NiSn-ReO x / TiO2 catalyst and preparation method thereof, and application of the catalyst in preparing cyclopentanone from furfural in aqueous phase

Abstract

The application relates to a supported NiSn-ReO x / TiO2 catalyst and a preparation method thereof and application thereof in selective hydrogenation of furfural. In the preparation method, a continuous impregnation method is used to load NiSn alloy and ReO x on a titanium dioxide carrier, formation of the NiSn alloy effectively inhibits deep hydrogenation of a furan ring by a Ni-based catalyst, and ReO x doping greatly improves hydrogenation activity of the catalyst for a C=O bond and a rearrangement rate of furfuryl alcohol. The prepared catalyst is used for catalyzing water-phase hydrogenation of furfural to prepare cyclopentanone, and at a lower reaction temperature and hydrogen pressure, the catalyst has higher catalytic conversion efficiency and cyclopentanone selectivity, furfural conversion rate is close to 100%, and cyclopentanone yield is as high as 92.5%. The prepared NiSn-ReO x / TiO2 catalyst has high dispersion of active components, good stability and is easy to recover.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of biomass catalytic conversion, and particularly relates to a supported NiSn-ReO x / TiO2 catalyst and a preparation method thereof and application thereof in a reaction of preparing cyclopentanone from water-phase hydrogenation of furfural. BACKGROUND

[0002] Cyclopentanone is an important chemical product with great market potential, and is widely used in the fields of medicine, perfume and the like. It can be used as a raw material to produce various anti-inflammatory and anticancer drugs, and new perfumes such as dihydrojasmone acid methyl ester, white ketone and 2-n-hexyl cyclopentanone. In addition, cyclopentanone is also used to synthesize rubber, herbicides and pesticides.

[0003] At present, the synthesis methods of cyclopentanone mainly include adipic acid pyrolysis and cyclopentene oxidation, but the raw materials used in these methods are derived from fossil resources, and the reaction conditions are relatively harsh. In today's energy shortage and environmental pollution, using renewable resources instead of fossil resources as raw materials not only meets the requirements of sustainable development, but also helps to improve economic benefits and alleviate environmental pollution. In recent years, the process of producing cyclopentanone from furfural has attracted widespread attention. This cheap, easily available and renewable biomass resource is obviously more in line with the development trend than the scarce fossil resources, and also has more market potential. SUMMARY

[0004] One of the purposes of the present application is to provide a preparation method of a supported NiSn-ReO x / TiO2 bifunctional catalyst, which is prepared by a simple continuous impregnation method, and the NiSn alloy and ReO x are loaded on the TiO2 carrier, respectively. The process is simple, the raw materials are easily available, and it is conducive to large-scale promotion. The catalyst prepared by the method can realize the preparation of cyclopentanone from water-phase hydrogenation of furfural in a mild reaction system, and has high selectivity.

[0005] To achieve the above purpose, the present application provides a preparation method of a NiSn-ReO x / TiO2 bifunctional catalyst, which comprises the following steps:

[0006] 1) nickel salt, tin salt and carrier titanium dioxide are added into a first solvent, stirred at room temperature, rotary evaporated, dried, air calcined, and then the obtained product is reduced in a hydrogen atmosphere, passivated to obtain a NiSn / TiO2 catalyst;

[0007] 2) the NiSn / TiO2 catalyst and rhenium salt are added into a second solvent, stirred at room temperature, rotary evaporated, vacuum dried, and then the obtained product is reduced in a hydrogen atmosphere, passivated to obtain a NiSn-ReO xA bifunctional catalyst of / TiO2.

[0008] Preferably, the nickel salt in step 1) is one of nickel nitrate hexahydrate, nickel chloride hexahydrate or nickel acetate, the tin salt is tetrachloride tin pentahydrate, the carrier titanium dioxide is nanoscale P25 TiO2, and the first solvent is one of de-ethanol, methanol or isopropanol.

[0009] Preferably, the mass percentage of Ni in the nickel salt to the carrier titanium dioxide is 5-20% in step 1), and the mass ratio of Ni in the nickel salt to Sn in the tin salt is 3:1-4.

[0010] Preferably, the stirring time at room temperature in step 1) is 1-5h, the drying temperature is 30-80℃, the drying time is 10-20h, the air calcination temperature is 300-600℃, the calcination time is 0.5-4h, the hydrogen reduction temperature is 300-600℃, the reduction time is 0.5-4h, the passivation time is 0.2-3h, and the passivation gas is O2 / N2 mixed gas.

[0011] Preferably, the rhenium salt in step 2) is ammonium perrhenate, and the second solvent is one of deionized water, ethanol or methanol.

[0012] Preferably, the mass percentage of Re in the rhenium salt to TiO2 in the NiSn / TiO2 catalyst is 1%-10% in step 2).

[0013] Preferably, the stirring time at room temperature in step 2) is 1-5h, the vacuum drying temperature is 30-80℃, the vacuum drying time is 10-20h, the hydrogen reduction temperature is 200-400℃, the reduction time is 0.5-4h, the passivation time is 0.2-3h, and the passivation gas is O2 / N2 mixed gas.

[0014] The second object of the present application is to provide a NiSn-ReO x A bifunctional catalyst of / TiO2.

[0015] The third object of the present application is to provide a NiSn-ReO x Application of the bifunctional catalyst of / TiO2 in the reaction of preparing cyclopentanone by selective hydrogenation of furfural.

[0016] The method comprises the following steps:

[0017] Furfural is used as raw material, hydrogen is used as hydrogen source, deionized water is used as solvent, and the NiSn-ReO xThe catalytic hydrogenation reaction of furfural is carried out by using the NiSn-ReO x / TiO2 bifunctional catalyst under the conditions that the reaction temperature is 50-150 DEG C, the reaction time is 0.5-6 h, and the hydrogen pressure is 0.5-3 MPa.

[0018] P25 TiO2 is a commercially available titanium dioxide product with an average particle size of 25 nm.

[0019] Compared with the existing supported Ni-ReO x Compared with the existing supported Ni-ReO

[0020] The NiSn-ReO x / TiO2 catalyst of the present application is not a simple superposition of Ni and Sn, but realizes the synergistic effect between Ni and Sn through alloying, thereby effectively inhibiting the deep hydrogenation of the furan ring by Ni and providing an advanced strategy for rationally designing excellent catalysts to adjust product selectivity.

[0021] The beneficial effects of the present application are as follows:

[0022] 1) The present application loads NiSn alloy and ReO x on the TiO2 carrier by a simple impregnation method, and the NiSn alloy effectively inhibits the generation of the byproduct tetrahydrofurfuryl alcohol, and the metal Re enhances the hydrogenation activity of the C=O bond and the rearrangement rate of the furan ring, so that furfural can be efficiently and selectively hydrogenated to form cyclopentanone, avoiding the separation of intermediate steps and intermediate products and effectively reducing the production cost.

[0023] 2) When the catalyst of the present application is used to catalyze the preparation of cyclopentanone from furfural, the catalytic conversion efficiency is as high as 100%, the reaction temperature is low, the time is short, the pressure is low, and high-pressure hydrogen is not required.

[0024] 3) The catalyst of the present application has high dispersion of active components, good stability, and easy recovery, etc.

[0025] 4) The preparation method of the NiSn-ReO x / TiO2 catalyst of the present application is simple, the raw materials are easy to obtain, and is suitable for popularization and use.

[0026] The above description is only a summary of the technical scheme of the present application. In order to make the technical means of the present application more clearly understood and implemented according to the content of the description, the following will describe the preferred embodiments of the present application in detail with reference to the accompanying drawings. The specific embodiments of the present application are described in detail by the following examples and accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 TEM image of the NiSn-ReO x / TiO2 bifunctional catalyst with a scale of 100 nm;

[0028] Figure 2 TEM image of the NiSn-ReO x / TiO2 bifunctional catalyst with a scale of 50 nm. DETAILED DESCRIPTION

[0029] The present application will be further described in detail below with reference to specific embodiments, so as to make the present application more clearly understood, but the present application is not limited to the following specific embodiments. Any changes and variations made by any person skilled in the art within the scope disclosed by the present application are covered by the protection scope of the present application. The medicines used in the examples are all commercially available products unless otherwise specified, and the methods used are all conventional methods in the art unless otherwise specified.

[0030] The working principle of the present application is:

[0031] Metal Sn doping can effectively inhibit the activity of metal Ni for the hydrogenation of C=C bond on the furan ring, thereby avoiding the generation of tetrahydrofurfuryl alcohol and obtaining high-selectivity cyclopentanone, but Sn doping will also reduce the activity of the catalyst, ReO x not only has a very significant promoting effect on the hydrogenation of C=O bond, but also can improve the water-phase rearrangement rate of furfuryl alcohol. Under the interaction of NiSn alloy and ReO x , the selectivity and reaction activity of the NiSn-ReO x / TiO2 catalyst are much higher than those of the Ni / TiO2 and NiSn / TiO2 catalysts.

[0032] Comparative Example 1

[0033] 1 g of Ni(NO3)2·6H2O and 2 g of TiO2 were added to 100 mL of distilled water, stirred at room temperature for 1 h, and then rotary evaporated at 60°C until the solvent was evaporated. The evaporated sample was further dried in an oven at 60°C for 12 h. The dried sample was reduced in a tube furnace with H2 atmosphere at 400°C for 1 h, and after the sample temperature dropped to room temperature, an O2 / N2 (1.5 / 98.5, v / v) atmosphere was introduced for passivation for 1 h, thereby obtaining a metal nickel-based catalyst with a nickel loading of 10%, which is denoted as Ni / TiO2 catalyst.

[0034] The above prepared catalyst Ni / TiO2 was used for selective catalytic hydrogenation of furfural: 50 mg of the above prepared catalyst Ni / TiO2, 96 mg of furfural (1 mmol), 3.5 g of deionized water and a magnetic bar were put into a polytetrafluoroethylene liner, and then the liner was put into a stainless steel autoclave, the autoclave was tightly closed, and then filled with H2 twice and discharged with air, the airtightness of the autoclave was checked and filled with 3 MPa of H2, the autoclave was put into a heater with a set temperature of 140°C, a thermocouple was put in place, stirring was started, and reaction was carried out for 3 h, after the set reaction time, the reaction was stopped, the reaction liquid was added to an appropriate amount of anhydrous ethanol for dissolution and centrifuged, and the supernatant was analyzed by gas chromatography. The experimental results showed that the conversion rate of furfural was 100%, and the yield of cyclopentanone was 11.5%.

[0035] Example 1

[0036] 1 g of Ni(NO3)2·6H2O and 0.4 g of SnCl4·5H2O were added to 2 g of TiO2 in 100 mL of ethanol, stirred at room temperature for 1 h, and then rotary evaporated at 30°C until the solvent was evaporated. The evaporated sample was further dried in an oven at 60°C for 12 h. The dried sample was calcined in a muffle furnace with air at 400°C for 4 h, and then reduced in a tube furnace with a hydrogen atmosphere at 400°C for 1 h. After the sample temperature dropped to room temperature, an O2 / N2 (1.5 / 98.5, v / v) atmosphere was introduced for passivation for 1 h, to obtain a NiSn alloy catalyst with a nickel loading of 10% and a nickel-tin mass ratio of about 3 / 2, which was recorded as Ni3Sn2 / TiO2 catalyst.

[0037] The above prepared catalyst Ni3Sn2 / TiO2 was used for selective catalytic hydrogenation of furfural: 50 mg of the above prepared catalyst Ni / TiO2, 96 mg of furfural (1 mmol), 3.5 g of deionized water and a magnetic bar were put into a polytetrafluoroethylene liner, and then the liner was put into a stainless steel autoclave, the autoclave was tightly closed, and then filled with H2 twice and discharged with air, the airtightness of the autoclave was checked and filled with 3 MPa of H2, the autoclave was put into a heater with a set temperature of 140°C, a thermocouple was put in place, stirring was started, and reaction was carried out for 3 h, after the set reaction time, the reaction was stopped, the reaction liquid was added to an appropriate amount of anhydrous ethanol for dissolution and centrifuged, and the supernatant was analyzed by gas chromatography. The experimental results showed that the conversion rate of furfural was 100%, and the yield of cyclopentanone was 11.5%.

[0038] Example 2

[0039] 1 g of Ni3Sn2 / TiO2 catalyst synthesized in Example 1 and 0.0655 g of NH4ReO4 were added to 100 mL of distilled water, stirred at room temperature for 1 h, and then rotary evaporated at 60°C until the solvent was evaporated. After the sample temperature dropped to room temperature, it was taken out and dried in a vacuum oven at 60°C for 12 h. The dried sample was reduced in a tube furnace with a hydrogen atmosphere at 200°C for 1 h. After the sample temperature dropped to room temperature, an O2 / N2 (1.5 / 98.5, v / v) atmosphere was introduced for passivation for 1 h, to obtain a Ni3Sn2-ReO4 / TiO2 catalyst with a nickel loading of 10%, a nickel-tin mass ratio of about 3 / 2, and a rhenium loading of 5%. x x Example 2 ​

[0040] The catalyst Ni3Sn2-ReO / TiO2 thus prepared was subjected to catalytic activity test with reference to the method of catalytic hydrogenation of furfural of Comparative Example 1, and the experimental results showed that the conversion of furfural was 89.1% and the yield of cyclopentanone was 72.5%. x x The catalyst Ni3Sn2-ReO / TiO2 thus prepared was subjected to catalytic activity test with reference to the method of catalytic hydrogenation of furfural of Comparative Example 1, and the experimental results showed that the conversion of furfural was 89.1% and the yield of cyclopentanone was 72.5%.

[0041] Example 3

[0042] 1 g of Ni(NO3)2·6H2O, 0.2 g of SnCl4·5H2O and 2 g of TiO2 were added into 100 mL of ethanol, stirred at room temperature for 1 h, and then rotary evaporated at 30°C until the solvent was evaporated. The evaporated sample was continuously dried in an oven at 60°C for 12 h. The dried sample was calcined in a muffle furnace with air at 400°C for 4 h, and then reduced in a tube furnace with hydrogen atmosphere at 400°C for 1 h. After the sample temperature was lowered to room temperature, O2 / N2 (1.5 / 98.5, v / v) atmosphere was introduced for passivation for 1 h, thus obtaining a NiSn alloy catalyst with nickel loading of 10% and nickel-tin mass ratio of about 3 / 1, which was recorded as Ni3Sn1 / TiO2 catalyst. The catalyst Ni3Sn1-ReO / TiO2 was prepared with reference to the synthesis method of Example 2. x x The catalyst Ni3Sn1-ReO / TiO2 thus prepared was subjected to catalytic activity test with reference to the method of catalytic hydrogenation of furfural of Comparative Example 1, and the experimental results showed that the conversion of furfural was 89.1% and the yield of cyclopentanone was 72.5%.

[0043] The catalyst Ni3Sn1-ReO / TiO2 thus prepared was subjected to catalytic activity test with reference to the method of catalytic hydrogenation of furfural of Comparative Example 1, and the experimental results showed that the conversion of furfural was 89.1% and the yield of cyclopentanone was 72.5%. x

[0044] Example 4

[0045] 1 g of Ni(NO3)2·6H2O, 0.2 g of SnCl4·5H2O and 2 g of TiO2 were added into 100 mL of ethanol, stirred at room temperature for 1 h, and then rotary evaporated at 30°C until the solvent was evaporated. The evaporated sample was continuously dried in an oven at 60°C for 12 h. The dried sample was calcined in a muffle furnace with air at 400°C for 4 h, and then reduced in a tube furnace with hydrogen atmosphere at 400°C for 1 h. After the sample temperature was lowered to room temperature, O2 / N2 (1.5 / 98.5, v / v) atmosphere was introduced for passivation for 1 h, thus obtaining a NiSn alloy catalyst with nickel loading of 10% and nickel-tin mass ratio of about 3 / 1, which was recorded as Ni3Sn1 / TiO2 catalyst. The catalyst Ni3Sn1-ReO / TiO2 was prepared with reference to the synthesis method of Example 2. x x The catalyst Ni3Sn1-ReO / TiO2 thus prepared was subjected to catalytic activity test with reference to the method of catalytic hydrogenation of furfural of Comparative Example 1, and the experimental results showed that the conversion of furfural was 89.1% and the yield of cyclopentanone was 72.5%.

[0046] The catalyst Ni3Sn1-ReO / TiO2 thus prepared was subjected to catalytic activity test with reference to the method of catalytic hydrogenation of furfural of Comparative Example 1, and the experimental results showed that the conversion of furfural was 89.1% and the yield of cyclopentanone was 72.5%. xThe catalytic activity test of the Ni3Sn2 / TiO2 was carried out. The results showed that the conversion of furfural was 55.3% and the yield of cyclopentanone was 21.2%.

[0047] Examples 5-10

[0048] The 1 g of Ni3Sn2 / TiO2 synthesized in Example 1 was added to 100 mL of distilled water with 0.0655 g of NH4ReO4, stirred at room temperature for 1 h, and then rotary evaporated at 60 °C until the solvent was evaporated. After the sample temperature dropped to room temperature, it was taken out and dried in a vacuum oven at 60 °C for 12 h. The dried sample was reduced with H2atmosphere at 200 °C for 1 h in a tube furnace, and after the sample temperature dropped to room temperature, it was passivated with O2 / N2(1.5 / 98.5, v / v) atmosphere for 1 h to obtain a Ni3Sn2-ReO x catalyst with 10% of nickel loading, about 3 / 2 of nickel to tin mass ratio, and 5% of rhenium loading, which was recorded as Ni3Sn2-ReO x / TiO2.

[0049] The catalytic activity test of the Ni3Sn2-ReO x / TiO2 synthesized above was carried out according to the method of catalytic hydrogenation of furfural in Comparative Example 1, except that the reaction time was 0.5 h, 1 h, 2 h, 4 h, 5 h, and 6 h, respectively. The results showed that the conversion of furfural was 37.4%, 49.1%, 80.4%, 95%, 100%, and 100%, respectively, and the yield of cyclopentanone was 3.8%, 28.1%, 54.2%, 81.5%, 87.1%, and 92.5%, respectively.

[0050] Examples 11-14

[0051] The 1 g of Ni3Sn2 / TiO2 synthesized in Example 1 was added to 100 mL of distilled water with 0.0655 g of NH4ReO4, stirred at room temperature for 1 h, and then rotary evaporated at 60 °C until the solvent was evaporated. After the sample temperature dropped to room temperature, it was taken out and dried in a vacuum oven at 60 °C for 12 h. The dried sample was reduced with H2atmosphere at 200 °C for 1 h in a tube furnace, and after the sample temperature dropped to room temperature, it was passivated with O2 / N2(1.5 / 98.5, v / v) atmosphere for 1 h to obtain a Ni3Sn2-ReO x catalyst with 10% of nickel loading, about 3 / 2 of nickel to tin mass ratio, and 5% of rhenium loading, which was recorded as Ni3Sn2-ReO x / TiO2.

[0052] The catalytic activity test of the Ni3Sn2-ReO xCatalytic activity tests were conducted using TiO2, with the difference being that the reaction time was 6 hours and the reaction temperatures were 80℃, 100℃, 110℃, and 120℃. The experimental results showed that the conversion rates of furfural were 100%, 100%, 100%, and 100%, respectively, and the yields of cyclopentanone were 0%, 4.1%, 55.5%, and 70.1%, respectively.

[0053] Examples 15-18

[0054] 1 g of Ni3Sn2 / TiO2 catalyst synthesized in Example 1 and 0.0655 g of NH4ReO4 were added to 100 mL of distilled water and stirred at room temperature for 1 h. Then, the mixture was rotary evaporated at 60 °C until the solvent was completely evaporated. After the sample temperature cooled to room temperature, it was removed and dried in a vacuum oven at 60 °C for 12 h. The dried sample was then reduced in a tube furnace at 200 °C with H2 atmosphere for 1 h. After the sample temperature cooled to room temperature, it was passivated with O2 / N2 (1.5 / 98.5, v / v) atmosphere for 1 h to obtain Ni3Sn2-ReO4 with a nickel loading of 10%, a nickel-tin mass ratio of approximately 3 / 2, and a rhenium loading of 5%. x Catalyst, denoted as Ni3Sn2-ReO x / TiO2.

[0055] The catalyst Ni3Sn2-ReO prepared above was prepared using the same method as that used in Comparative Example 1 for the catalytic hydrogenation of furfural. x Catalytic activity tests were conducted using TiO2, with the exception of reaction times of 6 hours and hydrogen pressures of 0.5 MPa, 1 MPa, 1.5 MPa, and 2 MPa. The results showed that the conversion rates of furfural were 56.9%, 78.3%, 94.4%, and 100%, respectively, and the yields of cyclopentanone were 24.5%, 54.1%, 79.5%, and 88.8%, respectively.

[0056] Examples 19-23

[0057] Ni3Sn2-ReO with a nickel loading of 10%, a nickel-tin mass ratio of approximately 3 / 2, and a rhenium loading of 5% was prepared according to the preparation method in Example 2. x Catalyst, denoted as Ni3Sn2-ReO x / TiO2.

[0058] The catalyst Ni3Sn2-ReO prepared above was prepared using the same method as that used in Comparative Example 1 for the catalytic hydrogenation of furfural. x TiO2 was recycled and reused 1st, 2nd, 3rd, 4th, and 5th times for catalytic hydrogenation of furfural, with the reaction time varying to 6 hours. Experimental results showed that the conversion rates of furfural were 100%, 100%, 98.4%, 96.3%, and 95.9%, respectively, while the yields of cyclopentanone were 92.5%, 86.1%, 82.5%, 78.6%, and 76.4%, respectively.

[0059] The experimental results of Examples 1-4 and Comparative Examples are shown in Table 1 below;

[0060] The experimental results of Examples 5-10 are shown in Table 2 below;

[0061] The experimental results of Examples 11-18 are shown in Table 3 below;

[0062] The experimental results of Examples 19-23 are shown in Table 4 below.

[0063] Table 1

[0064] Number Catalyst Furfural conversion % Cyclopentanone selectivity % Cyclopentanone yield % Example 1 Ni3Sn2 / TiO2 65.6 62.2 40.8 Example 2 Ni3Sn2-ReO x / TiO2]]> 89.1 81.4 72.5 Example 3 Ni3Sn1-ReO x / TiO2]]> 75.8 77.7 58.9 Example 4 Ni3Sn4-ReO x / TiO 22 ]]> 55.3 38.3 21.2 Comparative Example 1 [Ni / TiO2] 100 11.5 11.5

[0065] From the data in Table 1, it can be seen that the monometallic Ni / TiO2 catalyst with a nickel loading of 10% has a low selectivity for the production of cyclopentanone from the hydrogenation of furfural. Under the conditions of a reaction temperature of 140°C, a reaction hydrogen pressure of 3 MPa, a solvent of deionized water, and a reaction time of 3 h, the conversion of furfural is 100%, and the selectivity of cyclopentanone is only 11.5%. After the incorporation of tin into the Ni / TiO2 catalyst, the Ni3Sn2 / TiO2 catalyst with a nickel / tin ratio of 3 / 2 is obtained, and the selectivity for cyclopentanone is greatly improved. Under the same conditions, the conversion of furfural is 65.6%, and the selectivity of cyclopentanone is 62.2%. The Ni3Sn2-ReO x / TiO2 catalyst obtained after the incorporation of rhenium has a furfural conversion of 89.1% and a selectivity for cyclopentanone of 81.4%. x The NiSn-ReO x / TiO2 catalyst with a nickel / tin ratio of 3 / 1-3 / 4 has a furfural conversion of 75.8%, 89.1%, and 55.3%, respectively, and a selectivity for cyclopentanone of 77.7%, 81.4%, and 38.3%, respectively.

[0066] Table 2

[0067]

[0068]

[0069] From the data in Table 2, it can be seen that the supported Ni3Sn2-ReO x / TiO2 catalyst with a nickel loading of 10%, a nickel / tin ratio of 3 / 2, and a rhenium loading of 5% has excellent activity and selectivity for the production of cyclopentanone from the hydrogenation of furfural. Under the conditions of a reaction temperature of 140°C, a reaction hydrogen pressure of 3 MPa, a solvent of deionized water, and a reaction time of 6 h, the conversion of furfural is 100%, and the selectivity of cyclopentanone can reach 92.5%.

[0070] Table 3

[0071]

[0072] As can be seen from the data in Table 3, the supported Ni3Sn2-ReO of this invention... x The TiO2 catalyst maintained good activity and selectivity for the aqueous hydrogenation of furfural to cyclopentanone under relatively mild reaction conditions. When the temperature was reduced to 110℃, the conversion of furfural was 100%, and the selectivity for cyclopentanone reached 55.5%. When the pressure was reduced to 0.5 MPa, the conversion of furfural was 56.9%, and the selectivity for cyclopentanone was 43.1%.

[0073] Table 4

[0074]

[0075] As can be seen from the data in Table 4, the supported Ni3Sn2-ReO of this invention... x The TiO2 catalyst can be reused multiple times and has little impact on the catalytic conversion efficiency of furfural.

[0076] This invention NiSn-ReO x TEM image of the TiO2 bifunctional catalyst is shown below. Figures 1-2 As shown, from Figures 1-2 It can be seen that the carrier is in the form of 10-100nm particles, and the loaded metal is highly dispersed on the surface of the carrier.

Claims

1. Use of a NiSn-ReO x / TiO2 bifunctional catalyst in the reaction of selective hydrogenation of furfural to prepare cyclopentanone, characterized in that: The preparation method of the NiSn-ReOx / TiO2 bifunctional catalyst comprises the following steps: 1) adding a nickel salt, a tin salt and a carrier TiO2 into a first solvent, stirring at room temperature, rotary evaporation, drying, air calcination, the mass percentage of Ni contained in the nickel salt and the carrier TiO2 being 5-20%, the mass ratio of Ni contained in the nickel salt and Sn contained in the tin salt being 3:1-4, then reducing, passivating the obtained product in a hydrogen atmosphere to obtain a NiSn / TiO2 catalyst; 2) The NiSn / TiO2catalyst is added to a second solvent with a rhenium salt, stirred at room temperature, rotary evaporated, vacuum dried, and the resulting product is reduced, passivated in a hydrogen atmosphere to obtain a NiSn-ReO x / TiO2bifunctional catalyst.

2. The NiSn-ReO according to claim 1 x The application of the bifunctional catalyst of NiSn-ReO / TiO2 in the reaction of preparing cyclopentanone by selectively hydrogenating furfural, characterized in that: The nickel salt in the step 1) is one of nickel nitrate hexahydrate, nickel chloride hexahydrate or nickel acetate, the tin salt is tin tetrachloride pentahydrate, the carrier TiO2 is nanoscale P25 TiO2, and the first solvent is one of ethanol, methanol or isopropyl alcohol.

3. The NiSn-ReO catalyst according to claim 1 x The application of the bifunctional catalyst of NiSn-ReO / TiO2 in the reaction of preparing cyclopentanone by selectively hydrogenating furfural, characterized in that: The stirring time in the step 1) is 1-5 h, the drying temperature is 30-80°C, the drying time is 10-20 h, the air calcination temperature is 300-600°C, the calcination time is 0.5-4 h, the hydrogen reduction temperature is 300-600°C, the reduction time is 0.5-4 h, the passivation time is 0.2-3 h, and the passivation gas is O2 / N2 mixed gas.

4. The NiSn-ReO catalyst according to claim 1 x The application of the bifunctional catalyst of NiSn-ReO / TiO2 in the reaction of preparing cyclopentanone by selectively hydrogenating furfural, characterized in that: The rhenium salt in the step 2) is ammonium perrhenate, and the second solvent is one of deionized water, ethanol or methanol.

5. The NiSn-ReO of claim 1 x The application of the bifunctional catalyst of NiSn-ReO / TiO2 in the reaction of selective hydrogenation of furfural to prepare cyclopentanone, characterized in that: The mass percentage of Re contained in the rhenium salt and TiO2 in the NiSn / TiO2 catalyst is 1%-10% in the step 2).

6. The NiSn-ReO bifunctional catalyst according to claim 1 x The application of the TiO2 dual functional catalyst in the reaction of preparing cyclopentanone by selectively hydrogenating furfural, characterized in that: The stirring time in the step 2) is 1-5 h, the vacuum drying temperature is 30-80°C, the vacuum drying time is 10-20 h, the hydrogen reduction temperature is 200-400°C, the reduction time is 0.5-4 h, the passivation time is 0.2-3 h, and the passivation gas is O2 / N2 mixed gas.

7. The NiSn-ReO as claimed in claim 1 x The application of the bifunctional catalyst of NiSn-ReO / TiO2 in the reaction of preparing cyclopentanone by selectively hydrogenating furfural, characterized in that: With furfural as raw material, hydrogen as hydrogen source, deionized water as solvent, and NiSn-ReO x The catalytic hydrogenation reaction of furfural is carried out on the bifunctional catalyst of NiSn-ReO

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