Catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane, preparation method and application thereof

Abstract

This invention proposes a catalyst, preparation method, and application for the hydrodeoxygenation of sulfolane to tetrahydrothiophene. These catalysts address the technical challenges of expensive raw materials and catalysts, as well as complex process conditions, in the catalytic hydrogenation of thiophene and direct sulfidation of tetrahydrofuran. The synthesis of tetrahydrothiophene from sulfolane undergoes mild reaction conditions, and the entire production process produces only water as a byproduct, with no other pollutants. The catalyst incorporates a nickel-containing compound and a precious metal salt as active components. The active components are then reacted with a solution of a metal oxide (aluminum oxide or molybdenum oxide) precursor in a water bath with stirring. The resulting sample is then dried and calcined to produce the catalyst. Catalytic performance evaluation demonstrated a maximum sulfolane conversion of 97.5% and a tetrahydrothiophene selectivity of 98.0%.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalysts and their preparation, and in particular relates to a catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane, a preparation method and application thereof. Background Art

[0002] Tetrahydrothiophene is chemically stable and has a distinctive odor, making it a useful leak warning agent for gaseous fuels such as city gas and natural gas, replacing previously used odorizers like ethyl mercaptan. Furthermore, tetrahydrothiophene can be used as an intermediate in the synthesis of a variety of new pharmaceuticals, pesticides, and additives for polymer synthesis, and is also used as a solvent, chain transfer inhibitor, modifier, catalyst, petroleum model compound, and dielectric for lithium batteries.

[0003] CN 109046393 A discloses a method for preparing a molybdenum-nickel solid superacid catalyst and its application in the synthesis of tetrahydrothiophene. The method comprises adding an ethanolic ammonium molybdate solution to an ammoniacal solution of nickel nitrate, adding citric acid and mixing uniformly, adjusting the pH of the system to 1-1.5, and ultrasonically heating the solution to obtain a molybdenum-nickel precursor gel. Ammoniacal aqueous solution is added to an ethanolic aqueous solution of zirconium oxychloride and stirred to obtain a pretreated zirconium sol. After mixing the sodium silicate solution uniformly, ammoniacal aqueous solution is added to react, and sulfuric acid is added to adjust the pH to 7-8. The mixture is stirred uniformly, aged overnight at room temperature, and washed with water to obtain a solid superacid precursor. The mixture is ground and dried, sieved, and subjected to high-temperature heat treatment to obtain a molybdenum-nickel solid superacid catalyst. The molybdenum-nickel solid superacid catalyst is used as a catalyst, 1,4-butanediol, and hydrogen bromide are used as raw materials to prepare 1,4-dibromobutane. The 1,4-dibromobutane and sodium sulfide are then added to an ethanolic aqueous solution for reaction, and vacuum distillation is performed to obtain purified tetrahydrothiophene.

[0004] The hydrodeoxygenation of sulfolane to tetrahydrothiophene (THP) is a process whereby butadiene reacts with sulfur dioxide to produce sulfolane on an industrial scale. However, research on catalysts for this process is limited. Given its environmentally friendly and low-cost advantages, the development of a catalyst for this process is of great social significance. Summary of the Invention

[0005] In view of the problems of the prior art, the present invention provides a method for preparing a catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane, which overcomes the shortcomings of the prior catalysts in terms of low conversion rate and selectivity.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0007] A method for preparing a catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane, characterized by comprising the following steps:

[0008] (1) Under certain reaction conditions, a nickel-containing metal compound and a noble metal salt are dissolved in a solvent in a certain proportion to prepare an active component stock solution;

[0009] (2) Under certain reaction conditions, the active component stock solution is mixed and stirred with a metal oxide (aluminum oxide or molybdenum oxide) precursor, and then dried to obtain a catalyst precursor;

[0010] (3) Under certain conditions, the catalyst precursor is reduced with hydrogen and calcined at high temperature to obtain the catalyst.

[0011] Furthermore, in step (1), the nickel-containing compound, the noble metal salt and the solvent are mixed and placed in a closed container for magnetic stirring reaction, the reaction temperature is 30-80°C, the stirring speed is 200-1400 r / min, and the stirring time is 1-24h to obtain an active component stock solution, wherein the mass ratio of the nickel-containing compound, the noble metal salt and the solvent is (1-15):5:80.

[0012] Furthermore, the nickel-containing compound is one of nickel chloride, nickel sulfate, nickel nitrate, nickel phosphate, nickel acetate, nickel carbonate, nickel chromite, and nickel thiocyanate.

[0013] Furthermore, the noble metal salt is one of platinum chloride, palladium chloride, ruthenium chloride, iridium chloride, and osmium chloride.

[0014] Furthermore, the solvent is one of methanol, ethanol, acetone and deionized water.

[0015] Furthermore, in the step (2), the active component stock solution and the metal oxide (aluminum oxide or molybdenum oxide) precursor are mixed and placed in a closed container for magnetic stirring reaction, the reaction temperature is 30-80°C, the stirring speed is 200-1400r / min, the stirring time is 1-24h, and then dried, the drying temperature is 100-120°C, and the drying time is 12-24h, to finally obtain a catalyst precursor, wherein the mass ratio of the active component stock solution and the metal oxide (aluminum oxide or molybdenum oxide) precursor is (1-4):2, preferably 3:2.

[0016] Furthermore, the metal oxide (aluminum oxide or molybdenum oxide) precursor is one of aluminum isopropoxide, aluminum hydroxide, ammonium molybdate, silicomolybdic acid, phosphomolybdic acid, and molybdic acid.

[0017] Furthermore, in step (3), the catalyst precursor is placed in a hydrogen reduction furnace, the reduction temperature is set to 450-650°C, the flow rate of 2% (referring to the hydrogen gas volume fraction) hydrogen-argon mixture is 5-50mL / min, and the reduction time is 1-4h. Finally, under air atmosphere conditions, the reduced catalyst precursor is calcined at a calcination temperature of 500-700°C, a calcination time of 1-12h, and a heating rate of 10-20°C / min.

[0018] The present invention also provides a catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane prepared by the above method.

[0019] The present invention also provides use of the catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane in a catalytic synthesis of tetrahydrothiophene. The sulfolane and the catalyst are added to a high-pressure catalytic reactor, the reaction temperature is 180-260° C., the reaction pressure is 0.2-2.0 MPa, and the reaction time is 60-360 minutes. The mass ratio of the catalyst to the sulfolane is 1:(10-50), preferably 1:10, and the mass ratio of hydrogen to the sulfolane is 1:(1-10), preferably 1:2.

[0020] The present invention has the following beneficial effects: The catalyst comprises a nickel-containing compound and a precious metal salt as active components; the active components are then reacted with a solution of a metal oxide (aluminum oxide or molybdenum oxide) precursor in a water bath with stirring, and the resulting sample is dried and calcined to produce the catalyst. The present invention utilizes sulfolane as a raw material to synthesize tetrahydrothiophene under mild reaction conditions, and the entire production process produces only water as a byproduct, with no other pollutants. Catalytic performance evaluation showed that the catalyst achieved a maximum sulfolane conversion rate of 97.5% and a tetrahydrothiophene selectivity of 98.0%. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is the SEM image of the catalyst in Example 1. DETAILED DESCRIPTION

[0022] The present invention will be further described below with reference to specific examples. It should be understood that the following examples are intended only to illustrate the present invention and are not intended to limit the scope of the present invention, and that those skilled in the art may make non-essential improvements and adjustments based on the contents of the above invention.

[0023] Example 1

[0024] The preparation method of the catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane in this embodiment is as follows:

[0025] (1) Place 2 g of nickel sulfate, 5 g of platinum chloride and 80 g of deionized water in a sealed 200 ml beaker and stir magnetically at a water bath temperature of 50 ° C, a stirring speed of 1000 r / min, and a stirring time of 4 h to obtain an active component stock solution.

[0026] (2) 60 g of the active component stock solution was placed in a beaker, and 40 g of aluminum isopropoxide was slowly added dropwise under ice bath conditions. The mixture was stirred at 80°C for 2 h at a stirring speed of 1000 r / min, and then dried in an oven at 100°C for 12 h to obtain a catalyst precursor.

[0027] (3) 2 g of catalyst precursor was placed in a hydrogen reduction furnace, the reduction temperature was set to 500 ° C, the flow rate of 2% hydrogen-argon mixture was 10 mL / min, and the reduction time was 1 h. Finally, the reduced catalyst precursor was calcined under air atmosphere at a calcination temperature of 700 ° C, a calcination time of 12 h, and a heating rate of 10 ° C / min to obtain catalyst 1. The SEM image of the sample ( Figure 1 ) It can be seen that there are small particles on the surface, indicating that the active components have been evenly distributed on the surface.

[0028] Sulfolane and catalyst 1 were added to a high-pressure catalytic reactor. The reaction temperature was 200° C., the reaction pressure was 1.1 MPa, and the reaction time was 120 min. The mass ratio of catalyst 1 to sulfolane was 1:10, the mass ratio of hydrogen to sulfolane was 1:2, the sulfolane conversion rate was 97.5%, and the tetrahydrothiophene selectivity was 97.6%.

[0029] Comparative Example 1

[0030] The preparation method of the catalyst of this embodiment is as follows:

[0031] (1) Place 5 g of platinum chloride and 80 g of deionized water in a sealed 200 ml beaker and stir magnetically at a water bath temperature of 50 ° C, a stirring speed of 1000 r / min, and a stirring time of 4 h to obtain an active component stock solution.

[0032] (2) 60 g of the active component stock solution was placed in a beaker, and 40 g of aluminum isopropoxide was slowly added dropwise under ice bath conditions. The mixture was stirred at 80°C for 2 h at a stirring speed of 1000 r / min, and then dried in an oven at 100°C for 12 h to obtain a catalyst precursor.

[0033] (3) 2 g of the catalyst precursor was placed in a hydrogen reduction furnace at a reduction temperature of 500°C, a 2% hydrogen-argon mixture flow rate of 10 mL / min, and a reduction time of 1 h. Finally, the reduced catalyst precursor was calcined in air at a temperature of 700°C for 12 h at a heating rate of 10°C / min to produce Comparative Catalyst 1.

[0034] Sulfolane and catalyst 1 were added to a high-pressure catalytic reactor. The reaction temperature was 200° C., the reaction pressure was 1.1 MPa, and the reaction time was 120 min. The mass ratio of comparative catalyst 1 to sulfolane was 1:10, the mass ratio of hydrogen to sulfolane was 1:2, the sulfolane conversion rate was 82.0%, and the tetrahydrothiophene selectivity was 95.9%.

[0035] Comparative Example 2

[0036] The preparation method of the catalyst of this embodiment is as follows:

[0037] (1) Place 2 g of nickel sulfate and 80 g of deionized water in a sealed 200 ml beaker and stir magnetically at a water bath temperature of 50 ° C, a stirring speed of 1000 r / min, and a stirring time of 4 h to obtain an active component stock solution.

[0038] (2) 60 g of the active component stock solution was placed in a beaker, and 40 g of aluminum isopropoxide was slowly added dropwise under ice bath conditions. The mixture was stirred at 80°C for 2 h at a stirring speed of 1000 r / min, and then dried in an oven at 100°C for 12 h to obtain a catalyst precursor.

[0039] (3) 2 g of the catalyst precursor was placed in a hydrogen reduction furnace at a reduction temperature of 500°C, a 2% hydrogen-argon mixture flow rate of 10 mL / min, and a reduction time of 1 h. Finally, the reduced catalyst precursor was calcined in air at a temperature of 700°C for 12 h at a heating rate of 10°C / min to produce Comparative Catalyst 2.

[0040] Sulfolane and comparative catalyst 2 were added to a high-pressure catalytic reactor, the reaction temperature was 200°C, the reaction pressure was 1.1 MPa, and the reaction time was 120 min. The mass ratio of comparative catalyst 2 to sulfolane was 1:10, the mass ratio of hydrogen to sulfolane was 1:2, the sulfolane conversion rate was 27.2%, and the tetrahydrothiophene selectivity was 98.0%.

[0041] Comparative Example 3

[0042] The preparation method of the catalyst of this embodiment is as follows:

[0043] (1) Place 2 g of nickel sulfate, 5 g of platinum chloride and 80 g of deionized water in a sealed 200 ml beaker and stir magnetically at a water bath temperature of 50 ° C, a stirring speed of 1000 r / min, and a stirring time of 4 h to obtain an active component stock solution.

[0044] (2) 60 g of the active component stock solution was placed in a beaker, stirred at 80°C for 2 h at a stirring speed of 1000 r / min, and then dried in an oven at 100°C for 12 h to obtain a catalyst precursor.

[0045] (3) 2 g of the catalyst precursor was placed in a hydrogen reduction furnace at a reduction temperature of 500°C, a 2% hydrogen-argon mixture flow rate of 10 mL / min, and a reduction time of 1 h. Finally, the reduced catalyst precursor was calcined in air at a temperature of 700°C for 12 h at a heating rate of 10°C / min to produce Comparative Catalyst 3.

[0046] Sulfolane and comparative catalyst 3 were added to a high-pressure catalytic reactor. The reaction temperature was 200° C., the reaction pressure was 1.1 MPa, and the reaction time was 120 min. The mass ratio of comparative catalyst 3 to sulfolane was 1:10, the mass ratio of hydrogen to sulfolane was 1:2, the sulfolane conversion rate was 81.8%, and the tetrahydrothiophene selectivity was 77.4%.

[0047] Example 2

[0048] The preparation method of the catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane in this embodiment is as follows:

[0049] (1) Place 5 g of nickel sulfate, 5 g of iridium chloride and 80 g of deionized water in a sealed 200 ml beaker and stir magnetically at a water bath temperature of 80°C, a stirring speed of 800 r / min, and a stirring time of 4 h to obtain an active component stock solution.

[0050] (2) 60 g of the active component stock solution was placed in a beaker, and 40 g of aluminum isopropoxide was slowly added dropwise in an ice bath. The mixture was stirred at 80 ° C for 2 h at a stirring speed of 1000 r / min, and then dried in an oven at 100 ° C for 24 h to obtain a catalyst precursor.

[0051] (3) 2 g of the catalyst precursor was placed in a hydrogen reduction furnace with a reduction temperature of 500°C, a 2% hydrogen-argon mixture flow rate of 15 mL / min, and a reduction time of 1 h. Finally, the reduced catalyst precursor was calcined in air at a temperature of 700°C for 12 h at a heating rate of 10°C / min to produce Catalyst 2.

[0052] Sulfolane and catalyst 2 were added to a high-pressure catalytic reactor. The reaction temperature was 240° C., the reaction pressure was 1.2 MPa, and the reaction time was 120 min. The mass ratio of catalyst 2 to sulfolane was 1:10, the mass ratio of hydrogen to sulfolane was 1:2, the sulfolane conversion rate was 96.4%, and the tetrahydrothiophene selectivity was 97.8%.

[0053] Example 3

[0054] The preparation method of the catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane in this embodiment is as follows:

[0055] (1) 2 g of nickel phosphate, 5 g of ruthenium chloride, and 80 g of methanol were placed in a sealed 200 ml beaker and magnetically stirred at a water bath temperature of 60°C, a stirring speed of 1000 r / min, and a stirring time of 4 h to obtain an active component stock solution.

[0056] (2) 60 g of the active component stock solution was placed in a beaker, and 40 g of aluminum isopropoxide was slowly added dropwise under ice bath conditions. The mixture was stirred at 80°C for 2 h at a stirring speed of 1000 r / min, and then dried in an oven at 100°C for 12 h to obtain a catalyst precursor.

[0057] (3) 2 g of the catalyst precursor was placed in a hydrogen reduction furnace with a reduction temperature of 500°C, a 2% hydrogen-argon mixture flow rate of 50 mL / min, and a reduction time of 4 h. Finally, the reduced catalyst precursor was calcined in air at a temperature of 500°C, a time of 12 h, and a heating rate of 20°C / min to produce Catalyst 3.

[0058] Sulfolane and catalyst 3 were added to a high-pressure catalytic reactor. The reaction temperature was 200° C., the reaction pressure was 1.1 MPa, and the reaction time was 120 min. The mass ratio of catalyst 3 to sulfolane was 1:10, the mass ratio of hydrogen to sulfolane was 1:2, the sulfolane conversion rate was 95.5%, and the tetrahydrothiophene selectivity was 97.3%.

[0059] Example 4

[0060] The preparation method of the catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane in this embodiment is as follows:

[0061] (1) Place 10 g of nickel acetate, 5 g of platinum chloride and 80 g of deionized water in a sealed 200 ml beaker and stir magnetically at a water bath temperature of 50 ° C, a stirring speed of 1000 r / min, and a stirring time of 4 h to obtain an active component stock solution.

[0062] (2) 60 g of the active component stock solution was placed in a beaker, and 40 g of aluminum isopropoxide was slowly added dropwise under ice bath conditions. The mixture was stirred at 80°C for 2 h at a stirring speed of 1000 r / min, and then dried in an oven at 100°C for 12 h to obtain a catalyst precursor.

[0063] (3) 2 g of the catalyst precursor was placed in a hydrogen reduction furnace with a reduction temperature of 500°C, a 2% hydrogen-argon mixture flow rate of 10 mL / min, and a reduction time of 1 h. Finally, the reduced catalyst precursor was calcined in air at a temperature of 700°C for 12 h at a heating rate of 10°C / min to produce Catalyst 4.

[0064] Sulfolane and catalyst 4 were added to a high-pressure catalytic reactor. The reaction temperature was 180° C., the reaction pressure was 1.1 MPa, and the reaction time was 120 min. The mass ratio of catalyst 4 to sulfolane was 1:10, the mass ratio of hydrogen to sulfolane was 1:2, the sulfolane conversion rate was 97.2%, and the tetrahydrothiophene selectivity was 97.9%.

[0065] Example 5

[0066] The preparation method of the catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane in this embodiment is as follows:

[0067] (1) Place 2 g of nickel sulfate, 5 g of platinum chloride and 80 g of deionized water in a sealed 200 ml beaker and stir magnetically at a water bath temperature of 50 ° C, a stirring speed of 1000 r / min, and a stirring time of 4 h to obtain an active component stock solution.

[0068] (2) 60 g of the active component stock solution was placed in a beaker, and 40 g of ammonium molybdate was slowly added dropwise in an ice bath. The mixture was stirred at 80 ° C for 2 h at a stirring speed of 800 r / min, and then dried in an oven at 100 ° C for 12 h to obtain a catalyst precursor.

[0069] (3) 2 g of the catalyst precursor was placed in a hydrogen reduction furnace with a reduction temperature of 500°C, a 2% hydrogen-argon mixture flow rate of 10 mL / min, and a reduction time of 1 h. Finally, the reduced catalyst precursor was calcined in air at a temperature of 700°C for 12 h at a heating rate of 10°C / min to produce Catalyst 5.

[0070] Sulfolane and catalyst 5 were added to a high-pressure catalytic reactor. The reaction temperature was 260° C., the reaction pressure was 2.0 MPa, and the reaction time was 360 min. The mass ratio of catalyst 5 to sulfolane was 1:10, the mass ratio of hydrogen to sulfolane was 1:1, the sulfolane conversion rate was 97.4%, and the tetrahydrothiophene selectivity was 98.0%.

[0071] Example 6

[0072] The preparation method of the catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane in this embodiment is as follows:

[0073] (1) Place 2 g of nickel sulfate, 5 g of platinum chloride and 80 g of deionized water in a sealed 200 ml beaker and stir magnetically at a water bath temperature of 50 ° C, a stirring speed of 1000 r / min, and a stirring time of 4 h to obtain an active component stock solution.

[0074] (2) 60 g of the active component stock solution was placed in a beaker, and 40 g of silicomolybdic acid was slowly added dropwise in an ice bath. The mixture was stirred at 80 ° C for 2 h at a stirring speed of 1000 r / min, and then dried in an oven at 100 ° C for 12 h to obtain a catalyst precursor.

[0075] (3) 2 g of the catalyst precursor was placed in a hydrogen reduction furnace with a reduction temperature of 500°C, a 2% hydrogen-argon mixture flow rate of 10 mL / min, and a reduction time of 1 h. Finally, the reduced catalyst precursor was calcined in air at a temperature of 700°C for 12 h at a heating rate of 10°C / min to produce Catalyst 7.

[0076] Sulfolane and catalyst 1 were added to a high-pressure catalytic reactor. The reaction temperature was 200° C., the reaction pressure was 1.1 MPa, and the reaction time was 120 min. The mass ratio of catalyst 7 to sulfolane was 1:10, the mass ratio of hydrogen to sulfolane was 1:2, the sulfolane conversion rate was 89.8%, and the tetrahydrothiophene selectivity was 96.7%.

[0077]

[0078] Combining Example 1, Comparative Example 1 and Comparative Example 2, it is illustrated that the synergistic effect of nickel and platinum atoms in the active components is an important factor affecting the catalytic performance of the catalyst.

[0079] In combination with Example 1 and Comparative Example 3, it is illustrated that the addition of a metal oxide (aluminum oxide or molybdenum oxide) precursor during the catalyst synthesis process improves the catalytic performance of the catalyst.

[0080] In combination with Example 1, Comparative Examples 1, 2 and 3, it is illustrated that the synergistic effect of nickel and noble metal atoms in the active components and the addition of metal oxide (aluminum oxide or molybdenum oxide) precursors enable the catalytic performance of the sub-catalyst to reach the optimal value.

[0081] The basic principles, main features, and advantages of the present invention are shown and described above. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are merely illustrative of the principles of the present invention. Various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention. Such changes and modifications are intended to fall within the scope of the present invention. The scope of protection claimed in the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane, characterized in that: The following steps are involved: (1) Under certain reaction conditions, nickel-containing metal compounds and noble metal salts are dissolved in a solvent in a certain proportion to prepare an active component stock solution; (2) Under certain reaction conditions, the active component stock solution and the metal oxide precursor are mixed and stirred, and then dried to obtain a catalyst precursor; (3) Under certain conditions, the catalyst precursor is reduced with hydrogen and calcined at high temperature to obtain the catalyst; In the step (1), the nickel-containing compound, the noble metal salt and the solvent are mixed and placed in a sealed container for magnetic stirring reaction, the reaction temperature is 30-80°C, the stirring speed is 200-1400 r / min, and the stirring time is 1-24 hours to obtain an active component stock solution, wherein the mass ratio of the nickel-containing compound, the noble metal salt and the solvent is (1-15):5:80; In the step (2), the active component stock solution and the metal oxide precursor are mixed and placed in a sealed container for magnetic stirring reaction, the reaction temperature is 30-80°C, the stirring speed is 200-1400 r / min, and the stirring time is 1-24 hours, and then dried at a drying temperature of 100-120°C and a drying time of 12-24 hours to finally obtain a catalyst precursor, wherein the mass ratio of the active component stock solution to the metal oxide precursor is (1-4):2; The metal oxide precursor is one of aluminum or molybdenum metal oxide precursors; In the step (3), the catalyst precursor is placed in a hydrogen reduction furnace, the reduction temperature is set to 450-650°C, the flow rate of the hydrogen-argon mixture with a hydrogen volume fraction of 2% is 5-50 mL / min, and the reduction time is 1-4 h. Finally, the reduced catalyst precursor is calcined under air atmosphere conditions, the calcination temperature is 500-700°C, the calcination time is 1-12 h, and the heating rate is 10-20°C / min.

2. The method for preparing a catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane according to claim 1, wherein: The nickel-containing compound in step (1) is one of nickel chloride, nickel sulfate, nickel nitrate, nickel phosphate, nickel acetate, nickel carbonate, nickel chromite, and nickel thiocyanate.

3. The method for preparing a catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane according to claim 1, wherein: The noble metal salt in step (1) is one of platinum chloride, palladium chloride, ruthenium chloride, iridium chloride and osmium chloride.

4. The method for preparing a catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane according to claim 1, wherein: The solvent in step (1) is one of methanol, ethanol, acetone and deionized water.

5. The method for preparing a catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane according to claim 1, wherein: The metal oxide precursor is one of aluminum isopropoxide, aluminum hydroxide, ammonium molybdate, silicomolybdic acid, phosphomolybdic acid, and molybdic acid.

6. A catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane prepared by the method according to any one of claims 1 to 5.

7. Use of the catalyst for preparing tetrahydrothiophene by hydrodeoxygenation of sulfolane according to claim 6 in the catalytic synthesis of tetrahydrothiophene, characterized in that: Add sulfolane and catalyst into a high-pressure catalytic reactor, the reaction temperature is 180-260°C, the reaction pressure is 0.2-2.0 MPa, the reaction time is 60-360 min, wherein the mass ratio of the catalyst to the sulfolane is 1:(10-50), and the mass ratio of hydrogen to the sulfolane is 1:(1-10).

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