A hydrodesulfurization catalyst and its preparation method and application

Abstract

The present invention discloses a hydrodesulfurization catalyst, its preparation method, and application. The method comprises: mixing raw alumina with distilled water, drying, mixing with an alcohol, drying again, and high-temperature treatment, then mixing with aluminum nitrate and distilled water, filtering directly, then filtering, washing with a mixture of acetic acid and distilled water, and heat-treating to obtain modified alumina; then, sequentially impregnating the modified alumina with a molybdenum-containing solution and a cobalt-containing solution, and subjecting the mixture to high-temperature treatment to obtain the hydrodesulfurization catalyst. The hydrodesulfurization catalyst provided by the present invention has a high active metal utilization rate and can be used in the hydrodesulfurization process of petroleum hydrocarbons to remove sulfur compounds from oil products and improve the hydrodesulfurization activity of the catalyst.

Description

Technical Field

[0001] The invention belongs to the field of catalytic material synthesis, and in particular relates to a hydrodesulfurization catalyst and a preparation method and application thereof. Background Art

[0002] With technological advancements, hydrogenation catalysts are playing an increasingly important role in the petroleum refining process. However, improving the performance of hydrogenation catalysts is becoming increasingly difficult, and researchers have been constantly trying various methods to improve catalyst performance.

[0003] CN109718820A discloses a phosphorus-modified composite hydrodesulfurization catalyst, which is composed of nickel, molybdenum, tungsten sulfide and phosphorus-modified clay. Nickel, molybdenum, tungsten are used as the desulfurization active components, and phosphorus-modified clay is used as the carrier. The nickel, molybdenum, tungsten is uniformly dispersed in the structure of the phosphorus-modified clay through adsorption, ion exchange, impregnation, drying, extrusion molding, and then roasting and pre-sulfurization treatment to form a phosphorus-modified composite hydrodesulfurization catalyst. The catalyst is suitable for deep removal of sulfur from oil products, but the catalytic performance of the catalyst needs to be further improved to meet more stringent reaction requirements.

[0004] CN105107521A discloses a Mn-Fe bimetallic doped activated carbon-based desulfurization catalyst and its preparation method. The catalyst uses activated carbon modified with nitric acid as a carrier and metal Mn and Fe as active components. The active components are loaded on the carrier by impregnation and high-temperature calcination in a nitrogen atmosphere. The specific preparation method is to first immerse the activated carbon in nitric acid for modification, then immerse the modified activated carbon in a mixed solution of manganese nitrate solution and ferric nitrate solution to load the active components Mn and Fe on the modified activated carbon carrier, and then calcine the modified activated carbon loaded with Mn and Fe to prepare the desulfurization catalyst. However, the scope of application of this catalyst is relatively narrow, and its application in petroleum refining is relatively limited.

[0005] CN108101081A discloses a method for preparing modified alumina. The alumina prepared by this method is γ-alumina, and the surface area of ​​the alumina is 100 to 500 m 2 / g, pore volume is 0.1~0.6cm 3 / g. The preparation method comprises: mixing alumina with deionized water, stirring, and drying; then mixing with ethanol, stirring, and drying, followed by treatment at a certain temperature; then mixing with an additive and deionized water, stirring, and then directly separating, drying, and treating at a high temperature; then mixing with an additive and deionized water, stirring, and then directly separating, drying, and treating at a high temperature to obtain the modified alumina product. Although the alumina produced by this method has the characteristic of adjustable alkalinity, it introduces some other ions, which can reduce the catalytic activity when the alumina is used as a catalyst. Summary of the Invention

[0006] To address the shortcomings of the prior art, the present invention provides a hydrodesulfurization catalyst, its preparation method, and its application. The hydrodesulfurization catalyst provided by the present invention has a high efficiency in active metal utilization and is used for the hydrodesulfurization of petroleum hydrocarbons. It can remove sulfur compounds from oil products and improve the catalyst's hydrodesulfurization efficiency, resulting in a highly efficient and low-cost hydrodesulfurization catalyst.

[0007] The first aspect of the present invention provides a hydrodesulfurization catalyst comprising a carrier and an active metal oxide, wherein the carrier is modified alumina obtained by modifying original alumina, and the active metal oxides are molybdenum oxide and cobalt oxide; the alkali content of the modified alumina is reduced by less than 1% compared with the alkali content of the original alumina, preferably 0.9% to 0.5%.

[0008] In the present invention, the aluminum oxide in the modified aluminum oxide is γ-alumina.

[0009] In the present invention, based on the weight of the catalyst, the active metal is calculated as oxide, the content of molybdenum oxide is 4% to 24%, preferably 5.6% to 22%, the content of cobalt oxide is 0.05% to 5%, preferably 0.9% to 4.4%, and the content of the carrier is 71% to 95%, preferably 74% to 93%.

[0010] In the present invention, the specific surface area of ​​the catalyst is 200 to 500 m 2 / g, pore volume is 0.2~0.7cm 3 / g, and the total acid content is 0.3~1.2mmol / g.

[0011] In the present invention, the size of the active metal particles in the catalyst is about 0.5 to 1.35 nm.

[0012] The second aspect of the present invention provides a method for preparing the above-mentioned hydrodesulfurization catalyst, comprising the following steps:

[0013] (1) mixing the raw alumina with deionized water and drying at 90-220° C. for 9-24 hours, preferably at 100-200° C. for 10-20 hours;

[0014] (2) mixing the solid obtained in step (1) with an alcohol, and then drying at 90-220° C. for 9-24 h, preferably at 100-200° C. for 10-20 h, and then high-temperature treating at 280-410° C. for 1-6 h, preferably at 300-400° C. for 2-5 h;

[0015] (3) mixing the solid obtained in step (2) with aluminum nitrate and deionized water, and then filtering directly;

[0016] (4) washing and filtering the solid obtained in step (3) with a mixture of acetic acid and deionized water;

[0017] (5) treating the solid obtained in step (4) at 80-150° C. for 1-12 h, preferably at 100-140° C. for 2-10 h, to obtain modified alumina;

[0018] (6) The modified alumina obtained in step (5) is mixed with an auxiliary agent and a peptizing agent and then formed into a mold, and then active metals molybdenum and cobalt are sequentially impregnated on the molded body, and the hydrodesulfurization catalyst is obtained by high-temperature treatment.

[0019] In the method of the present invention, the alumina in step (1) is γ-alumina, which can be homemade or commercially available.

[0020] In the method of the present invention, the mass ratio of the original aluminum oxide to deionized water in step (1) is 0.5 to 5:10, preferably 1 to 4:10.

[0021] In the method of the present invention, the alcohol in step (2) is at least one of pure (analytical grade) ethanol or propanol.

[0022] In the method of the present invention, the mass ratio of the solid to the alcohol in step (2) is 0.5 to 5:10, preferably 1 to 4:10.

[0023] In the method of the present invention, the mass ratio of the solid, aluminum nitrate and deionized water in step (3) is 0.9-12:0.9-24:100, preferably 1-10:1-20:100.

[0024] In the method of the present invention, the direct separation in step (3) does not require washing with water or other solvents, and only requires filtering the mixture directly for separation.

[0025] In the method of the present invention, the mass ratio of the solid, acetic acid and deionized water in step (4) is 0.9-12:18-65:1000, preferably 1-10:20-60:1000.

[0026] In the method of the present invention, the temperature of the mixture of acetic acid and deionized water in step (4) should be maintained at 70-95°C, preferably 80-90°C.

[0027] In the method of the present invention, the auxiliary agent in step (6) is at least one of sesbania powder, starch, methyl cellulose, etc., preferably sesbania powder; the peptizing agent is at least one of formic acid, acetic acid, citric acid, nitric acid, etc. The mass ratio of the modified alumina, auxiliary agent, and peptizing agent is 100:2-6:2-11, preferably 100:3-5:3-10. The molding is conventional extrusion molding. Preferably, heat treatment is performed after molding, the treatment temperature is 100-150°C, preferably 110-120°C, and the treatment time is 0.5-3 hours, preferably 1-2 hours.

[0028] In the method of the present invention, the method for impregnating and loading the active metal in step (6) is a stepwise impregnation method, specifically, first impregnating and loading the active metal molybdenum, and then impregnating and loading the active metal cobalt. Furthermore, after impregnating and loading the molybdenum, the solution is treated in a vacuum environment, and then impregnated and loaded with cobalt. The impregnation and loading method of molybdenum and cobalt preferably adopts the equal volume saturation impregnation method; the amount of solution used is determined according to the equal volume saturation impregnation method.

[0029] In the method of the present invention, the vacuum treatment conditions are: in a vacuum degree of 50 to 100 micrometers of mercury, the treatment temperature is 100 to 150° C., preferably 110 to 120° C.; the treatment time is 0.5 to 3 hours, preferably 1 to 2 hours.

[0030] In the method of the present invention, the impregnation liquid used for impregnating the loaded molybdenum in step (6) is a molybdenum salt solution, in which the mass ratio of molybdenum salt (in the form of MoO3) to deionized water is 5 to 32:100, preferably 6 to 30:100.

[0031] In the method of the present invention, the impregnation solution used for impregnating the loaded cobalt in step (6) is a mixed solution of a cobalt salt, 2-dimethylimidazole, and water. The mass ratio of the cobalt salt (calculated as CoO) to deionized water is 0.5 to 7:100, preferably 1 to 6:100; and the mass ratio of the cobalt salt (calculated as CoO) to 2-dimethylimidazole is 0.4 to 1.1:1, preferably 0.5 to 1:1. The operation process is to first mix the cobalt salt, 2-dimethylimidazole, and water, and then impregnate the cobalt salt onto the carrier using a saturated impregnation method.

[0032] In the method of the present invention, the molybdenum salt in step (6) includes one of ammonium heptamolybdate, ammonium dimolybdate, ammonium tetramolybdate, and ammonium octamolybdate; and the cobalt salt includes at least one of cobalt nitrate and cobalt acetate.

[0033] In the method of the present invention, the high temperature treatment temperature in step (6) is 400-650° C., preferably 450-600° C.; the treatment time is 2-10 hours, preferably 3-8 hours.

[0034] A third aspect of the present invention provides use of the hydrodesulfurization catalyst in removing sulfur-containing compounds from oil products.

[0035] The hydrodesulfurization catalyst of the present invention needs to be sulfurized before use. The sulfurization can be carried out by any of the existing sulfurization methods in the art.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] The catalyst prepared by the method of the present invention has more efficient hydrodesulfurization activity. The carrier-modified alumina used in the catalyst of the present invention is almost free of alkalinity after being treated by the specific method of the present invention. Because the alkaline sites of alumina are not ideal loading sites for molybdenum metal, the molybdenum metal loaded on the alkaline sites will greatly reduce the catalytic activity, resulting in huge waste. The method of the present invention can combine aluminum nitrate and acetic acid and cover the alkaline sites of alumina, thereby promoting the loading of active metal molybdenum on the non-alkaline sites of alumina, improving the utilization rate of active metal molybdenum, greatly reducing the proportion of ineffective molybdenum metal in the catalyst, and especially improving the hydrodesulfurization performance of low-metal content catalysts, so that low-metal content catalysts have higher hydrodesulfurization activity, thereby improving the catalytic ability of the catalyst.

[0038] In the present invention, 2-dimethylimidazole is added to the cobalt salt solution during the impregnation of cobalt metal, and vacuum treatment is performed after the molybdenum is loaded, which can promote better coordination between the cobalt metal and the molybdenum metal and further improve the hydrodesulfurization activity of the catalyst.

[0039] The size of the active metal particles of the catalyst prepared by the method of the present invention is larger than that of the molybdenum oxide of the catalyst prepared by the conventional method under the same conditions, and the hydrodesulfurization activity of the catalyst is higher. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 This is a TEM photo of the sample prepared in Example 1;

[0041] Figure 2 This is a TEM photo of the sample prepared in Comparative Example 3. DETAILED DESCRIPTION

[0042] The pore structure of the samples provided by the present invention is measured using N2 adsorption-desorption. Prior to the measurement, the samples are vacuum treated at 300°C for more than 4 hours. Parameters such as the total specific surface area are calculated using the BET isotherm equation.

[0043] The acid properties of the prepared aluminum oxide provided by the present invention are measured using ammonia-TPD. The sample is pretreated in a helium atmosphere at 500°C for 1 hour, ammonia is adsorbed at 150°C until saturation, and the temperature is increased to 550°C at a heating rate of 10°C / min to obtain an NH3-TPD spectrum of the molecular sieve.

[0044] The alkalinity of the sample provided by the present invention is characterized by a carbon dioxide temperature-programmed desorption (CO2-TPD) method. The specific characterization process is as follows: the sample is treated at 300°C in a 30mL / min helium atmosphere for 1 hour; then the temperature is lowered to 70°C and treated in a 30mL / min CO2-He atmosphere (CO2 accounts for 5%, He accounts for 95%) for 2 hours; then treated in a 30mL / min He atmosphere at 70°C for 1 hour; and finally, the sample is characterized by CO2-TPD in a 10mL / min He atmosphere at a rate of 10°C / min. The alkalinity is calculated using the peak area integration method, with the alkalinity of the original alumina being 100%, and the ratio of the alkalinity of the test sample to that of the original alumina being used as the alkalinity of the test sample.

[0045] The microstructure of the sample provided by the present invention was characterized by a high-resolution electron microscope, a JEM-2100LaB6 high-resolution transmission electron microscope (TEM) from JEOL, Japan, was used for sample morphology observation and electron diffraction analysis, and an 832CCD camera from Gatan, USA, was used to capture images and electron diffraction spectra.

[0046] The present invention will be further described below by way of examples, but the protection scope of the present invention is not limited by the examples.

[0047] The alumina raw materials used in the following examples and comparative examples are all γ-alumina, and the specific surface area of ​​γ-alumina is 387m 2 / g, pore volume is 0.58cm 3 / g, and the total acid content is 0.69mmol / g.

[0048] Example 1

[0049] First, 17.6g of alumina was mixed with 100g of deionized water, filtered, and dried at 110°C for 15h. The mixture was then mixed with 100g of ethanol, filtered, dried at 120°C for 15h, and then treated at 351°C for 5h. Next, 8g of the solid from the previous step was mixed with 16g of aluminum nitrate and 100g of deionized water, then filtered. The solid was then washed with a mixture of 50g of acetic acid and 1000g of deionized water (85°C). The mixture was then treated at 130°C for 10h to obtain modified alumina S-1. The basicity of the modified alumina S-1 was measured to be 0.6%, based on the basicity of the original alumina as 100%.

[0050] Then, 10g of the modified alumina prepared in the previous step was mixed with 3.5g of sesbania powder and 3.5g of acetic acid, extruded into strips, and treated at 110°C for 1h. 29.5g of ammonium heptamolybdate and 100g of distilled water were then mixed evenly. Then, 9.3g of molybdenum metal solution was mixed evenly with the molded body prepared in the previous step (measured by an equal volume saturation impregnation method, 0.93g of water / 1g of carrier), and treated at 110°C in a vacuum environment below 100 microns of mercury for 1h. Then, 2.4g of 2-dimethylimidazole, 4.8g of cobalt nitrate, and 100g of distilled water were mixed evenly. 9.3g of cobalt metal solution was mixed evenly with the catalyst from the previous step, and treated at 110°C in a vacuum environment below 100 microns of mercury for 1h. Finally, the mixture was treated at 560°C for 7h to obtain Catalyst Sample A.

[0051] Based on N2 adsorption-desorption analysis, the specific surface area of ​​catalyst A is 378m 2 / g, pore volume is 0.56cm 3 / g; based on ammonia-TPD analysis, the total acid content was 0.70 mmol / g; based on transmission electron microscopy analysis, the size of the active metal particles of the catalyst was about 1.11 nm.

[0052] Example 2

[0053] First, 10g of alumina was mixed with 100g of deionized water, filtered, and dried at 120°C for 8h. The mixture was then mixed with 100g of ethanol, filtered, dried at 120°C for 10h, and then treated at 300°C for 2h. Then, 1g of the solid from the previous step was mixed with 1g of aluminum nitrate and 100g of deionized water, then filtered. The solid was then washed with a mixture of 20g of acetic acid and 1000g of deionized water (80°C). The solid was then treated at 100°C for 10h to obtain modified alumina S-2. The basicity of the modified alumina S-2 was measured to be 0.8%, based on the basicity of the original alumina as 100%.

[0054] Then, 10g of the modified alumina prepared in the previous step was mixed with 3g of sesbania powder and 3g of acetic acid, and after extrusion, the mixture was treated at 110°C for 1h. 9.8g of ammonium heptamolybdate and 100g of distilled water were then mixed evenly. Then, 9.3g of molybdenum metal solution was mixed evenly with the molded body prepared in the previous step (measured by the equal volume saturation impregnation method, 0.93g of water / 1g of carrier), and the mixture was placed in a vacuum environment below 100 microns of mercury and treated at 110°C for 1h. Then, 11.7g of 2-dimethylimidazole, 14.6g of cobalt nitrate, and 100g of distilled water were mixed evenly. 9.3g of cobalt metal solution was mixed evenly with the catalyst from the previous step, and the mixture was placed in a vacuum environment below 100 microns of mercury and treated at 110°C for 1h. Finally, the mixture was treated at 450°C for 8h to obtain Catalyst Sample B.

[0055] Based on N2 adsorption-desorption analysis, the specific surface area of ​​catalyst B is 393m 2 / g, pore volume is 0.53cm 3 / g; based on ammonia-TPD analysis, the total acid content was 0.78 mmol / g; based on transmission electron microscopy analysis, the size of the active metal particles of the catalyst was about 0.56 nm.

[0056] Example 3

[0057] First, 40g of alumina was mixed with 100g of deionized water, filtered, and dried at 200°C for 20h. The mixture was then mixed with 100g of ethanol, filtered, and dried at 200°C for 20h. The mixture was then treated at 400°C for 5h. Then, 10g of the solid from the previous step was mixed with 20g of aluminum nitrate and 100g of deionized water, and filtered. The solid was then washed with a mixture of 60g of acetic acid and 1000g of deionized water (at 90°C). The mixture was then treated at 140°C for 2h to obtain modified alumina S-3. The basicity of the modified alumina S-3 was measured to be 0.7%, based on the basicity of the original alumina as 100%.

[0058] Then, 10g of the modified alumina prepared in the previous step was mixed with 5g of sesbania powder and 10g of acetic acid, and after extrusion, the mixture was treated at 110°C for 1h. 49.4g of ammonium heptamolybdate and 100g of distilled water were then mixed evenly. Then, 9.3g of molybdenum metal solution was mixed evenly with the molded body prepared in the previous step (measured by the equal volume saturation impregnation method, 0.93g of water / 1g of carrier), and the mixture was placed in a vacuum environment below 100 microns of mercury and treated at 110°C for 1h. Then, 2.4g of 2-dimethylimidazole, 2.4g of cobalt nitrate, and 100g of distilled water were mixed evenly. Then, 9.3g of cobalt metal solution was mixed evenly with the catalyst in the previous step, and the mixture was placed in a vacuum environment below 100 microns of mercury and treated at 110°C for 1h. Finally, the mixture was treated at 600°C for 3h to obtain Catalyst Sample C.

[0059] Based on N2 adsorption-desorption analysis, the specific surface area of ​​catalyst C is 358m 2 / g, pore volume is 0.57cm 3 / g; based on ammonia-TPD analysis, the total acid content was 0.69 mmol / g; based on transmission electron microscopy analysis, the size of the active metal particles of the catalyst was about 1.27 nm.

[0060] Example 4

[0061] First, 30.3g of alumina was mixed with 95g of deionized water, filtered, and dried at 125°C for 11 hours. The mixture was then mixed with 100g of ethanol, filtered, dried at 135°C for 16 hours, and then treated at 350°C for 4.5 hours. Next, 7.6g of the solid from the previous step was mixed with 13.5g of aluminum nitrate and 100g of deionized water, then filtered. The solid was then washed with a mixture of 52g of acetic acid and 1000g of deionized water (88°C). The mixture was then treated at 125°C for 10 hours to obtain modified alumina S-4. The basicity of the modified alumina S-4 was measured to be 0.6%, based on the basicity of the original alumina as 100%.

[0062] Then, 10g of the modified alumina prepared in the previous step was mixed with 4g of sesbania powder and 7g of acetic acid. After extrusion, the mixture was treated at 110°C for 1h. 20g of ammonium heptamolybdate and 100g of distilled water were then mixed evenly. Then, 9.3g of molybdenum metal solution was mixed evenly with the molded body prepared in the previous step (measured by an equal volume saturation impregnation method, 0.93g of water / 1g of carrier), and the mixture was placed in a vacuum environment below 100 microns of mercury and treated at 110°C for 1h. Then, 7.3g of 2-dimethylimidazole, 7.3g of cobalt nitrate, and 100g of distilled water were mixed evenly. Then, 9.3g of cobalt metal solution was mixed evenly with the catalyst from the previous step, and the mixture was placed in a vacuum environment below 100 microns of mercury and treated at 110°C for 1h. Finally, the mixture was treated at 550°C for 5.5h to obtain Catalyst Sample D.

[0063] Based on N2 adsorption-desorption analysis, the specific surface area of ​​catalyst D is 371m 2 / g, pore volume is 0.51cm 3 / g; based on ammonia-TPD analysis, the total acid content was 0.72 mmol / g; based on transmission electron microscopy analysis, the size of the active metal particles of the catalyst was about 1.17 nm.

[0064] Example 5

[0065] First, 17.1g of alumina was mixed with 110g of deionized water, filtered, and dried at 160°C for 18 hours. The mixture was then mixed with 100g of ethanol, filtered, dried at 150°C for 18 hours, and then treated at 385°C for 3 hours. 5.5g of the solid from the previous step was then mixed with 11g of aluminum nitrate and 100g of deionized water, then filtered. The solid was then washed with a mixture of 32g of acetic acid and 1000g of deionized water (83°C). The mixture was then treated at 140°C for 10 hours to obtain modified alumina S-5. The basicity of the modified alumina S-5 was measured to be 0.8%, based on the basicity of the original alumina as 100%.

[0066] Then, 10g of the modified alumina prepared in the previous step was mixed with 5.2g of sesbania powder and 7.5g of acetic acid. After extrusion, the mixture was treated at 110°C for 1h. 22.6g of ammonium heptamolybdate and 100g of distilled water were then mixed evenly. Then, 9.3g of molybdenum metal solution was mixed evenly with the molded body prepared in the previous step (measured by the equal volume saturation impregnation method, 0.93g of water / 1g of carrier), and the mixture was placed in a vacuum environment below 100 microns of mercury and treated at 110°C for 1h. Then, 10.3g of 2-dimethylimidazole, 12.2g of cobalt nitrate, and 100g of distilled water were mixed evenly. Then, 9.3g of cobalt metal solution was mixed evenly with the catalyst from the previous step, and the mixture was placed in a vacuum environment below 100 microns of mercury and treated at 110°C for 1h. Finally, the mixture was treated at 520°C for 4h to obtain Catalyst Sample E.

[0067] Based on N2 adsorption-desorption analysis, the specific surface area of ​​catalyst E is 384 m 2 / g, pore volume is 0.52cm 3 / g; based on ammonia-TPD analysis, the total acid content was 0.79 mmol / g; based on transmission electron microscopy analysis, the size of the active metal particles of the catalyst was about 1.23 nm.

[0068] Example 6

[0069] 10 mL of the catalyst prepared in Example 1 was loaded into a reactor. Then, 15 mL / h of n-octane containing 5% by weight carbon disulfide and 150 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 320°C for 4 hours to sulfurize the catalyst. Then, 15 mL / h of n-nonane containing 350 ppm by weight thiophene and 180 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 350°C. The liquid product from the 4th to 5th hour of the reaction was analyzed for sulfur content. The result showed that the sulfur content of the liquid product after hydrodesulfurization was 35 ppm by weight.

[0070] Example 7

[0071] Comparative Example 6 is different in that the catalyst prepared in Example 1 is replaced by the catalyst prepared in Example 2. The measurement results show that the sulfur content of the liquid product after hydrodesulfurization is 59 ppm (weight).

[0072] Example 8

[0073] Comparative Example 6 is different in that the catalyst prepared in Example 1 is replaced by the catalyst prepared in Example 3. The measurement results show that the sulfur content of the liquid product after hydrodesulfurization is 18 ppm (weight).

[0074] Example 9

[0075] Comparative Example 6 is different in that the catalyst prepared in Example 1 is replaced by the catalyst prepared in Example 4. The measurement results show that the sulfur content of the liquid product after hydrodesulfurization is 27 ppm (weight).

[0076] Example 10

[0077] Comparative Example 6 is different in that the catalyst prepared in Example 1 is replaced by the catalyst prepared in Example 5. The measurement results show that the sulfur content of the liquid product after hydrodesulfurization is 20 ppm (weight).

[0078] Comparative Example 1

[0079] First, 17.6g of alumina was mixed with 100g of deionized water, filtered, and dried at 110°C for 15 hours. The mixture was then mixed with 100mL of ethanol, filtered, dried at 120°C for 15 hours, and then treated at 351°C for 5 hours. Next, 8g of the solid from the previous step was mixed with 16g of aluminum nitrate and 100g of deionized water. The mixture was then treated at 130°C for 10 hours to obtain modified alumina S-6. The basicity of the modified alumina S-6 was measured to be 55%, based on the basicity of the original alumina as 100%.

[0080] Then, 10g of the modified alumina prepared in the previous step was mixed with 3.5g of sesbania powder and 3.5g of acetic acid. After extrusion, the mixture was treated at 110°C for 1h. 29.5g of ammonium heptamolybdate and 100g of distilled water were then mixed evenly. Then, 9.3g of molybdenum metal solution was mixed evenly with the molded body prepared in the previous step (measured by the equal volume saturation impregnation method, 0.93g of water / 1g of carrier), and the mixture was placed in a vacuum environment below 100 microns of mercury and treated at 110°C for 1h. Then, 2.4g of 2-dimethylimidazole, 4.8g of cobalt nitrate, and 100g of distilled water were mixed evenly. Then, 9.3g of cobalt metal solution was mixed evenly with the catalyst from the previous step, and the mixture was placed in a vacuum environment below 100 microns of mercury and treated at 110°C for 1h. Finally, the mixture was treated at 560°C for 7h to obtain Catalyst Sample F.

[0081] Based on N2 adsorption-desorption analysis, the specific surface area of ​​the catalyst F is 371m 2 / g, pore volume is 0.54m 3 / g; based on ammonia-TPD analysis, the total acid content was 0.64 mmol / g; based on transmission electron microscopy analysis, the size of the active metal particles of the catalyst was about 0.80 nm.

[0082] Comparative Example 2

[0083] First, 17.6g of alumina was mixed with 100g of deionized water, filtered, and dried at 110°C for 15 hours. The mixture was then mixed with 100mL of ethanol, filtered, dried at 120°C for 15 hours, and then treated at 351°C for 5 hours. The solid was then washed with a mixture of 50g of acetic acid and 1000g of deionized water (85°C). The solid was then treated at 130°C for 10 hours to obtain modified alumina S-7. The basicity of the modified alumina S-7 was measured to be 58%, based on the basicity of the original alumina as 100%.

[0084] Then, 10g of the modified alumina prepared in the previous step was mixed with 3.5g of sesbania powder and 3.5g of acetic acid. After extrusion, the mixture was treated at 110°C for 1h. 29.5g of ammonium heptamolybdate and 100g of distilled water were then mixed evenly. 9.3g of molybdenum metal solution was then mixed evenly with the molded body prepared in the previous step (measured by the equal volume saturation impregnation method, 0.93g of water / 1g of carrier), and the mixture was placed in a vacuum environment below 100 microns of mercury and treated at 110°C for 1h. 2.4g of 2-dimethylimidazole, 4.8g of cobalt nitrate, and 100g of distilled water were then mixed evenly. 9.3g of cobalt metal solution was then mixed evenly with the catalyst from the previous step, and the mixture was placed in a vacuum environment below 100 microns of mercury and treated at 110°C for 1h. Finally, the mixture was treated at 560°C for 7h to obtain Catalyst Sample G.

[0085] Based on N2 adsorption-desorption analysis, the specific surface area of ​​catalyst G is 358m 2 / g, pore volume is 0.51cm 3 / g; based on ammonia-TPD analysis, the total acid content was 0.64 mmol / g; based on transmission electron microscopy analysis, the size of the active metal particles of the catalyst was approximately 0.82 nm.

[0086] Comparative Example 3

[0087] First, 17.6g of alumina and 100g of deionized water were mixed, filtered, and dried at 110°C for 15 hours. The mixture was then mixed with 100mL of ethanol, filtered, and dried at 120°C for 15 hours. The mixture was then treated at 351°C for 5 hours to obtain modified alumina S-8. Measurements showed that the basicity of the modified alumina S-8 was 100%, with the basicity of the original alumina as 100%.

[0088] Then, 10g of the modified alumina prepared in the previous step was mixed with 3.5g of sesbania powder and 3.5g of acetic acid. After extrusion, the mixture was treated at 110°C for 1h. 29.5g of ammonium heptamolybdate and 100g of distilled water were then mixed evenly. Then, 9.3g of molybdenum metal solution was mixed evenly with the molded body prepared in the previous step (measured by the equal volume saturation impregnation method, 0.93g of water / 1g of carrier), and the mixture was placed in a vacuum environment below 100 microns of mercury and treated at 110°C for 1h. Then, 2.4g of 2-dimethylimidazole, 4.8g of cobalt nitrate, and 100g of distilled water were mixed evenly. Then, 9.3g of cobalt metal solution was mixed evenly with the catalyst from the previous step, and the mixture was placed in a vacuum environment below 100 microns of mercury and treated at 110°C for 1h. Finally, the mixture was treated at 560°C for 7h to obtain Catalyst Sample H.

[0089] Based on N2 adsorption-desorption analysis, the specific surface area of ​​the catalyst H is 357m 2 / g, pore volume is 0.63cm 3 / g; based on ammonia-TPD analysis, the total acid content was 0.61 mmol / g; based on transmission electron microscopy analysis, the size of the active metal particles of the catalyst was approximately 0.76 nm.

[0090] Comparative Example 4

[0091] First, 17.6g of alumina was mixed with 100g of deionized water, filtered, and dried at 110°C for 15 hours. The mixture was then mixed with 100g of ethanol, filtered, and dried at 120°C for 15 hours. The mixture was then treated at 351°C for 5 hours. Next, 8g of the solid from the previous step was mixed with 14g of acetic acid, 16g of aluminum nitrate, and 100g of deionized water, filtered, and treated at 130°C for 10 hours to obtain modified alumina S-9. The basicity of the modified alumina S-9 was measured to be 58%, based on the basicity of the original alumina as 100%.

[0092] Then, 10g of the modified alumina prepared in the previous step was mixed with 3.5g of sesbania powder and 3.5g of acetic acid, extruded into strips, and treated at 110°C for 1h. 29.5g of ammonium heptamolybdate and 100g of distilled water were then mixed evenly. Then, 9.3g of molybdenum metal solution was mixed evenly with the molded body prepared in the previous step (measured by an equal volume saturation impregnation method, 0.93g of water / 1g of carrier), and treated at 110°C in a vacuum environment below 100 microns of mercury for 1h. Then, 2.4g of 2-dimethylimidazole, 4.8g of cobalt nitrate, and 100g of distilled water were mixed evenly. Then, 9.3g of cobalt metal solution was mixed evenly with the catalyst in the previous step, and treated at 110°C in a vacuum environment below 100 microns of mercury for 1h. Finally, the mixture was treated at 560°C for 7h to obtain Catalyst Sample I.

[0093] Based on N2 adsorption-desorption analysis, the specific surface area of ​​the catalyst I is 348m 2 / g, pore volume is 0.55cm 3 / g; based on ammonia-TPD analysis, the total acid content was 0.57 mmol / g; based on transmission electron microscopy analysis, the size of the active metal particles of the catalyst was about 0.75 nm.

[0094] Comparative Example 5

[0095] First, 17.6g of aluminum oxide was mixed with 100g of deionized water, filtered, and dried at 110°C for 15h. The mixture was then mixed with 100g of ethanol, filtered, dried at 120°C for 15h, and then treated at 351°C for 5h. Eight g of the solid from the previous step was then washed with a mixture of 50g of acetic acid and 1000g of deionized water (85°C). The mixture was then mixed with 16g of aluminum nitrate and 100g of deionized water, filtered, and treated at 130°C for 10h to obtain modified aluminum oxide S-10. The basicity of the modified aluminum oxide S-10 was measured to be 54%, based on the basicity of the original aluminum oxide as 100%.

[0096] Then, 10g of the modified alumina prepared in the previous step was mixed with 3.5g of sesbania powder and 3.5g of acetic acid, extruded into strips, and treated at 110°C for 1h. 29.5g of ammonium heptamolybdate and 100g of distilled water were then mixed evenly. Then, 9.3g of molybdenum metal solution was mixed evenly with the molded body prepared in the previous step (measured by an equal volume saturation impregnation method, 0.93g of water / 1g of carrier), and treated at 110°C in a vacuum environment below 100 microns of mercury for 1h. Then, 2.4g of 2-dimethylimidazole, 4.8g of cobalt nitrate, and 100g of distilled water were mixed evenly. 9.3g of cobalt metal solution was mixed evenly with the catalyst from the previous step, and treated at 110°C in a vacuum environment below 100 microns of mercury for 1h. Finally, the mixture was treated at 560°C for 7h to obtain Catalyst Sample J.

[0097] Based on N2 adsorption-desorption analysis, the specific surface area of ​​catalyst J is 366 m 2 / g, pore volume is 0.50cm 3 / g; based on ammonia-TPD analysis, the total acid content was 0.73 mmol / g; based on transmission electron microscopy analysis, the size of the active metal particles of the catalyst was approximately 0.69 nm.

[0098] Comparative Example 6

[0099] Alumina was treated according to the method provided in CN108101081A to prepare the catalyst.

[0100] First, 18.8g of aluminum oxide was stirred with 70g of distilled water for 30 minutes to mix uniformly, then dried at 110°C for 15 hours. The mixture was then stirred with 70g of ethanol for 30 minutes to mix uniformly, filtered, and dried at 120°C for 15 hours. The mixture was then treated at 235°C for 5 hours. The mixture was then stirred with 3.8g of aluminum chloride and 100g of distilled water for 8 hours to mix uniformly, and then filtered and separated. The mixture was then treated at 150°C for 15 hours, and then treated at 600°C in a nitrogen atmosphere for 6 hours. The nitrogen-treated aluminum oxide was then mixed with 3g of aluminum chloride and 100mL of distilled water and stirred for 8 hours, then filtered and separated. The mixture was then dried at 150°C for 15 hours, and then treated at 600°C in a nitrogen atmosphere for 6 hours to obtain modified aluminum oxide S-11. The basicity of the prepared modified aluminum oxide S-11 was measured to be 1.8%, based on the basicity of the original aluminum oxide as 100%.

[0101] Then, 10g of the modified alumina prepared in the previous step was mixed with 3.5g of sesbania powder and 3.5g of acetic acid, extruded into strips, and treated at 110°C for 1h. 29.5g of ammonium heptamolybdate and 100g of distilled water were then mixed evenly. Then, 9.3g of molybdenum metal solution was mixed evenly with the molded body prepared in the previous step (measured by the equal volume saturation impregnation method, 0.93g of water / 1g of carrier), and treated at 110°C in a vacuum environment below 100 microns of mercury for 1h. Then, 2.4g of 2-dimethylimidazole, 4.8g of cobalt nitrate, and 100g of distilled water were mixed evenly. 9.3g of cobalt metal solution was mixed evenly with the catalyst from the previous step, and treated at 110°C in a vacuum environment below 100 microns of mercury for 1h. Finally, the catalyst was treated at 560°C for 7h to obtain Catalyst Sample K.

[0102] Based on N2 adsorption-desorption analysis, the specific surface area of ​​catalyst K is 361m 2 / g, pore volume is 0.64cm 3 / g; based on ammonia-TPD analysis, the total acid content was 0.62 mmol / g; based on transmission electron microscopy analysis, the size of the active metal particles of the catalyst was about 0.73 nm.

[0103] Comparative Example 7

[0104] 10 mL of the catalyst obtained in Comparative Example 1 was loaded into a microreactor. Then, 15 mL / h of n-octane containing 5% by weight carbon disulfide and 150 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 320°C for 4 hours to sulfurize the catalyst. Then, 15 mL / h of n-nonane containing 350 ppm by weight thiophene and 180 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 350°C. The liquid product was collected from the 4th to 5th hour of the reaction and analyzed for sulfur content. The results showed that the sulfur content of the liquid product after hydrodesulfurization was 134 ppm by weight, a desulfurization rate far lower than that of Example 6 (which had the same catalyst metal content and reaction conditions). This demonstrates that the catalyst prepared by the present method has superior catalytic performance.

[0105] Comparative Example 8

[0106] 10 mL of the catalyst obtained in Comparative Example 2 was loaded into a microreactor. Then, 15 mL / h of n-octane containing 5% by weight carbon disulfide and 150 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 320°C for 4 hours to sulfurize the catalyst. Then, 15 mL / h of n-nonane containing 350 ppm by weight thiophene and 180 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 350°C. The liquid product was collected from the 4th to 5th hour of the reaction and analyzed for sulfur content. The results showed that the sulfur content of the liquid product after hydrodesulfurization was 157 ppm by weight, a desulfurization rate far lower than that of Example 6 (which had the same catalyst metal content and reaction conditions). This demonstrates that the catalyst prepared by the method of the present invention has superior catalytic performance.

[0107] Comparative Example 9

[0108] 10 mL of the catalyst obtained in Comparative Example 3 was loaded into a microreactor. Then, 15 mL / h of n-octane containing 5% by weight carbon disulfide and 150 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 320°C for 4 hours to sulfurize the catalyst. Then, 15 mL / h of n-nonane containing 350 ppm by weight thiophene and 180 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 350°C. The liquid product was collected from the 4th to 5th hour of the reaction and analyzed for sulfur content. The results showed that the sulfur content of the liquid product after hydrodesulfurization was 152 ppm by weight, a desulfurization rate far lower than that of Example 6 (which had the same catalyst metal content and reaction conditions). This demonstrates that the catalyst prepared by the present method has superior catalytic performance.

[0109] Comparative Example 10

[0110] 10 mL of the catalyst obtained in Comparative Example 4 was loaded into a microreactor. Then, 15 mL / h of n-octane containing 5% by weight carbon disulfide and 150 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 320°C for 4 hours to sulfurize the catalyst. Then, 15 mL / h of n-nonane containing 350 ppm by weight thiophene and 180 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 350°C. The liquid product from the 4th to 5th hour of the reaction was analyzed for sulfur content. The results showed that the sulfur content of the liquid product after hydrodesulfurization was 177 ppm by weight, a desulfurization rate far lower than that of Example 6 (which had the same catalyst metal content and reaction conditions). This demonstrates that the catalyst prepared by the present method has superior catalytic performance.

[0111] Comparative Example 11

[0112] 10 mL of the catalyst obtained in Comparative Example 5 was loaded into a microreactor. Then, 15 mL / h of n-octane containing 5% by weight carbon disulfide and 150 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 320°C for 4 hours to sulfurize the catalyst. Then, 15 mL / h of n-nonane containing 350 ppm by weight thiophene and 180 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 350°C. The liquid product from the 4th to 5th hour of the reaction was analyzed for sulfur content. The results showed that the sulfur content of the liquid product after hydrodesulfurization was 181 ppm by weight, a desulfurization rate far lower than that of Example 6 (which had the same catalyst metal content and reaction conditions). This demonstrates that the catalyst prepared by the present method has superior catalytic performance.

[0113] Comparative Example 12

[0114] 10 mL of the catalyst obtained in Comparative Example 6 was loaded into a microreactor. Then, 15 mL / h of n-octane containing 5% by weight carbon disulfide and 150 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 320°C for 4 hours to sulfurize the catalyst. Then, 15 mL / h of n-nonane containing 350 ppm by weight thiophene and 180 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 350°C. The liquid product was collected from the 4th to 5th hour of the reaction and analyzed for sulfur content. The results showed that the sulfur content of the liquid product after hydrodesulfurization was 173 ppm by weight, a desulfurization rate far lower than that of Example 6 (which had the same catalyst metal content and reaction conditions). This demonstrates that the catalyst prepared by the present method has superior catalytic performance.

[0115] Example 11

[0116] First, 17.6g of alumina was mixed with 100g of deionized water, filtered, and dried at 110°C for 15 hours. The mixture was then mixed with 100g of ethanol, filtered, dried at 120°C for 15 hours, and then treated at 351°C for 5 hours. Next, 8g of the solid from the previous step was mixed with 16g of aluminum nitrate and 100g of deionized water, then filtered. The solid was then washed with a mixture of 50g of acetic acid and 1000g of deionized water (85°C). The mixture was then treated at 130°C for 10 hours to obtain modified alumina S-12. The basicity of the modified alumina S-12 was measured to be 0.6%, based on the basicity of the original alumina as 100%.

[0117] Then, 10g of the modified alumina prepared in the previous step was mixed with 3.5g of sesbania powder and 3.5g of acetic acid, extruded into strips, and treated at 110°C for 1h. 29.5g of ammonium heptamolybdate and 100g of distilled water were then mixed evenly. Then, 9.3g of molybdenum metal solution was mixed evenly with the molded body prepared in the previous step (measured by the equal volume saturation impregnation method, 0.93g of water / 1g of carrier), and treated at 110°C for 1h in a vacuum environment below 100 microns of mercury. Then, 4.8g of cobalt nitrate and 100g of distilled water were mixed evenly. 9.3g of cobalt metal solution was mixed evenly with the catalyst in the previous step, and treated at 110°C for 1h in a vacuum environment below 100 microns of mercury. Finally, the catalyst was treated at 560°C for 7h to obtain Catalyst Sample L.

[0118] Based on N2 adsorption-desorption analysis, the specific surface area of ​​the catalyst L is 366m 2 / g, pore volume is 0.55cm 3 / g; based on ammonia-TPD analysis, the total acid content was 0.73 mmol / g; based on transmission electron microscopy analysis, the size of the active metal particles of the catalyst was about 1.10 nm.

[0119] Example 12

[0120] 10 mL of the catalyst obtained in Example 11 was charged into a microreactor. Then, 15 mL / h of n-octane containing 5% by weight carbon disulfide and 150 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 320°C for 4 hours to sulfurize the catalyst. Then, 15 mL / h of n-nonane containing 350 ppm by weight thiophene and 180 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 350°C. The liquid product was collected from the 4th to 5th hour of the reaction and analyzed for sulfur content. The result showed that the sulfur content of the liquid product after hydrodesulfurization was 44 ppm by weight.

[0121] Comparative Example 13

[0122] First, 17.6g of alumina was mixed with 100g of deionized water, filtered, and dried at 110°C for 15h. The mixture was then mixed with 100g of ethanol, filtered, dried at 120°C for 15h, and then treated at 351°C for 5h. Next, 8g of the solid from the previous step was mixed with 16g of aluminum nitrate and 100g of deionized water, then filtered. The solid was then washed with a mixture of 50g of acetic acid and 1000g of deionized water (85°C). The mixture was then treated at 130°C for 10h to obtain modified alumina S-13. The basicity of the modified alumina S-13 was measured to be 0.6%, based on the basicity of the original alumina as 100%.

[0123] Then, 10g of the modified alumina prepared in the previous step was mixed with 3.5g of sesbania powder and 3.5g of acetic acid, extruded into strips, and treated at 110°C for 1 hour. 29.5g of ammonium heptamolybdate and 100g of distilled water were then mixed evenly. Then, 4.8g of cobalt nitrate and 9.3g of molybdenum metal solution were mixed evenly with the shaped body prepared in the previous step (measured by an equal volume saturation impregnation method, 0.93g of water / 1g of support). The mixture was then placed in a vacuum environment below 100 microns of mercury and treated at 110°C for 1 hour. Finally, the mixture was treated at 560°C for 7 hours to obtain Catalyst Sample M.

[0124] Based on N2 adsorption-desorption analysis, the specific surface area of ​​the catalyst M is 378m 2 / g, pore volume is 0.58cm 3 / g; based on ammonia-TPD analysis, the total acid content was 0.72 mmol / g; based on transmission electron microscopy analysis, the size of the active metal particles of the catalyst was approximately 0.57 nm.

[0125] Comparative Example 14

[0126] 10 mL of the catalyst obtained in Comparative Example 13 was loaded into a microreactor. Then, 15 mL / h of n-octane containing 5% by weight carbon disulfide and 150 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 320°C for 4 hours to sulfurize the catalyst. Then, 15 mL / h of n-nonane containing 350 ppm by weight thiophene and 180 mL / min of hydrogen were introduced, maintaining the system pressure at 3 MPa and the system temperature at 350°C. The liquid product from the 4th to 5th hour of the reaction was analyzed for sulfur content. The results showed that the sulfur content of the liquid product after hydrodesulfurization was 184 ppm by weight, a desulfurization rate far lower than that of Example 6 (which had the same catalyst metal content and reaction conditions). This demonstrates that the catalyst prepared by the present method has superior catalytic performance.

Claims

1. A hydrodesulfurization catalyst for removing sulfur compounds from oil products, comprising a carrier and an active metal oxide, wherein the carrier is modified alumina obtained by modifying original alumina, and the active metal oxides are molybdenum oxide and cobalt oxide; the modified alumina has an alkalinity reduced by 0.9% to 0.5% compared to the original alumina; The preparation method of the hydrodesulfurization catalyst comprises the following steps: (1) Mix the raw alumina with deionized water and dry at 90-220°C for 9-24 hours; (2) mixing the solid obtained in step (1) with an alcoholic substance, drying the mixture at 90-220°C for 9-24 hours, and then high-temperature treating the mixture at 280-410°C for 1-6 hours; (3) mixing the solid obtained in step (2) with aluminum nitrate and deionized water, and then filtering directly; (4) washing and filtering the solid obtained in step (3) with a mixture of acetic acid and deionized water; (5) treating the solid obtained in step (4) at 80-150° C. for 1-12 hours to obtain modified alumina; (6) The modified alumina obtained in step (5) is mixed with an additive and a peptizing agent and then formed into a molded body, and then active metals molybdenum and cobalt are sequentially impregnated onto the molded body, and subjected to high-temperature treatment at 400-650° C. to obtain the hydrodesulfurization catalyst; The mass ratio of the solid, aluminum nitrate, and deionized water in step (3) is 0.9-12:0.9-24:100; The mass ratio of the solid, acetic acid and deionized water in step (4) is 0.9-12:18-65:1000.

2. The use according to claim 1, characterized in that The aluminum oxide in the modified aluminum oxide is γ-aluminum oxide.

3. The use according to claim 1, characterized in that Based on the weight of the catalyst, the content of molybdenum oxide is 4% to 24%, the content of cobalt oxide is 0.05% to 5%, and the content of the carrier is 71% to 95%.

4. The use according to claim 1, characterized in that Based on the weight of the catalyst, the content of molybdenum oxide is 5.6% to 22%, the content of cobalt oxide is 0.9% to 4.4%, and the content of the carrier is 74% to 93%.

5. The use according to claim 1, characterized in that The specific surface area of ​​the catalyst is 200~500m 2 / g, pore volume is 0.2~0.7cm 3 / g, and the total acid content is 0.3~1.2mmol / g.

6. The use according to claim 1, characterized in that The preparation method of the hydrodesulfurization catalyst comprises the following steps: (1) Mix the original alumina with deionized water and dry it at 100-200°C for 10-20 h; (2) mixing the solid obtained in step (1) with an alcoholic substance, drying the mixture at 100-200°C for 10-20 hours, and then subjecting the mixture to a high-temperature treatment at 300-400°C for 2-5 hours; (3) mixing the solid obtained in step (2) with aluminum nitrate and deionized water, and then filtering directly; (4) washing and filtering the solid obtained in step (3) with a mixture of acetic acid and deionized water; (5) treating the solid obtained in step (4) at 100-140° C. for 2-10 hours to obtain modified alumina; (6) The modified alumina obtained in step (5) is mixed with an auxiliary agent and a peptizing agent and then formed into a mold, and then active metals molybdenum and cobalt are sequentially impregnated on the molded body, and the hydrodesulfurization catalyst is obtained by high-temperature treatment.

7. The use according to claim 1, characterized in that The mass ratio of the original alumina and deionized water in step (1) is 0.5-5:10; the alcohol substance in step (2) is at least one of pure ethanol or propanol; the mass ratio of the solid and the alcohol substance in step (2) is 0.5-5:

10.

8. The use according to claim 1, characterized in that The mass ratio of the original alumina and deionized water in step (1) is 1-4:10; the mass ratio of the solid and alcohol in step (2) is 1-4:

10.

9. The use according to claim 1, characterized in that The mass ratio of the solid, aluminum nitrate, and deionized water in step (3) is 1-10:1-20:100; and / or the mass ratio of the solid, acetic acid, and deionized water in step (4) is 1-10:20-60:1000; and / or the mass ratio of the modified alumina, auxiliary agent, and peptizing agent in step (6) is 100:3-5:3-10.

10. The use according to claim 1, characterized in that The temperature of the mixture of acetic acid and deionized water in step (4) is maintained at 70-95°C.

11. The use according to claim 1, characterized in that The temperature of the mixture of acetic acid and deionized water in step (4) is maintained at 80-90°C.

12. The use according to claim 1, characterized in that After impregnation with loaded molybdenum, the mixture is treated in a vacuum environment, and then impregnation with loaded cobalt; the vacuum treatment conditions are: in a vacuum degree of 50-100 microns of mercury column, the treatment temperature is 100-150° C.; the treatment time is 0.5-3 hours.

13. The use according to claim 12, characterized in that The vacuum treatment conditions are: treatment temperature of 110-120° C.; treatment time of 1-2 hours.

14. The use according to claim 1, characterized in that The impregnation liquid used for impregnating the loaded molybdenum in step (6) is a molybdenum salt solution, in which the mass concentration of the molybdenum salt in the form of MoO3 is 5% to 32%.

15. The use according to claim 1, characterized in that The impregnation liquid used for impregnating the loaded molybdenum in step (6) is a molybdenum salt solution, in which the mass concentration of the molybdenum salt in the form of MoO3 is 6% to 30%.

16. The use according to claim 1, characterized in that The impregnation solution used for impregnating the loaded cobalt in step (6) is a mixed solution of cobalt salt, 2-dimethylimidazole and water; wherein the mass ratio of cobalt salt calculated as CoO to water is 0.5-7:100; and the mass ratio of cobalt salt calculated as CoO to 2-dimethylimidazole is 0.4-1.1:

1.

17. The use according to claim 1, characterized in that The impregnation solution used for impregnating the loaded cobalt in step (6) is a mixed solution of cobalt salt, 2-dimethylimidazole and water; wherein the mass ratio of cobalt salt calculated as CoO to water is 1-6:100; and the mass ratio of cobalt salt calculated as CoO to 2-dimethylimidazole is 0.5-1:

1.

18. The use according to claim 14 or 15, characterized in that The molybdenum salt described in step (6) includes one of ammonium heptamolybdate, ammonium dimolybdate, ammonium tetramolybdate and ammonium octamolybdate.

19. The use according to claim 16 or 17, characterized in that The cobalt salt described in step (6) includes at least one of cobalt nitrate and cobalt acetate.

20. The use according to claim 1, characterized in that The high temperature treatment temperature in step (6) is 450-600°C; the treatment time is 2-10 hours.

21. The use according to claim 20, characterized in that The high temperature treatment time in step (6) is 3 to 8 hours.

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