C for 3 h to obtain a clear isopropanol solution of aluminum isopropoxide. Use a peristaltic pump to add the hydrolyzate to the isopropanol solution of aluminum isopropoxide at a rate of 1 mL / min. The hydrolyzate consists of water, isopropanol and a pH adjuster (25% ammonia water). The molar ratio of aluminum isopropoxide to water in the hydrolyzate is 1:9, the mass ratio of isopropanol to water in the hydrolyzate is 5:1, and the pH of the hydrolyzate is 10. After the hydrolyzate is added, continue stirring at 80°C for 3 h to obtain AlOOH. After centrifugation, place it in a 40°C oven and dry it for 12 h. The resulting sample is pseudo-boehmite powder. It is then calcined at 600°C for 2 h in an air atmosphere with a heating rate of 10°C / min to obtain Al 2 O 3 The BET diagram of the obtained carrier is shown in Figure 1 As shown, the specific surface area is 427.5m 2 / g, pore volume is 1.4cm 3 / g, pore size is 10.7nm.

[0044] (2) 0.85 g Cu(NO 3 ) 2 ·3H 2 O was dissolved in 50 mL of methanol and stirred magnetically for 5 min to obtain a uniformly mixed solution. Then 2 g of the above-prepared alumina was weighed and added to the solution and stirred at room temperature for 8 h. Then, it was rotary evaporated to evaporate the methanol to dryness. After evaporation, it was placed in an oven at 80 °C for 12 h. After the solid was taken out and ground, it was placed in a tube furnace and reduced at 400 °C for 2 h in a hydrogen atmosphere with a heating rate of 10 °C / min to obtain 10Cu / Al 2 O 3 The catalyst contains 10% copper by mass.

[0045] Example 2

[0046] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural is as described in Example 1, except that: in step (1), the pH of the hydrolyzate is 3 (the pH regulator is a nitric acid aqueous solution with a mass fraction of 0.96%); the other steps and conditions are the same as those in Example 1.

[0047] Example 3

[0048] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural is as described in Example 1, except that: in step (1), the pH of the hydrolyzate is 5 (the pH regulator is a nitric acid aqueous solution with a mass fraction of 0.96%); the other steps and conditions are the same as in Example 1.

[0049] Example 4

[0050] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural is as described in Example 1, except that: in step (1), the pH of the hydrolyzate is 7 (the pH regulator is a nitric acid aqueous solution with a mass fraction of 0.96%); the other steps and conditions are the same as those in Example 1.

[0051] Example 5

[0052] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural is as described in Example 1, except that: in step (1), the pH of the hydrolyzate is 12 (the pH regulator is 25% by mass of ammonia water); the other steps and conditions are the same as in Example 1.

[0053] Example 6

[0054] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural is as described in Example 1, except that in step (1), the calcination temperature is 400° C.; the other steps and conditions are the same as in Example 1.

[0055] Example 7

[0056] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural is as described in Example 1, except that: in step (1), the calcination temperature is 500° C.; the other steps and conditions are the same as in Example 1.

[0057] Example 8

[0058] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural is as described in Example 1, except that in step (1), the calcination temperature is 700° C.; the other steps and conditions are the same as in Example 1.

[0059] Example 9

[0060] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural is as described in Example 1, except that in step (2), the reduction temperature is 200° C.; the other steps and conditions are the same as in Example 1.

[0061] Example 10

[0062] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural is as described in Example 1, except that in step (2), the reduction temperature is 300° C.; the other steps and conditions are the same as in Example 1.

[0063] Embodiment 11

[0064] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural is as described in Example 1, except that in step (2), the reduction temperature is 500° C.; the other steps and conditions are the same as in Example 1.

[0065] Example 12

[0066] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural comprises the following steps:

[0067] (1) Aluminum isopropoxide is added to isopropanol in a ratio of 100 mL:10 g. The mixture is stirred at 80 °C for 3 h to obtain a clear isopropanol solution of aluminum isopropoxide. Zirconium nitrate is added to the isopropanol solution of aluminum isopropoxide in a ratio of 1:152.1 to the mass of zirconium nitrate added to the mass of aluminum isopropoxide, and the mixture is thoroughly mixed. The hydrolyzate is added to the above solution at a rate of 1 mL / min using a peristaltic pump. The hydrolyzate consists of water, isopropanol and a pH regulator (25% ammonia water). The molar ratio of aluminum isopropoxide to water in the hydrolyzate is 1:9, the mass ratio of isopropanol to water in the hydrolyzate is 5:1, and the pH of the hydrolyzate is 10. After the hydrolyzate is added, it is stirred at 80 °C for 3 h. After centrifugation, it is placed in a 40 °C oven for drying for 12 h. It is then calcined at 600 °C for 2 h in an air atmosphere at a heating rate of 10 °C / min to obtain ZrO 2 @Al 2 O 3 Support, among which ZrO 2 The mass of Al 2 O 3 1% of mass.

[0068] (2) 0.85 g Cu(NO 3 ) 2 ·3H 2 O was dissolved in 50 mL of methanol and magnetically stirred for 5 min to obtain a uniform solution. Then 2 g of the above-prepared ZrO 2 @Al 2 O 3 The carrier was added to the solution and stirred at room temperature for 8 hours, then the solution was subjected to rotary evaporation to evaporate the methanol to dryness, and then placed in an oven at 80°C for 12 hours. The solid was taken out and ground, and then placed in a tube furnace for reduction at 400°C for 2 hours under a hydrogen atmosphere with a heating rate of 10°C / min to obtain 10Cu / 1ZrO 2 @Al 2 O 3 The catalyst contains 10% copper by mass.

[0069] Example 13

[0070] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural, as described in Example 12, except that: in step (1), the mass ratio of zirconium nitrate added to aluminum isopropoxide is 1:29.2, and ZrO 2 @Al2 O 3 Support, among which ZrO 2 The mass of Al 2 O 3 The other steps and conditions were the same as those in Example 12. The obtained catalyst was recorded as 10Cu / 5ZrO 2 @Al 2 O 3 .

[0071] Embodiment 14

[0072] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural, as described in Example 12, except that: in step (1), the mass ratio of zirconium nitrate added to aluminum isopropoxide is 1:13.8, and ZrO 2 @Al 2 O 3 Support, among which ZrO 2 The mass of Al 2 O 3 The other steps and conditions are the same as those in Example 12. The obtained catalyst is denoted as 10Cu / 10ZrO 2 @Al 2 O 3 .

[0073] The obtained carrier 10ZrO 2 @Al 2 O 3 BET pictures Figure 1 As shown, the specific surface area is 371.9m 2 / g, pore volume is 0.7cm 3 / g, pore size is 8.7nm.

[0074] Embodiment 15

[0075] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural, as described in Example 12, except that: in step (1), the mass ratio of zirconium nitrate added to aluminum isopropoxide is 1:8.7, and ZrO 2 @Al 2 O 3 Support, among which ZrO 2 The mass of Al 2 O 3 The other steps and conditions are the same as those in Example 12. The obtained catalyst is denoted as 10Cu / 15ZrO 2 @Al 2 O 3 .

[0076] Example 16

[0077] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural, as described in Example 12, except that: in step (1), zirconium nitrate is replaced by cerium nitrate, and the mass ratio of the added cerium nitrate to the mass ratio of aluminum isopropoxide is 1:157, and CeO 2 @Al 2 O 3 Support, among which CeO 2 The mass of Al 2 O 3 The other steps and conditions were the same as those in Example 12. The obtained catalyst was recorded as 10Cu / 1CeO 2 @Al 2 O 3 .

[0078] Embodiment 17

[0079] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural, as described in Example 12, except that: in step (1), zirconium nitrate is replaced by cerium nitrate, and the mass ratio of the added cerium nitrate to the mass ratio of aluminum isopropoxide is 1:30.1, and CeO 2 @Al 2 O 3 Support, among which CeO 2 The mass of Al 2 O 3 The other steps and conditions were the same as those in Example 12. The obtained catalyst was recorded as 10Cu / 5CeO 2 @Al 2 O 3 .

[0080] Embodiment 18

[0081] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural, as described in Example 12, except that: in step (1), zirconium nitrate is replaced by cerium nitrate, and the mass ratio of the added cerium nitrate to the mass ratio of aluminum isopropoxide is 1:14.3, to obtain CeO 2 @Al 2 O 3 Support, among which CeO 2 The mass of Al 2 O 3 The other steps and conditions are the same as those in Example 12. The obtained catalyst is recorded as 10Cu / 10CeO 2 @Al 2 O 3 .

[0082] The obtained support 10CeO 2 @Al 2 O 3 BET pictures Figure 1 As shown, the specific surface area is 390.8m 2 / g, pore volume is 1.1cm 3 / g, pore size is 9.4nm.

[0083] Embodiment 19

[0084] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural, as described in Example 12, except that: in step (1), zirconium nitrate is replaced by cerium nitrate, and the mass ratio of the added cerium nitrate to the mass ratio of aluminum isopropoxide is 1:9, to obtain CeO 2 @Al 2 O 3 Support, among which CeO 2 The mass of Al 2 O 3 The other steps and conditions were the same as those in Example 12. The obtained catalyst was recorded as 10Cu / 15CeO 2 @Al 2 O 3 .

[0085] Embodiment 20

[0086] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural, as described in Example 12, except that: in step (1), zirconium nitrate is replaced by tetrabutyl titanate, and the mass ratio of the added tetrabutyl titanate to the mass ratio of aluminum isopropoxide is 1:93.0, to obtain TiO 2 @Al 2 O 3 Support, wherein TiO 2 The mass of Al 2 O 3 The other steps and conditions were the same as those in Example 12. The obtained catalyst was recorded as 10Cu / 1TiO 2 @Al 2 O 3 .

[0087] Embodiment 21

[0088] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural, as described in Example 12, except that: in step (1), zirconium nitrate is replaced by tetrabutyl titanate, and the mass ratio of the added tetrabutyl titanate to the mass ratio of aluminum isopropoxide is 1:18.1, and TiO 2 @Al 2 O 3 Support, wherein TiO 2 The mass of Al 2 O 3 The other steps and conditions were the same as those in Example 12. The obtained catalyst was recorded as 10Cu / 5TiO2 @Al 2 O 3 .

[0089] Embodiment 22

[0090] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural, as described in Example 12, except that: in step (1), zirconium nitrate is replaced by tetrabutyl titanate, and the mass ratio of the added tetrabutyl titanate to the mass ratio of aluminum isopropoxide is 1:8.5, to obtain TiO 2 @Al 2 O 3 Support, wherein TiO 2 The mass of Al 2 O 3 The other steps and conditions were the same as those in Example 12. The obtained catalyst was recorded as 10Cu / 10TiO 2 @Al 2 O 3 .

[0091] The obtained support 10TiO 2 @Al 2 O 3 BET pictures Figure 1 As shown, the specific surface area is 407.7m 2 / g, pore volume is 1.2cm 3 / g, pore size is 9.1nm.

[0092] The TEM image of the obtained catalyst is shown in Figure 2 As shown in the figure, TiO 2 @Al 2 O 3 The surface is uniformly loaded with copper metal nanoparticles.

[0093] Embodiment 23

[0094] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural, as described in Example 12, except that: in step (1), zirconium nitrate is replaced by tetrabutyl titanate, and the mass ratio of the added tetrabutyl titanate to the mass ratio of aluminum isopropoxide is 1:5.3, to obtain TiO 2 @Al 2 O 3 Support, wherein TiO 2 The mass of Al 2 O 3 The other steps and conditions were the same as those in Example 12. The obtained catalyst was recorded as 10Cu / 15TiO 2 @Al 2 O 3 .

[0095] Embodiment 24

[0096] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural, as described in Example 22, except that: in step (2), Cu(NO 3 ) 2 ·3H 2 The amount of O used is such that the mass content of copper in the catalyst is 5%, and the other steps and conditions are the same as those in Example 22. The obtained catalyst is recorded as 5Cu / 10TiO 2 @Al 2 O 3 catalyst.

[0097] Embodiment 25

[0098] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural, as described in Example 22, except that: in step (2), Cu(NO 3 ) 2 ·3H 2 The amount of O used is such that the mass content of copper in the catalyst is 15%, and the other steps and conditions are the same as those in Example 22. The obtained catalyst is recorded as 15Cu / 10TiO 2 @Al 2 O 3 catalyst.

[0099] Embodiment 26

[0100] A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural, as described in Example 22, except that: in step (2), Cu(NO 3 ) 2 ·3H 2 The amount of O used is such that the mass content of copper in the catalyst is 20%, and the other steps and conditions are the same as those in Example 22. The obtained catalyst is recorded as 20Cu / 10TiO 2 @Al 2 O 3 catalyst.

[0101] Application Example 1

[0102] The method for preparing furfuryl alcohol by hydrogenation of furfural is as follows: 100 mg of 10Cu / Al prepared in Example 1-5 is added to 2 O 3 Catalyst, 0.48g furfural and 23.55g isopropanol were added to a 100mL intermittent reactor, and the air in the reactor was removed by hydrogen three times, and then the hydrogen pressure was adjusted to 1MPa, the speed was 1000rpm, and the reactor temperature was set to 90°C for 3h. After the reaction was completed, the reaction liquid was taken for gas chromatography quantitative detection. The results are shown in Table 1 below.

[0103] Table 1. Catalyst performance test table of alumina carrier synthesized at different pH of hydrolyzate

[0104]

[0105] Application Example 2

[0106] The method for preparing furfuryl alcohol by hydrogenating furfural is as described in Application Example 1, except that the catalyst is the catalyst prepared in Examples 6-8; the other steps and conditions are the same as in Application Example 1. The results are shown in Table 2 below.

[0107] Table 2. Catalyst performance test table of alumina at different calcination temperatures

[0108]

[0109] Application Example 3

[0110] The method for preparing furfuryl alcohol by hydrogenation of furfural is as described in Application Example 1, except that the catalyst is the catalyst prepared in Examples 9-11; the other steps and conditions are the same as in Application Example 1. The results are shown in Table 3 below.

[0111] Table 3. Catalyst performance test table at different reduction temperatures

[0112]

[0113] Application Example 4

[0114] The method for preparing furfuryl alcohol by hydrogenation of furfural is as described in Application Example 1, except that the catalyst used is the catalyst obtained by the method of Example 1, the reaction temperature is replaced with 80, 85, and 95° C. respectively; the other steps and conditions are the same as those of Application Example 1. The results are shown in Table 4 below.

[0115] Table 4. Catalyst performance test table with the same reactor temperature at different reactors

[0116]

[0117] Application Example 5

[0118] The method for preparing furfuryl alcohol by hydrogenation of furfural is as described in Application Example 1, except that the catalyst used is the catalyst obtained by the method of Example 1, and the reaction pressure is replaced with 0.5 and 1.5 MPa respectively; the other steps and conditions are the same as those of Application Example 1. The results are shown in Table 5 below.

[0119] Table 5. Catalyst performance test table with the same pressure in different reactors

[0120]

[0121] Application Example 6

[0122] The method for preparing furfuryl alcohol by hydrogenating furfural is as described in Application Example 1, except that the catalyst used is the catalyst prepared in Examples 12-15; the other steps and conditions are the same as in Application Example 1. The results are shown in Table 6 below.

[0123] Table 6. Catalytic performance test table of different Zr loadings

[0124]

[0125] Application Example 7

[0126] The method for preparing furfuryl alcohol by hydrogenating furfural is as described in Application Example 1, except that the catalyst used is the catalyst prepared in Examples 16-19; the other steps and conditions are the same as in Application Example 1. The results are shown in Table 7 below.

[0127] Table 7. Catalytic performance test table of different Ce loadings

[0128]

[0129] Application Example 8

[0130] The method for preparing furfuryl alcohol by hydrogenating furfural is as described in Application Example 1, except that the catalyst used is the catalyst prepared in Examples 20-23; the other steps and conditions are the same as in Application Example 1. The results are shown in Table 8 below.

[0131] Table 8. Catalytic performance test table of different Ti loading amounts

[0132]

[0133] Application Example 9

[0134] The method for preparing furfuryl alcohol by hydrogenating furfural is as described in Application Example 1, except that the catalyst used is the catalyst prepared in Examples 24-26; the other steps and conditions are the same as in Application Example 1. The results are shown in Table 9 below.

[0135] Table 9. Catalytic performance test table of different Cu loading amounts

[0136]

Claims

1. A supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural, characterized in that: The catalyst is an Al2O3 carrier or a composite Al2O3 carrier with copper metal nanoparticles loaded on its surface; wherein the composite Al2O3 carrier is ZrO2@Al2O3, CeO2@Al2O3 or TiO2@Al2O3.

2. The supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural according to claim 1, characterized in that: In the composite Al2O3 carrier, the mass of ZrO2, CeO2 or TiO2 is 1wt%-15wt% of the mass of Al2O3; the mass content of copper element in the catalyst is 5%-20%.

3. The supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural according to claim 1, characterized in that: The specific surface area of ​​Al2O3 carrier or composite Al2O3 carrier is 300-450m 2 / g, and the particle size of copper metal nanoparticles is 4.2nm-10nm.

4. A method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural as claimed in any one of claims 1 to 3, comprising the steps of: (1) adding zirconium nitrate, cerium nitrate or tetrabutyl titanate to an isopropanol solution of aluminum isopropoxide, mixing well and uniformly, adding a hydrolyzate, reacting, centrifuging, drying and calcining to obtain a composite Al2O3 carrier; Alternatively, the isopropanol solution of aluminum isopropoxide and the hydrolyzate are mixed evenly, reacted, and then centrifuged, dried, and calcined to obtain an Al2O3 carrier; (2) The composite Al2O3 carrier or the Al2O3 carrier is immersed in a copper nitrate solution, and after reaction, solid-liquid separation, drying, calcination and reduction, a supported catalyst for preparing furfural alcohol by liquid phase hydrogenation of furfural is obtained.

5. The method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural according to claim 4, wherein: In step (1), one or more of the following conditions are included: i. The concentration of the isopropanol solution of aluminum isopropoxide is 1-30 g:100 mL; ii. A method for preparing an isopropanol solution of aluminum isopropoxide comprises the steps of: adding aluminum isopropoxide to isopropanol, stirring at 40-90° C. for 1-3 hours, to obtain an isopropanol solution of aluminum isopropoxide; iii. The amount of zirconium nitrate, cerium nitrate or tetrabutyl titanate is such that the mass of ZrO2, CeO2 or TiO2 in the composite Al2O3 carrier is 1wt%-15wt% of the mass of Al2O3; iv. The pH of the hydrolyzate is 3-12, preferably 7-12, and most preferably 10; the hydrolyzate consists of water, isopropanol and a pH adjuster, wherein the pH adjuster is 20-30% by mass of ammonia water or 0.1-2% by mass of a nitric acid aqueous solution; in the hydrolyzate, the mass ratio of water to isopropanol is 1:1-7; the molar ratio of aluminum isopropoxide to water in the hydrolyzate is 1:2-15; and the addition rate of the hydrolyzate is 0.2-50 mL / min.

6. The method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural according to claim 4, characterized in that: In step (1), one or more of the following conditions are included: i. The reaction temperature is 40-90°C, the reaction time is 1-12h, and the reaction is carried out under stirring conditions; ii. The calcination temperature is 400-700°C, the calcination time is 1-3h, and the calcination atmosphere is air; the preferred calcination temperature is 500-700°C, and the most preferred is 600°C.

7. The method for preparing a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural according to claim 4, wherein: In step (2), one or more of the following conditions are included: i. 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 0.01-1 g / mL; ii. The mass of copper nitrate is such that the mass content of copper in the catalyst is 5%-20%; iii. The reaction temperature is room temperature, the reaction time is 2-12 hours, and the reaction is carried out under stirring conditions; iv. Calcination reduction conditions: reduction at 200-500°C for 1-4h under hydrogen atmosphere; preferably the reduction temperature is 300-500°C, most preferably 400°C.

8. Use of a supported catalyst for preparing furfuryl alcohol by liquid phase hydrogenation of furfural as claimed in any one of claims 1 to 3 in preparing furfuryl alcohol by hydrogenation of furfural.

9. The use according to claim 8, characterized in that: The method for preparing furfuryl alcohol by hydrogenating furfural is as follows: furfural, solvent and catalyst are fully mixed, and furfuryl alcohol is obtained by hydrogenation reaction.

10. The use according to claim 9, characterized in that: Includes one or more of the following conditions: i. The solvent is isopropanol; the mass ratio of furfural to solvent is 1:20-50; ii. The mass ratio of catalyst to furfural is 1:4-20; iii. The hydrogenation reaction conditions are as follows: hydrogen pressure 0.5-2MPa, temperature 80-120°C, reaction time 1-8h, stirring at 600-1000rpm; preferably, the hydrogen pressure is 1-1.5MPa and the temperature is 90-95°C.

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