A catalyst for the continuous hydrogenation of furan to tetrahydrofuran, its preparation and application

Abstract

This invention discloses a catalyst for the continuous hydrogenation of furan to tetrahydrofuran. According to the invention, the catalyst is composed of nickel, zinc oxide, cerium dioxide, and silicon dioxide. Based on the mass percentage of the catalyst, its composition is: Ni content 20-60%, zinc oxide content 0.5-5%, cerium dioxide content 10-30%, and the remainder being silicon dioxide. This catalyst is prepared by a co-precipitation method, requires mild catalytic reaction conditions, and possesses advantages such as high activity at low temperatures and high selectivity for tetrahydrofuran, showing promising prospects for industrial application.

Description

Technical Field

[0001] This invention relates to a catalyst for the continuous hydrogenation of furan to tetrahydrofuran; this invention also relates to a method for preparing the above-mentioned catalyst; and this invention further relates to the application of the above-mentioned catalyst in the continuous hydrogenation of furan to tetrahydrofuran reaction. Background Technology

[0002] Tetrahydrofuran is widely used as a solvent due to its advantages such as low toxicity, low boiling point, good fluidity, and good solubility. Furthermore, tetrahydrofuran is an important chemical used in the production of PTMEG, a raw material for spandex and polyurethane. Currently, industrially, tetrahydrofuran is mainly obtained through the dehydration of 1,4-butanediol. Hydrogenation of furan to produce tetrahydrofuran is another production route.

[0003] US Patent 2033292 discloses a method for preparing tetrahydrofuran from furan using an iron-based catalyst in a liquid-phase system under high temperature and high pressure conditions, requiring ethanol as a diluent during the reaction. Korean Patent KR1020200022575 discloses a method for catalyzing the hydrogenation of furan to tetrahydrofuran using a biomass porous carbon-supported Ru-Re bimetallic catalyst, achieving a tetrahydrofuran content of approximately 70% in the product. CN115445623A discloses a catalyst for the continuous hydrogenation of furan to tetrahydrofuran, its preparation method, and its applications. Using silica-supported alkaline earth metal-promoted nickel as a catalyst, the hydrogenation of furan to tetrahydrofuran is catalyzed at 180–200°C and 2–10 MPa pressure, achieving a maximum tetrahydrofuran selectivity of approximately 96%. After 240 hours of catalyst operation, the residual furan content in the product increased from 1% to 6.9%, indicating slow deactivation of the catalyst during operation. CN112547071A discloses a catalyst for the hydrogenation of furan to tetrahydrofuran, its preparation method, and its application. A nickel catalyst is supported on a TiO2-Al2O3 composite support. Under reaction conditions of 210℃ and 3MPa, the liquid hourly space velocity (LHSV) of furan is 1 h⁻¹. -1 When the hydrogen-to-oil molar ratio is 1000, the furan conversion rate is 98.09% and the tetrahydrofuran selectivity is 92.01%.

[0004] The published patents suffer from one or more of the following problems: use of precious metal catalysts, high reaction temperatures, high reaction pressures, poor stability, and low selectivity for tetrahydrofuran. To address these problems, this invention discloses a low-cost nickel-based catalyst for the highly selective continuous hydrogenation of furan to tetrahydrofuran under mild reaction conditions. The catalyst achieves a 98% furan conversion while maintaining a tetrahydrofuran selectivity of at least 99%, and its stability exceeds 1000 hours. Summary of the Invention

[0005] To address the issues of low selectivity and stability in existing methods for the hydrogenation of furan to tetrahydrofuran, a supported, inexpensive nickel-based catalyst with high low-temperature activity, high selectivity for tetrahydrofuran, and excellent stability, along with its preparation method, has been invented. The specific details of the invention are as follows:

[0006] In a preferred embodiment, the catalyst is composed of nickel, zinc oxide, cerium dioxide, and silicon dioxide.

[0007] In a preferred embodiment, the catalyst contains 20-60% nickel by mass, preferably 25-55%, more preferably 30-50%, and most preferably 40-50%; zinc oxide contains 0.5-5% zinc oxide by mass, preferably 0.8-4.5%, more preferably 1-4%, and most preferably 2-3%; cerium dioxide contains 10-30% cerium dioxide by mass, preferably 13-27%, more preferably 16-25%, and most preferably 20-25%; the remainder is silicon dioxide.

[0008] A method for preparing a catalyst for the continuous hydrogenation of furan to tetrahydrofuran, characterized in that: the catalyst is prepared by a co-precipitation method, specifically according to the following steps:

[0009] a) Dissolve the precursors of nickel, zinc and cerium in water and / or an organic solvent, stir to mix them evenly, and obtain a metal salt solution with a metal molar concentration of 0.2 to 2 mol / L;

[0010] b) Add silica sol and / or solid silica to the mixed salt solution in step a) above, and stir to mix evenly;

[0011] c) Prepare a sodium hydroxide solution, or a sodium carbonate solution, or a mixed solution of sodium hydroxide and sodium carbonate to obtain a precipitant solution with a sodium ion concentration of 0.4 to 4 mol / L;

[0012] d) The precipitant solution obtained in step c is added dropwise to the metal salt solution obtained in step b for precipitation. The volume ratio of the precipitant solution to the metal salt solution is 1 to 4. After precipitation, the mixture is aged and stirred at 50 to 80°C for 1 to 10 hours. The mixture is then filtered or vacuum filtered to obtain a filter cake. The filter cake is washed until the filtrate is neutral.

[0013] e) The sample obtained in step d is dried in air at a temperature of 50–150°C (preferably 60–140°C, more preferably 70–130°C, and most preferably 80–120°C) for 4–48 hours (preferably 6–40 hours, more preferably 10–30 hours, and most preferably 12–24 hours), and then calcined at a temperature of 300–600°C (preferably 350–550°C, more preferably 400–500°C, and most preferably 425–475°C) for 2–48 hours (preferably 3–36 hours, more preferably 4–24 hours, and most preferably 4–10 hours) to obtain the catalyst precursor;

[0014] f) The catalyst precursor obtained in step e is activated to obtain a catalyst for the continuous hydrogenation of furan to tetrahydrofuran.

[0015] In a preferred embodiment, the catalyst activation treatment in step f is carried out in a hydrogen or hydrogen-containing mixed atmosphere, wherein the hydrogen volume content in the activation gas is 1-100%, and the other gases in the mixed gas besides hydrogen are one or more of nitrogen, argon, or helium; the space velocity of the hydrogen-containing mixed gas is 500-10000 h⁻¹. -1 Preferred operating time: 700-8000h -1 More preferably 1000-6000h -1 The optimal range is 1000-4000h. -1 The activation temperature is 200–700℃, preferably 250–650℃, more preferably 300–600℃, and most preferably 400–550℃; the activation time is 1–100 hours, preferably 3–80 hours, more preferably 5–60 hours, and most preferably 12–48 hours; and the activation pressure is 0.1–5.0 MPa, preferably 0.1–4.0 MPa, more preferably 0.1–3.0 MPa, and most preferably 0.1–1.0 MPa.

[0016] In a preferred embodiment, the catalyst is activated either outside the reactor or in situ within the reactor.

[0017] In a preferred embodiment, the precursors of nickel, zinc, and cerium are nitrates of nickel, zinc, and cerium, respectively.

[0018] Application of a furan hydrogenation catalyst in the catalytic continuous hydrogenation of furan to tetrahydrofuran.

[0019] In a preferred embodiment, the furan hydrogenation reaction is carried out under the following conditions: a reaction temperature of 50–200°C, preferably 60–170°C, more preferably 70–150°C, and most preferably 80–130°C; a reaction pressure of 0.1–6.0 MPa, preferably 0.5–5.0 MPa, more preferably 0.8–4.0 MPa, and most preferably 1–3.0 MPa; and a space velocity of 0.01–6 h⁻¹.-1 Preferred time: 0.1–5 h -1 More preferably 0.5 to 4 hours -1 The optimal time is 0.5 to 2 hours. -1 The molar ratio of hydrogen to furan is 4–400, preferably 10–300, more preferably 20–200, and most preferably 30–60.

[0020] In a preferred embodiment, the continuous hydrogenation reaction of furan is carried out in a fixed-bed reactor.

[0021] This catalyst was prepared by co-precipitation. The catalyst requires mild catalytic reaction conditions and has the advantages of high activity at low temperatures and high selectivity for tetrahydrofuran, showing good prospects for industrial application.

[0022] The beneficial effects of this invention include, but are not limited to, the following: Compared with existing catalysts for the hydrogenation of furan to tetrahydrofuran, this invention constructs a multi-component composite catalyst of nickel-zinc oxide-cerium dioxide-silica. The multi-component catalyst prepared by the co-precipitation method has excellent low-temperature furan hydrogenation activity and tetrahydrofuran selectivity, endows the catalyst with excellent long-range stability, and effectively improves the economic benefits of the reaction process for the hydrogenation of furan to tetrahydrofuran. Detailed Implementation

[0023] The catalyst of the present invention is implemented according to the above steps. The following is a detailed description through examples. Unless otherwise specified, the content and percentage in this application are calculated by "mass".

[0024] Example 1

[0025] 49.5 g of Ni(NO3)2·6H2O, 2.2 g of Zn(NO3)2·6H2O, and 12.6 g of Ce(NO3)3·6H2O were dissolved in 170 mL of water and stirred until homogeneous. Then, 14.7 g of 30% silica sol was added to obtain a salt solution. 33 g of sodium carbonate was dissolved in 310 mL of deionized water to obtain a precipitant solvent. Under stirring at 50 °C, the sodium carbonate solution was added dropwise to the metal salt solution at a rate of 10 mL / min. After the addition was complete, aging and stirring continued for 4 hours. The solution was then filtered, and the filter cake was washed with deionized water until the filtrate became colorless. The filter cake was dried at 120 °C for 10 hours to constant weight and calcined at 400 °C for 5 hours. The catalyst was prepared by granulation and tableting. The catalyst designation is A, with a composition of 50Ni-3ZnO-25CeO2-22SiO2. (The numbers represent their mass content in the catalyst, % below) The catalyst obtained above was applied to the continuous hydrogenation of furan to tetrahydrofuran. The catalyst was reduced in hydrogen at a temperature of 400℃, a reduction time of 4 h, a reduction pressure of 0.5 MPa, and a reducing gas space velocity of 1000 h⁻¹. -1The hydrogenation reaction of furan was carried out at a temperature of 100℃, a reaction pressure of 1.5 MPa, and a liquid hourly space velocity (LISH) of 1.0 h⁻¹. -1 The results of the hydrogen / furan hydrogenation reaction with a hydrogen / furan molar ratio of 50 and a catalyst are listed in Table 1.

[0026] Example 2

[0027] Except for changing the amount of Zn(NO3)2·6H2O to 1.5 g and the mass of 30% silica sol to 15.3 g, the other steps (process and conditions) for catalyst preparation are the same as in Example 1. The catalyst is designated as B, with a composition of 50Ni-2ZnO-25CeO2-23SiO2. The catalyst reaction conditions are the same as in Example 1, and the results of the furan hydrogenation reaction of the catalyst are listed in Table 1.

[0028] Example 3

[0029] Except for changing the amount of Ce(NO3)3·6H2O to 10.1 g and the mass of 30% silica sol to 18 g, the other steps (process and conditions) for catalyst preparation are the same as in Example 1. The catalyst is designated as C, and its composition is 50Ni-3ZnO-20CeO2-27SiO2. The catalyst reaction conditions are the same as in Example 1, and the results of the furan hydrogenation reaction of the catalyst are listed in Table 1.

[0030] Example 4

[0031] Except for changing the amount of Ce(NO3)3·6H2O to 11.6 g and the mass of 30% silica sol to 16 g, the other steps (process and conditions) for catalyst preparation are the same as in Example 1. The catalyst is designated as D, with a composition of 50Ni-3ZnO-23CeO2-24SiO2. The catalyst reaction conditions are the same as in Example 1, and the results of the furan hydrogenation reaction of the catalyst are listed in Table 1.

[0032] Example 5

[0033] Except for changing the amount of Ni(NO3)2·6H2O to 39.6 g and the mass of 30% silica sol to 21.3 g, the other steps (process and conditions) for catalyst preparation are the same as in Example 1. The catalyst is designated as E, with a composition of 40Ni-3ZnO-25CeO2-32SiO2. The catalyst reaction conditions are the same as in Example 1, and the results of the furan hydrogenation reaction of the catalyst are listed in Table 1.

[0034] Example 6

[0035] Except for replacing the precipitant in Example 1 with sodium hydroxide, the other steps (process and conditions) for catalyst preparation are the same as in Example 1. Specifically, 24.8 g of sodium hydroxide was weighed and dissolved in 620 mL of water to obtain a precipitant solution. The catalyst is designated as F, with a composition of 50Ni-3ZnO-25CeO2-22SiO2. The catalyst reaction conditions are the same as in Example 1, and the results of the furan hydrogenation reaction of the catalyst are listed in Table 1.

[0036] Example 7

[0037] Except for changing the precipitation aging temperature in Example 1 to 70 degrees Celsius, the other steps (process and conditions) for catalyst preparation are the same as in Example 1. The catalyst is designated as G, with a composition of 50Ni-3ZnO-25CeO2-22SiO2. The catalyst reaction conditions are the same as in Example 1, and the results of the furan hydrogenation reaction of the catalyst are listed in Table 1.

[0038] Example 8

[0039] The composition and preparation process of the catalyst are the same as in Example 1. The reaction conditions of the catalyst in Example 1 are changed to: the catalyst is reduced in hydrogen at a temperature of 450°C, a reduction time of 4 h, a reduction pressure of 0.5 MPa, and a reducing gas space velocity of 1000 h⁻¹. -1 The reaction temperature for furan hydrogenation was 110℃, the reaction pressure was 3.0 MPa, and the liquid hourly space velocity (LISH) for furan was 2.0 h⁻¹. -1 The hydrogen / furan molar ratio was 30, and the results of the furan hydrogenation reaction with catalyst are listed in Table 1.

[0040] Example 9

[0041] The composition and preparation process of the catalyst are the same as in Example 1. The reaction conditions of the catalyst in Example 1 are changed to: reduction of the catalyst in hydrogen at a temperature of 380°C, a reduction time of 10 h, a reduction pressure of 1.0 MPa, and a reducing gas space velocity of 1000 h⁻¹. -1 The reaction temperature for furan hydrogenation was 80℃, the reaction pressure was 3.0 MPa, and the liquid hourly space velocity (LISH) for furan was 0.5 h⁻¹. -1 The hydrogen / furan molar ratio was 60, and the results of the furan hydrogenation reaction with catalyst are listed in Table 1.

[0042] Example 10

[0043] The composition and preparation process of the catalyst are the same as in Example 1. The reaction conditions of the catalyst in Example 1 are changed to: reduction of the catalyst in hydrogen at a temperature of 430°C, a reduction time of 24 h, a reduction pressure of 0.1 MPa, and a reducing gas space velocity of 1000 h⁻¹. -1 The reaction temperature for furan hydrogenation was 130℃, the reaction pressure was 2.0 MPa, and the liquid hourly space velocity (LISH) for furan was 0.5 h⁻¹. -1 The stability results of continuous operation of the hydrogen / furan hydrogenation catalyst with a hydrogen / furan molar ratio of 40 are listed in Table 2.

[0044] Comparative Example 1

[0045] 49.5 g of Ni(NO3)2·6H2O was dissolved in 130 mL of water and stirred until homogeneous. Then, 33.3 g of 30% silica sol was added to obtain a salt solution. 27.1 g of sodium carbonate was dissolved in 255 mL of deionized water to obtain a precipitant solvent. Under stirring at 50 °C, the sodium carbonate solution was added dropwise to the metal salt solution at a rate of 10 mL / min. After the addition was complete, aging and stirring continued for 4 hours. The solution was then filtered, and the filter cake was washed with deionized water until the filtrate became colorless. The filter cake was dried at 120 °C for 10 hours to constant weight and calcined at 400 °C for 5 hours. The catalyst was prepared by granulation and tableting. The catalyst designation is H, and the composition is 50Ni-50SiO2. The catalyst obtained above was applied to the continuous hydrogenation of furan to tetrahydrofuran reaction. The catalyst was reduced in hydrogen at a temperature of 400 °C, a reduction time of 4 h, a reduction pressure of 0.5 MPa, and a reducing gas space velocity of 1000 h⁻¹. -1 The hydrogenation reaction of furan was carried out at a temperature of 100℃, a reaction pressure of 1.5 MPa, and a liquid hourly space velocity (LISH) of 1.0 h⁻¹. -1 The results of the hydrogen / furan hydrogenation reaction with a hydrogen / furan molar ratio of 50 and a catalyst are listed in Table 1.

[0046] Comparative Example 2

[0047] 49.5 g of Ni(NO3)2·6H2O and 12.6 g of Ce(NO3)3·6H2O were dissolved in 170 mL of water and stirred until homogeneous. Then, 16.7 g of 30% silica sol was added to obtain a salt solution. 33 g of sodium carbonate was dissolved in 310 mL of deionized water to obtain a precipitant solvent. Under stirring at 50 °C, the sodium carbonate solution was added dropwise to the metal salt solution at a rate of 10 mL / min. After the addition was complete, aging and stirring continued for 4 hours. The solution was then filtered, and the filter cake was washed with deionized water until the filtrate became colorless. The filter cake was dried at 120 °C for 10 hours to constant weight and calcined at 400 °C for 5 hours. The catalyst was prepared by granulation and tableting. The catalyst designation is I, with a composition of 50Ni-25CeO2-25SiO2. The catalyst obtained above was applied to the continuous hydrogenation of furan to tetrahydrofuran. The catalyst was reduced in hydrogen at a temperature of 400°C for 4 hours, a reduction pressure of 0.5 MPa, and a reducing gas space velocity of 1000 h⁻¹. -1 The hydrogenation reaction of furan was carried out at a temperature of 100℃, a reaction pressure of 1.5 MPa, and a liquid hourly space velocity (LISH) of 1.0 h⁻¹. -1 The results of the hydrogen / furan hydrogenation reaction with a hydrogen / furan molar ratio of 50 and a catalyst are listed in Table 1.

[0048] Comparative Example 3

[0049] 49.5 g of Ni(NO3)2·6H2O, 2.2 g of Zn(NO3)2·6H2O, and 12.6 g of Ce(NO3)3·6H2O were dissolved in 170 mL of water and stirred until homogeneous. Then, 4.4 g of 100-mesh coconut shell carbon powder was added to obtain a salt precursor suspension. 33 g of sodium carbonate was dissolved in 310 mL of deionized water to obtain a precipitant solvent. Under stirring at 50 °C, the sodium carbonate solution was added dropwise to the metal salt precursor suspension at a rate of 10 mL / min. After the addition was complete, aging and stirring continued for 4 hours. The mixture was then filtered, and the filter cake was washed with deionized water until the filtrate became colorless. The filter cake was dried at 120 °C for 10 hours to constant weight and calcined at 400 °C for 5 hours. The catalyst was prepared by granulation and tableting. The catalyst designation is J, and the composition is 50Ni-3ZnO-25CeO2-22AC. The catalyst obtained above was applied to the continuous hydrogenation of furan to tetrahydrofuran. The catalyst was reduced in hydrogen at a temperature of 400°C for 4 hours, a reduction pressure of 0.5 MPa, and a reducing gas space velocity of 1000 h⁻¹. -1 The hydrogenation reaction of furan was carried out at a temperature of 100℃, a reaction pressure of 1.5 MPa, and a liquid hourly space velocity (LISH) of 1.0 h⁻¹. -1 The results of the hydrogen / furan hydrogenation reaction with a hydrogen / furan molar ratio of 50 and a catalyst are listed in Table 1.

[0050] Table 1. Furan hydrogenation performance of different catalysts

[0051]

[0052]

[0053] Table 2. Stability data of furan continuous hydrogenation in Example 9

[0054] Reaction time / hour Furan conversion rate / % Tetrahydrofuran selectivity / % 24 99.91 99.52 96 99.86 99.49 168 99.76 99.69 240 99.43 99.61 312 99.57 99.48 384 99.29 99.57 456 99.74 99.44 528 99.65 99.61 600 99.59 99.39 672 99.40 99.47 744 99.29 99.46 816 99.76 99.55 888 99.49 99.61 960 99.32 99.51 1000 99.51 99.60

[0055] As shown in Table 1, the nickel-zinc oxide-cerium dioxide-silica multi-component inexpensive metal catalyst of this invention can catalyze the hydrogenation of furan with high activity and high selectivity to prepare tetrahydrofuran, achieving a furan conversion rate exceeding 98% and a tetrahydrofuran selectivity exceeding 99%. As shown in Table 2, the catalyst disclosed in this invention exhibits excellent stability; no significant performance degradation was observed after 1000 hours of operation. Therefore, the catalyst provided by this invention demonstrates excellent activity, tetrahydrofuran selectivity, and reaction stability in the continuous hydrogenation of furan to tetrahydrofuran. This invention demonstrates superior performance compared to existing patents in terms of reaction conditions, activity, product selectivity, and stability, and has considerable potential for industrial application.

Claims

1. A method for preparing a catalyst for the continuous hydrogenation of furan to tetrahydrofuran, characterized in that: The catalyst is composed of nickel, zinc oxide, cerium dioxide, and silicon dioxide; The catalyst was prepared by co-precipitation, specifically according to the following steps: a) Dissolve the precursors of nickel, zinc and cerium in water and stir to mix them evenly to obtain a metal salt solution with a metal molar concentration of 0.2~2 mol / L; b) Add silica sol and / or silica solid to the mixed salt solution in step a) above, and stir to mix evenly; c) Prepare a sodium hydroxide solution, or a sodium carbonate solution, or a mixed solution of sodium hydroxide and sodium carbonate to obtain a precipitant solution with a sodium ion concentration of 0.4~4 mol / L; d) Add the precipitant solution obtained in step c) dropwise to the metal salt solution obtained in step b for precipitation. The volume ratio of the precipitant solution to the metal salt solution is 1~4. After precipitation, the mixture is aged and stirred at 50~80℃ for 1~10 hours. Filter the mixture by suction or filtration to obtain a filter cake. Wash the filter cake until the filtrate is neutral. e) Dry the sample obtained in step d) in air at 50-150°C for 4-48 hours and calcine it at 300-600°C for 2-48 hours to obtain the catalyst precursor. f) The catalyst precursor obtained in step e) is activated to obtain a catalyst for the continuous hydrogenation of furan to tetrahydrofuran.

2. The method for preparing the catalyst according to claim 1, characterized in that: Step e) Dry the sample obtained in step d) in air at 60~140℃ for 6~40 hours and calcine it at 350~550℃ for 3~36 hours to obtain the catalyst precursor.

3. The method for preparing the catalyst according to claim 1, characterized in that: Step e) Dry the sample obtained in step d) in air at 70~130℃ for 10~30 hours and calcine it at 400~500℃ for 4~24 hours to obtain the catalyst precursor.

4. The method for preparing the catalyst according to claim 1, characterized in that: Step e) Dry the sample obtained in step d) in air at 80~120℃ for 12~24 hours and calcine it at 425~475℃ for 4~10 hours to obtain the catalyst precursor.

5. The method for preparing the catalyst according to claim 1, characterized in that: The nickel content in the catalyst is 20-60% of the catalyst mass. The zinc oxide content is 0.5-5% of the catalyst mass, the cerium dioxide content is 10-30% of the catalyst mass, and the remainder is silicon dioxide.

6. The method for preparing the catalyst according to claim 5, characterized in that: The catalyst contains 25-55% nickel and 0.8-4.5% zinc oxide by mass. The cerium dioxide content is 13-27% of the catalyst mass.

7. The method for preparing the catalyst according to claim 5, characterized in that: The catalyst contains 30-50% nickel by mass, 1-4% zinc oxide by mass, and 16-25% cerium dioxide by mass.

8. The method for preparing the catalyst according to claim 5, characterized in that: The catalyst contains 40-50% nickel by mass, 2-3% zinc oxide by mass, and 20-25% cerium dioxide by mass.

9. The method for preparing the catalyst according to claim 1, characterized in that: The activation treatment of the catalyst in step f) is carried out in a hydrogen or hydrogen-containing mixed atmosphere, wherein the hydrogen volume content in the activation gas is 1-100%, and the other gases in the mixed gas besides hydrogen are one or more of nitrogen, argon, or helium; the space velocity of the hydrogen-containing mixed gas is 500-10000 h⁻¹. -1 The activation temperature is 200~700℃, the activation time is 1~100 hours, and the activation pressure is 0.1~5.0MPa.

10. The method for preparing the catalyst according to claim 9, characterized in that: In step f), the space velocity of the hydrogen-containing gas mixture is 700~8000 h⁻¹. -1 The activation temperature is 250~650℃, the activation time is 3~80 hours, and the activation pressure is 0.1~4.0MPa.

11. The method for preparing the catalyst according to claim 9, characterized in that: In step f), the space velocity of the hydrogen-containing gas mixture is 1000~6000 h⁻¹. -1 The activation temperature is 300~600℃, the activation time is 5~60 hours, and the activation pressure is 0.1~3.0MPa.

12. The method for preparing the catalyst according to claim 9, characterized in that: In step f), the space velocity of the hydrogen-containing gas mixture is 1000~4000 h⁻¹. -1 The activation temperature is 400~550℃, the activation time is 12~48 hours, and the activation pressure is 0.1~1.0MPa.

13. The preparation method according to claim 1 or 9, characterized in that: The catalyst is activated either outside the reactor or in situ within the reactor.

14. The preparation method according to claim 1, characterized in that: The precursors of nickel, zinc, and cerium in step a) are nitrates of nickel, zinc, and cerium, respectively.

15. The use of a catalyst prepared by any one of the preparation methods described in claims 1-14 in the catalytic continuous hydrogenation of furan to tetrahydrofuran reaction.

16. The application according to claim 15, characterized in that: The furan hydrogenation reaction is carried out under the following conditions: reaction temperature of 50~200℃, reaction pressure of 0.1~6.0MPa, and space velocity of 0.01~6h. -1 The molar ratio of hydrogen to furan is 4 to 400.

17. The application according to claim 15, wherein the continuous hydrogenation reaction of furan is carried out in a fixed-bed reactor.

18. The application according to claim 16, characterized in that: The furan hydrogenation reaction is carried out under the following conditions: reaction temperature of 60~170℃, reaction pressure of 0.5~5.0MPa, and space velocity of 0.1~5h⁻¹. -1 The molar ratio of hydrogen to furan is 10 to 300.

19. The application according to claim 16, characterized in that: The furan hydrogenation reaction is carried out under the following conditions: reaction temperature of 70~150℃, reaction pressure of 0.8~4.0MPa, and space velocity of 0.5~4h. -1 The molar ratio of hydrogen to furan is 20 to 200.

20. The application according to claim 16, characterized in that: The furan hydrogenation reaction is carried out under the following conditions: reaction temperature of 80~130℃, reaction pressure of 1~3.0MPa, and space velocity of 0.5~2h. -1 The molar ratio of hydrogen to furan is 30 to 60.

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