A catalyst for hydrogenation of furan to tetrahydrofuran and its preparation and use

Abstract

The application discloses a catalyst for preparing tetrahydrofuran from furan hydrogenation and preparation and application thereof. According to the application, the catalyst comprises a first metal component, a second metal component, an auxiliary agent and a carrier, wherein the first metal component is nickel, the second metal component is copper, the auxiliary agent is cerium dioxide, and the carrier is silicon dioxide or diatomic aluminum oxide. The composition is as follows based on the catalyst mass percentage: the mass content of Ni element is 10-60%, the mass content of Cu element is 1-20%, the mass content of cerium dioxide is 0.5-5%, and the rest is the carrier. The catalyst is prepared by using a traditional impregnation method, the preparation method is simple, the required catalytic reaction condition is mild, the catalyst has the advantages of high catalytic activity and high tetrahydrofuran selectivity, the yield of tetrahydrofuran prepared from furan hydrogenation can be improved by using the catalyst, and the catalyst has a good industrial application prospect.

Description

Technical Field

[0001] This invention relates to a catalyst for the hydrogenation of furan to tetrahydrofuran.

[0002] The present invention also relates to a method for preparing the above-mentioned catalyst.

[0003] This invention also relates to the application of the above-mentioned catalyst in the hydrogenation of furan to tetrahydrofuran. Technical Background

[0004] Tetrahydrofuran is an important chemical, primarily used in the production of PTMEG, a raw material for spandex. Due to its advantages such as low toxicity, low boiling point, good flowability, and good solubility, tetrahydrofuran is widely used as a solvent. Currently, industrially, tetrahydrofuran is mainly obtained through the dehydration of 1,4-butanediol. Hydrogenation of furan to produce tetrahydrofuran is another production route.

[0005] 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%.

[0006] The published patents suffer from one or more of the following problems: use of precious metal catalysts, high reaction temperatures, high reaction pressures, use of diluent solvents, poor stability, and low selectivity for tetrahydrofuran. To address these problems, this invention discloses a supported multi-component non-precious metal catalyst that achieves highly selective continuous hydrogenation of furan to tetrahydrofuran under mild reaction conditions. The catalyst achieves a furan conversion rate exceeding 99% and a tetrahydrofuran selectivity greater than 98% under reaction conditions of 110°C and 2 MPa, and its stability exceeds 600 hours. Summary of the Invention

[0007] 1. A catalyst for the hydrogenation of furan to tetrahydrofuran, the catalyst comprising a first metal component, a second metal component, an additive, and a support, wherein the first metal component is nickel, the second metal component is copper, the additive is cerium dioxide, and the support is silicon dioxide or aluminum oxide.

[0008] 2. In a preferred embodiment, the catalyst contains 10-60% nickel by mass, preferably 15-50%, more preferably 20-45%, and most preferably 30-40% copper by mass, preferably 3-17% copper by mass, more preferably 5-15% copper by mass, and most preferably 8-10% cerium dioxide by mass, preferably 1-4.5% cerium dioxide by mass, more preferably 1.5-4% cerium dioxide by mass, and most preferably 2-4% cerium dioxide by mass.

[0009] 3. Another aspect of the present invention is to provide a method for preparing the above-mentioned catalyst for the hydrogenation of furan to tetrahydrofuran, said method being a two-stage impregnation method, specifically carried out according to the following steps:

[0010] a) Dissolve the precursors of nickel, copper and cerium salts in deionized water or an organic solvent. The amount of nickel, copper and cerium salts used is 30%-70% of the theoretical metal salt requirement. Stir to mix them evenly to obtain a salt solution of the metal precursors.

[0011] b) Slowly add the silica or alumina carrier to the above mixed salt solution and stir until homogeneous.

[0012] c) The sample obtained in step b is air-dried at room temperature for 4 to 96 hours, preferably 6 to 72 hours, more preferably 8 to 48 hours, and most preferably 12 to 24 hours; dried in air at a temperature of 323 to 423 K (preferably 333 to 413 K, more preferably 353 to 403 K, and most preferably 373 to 393 K) for 8 to 24 hours (preferably 8 to 20 hours, more preferably 10 to 18 hours, and most preferably 12 to 15 hours); and calcined at a temperature of 473 to 773 K (preferably 523 to 773 K, more preferably 573 to 773 K, and most preferably 623 to 723 K) for 2 to 48 hours (preferably 3 to 36 hours, more preferably 4 to 24 hours, and most preferably 4 to 12 hours) to obtain the first precursor loaded with the active component oxide.

[0013] d) Dissolve the precursors of nickel, copper and cerium salts in deionized water or an organic solvent. The amount of nickel, copper and cerium salts used is the theoretical amount of metal salts minus the amount used in the first impregnation. Stir to mix them evenly to obtain a salt solution of the metal precursors.

[0014] e) Slowly add the first precursor obtained in step c to the above mixed salt solution and stir until homogeneous.

[0015] f) The sample obtained in step c is air-dried at room temperature for 4–96 hours, preferably 6–72 hours, more preferably 8–48 hours, and most preferably 12–24 hours; then dried in air at a temperature of 323–423 K (preferably 333–413 K, more preferably 353–403 K, and most preferably 373–393 K) for 8–24 hours (preferably 8–20 hours, more preferably 10–18 hours, and most preferably 12–15 hours); and then calcined at a temperature of 473–773 K (preferably 523–773 K, more preferably 573–773 K, and most preferably 623–723 K) for 2–48 hours (preferably 3–36 hours, more preferably 4–24 hours, and most preferably 4–12 hours) to obtain the catalyst loaded with the active component oxide.

[0016] g) The sample obtained in step f is activated to obtain a catalyst for the hydrogenation of furan to tetrahydrofuran.

[0017] 4. In a preferred embodiment, the catalyst activation is carried out in a hydrogen-containing mixed atmosphere, wherein the hydrogen content of the mixed atmosphere is 1% to 100%, and the other gases in the mixed atmosphere besides hydrogen are nitrogen, argon, or helium; the space velocity of the hydrogen-containing mixed atmosphere is 500 to 10000 h⁻¹. -1 Preferred operating time: 700-8000h -1 More preferably 1000-6000h -1 The optimal time is 2000-4000h. -1 The activation temperature is 473K to 973K, preferably 523K to 873K, more preferably 573K to 773K, and most preferably 623K to 723K. The activation time is 1 to 100 hours, preferably 3 to 80 hours, more preferably 5 to 60 hours, and most preferably 12 to 48 hours. The activation pressure is 0.1 to 5.0MPa, preferably 0.1 to 4.0MPa, more preferably 0.1 to 3.0MPa, and most preferably 0.1 to 1.0MPa.

[0018] 5. In a preferred embodiment, the mass concentration of salt in the mixed salt solution of steps a) and d) is 20% to 60%, preferably 25% to 55%, more preferably 30% to 50%, and most preferably 35% to 45%.

[0019] The nickel, copper, and cerium salts are nitrates of nickel, copper, and cerium, respectively.

[0020] 6. In a preferred embodiment, the catalyst is activated either in vitro or in situ.

[0021] 7. Another aspect of the invention is to provide the application of the catalyst in the hydrogenation of furan to tetrahydrofuran, wherein the application is carried out under the following conditions: a reaction temperature of 323–473 K, preferably 333–453 K, more preferably 343–433 K, and most preferably 363–413 K; 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 Preferably 0.1–5 h -1 More preferably 0.3 to 4 hours -1 The optimal time is 0.5 to 3 hours. -1 The molar ratio of hydrogen to furan is 4–400, preferably 10–300, more preferably 20–200, and most preferably 50–100.

[0022] 8. In a preferred embodiment, the reaction is carried out in a fixed-bed reactor.

[0023] The catalyst prepared using the catalyst of the present invention or the preparation method of the present invention, or the application of the present invention for the hydrogenation of furan to tetrahydrofuran, exhibits a furan conversion rate of over 99%, a tetrahydrofuran selectivity of over 98%, and the catalyst can operate stably for over 600 hours.

[0024] This catalyst is prepared by a traditional impregnation method, which is simple to prepare and requires mild catalytic reaction conditions. It has the advantages of high catalytic activity and high selectivity for tetrahydrofuran. Using the catalyst of this invention can improve the yield of tetrahydrofuran produced by the hydrogenation of furan and has good prospects for industrial application. Attached Figure Description

[0025] Figure 1 Example 9: XRD pattern of the sample after catalyst activation.

[0026] Figure 2 Stability of tetrahydrofuran produced by hydrogenation of furan. Detailed Implementation

[0027] The present invention will be further described below through specific embodiments and comparative examples.

[0028] Example 1

[0029] Preparation of multi-component catalyst: 18.4 g of nickel nitrate hexahydrate, 3.5 g of copper nitrate trihydrate, and 0.9 g of cerium nitrate hexahydrate were added to 13 g of deionized water and dissolved under heating and stirring to obtain a clear solution. 10 g of γ-alumina support was added to the above solution, and the mixture was air-dried at room temperature for 24 hours, dried at 120°C for 12 hours, and calcined at 450°C for 4 hours to obtain precursor sample A. A was subjected to a second impregnation treatment using the same method. Specifically, 18.4 g of nickel nitrate hexahydrate, 3.5 g of copper nitrate trihydrate, and 0.9 g of cerium nitrate hexahydrate were added to 13 g of deionized water and dissolved under heating and stirring to obtain a clear solution. 10 g of precursor A was added to the above solution, and the mixture was allowed to stand at room temperature for 24 hours, dried at 120°C for 12 hours, and calcined at 450°C for 4 hours to obtain catalyst B. The catalyst composition is 40Ni10Cu4CeO2 / γ-Al2O3, where Ni contains 40% by mass, Cu contains 10% by mass, and CeO2 contains 4% by mass. The catalyst composition is the same as that of the hydrogen-activated sample (catalyst loading is 1g, and the catalyst was activated with hydrogen under the following conditions: 400℃, 0.1MPa, and hydrogen space velocity 2000h⁻¹). -1 The restoration process takes 20 hours.

[0030] Example 2

[0031] The catalyst C has the composition 35Ni10Cu4CeO2 / γ-Al2O3. Except for the weighing of 17.7 g of nickel nitrate hexahydrate, 3.9 g of copper nitrate trihydrate and 1.0 g of cerium nitrate hexahydrate in the first and second impregnation processes, the other steps (process and conditions) are the same as in Example 1.

[0032] Example 3

[0033] The catalyst D has the composition 30Ni10Cu4CeO2 / γ-Al2O3. Except for the weighing of 16.9 g of nickel nitrate hexahydrate, 4.3 g of copper nitrate trihydrate and 1.1 g of cerium nitrate hexahydrate in the first and second impregnation processes, the other steps (process and conditions) are the same as in Example 1.

[0034] Example 4

[0035] The catalyst E has the composition 40Ni9Cu4CeO2 / γ-Al2O3. Except for the weighing of 18.7 g of nickel nitrate hexahydrate, 3.2 g of copper nitrate trihydrate and 0.9 g of cerium nitrate hexahydrate in the first and second impregnation processes, the other steps (process and conditions) are the same as in Example 1.

[0036] Example 5

[0037] The catalyst F has the composition 40Ni8Cu4CeO2 / γ-Al2O3. Except for the weighing of 19 g of nickel nitrate hexahydrate, 2.9 g of copper nitrate trihydrate and 1.0 g of cerium nitrate hexahydrate in the first and second impregnation processes, the other steps (process and conditions) are the same as in Example 1.

[0038] Example 6

[0039] The catalyst G has the composition 40Ni10Cu3CeO2 / γ-Al2O3. Except for the weighing of 18.7 g of nickel nitrate hexahydrate, 3.6 g of copper nitrate trihydrate and 0.7 g of cerium nitrate hexahydrate in the first and second impregnation processes, the other steps (process and conditions) are the same as in Example 1.

[0040] Example 7

[0041] The catalyst H has the composition 40Ni10Cu2CeO2 / γ-Al2O3. Except for the weighing of 19 g of nickel nitrate hexahydrate, 3.6 g of copper nitrate trihydrate and 0.5 g of cerium nitrate hexahydrate in the first and second impregnation processes, the other steps (process and conditions) are the same as in Example 1.

[0042] Example 8

[0043] The catalyst K has the composition 40Ni10Cu4CeO2 / SiO2. Except for the use of SiO2 instead of γ-Al2O3, the other steps (process and conditions) are the same as in Example 1.

[0044] Example 9

[0045] The catalyst M has the composition 30Ni10Cu4CeO2 / SiO2. Except for the use of SiO2 instead of γ-Al2O3, the other steps (process and conditions) are the same as in Example 3.

[0046] Comparative Example 1

[0047] 24.8 g of nickel nitrate hexahydrate was added to 11 g of deionized water and dissolved under heating and stirring to obtain a clear solution. 10 g of γ-alumina support was added to the above solution, and the mixture was air-dried at room temperature for 24 hours, dried at 120°C for 12 hours, and calcined at 450°C for 4 hours to obtain precursor sample P. P was then subjected to a second impregnation treatment using the same method: 4.8 g of nickel nitrate hexahydrate was added to 11 g of deionized water and dissolved under heating and stirring to obtain a clear solution. 10 g of precursor P was added to the above solution, and the mixture was allowed to stand at room temperature for 24 hours, dried at 120°C for 12 hours, and calcined at 450°C for 4 hours to obtain catalyst Q. The catalyst composition was 40Ni / γ-Al₂O₃, where the Ni mass content was 40%.

[0048] Comparative Example 2

[0049] 19.8 g of nickel nitrate hexahydrate and 3.8 g of copper nitrate trihydrate were added to 11 g of deionized water and dissolved under heating and stirring to obtain a clear solution. 10 g of γ-alumina support was added to the above solution, and the mixture was air-dried at room temperature for 24 hours, dried at 120°C for 12 hours, and calcined at 450°C for 4 hours to obtain precursor sample R. R was subjected to a second impregnation treatment using the same method: 19.8 g of nickel nitrate hexahydrate and 3.8 g of copper nitrate trihydrate were added to 11 g of deionized water and dissolved under heating and stirring to obtain a clear solution. 10 g of precursor P was added to the above solution, and the mixture was allowed to stand at room temperature for 24 hours, dried at 120°C for 12 hours, and calcined at 450°C for 4 hours to obtain catalyst S. The catalyst composition was 40Ni10Cu / γ-Al2O3, where the mass content of Ni was 30% and the mass content of Cu was 10%.

[0050] Comparative Example 3

[0051] 23 g of nickel nitrate hexahydrate and 0.9 g of cerium nitrate hexahydrate were added to 11 g of deionized water and dissolved under heating and stirring to obtain a clear solution. 10 g of γ-alumina support was added to the above solution, and the mixture was air-dried at room temperature for 24 hours, dried at 120°C for 12 hours, and calcined at 450°C for 4 hours to obtain precursor sample T. T was subjected to a second impregnation treatment using the same method: 23 g of nickel nitrate hexahydrate and 0.9 g of cerium nitrate hexahydrate were added to 11 g of deionized water and dissolved under heating and stirring to obtain a clear solution. 10 g of precursor T was added to the above solution, and the mixture was allowed to stand at room temperature for 24 hours, dried at 120°C for 12 hours, and calcined at 450°C for 4 hours to obtain catalyst V. The catalyst composition was 40Ni3CeO2 / γ-Al2O3, where the mass content of Ni was 30% and the mass content of CeO2 was 3%.

[0052] Catalyst evaluation was conducted using a fixed-bed reactor with an inner diameter of 0.9 mm and a length of 420 mm. The catalyst loading was 1 g, followed by hydrogen activation under the following conditions: 400 °C, 0.1 MPa, and a hydrogen space velocity of 2000 h⁻¹. -1 The reduction treatment time was 20 hours. After activation, the reaction was evaluated at a lower temperature of 110°C, with a hydrogen pressure of 1 MPa and a furan mass hourly space velocity of 3 h⁻¹. -1 The molar ratio of hydrogen to furan was 60. The product was quantitatively analyzed by gas chromatography, and the results were selected based on data stable after 96 hours of reaction. The evaluation results are listed in Table 1.

[0053] Table 1. Furan hydrogenation performance of different catalysts

[0054]

[0055] As shown in Table 1, the nickel-copper-cerium dioxide multi-component non-noble metal catalyst supported on silica or alumina according to the present invention can catalyze the hydrogenation of furan with high activity and high selectivity to prepare tetrahydrofuran, with a tetrahydrofuran selectivity exceeding 98%. Furthermore, from Figure 1 It can be seen that, after activation by the catalyst of this invention, nickel in the sample mainly exists in the form of a nickel-copper alloy, while copper exists in the form of metallic copper and a nickel-copper alloy. For example... Figure 2 As can be seen, the catalyst disclosed in this invention exhibits excellent stability; no significant performance degradation was observed after 600 hours of operation. Therefore, the catalyst provided by this invention demonstrates excellent activity, tetrahydrofuran selectivity, and reaction stability in the hydrogenation of furan to tetrahydrofuran. This invention shows superior performance compared to existing patents in terms of reaction conditions, activity, product selectivity, and stability, and possesses promising prospects for industrial application.

[0056] The catalyst in Example 1 was used at a reaction temperature of 110°C, a hydrogen pressure of 1 MPa, and a furan mass hourly space velocity of 1 h⁻¹. -1 The stability was evaluated under a hydrogen to furan molar ratio of 60, and the evaluation results are as follows: Figure 2 As shown.

Claims

1. The application of a catalyst for the hydrogenation of furan to tetrahydrofuran in the catalytic reaction of furan to tetrahydrofuran, characterized in that: The catalyst comprises a first metal component, a second metal component, an additive, and a support, wherein the first metal component is nickel, the second metal component is copper, the additive is cerium dioxide, and the support is silicon dioxide and / or aluminum oxide. The activated catalyst is used in the catalytic hydrogenation of furan to tetrahydrofuran. After activation, nickel mainly exists in the form of a nickel-copper alloy, while copper exists in the form of metallic copper and a nickel-copper alloy.

2. The application of the catalyst according to claim 1 in the catalytic hydrogenation of furan to tetrahydrofuran, characterized in that: The nickel content in the catalyst is 10-60% of the catalyst mass. The copper content is 1-20% of the catalyst mass. The cerium dioxide content is 0.5-5% of the catalyst mass.

3. The application of the catalyst according to claim 2 in the catalytic hydrogenation of furan to tetrahydrofuran, characterized in that: The catalyst contains 15-50% nickel and 3-17% copper by mass. The cerium dioxide content is 1-4.5% of the catalyst mass.

4. The application of the catalyst according to claim 2 in the catalytic hydrogenation of furan to tetrahydrofuran, characterized in that: The nickel content in the catalyst is 20-45% of the catalyst mass. The copper content is 5-15% of the catalyst mass; The cerium dioxide content is 1.5 to 4% of the catalyst mass.

5. The application of the catalyst according to claim 2 in the catalytic hydrogenation of furan to tetrahydrofuran, characterized in that: The nickel content in the catalyst is 30-40% of the catalyst mass; The copper content is 8-10% of the catalyst mass; The cerium dioxide content is 2-4% of the catalyst mass.

6. The application of the catalyst according to any one of claims 1-5 in the catalytic hydrogenation of furan to tetrahydrofuran, characterized in that: The catalyst is prepared by a two-stage impregnation method, specifically following these steps: a) Dissolve the precursors of nickel, copper and cerium salts in water and / or organic solvent. The amount of nickel, copper and cerium salts used is 30%-70% of the theoretical metal salt requirement. Stir to mix them evenly to obtain a mixed salt solution of metal precursors. b) Add the silica and / or alumina support to the mixed salt solution in step a) above, and stir to mix evenly; c) The sample obtained in step b) is air-dried at room temperature for 4 to 96 hours, dried in air at 323 to 423 K for 8 to 24 hours, and calcined at 473 to 773 K for 2 to 48 hours to obtain the first precursor loaded with the active component oxide; d) Dissolve the precursors of nickel, copper and cerium salts in water and / or an organic solvent. The amount of nickel, copper and cerium salts used is the theoretical metal salt requirement minus the amount used in the first impregnation. Stir to mix them evenly to obtain a mixed salt solution of metal precursors. e) Add the first precursor obtained in step c) to the mixed salt solution in step d) above, and stir to mix evenly; f) Air-dry the sample obtained in step c) at room temperature for 4 to 96 hours; dry it in air at 323 to 423 K for 8 to 24 hours; and calcine it at 473 to 773 K for 2 to 48 hours to obtain the catalyst supported on the active component oxide. g) The sample obtained in step f) is activated to obtain a catalyst for the hydrogenation of furan to tetrahydrofuran.

7. The application of the catalyst according to claim 6 in the catalytic hydrogenation of furan to tetrahydrofuran, characterized in that: In step c), the sample obtained in step b) is air-dried at room temperature for 6 to 72 hours, dried in air at 333 to 413 K for 8 to 20 hours, and calcined at 523 to 773 K for 3 to 36 hours to obtain the first precursor loaded with active component oxide. In step f), the sample obtained in step c) is air-dried at room temperature for 6-72 hours, dried in air at 333-413 K for 8-20 hours, and calcined at 523-773 K for 3-36 hours to obtain a catalyst supported on the active component oxide.

8. The application of the catalyst according to claim 6 in the catalytic hydrogenation of furan to tetrahydrofuran, characterized in that: In step c), the sample obtained in step b) is air-dried at room temperature for 8 to 48 hours, dried in air at 353 to 403 K for 10 to 18 hours, and calcined at 573 to 773 K for 4 to 24 hours to obtain the first precursor loaded with active component oxide. In step f), the sample obtained in step c) is air-dried at room temperature for 8 to 48 hours; dried in air at 353 to 403 K for 10 to 18 hours; and calcined at 573 to 773 K for 4 to 24 hours to obtain the catalyst supported on the active component oxide.

9. The application of the catalyst according to claim 6 in the catalytic hydrogenation of furan to tetrahydrofuran, characterized in that: In step c), the sample obtained in step b) is air-dried at room temperature for 12-24 hours; dried in air at 373-393K for 12-15 hours; and calcined at 623-723K for 4-12 hours to obtain the first precursor loaded with active component oxide. In step f), the sample obtained in step c) is air-dried at room temperature for 12-24 hours; dried in air at 373-393 K for 12-15 hours; and calcined at 623-723 K for 4-12 hours to obtain a catalyst supported on the active component oxide.

10. The application of the catalyst according to claim 6 in the catalytic hydrogenation of furan to tetrahydrofuran, characterized in that: The catalyst activation is carried out in a hydrogen-containing mixed atmosphere, with a hydrogen content of 1-100%, and the other gases in the mixture being one or more of nitrogen, argon, or helium; the space velocity of the hydrogen-containing mixture is 500-10000 h⁻¹. -1 The activation temperature is 473K~973K, the activation time is 1~100 hours, and the activation pressure is 0.1~5.0MPa.

11. The application of the catalyst according to claim 10 in the catalytic hydrogenation of furan to tetrahydrofuran, characterized in that: The space velocity of the hydrogen-containing gas mixture is 700~8000 h⁻¹. -1 The activation temperature is 523~873K, the activation time is 3~80 hours, and the activation pressure is 0.1~4.0MPa.

12. The application of the catalyst according to claim 10 in the catalytic hydrogenation of furan to tetrahydrofuran, characterized in that: The space velocity of the hydrogen-containing gas mixture is 1000~6000 h⁻¹. -1 The activation temperature is 573~773K, the activation time is 5~60 hours, and the activation pressure is 0.1~3.0MPa.

13. The application of the catalyst according to claim 10 in the catalytic hydrogenation of furan to tetrahydrofuran, characterized in that: The space velocity of the hydrogen-containing gas mixture is 2000~4000 h⁻¹. -1 The activation temperature is 623~723K, the activation time is 12~48 hours, and the activation pressure is 0.1~1.0MPa.

14. The application of the catalyst according to claim 6 in the catalytic hydrogenation of furan to tetrahydrofuran, characterized in that: The catalyst is activated either in vitro or in situ.

15. The application of the catalyst according to claim 6 in the catalytic hydrogenation of furan to tetrahydrofuran, characterized in that: The salt concentration in the mixed salt solution of steps a) and d) is 20%–60% by mass. The nickel, copper, and cerium salts are nitrates of nickel, copper, and cerium, respectively.

16. The application of the catalyst according to claim 15 in the catalytic hydrogenation of furan to tetrahydrofuran, characterized in that: The mass concentration of salt in the mixed salt solution of steps a) and d) is 25% to 55%.

17. The application of the catalyst according to claim 15 in the catalytic hydrogenation of furan to tetrahydrofuran, characterized in that: The mass concentration of salt in the mixed salt solution of steps a) and d) is 30-50%.

18. The application of the catalyst according to claim 15 in the catalytic hydrogenation of furan to tetrahydrofuran, characterized in that: The mass concentration of salt in the mixed salt solution of steps a) and d) is 35% to 45%.

19. The application according to claim 1, characterized in that: The application was carried out under the following conditions: reaction temperature of 323~473K, 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.

20. The application according to claim 19, characterized in that: The application was carried out under the following conditions: reaction temperature of 333~453K, 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.

21. The application according to claim 19, characterized in that: The application was carried out under the following conditions: reaction temperature of 343~433K, reaction pressure of 0.8~4.0MPa, and space velocity of 0.3~4h. -1 The molar ratio of hydrogen to furan is 20 to 200.

22. The application according to claim 19, characterized in that: The application was carried out under the following conditions: reaction temperature of 363~413K, reaction pressure of 1~3.0MPa, and space velocity of 0.5~3h. -1 The molar ratio of hydrogen to furan is 50-100.

23. The application according to claim 1, characterized in that: The reaction takes place in a fixed-bed reactor.

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