Preparation method of hydrodesulfurization catalyst

Abstract

The invention discloses a preparation method of a hydrodesulfurization catalyst, which comprises the following steps: (1) impregnating a carrier with an impregnating solution containing active metal Mo, drying and roasting the impregnated carrier, and then vulcanizing; (2) after sulfuration in the step (1), the catalyst is subjected to saturated impregnation with liquid olefin, then heat treatment is performed, and the whole process is completed under the condition that a certain amount of CO2 is introduced into closed equipment; and (3) impregnating the thermally treated catalyst obtained in the step (2) with an impregnating solution containing active metal Co, drying, roasting and vulcanizing to obtain the hydrodesulfurization catalyst. According to the method disclosed by the invention, by protecting a MoS2 desulfurization active center, then carrying out carbon deposition treatment on an olefin saturation active center, and further promoting the MoS2 desulfurization active center by the aid of Co, high activity of the catalyst in a gasoline selective hydrodesulfurization process and high selectivity of gasoline hydrogenation are realized.

Description

Technical Field

[0001] The invention belongs to the field of petroleum refining, and specifically relates to a method for preparing a hydrodesulfurization catalyst. Background Art

[0002] As environmental regulations become increasingly stringent, countries around the world are requiring lower sulfur content in clean gasoline in order to effectively control the emission of harmful substances in automobile exhaust. FCC gasoline accounts for a large proportion of the gasoline pool in my country and is the main contributor of sulfur in finished gasoline. Therefore, deep desulfurization of FCC gasoline is the key to meeting my country's finished gasoline standards.

[0003] The representative FCC gasoline selective hydrodesulfurization process abroad is Prime-G developed by Axens of France. + Technology, Exxon Mobil developed SCANfining technology. The OCT-M, OCT-MD, OCT-ME series technologies and RSDS-I, RSDS-II, RSDS-III series technologies are widely used in domestic industry. These technologies provide effective technical support for oil refining enterprises to cope with oil quality upgrades. The core of these technologies is to effectively improve the selectivity of heavy gasoline hydrodesulfurization. Therefore, the development of highly selective heavy gasoline hydrodesulfurization catalysts is crucial.

[0004] CN111111701A discloses a hydrodesulfurization catalyst and a preparation method thereof. The preparation method of the hydrodesulfurization catalyst comprises the following contents: (1) loading active metals Co and Mo onto a carrier, drying and calcining to obtain a semi-finished catalyst; (2) impregnating the semi-finished catalyst with liquid olefin saturation, and then heat treating; (3) subjecting the heat-treated catalyst to a sulfurization treatment to obtain a catalyst. Although the catalyst is obtained by a special carbon deposition method, after sulfurization, the catalyst active phase crystal length is longer and the number of stacking layers is more, and the sulfurized catalyst of this structure has better hydrodesulfurization selectivity, but the desulfurization activity is inevitably damaged to a certain extent during the carbon deposition process, and the olefin saturation active center cannot be well inhibited alone. The desulfurization activity and hydrodesulfurization selectivity of the catalyst need to be further improved. Summary of the invention

[0005] In view of the shortcomings of the prior art, the present invention provides a method for preparing a hydrodesulfurization catalyst. The method of the present invention protects the desulfurization active center of MoS2, then performs carbon deposition treatment on the olefin saturation active center, and further promotes the desulfurization active center of MoS2 through the auxiliary agent Co, thereby achieving high activity of the catalyst in the process of selective hydrodesulfurization of gasoline and high selectivity of gasoline hydrogenation.

[0006] The preparation method of the hydrodesulfurization catalyst of the present invention comprises the following contents: (1) The carrier is impregnated with an impregnation solution containing active metal Mo, and the carrier is dried and calcined after impregnation, and then subjected to a sulfurization treatment; (2) After the sulfidation of step (1), the catalyst is saturated with a liquid olefin and then subjected to a closed heat treatment under a CO2 atmosphere of a certain concentration; (3) The heat-treated material obtained in step (2) is impregnated with an impregnation solution containing active metal Co, and after drying, calcining and sulfurization, a hydrodesulfurization catalyst is obtained.

[0007] In the method of the present invention, the carrier in step (1) is an inorganic refractory oxide selected from one or more of alumina, silicon oxide, zirconium oxide, titanium oxide, and magnesium oxide, preferably alumina. The carrier may be modified by adding an additive, and the modified additive may be K, Na, Mg, Si, P, Zr, or Ti.

[0008] In the method of the present invention, the preparation method of the impregnation solution containing active metal Mo is well known to those skilled in the art, for example, the following method can be adopted: adding ammonium molybdate into ammonia water, adjusting the solution volume to the final volume with ammonia water after dissolution, and storing in a sealed manner.

[0009] In the method of the present invention, the drying conditions in step (1) are: drying at 100-120° C. for 1-5 hours, and the roasting conditions are: roasting at 400-550° C. for 1-5 hours.

[0010] In the method of the present invention, the sulfurization treatment in step (1) adopts an in-situ or ex-situ sulfurization process, the amount of the introduced sulfurizing agent is 90% to 150% of the theoretical sulfur requirement of the catalyst, and the sulfurization process adopts a programmed temperature rise, the temperature is raised to 200 to 350° C. and the temperature is kept constant for 1 to 16 hours. The sulfurizing agent is generally one or more of carbon disulfide, dimethyl disulfide, methyl sulfide, and n-butyl sulfide.

[0011] In the method of the present invention, the liquid olefin in step (2) is one or more of olefins and diolefins having 2 to 10 carbon atoms, preferably hexadiene and / or n-heptene.

[0012] In the method of the present invention, the closed heat treatment process in step (2) is: heating at 300-400°C for 1-72h in a closed container; more preferably, heating at 50-250°C for 1-8h, heating at 250-300°C for 1-72h, and then heating at 300-400°C for 1-72h. The closed container can be selected according to the reaction conditions and material properties, such as a reactor, a tubular furnace and other equipment.

[0013] In the method of the present invention, the CO2 concentration in step (2) is ≮3000 μg / g, preferably ≮6000 μg / g.

[0014] In the method of the present invention, the preparation method of the impregnation solution containing active metal Co in step (2) is to first dissolve citric acid in clean water, add cobalt carbonate, boil and dissolve, cool, adjust the solution volume to the final volume with clean water, and store in a sealed container.

[0015] In the method of the present invention, the drying conditions in step (2) are: drying at 100-120°C for 1-5 hours; and the roasting conditions are: roasting at 300-350°C for 3-4 hours. The sulfurization treatment process adopts the sulfurization treatment method in step (1).

[0016] The hydrodesulfurization catalyst of the present invention, based on the total weight of the catalyst, has a MoS2 content of 2.0% to 30.0%, preferably 2.0% to 25.0%, a Co9S8 content of 0.1% to 7.0%, preferably 0.1% to 6.0%, a carbon content of 0.5% to 18.0%, preferably 5% to 18.0%, and a carrier content of the remainder; the carrier is an inorganic refractory oxide selected from one or more of alumina, silicon oxide, zirconium oxide, titanium oxide or magnesium oxide, preferably alumina.

[0017] The hydrodesulfurization catalyst of the present invention has a pore volume of 0.3-1.3 mL / g and a specific surface area of ​​150-400 m 2 / g, strength 100~250N / cm, bulk density 0.65~0.90g / mL.

[0018] The hydrodesulfurization catalyst of the present invention may also be added with an auxiliary agent as needed, such as one or more auxiliary elements such as K, Na, Mg, Si, P, Zr or Ti. Based on the total weight of the catalyst, the amount of the auxiliary agent added in terms of oxide is 1.0% to 10%, and the sum of the contents of the catalyst components is 100%.

[0019] The hydrodesulfurization catalyst of the present invention is suitable for use in the selective hydrodesulfurization of gasoline.

[0020] In the process of selective hydrogenation of gasoline, how to ensure the performance of the catalyst for hydrodesulfurization while suppressing the hydrogenation saturation of olefins has always been a contradiction that is difficult to balance. The inventor first impregnates Mo active metal, and then forms MoS2 active phase through drying, roasting and sulfurization operations. He also cleverly uses the characteristics of different active sites on the catalyst for the hydrodesulfurization reaction and the olefin hydrogenation saturation reaction, and adsorbs a large amount of acidic CO2 molecules on the active sites of the catalyst for hydrodesulfurization reaction, impregnates with liquid olefin saturation, and then heat treats to form carbon deposits. Due to the protective effect of CO2 molecules on the active sites of the hydrodesulfurization reaction, the carbon deposits mainly cover the active sites of the olefin hydrogenation saturation reaction, suppressing the olefin saturation activity. Then, by impregnating Co active metal, the sulfide Co active metal is not easily wrapped by the sulfide Mo active metal, and plays a good role in promoting the Mo active metal. Since the carbon deposits mainly cover the active sites of olefin hydrogenation saturation reaction, while the carbon deposits on the active sites of hydrodesulfurization reaction protected by CO2 molecules are not obvious, the promoting effect of Co active metal on Mo active metal is mainly concentrated on the hydrodesulfurization active sites, thereby increasing the hydrodesulfurization activity and selectivity of the catalyst. DETAILED DESCRIPTION

[0021] In the present invention, the specific surface area and pore volume are measured by low-temperature liquid nitrogen adsorption method, the strength is measured by intelligent particle strength tester, and the bulk density is measured by measuring cylinder method.

[0022] The specific preparation process of the catalyst of the present invention is as follows: The carrier is placed in a rolling pot, and under rotating conditions, the Mo ammonia solution of the carrier's saturated water absorption is sprayed into the carrier in the rolling pot in an atomized manner. After the solution is sprayed, continue to rotate in the rolling pot for 10 to 60 minutes, then place it for 1 to 24 hours, dry it at 100 to 120°C for 1 to 5 hours, and then heat it to 400 to 550°C at a heating rate of 150 to 250°C / hour for 1 to 5 hours, and then use an in-vessel or out-vessel sulfurization process for sulfurization treatment. The amount of sulfurizing agent introduced is 90% to 150% of the theoretical sulfur requirement of the catalyst. The sulfurization process adopts a programmed temperature increase, and the temperature is raised to 200 to 350°C and kept at a constant temperature for 1 to 16 hours; CO2 with a concentration of ≮3000μg / g is introduced into the closed equipment, and then the liquid olefin is saturated with water. The obtained sulfide material is placed in a rolling pot, and the Co solution with the saturated water absorption of the sulfide material is sprayed into the rolling pot in an atomized manner under rotating conditions. After the solution is sprayed, the rolling pot is continuously rotated for 10 to 60 minutes, and then placed for 1 to 24 hours, dried at 100 to 120°C for 1 to 5 hours, and then heated to 300 to 350°C at a heating rate of 150 to 250°C / hour for calcination for 3 to 4 hours, and then sulfurized by an in-vessel or out-vessel sulfurization process, the amount of the introduced sulfurizing agent is 90% to 150% of the theoretical sulfur requirement of the catalyst, and the sulfurization process adopts a programmed temperature increase, the temperature is raised to 200 to 350°C and kept at a constant temperature for 1 to 16 hours to obtain a finished catalyst.

[0023] In the above preparation method, the concentration of the impregnating solution is determined by the water absorption rate and the desired catalyst composition (content).

[0024] The catalyst used in the present invention is specifically described below with reference to examples. Example 1

[0025] 19.2g of ammonium molybdate was added to 130mL of 25% (weight) ammonia water, and after dissolving, the volume of the solution was adjusted to 150mL with 25% ammonia water, and then sealed and stored. 200g of the carrier was placed in a rolling pot, and 150mL of the prepared molybdenum and ammonia solution was used for spraying. After the solution was sprayed, it was continued to rotate in the rolling pot for 30 minutes, then placed for 18 hours, dried at 110°C for 3 hours, and then heated to 500°C at a heating rate of 200°C / hour for calcination for 3 hours, and then placed in 600mL of hexadiene solvent for 4 hours while maintaining the CO2 content at 6900μg / g atmosphere, and then heated at 200°C for 4 hours, heated to 300°C for 24 hours, and then heated to 400°C for 10 hours for heat treatment to obtain a first-stage oxidation state catalyst A. The first stage oxidized catalyst A was subjected to sulfurization treatment by an ex-situ sulfurization process, the amount of dimethyl disulfide introduced was 120% of the theoretical sulfur requirement of the catalyst, and the temperature was raised to 280°C and kept constant for 10 hours by programmed temperature rise during the sulfurization process to obtain a first stage sulfurized catalyst A; the first stage sulfurized catalyst A was placed in a rolling pot, and 80 mL of an aqueous solution containing 14.3 g of citric acid and 10.2 g of cobalt carbonate was sprayed into the alumina carrier in the rolling pot in an atomized manner under rotating conditions. After the solution was sprayed, the rolling pot was continued to rotate for 30 minutes, dried at 110°C for 4 hours, and calcined at 300°C for 3 hours. The first stage sulfidation process was used for sulfurization treatment, the amount of dimethyl disulfide introduced was 120% of the theoretical sulfur requirement of the catalyst, and the temperature was raised to 280°C and kept constant for 10 hours by programmed temperature rise during the sulfurization process to obtain a finished catalyst A. Example 2

[0026] 10.5g of ammonium molybdate was added to 130mL of 25% (weight) ammonia water, and after dissolving, the volume of the solution was adjusted to 150mL with 25% ammonia water, and then sealed and stored. 200g of the carrier was placed in a rolling pot and sprayed with 150mL of the prepared molybdenum ammonia solution. After the solution was sprayed, it continued to rotate in the rolling pot for 30 minutes, then placed for 18 hours, dried at 110°C for 3 hours, and then heated to 500°C at a rate of 200°C / hour for calcination for 3 hours, and then placed in 600mL of hexadiene solvent for 4 hours while maintaining the CO2 content at 4700μg / g. Then, it was heated at 400°C for 10 hours to obtain a first-stage oxidation state catalyst B. The first stage oxidized catalyst B was treated with sulfur by an ex-situ sulfurization process, the amount of dimethyl disulfide introduced was 120% of the theoretical sulfur requirement of the catalyst, and the temperature was raised to 280°C and kept constant for 10 hours to obtain a first stage sulfurized catalyst B; the first stage sulfurized catalyst B was placed in a rolling pot, and 90 mL of an aqueous solution containing 8.3 g of citric acid and 5.9 g of cobalt carbonate was sprayed into the alumina carrier in the rolling pot in an atomized manner under rotating conditions. After the solution was sprayed, the rolling pot was continued to rotate for 30 minutes, dried at 110°C for 4 hours, and dried at 350°C for 3 hours. The first stage sulfurization process was carried out, the amount of dimethyl disulfide introduced was 120% of the theoretical sulfur requirement of the catalyst, and the temperature was raised to 280°C and kept constant for 10 hours to obtain a finished catalyst B. Example 3

[0027] 29.4g of ammonium molybdate was added to 135mL of 25% (weight) ammonia water, and after dissolving, the volume of the solution was adjusted to 150mL with 25% ammonia water, and then sealed and stored. 200g of the carrier was placed in a rolling pot and sprayed with 150mL of the prepared molybdenum ammonia solution. After the solution was sprayed, it continued to rotate in the rolling pot for 30 minutes, then placed for 18 hours, dried at 110°C for 3 hours, and then heated to 500°C at a rate of 200°C / hour for calcination for 3 hours, and then kept the CO2 content at 5800μg / g in the atmosphere, placed in 600mL of hexadiene solvent for immersion for 4h, then heated at 200°C for 4h, heated to 300°C for 24h, and then heated to 400°C for 10h for heat treatment to obtain a first-stage oxidation state catalyst C. The first stage oxidized catalyst C was treated with sulfur by an ex-situ sulfurization process, the amount of dimethyl disulfide introduced was 120% of the theoretical sulfur requirement of the catalyst, and the temperature was raised to 280°C and kept constant for 10 hours to obtain a first stage sulfurized catalyst C; the first stage sulfurized catalyst C was placed in a rolling pot, and 76 mL of an aqueous solution containing 17.3 g of citric acid and 12.4 g of cobalt carbonate was sprayed into the alumina carrier in the rolling pot in an atomized manner under rotating conditions. After the solution was sprayed, the rolling pot was continued to rotate for 30 minutes, dried at 110°C for 4 hours, and dried at 300°C for 4 hours. The first stage sulfurization process was used for sulfurization, the amount of dimethyl disulfide introduced was 120% of the theoretical sulfur requirement of the catalyst, and the temperature was raised to 280°C and kept constant for 10 hours to obtain a finished catalyst C. Example 4

[0028] 40.1g of ammonium molybdate was added to 130mL of 25% (weight) ammonia water, and after dissolving, the volume of the solution was adjusted to 150mL with 25% ammonia water, and then sealed and stored. 200g of the carrier was placed in a rolling pot, and 150mL of the prepared molybdenum ammonia solution was sprayed. After the solution was sprayed, it continued to rotate in the rolling pot for 30 minutes, then placed for 18 hours, dried at 110°C for 3 hours, and then heated to 500°C at a rate of 200°C / hour for calcination for 3 hours, and then placed in 600mL of hexadiene solvent for 4 hours while maintaining the CO2 content at 7500μg / g atmosphere, and then heated at 400°C for 10 hours to obtain a first-stage oxidation state catalyst D. The first stage oxidized catalyst D was treated with sulfur by an ex-situ sulfurization process, the amount of dimethyl disulfide introduced was 120% of the theoretical sulfur requirement of the catalyst, and the temperature was raised to 280°C and kept constant for 10 hours to obtain a first stage sulfurized catalyst D; the first stage sulfurized catalyst D was placed in a rolling pot, and 76 mL of an aqueous solution containing 19.4 g of citric acid and 13.8 g of cobalt carbonate was sprayed into the alumina carrier in the rolling pot in an atomized manner under rotating conditions. After the solution was sprayed, the rolling pot was continued to rotate for 30 minutes, dried at 110°C for 4 hours, and calcined at 350°C for 4 hours. The first stage sulfurization process was used for sulfurization, the amount of dimethyl disulfide introduced was 120% of the theoretical sulfur requirement of the catalyst, and the temperature was raised to 280°C and kept constant for 10 hours to obtain a finished catalyst D.

[0029] Comparative Example 1 The preparation process is the same as that of Example 1, except that the catalyst is immersed in 600 mL of hexadiene solvent for 4 h, heated at 200°C for 4 h, heated to 300°C for 24 h, and then heated to 400°C for 10 h to obtain a first-stage oxidized catalyst E, instead of maintaining a CO2 atmosphere.

[0030] Comparative Example 2 The preparation process is the same as that of Example 2, except that the CO2 content is always kept at 700 μg / g under the atmospheric condition, and the catalyst is immersed in 600 mL of hexadiene solvent for 4 hours, and then heated at 400°C for 10 hours for heat treatment to obtain a first-stage oxidized catalyst F.

[0031] Comparative Example 3 Dissolve 21.7g of citric acid in 65mL of clean water, add 16.1g of cobalt carbonate, boil and dissolve, cool, add 25% (weight) ammonia water to 135mL, add 33.1g of ammonium molybdate to the above solution, adjust the solution volume to 150mL with 25% ammonia water after dissolution, and seal and store. Place 200g of the carrier in a rolling pot, spray with 150mL of the prepared molybdenum and cobalt ammonia solution, continue to rotate in the rolling pot for 30 minutes after the solution is sprayed, then place for 18 hours, dry at 110℃ for 3 hours, then heat to 500℃ at a heating rate of 200℃ / hour for calcination for 3 hours, then keep the CO2 content at 6900μg / g in the atmosphere, place in 600mL of hexadiene solvent for 4h, and then heat at 400℃ for 10h to obtain a first-stage oxidation state catalyst G. The first stage oxidation state catalyst G was subjected to sulfurization treatment by an ex situ sulfurization process, the amount of dimethyl disulfide introduced was 120% of the theoretical sulfur requirement of the catalyst, and the sulfurization process was subjected to programmed temperature rise, the temperature was raised to 280°C and kept constant for 10 hours, and the finished catalyst G was obtained; Comparative Example 4 Dissolve 25.9g of citric acid in 40mL of clean water, add 19.3g of cobalt carbonate, boil and dissolve, cool, add 25% (weight) ammonia water to 130mL, add 45.3g of ammonium molybdate to the above solution, adjust the solution volume to 150mL with 25% ammonia water after dissolution, and store in a sealed container. Place 200g of the carrier in a rolling pot and spray it with 150mL of the prepared molybdenum and cobalt ammonia solution. After the solution is sprayed, continue to rotate in the rolling pot for 30 minutes, then place it for 18 hours, dry it at 110℃ for 3 hours, then heat it to 500℃ at a heating rate of 200℃ / hour for calcination for 3 hours, then place it in 600mL of hexadiene solvent for 4h, and then heat it at 400℃ for 10h to obtain a first-stage oxidation state catalyst H. The first stage catalyst H was sulfurized by an in-situ sulfurization process, the amount of dimethyl disulfide introduced was 120% of the theoretical sulfur requirement of the catalyst, and the sulfurization process adopted a programmed temperature increase, the temperature was raised to 280°C and kept constant for 10 hours, and the finished catalyst H was obtained. Example 5

[0032] In a 200 mL fixed bed small hydrogenation unit, catalysts A, B, C, D, E, F, G and H (catalyst properties are shown in Table 1) were used respectively. The reaction pressure was 1.6 MPa and the liquid hourly volume space velocity was 3.0 h -1 , hydrogen oil volume ratio is 300 Nm 3 / m 3 , the gasoline feedstock with a sulfur content of 664 μg / g and a RON of 93.0 was subjected to selective hydrodesulfurization. The evaluation results of each catalyst after operating for 600 hours are shown in Table 2.

[0033] Table 1 Main properties of catalysts Catalyst No. A B C D E F G H C,wt% 7.9 9.6 10.7 7.3 8.9 10.1 9.2 7.5 <![CDATA[MoS2,wt%]]> 7.9 4.5 11.5 14.9 7.8 4.4 12.9 16.6 <![CDATA[Co9S8, wt%]]> 2.9 1.7 3.5 3.9 2.8 1.6 3.9 4.4 Pore ​​volume, mL / g 0.42 0.46 0.45 0.42 0.41 0.45 0.44 0.39 <![CDATA[Specific surface area, m 2 / g]]> 238 239 224 223 231 235 196 179 Bulk density, g / mL 0.73 0.72 0.75 0.77 0.73 0.73 0.78 0.80 Strength, N / cm 132 148 137 136 129 123 127 129 Table 2 Catalyst activity and selectivity catalyst A B C D E F G H Reaction temperature, °C 270 310 260 250 270 320 280 270 Sulfur, μg / g 8.1 8.6 8.2 8.0 9.2 9.4 9.5 9.4 RON 91.9 91.8 91.7 91.9 91.5 91.5 91.4 91.4 RON loss 1.1 1.2 1.3 1.1 1.5 1.5 1.6 1.6 Reaction conditions: P = 1.6MPa; LHSV = 3.0h -1 ;H2 / Oil=300Nm 3 / m 3 The results in Table 2 show that the catalyst of the present invention has better hydrodesulfurization selectivity and has a smaller octane number loss under the same desulfurization rate.

Claims

1. A method for preparing a hydrodesulfurization catalyst, characterized in that The method comprises the following contents: (1) impregnating a carrier with an impregnation solution containing active metal Mo, drying and calcining the carrier after impregnation, and then performing a sulfurization treatment; (2) after the sulfurization in step (1), the catalyst is saturated with a liquid olefin, and then subjected to a closed heat treatment under a CO2 atmosphere with a certain concentration; (3) impregnating the heat-treated material obtained in step (2) with an impregnation solution containing active metal Co, and drying, calcining and sulfurizing the carrier to obtain a hydrodesulfurization catalyst.

2. The method according to claim 1, characterized in that: The carrier in step (1) is an inorganic refractory oxide selected from one or more of alumina, silicon oxide, zirconium oxide, titanium oxide and magnesium oxide.

3. The method according to claim 1, characterized in that: The drying conditions in step (1) are: drying at 100-120° C. for 1-5 hours; and the roasting conditions are: roasting at 400-550° C. for 1-5 hours.

4. The method according to claim 1, characterized in that: The sulfurization treatment in step (1) adopts an in-vessel or out-vessel sulfurization process, the amount of the introduced sulfurizing agent is 90% to 150% of the theoretical sulfur requirement of the catalyst, and the sulfurization process adopts a programmed temperature rise, the temperature is raised to 200 to 350° C. and the temperature is kept constant for 1 to 16 hours. The sulfurizing agent is one or more of carbon disulfide, dimethyl disulfide, methyl sulfide, and n-butyl sulfide.

5. The method according to claim 1, characterized in that: The liquid olefin in step (2) is one or more of olefins and diolefins having 2 to 10 carbon atoms, preferably hexadiene and / or n-heptene.

6. The method according to claim 1, characterized in that: The CO2 concentration in step (2) is ≮3000 μg / g, preferably ≮6000 μg / g.

7. The method according to claim 1, characterized in that: The closed heat treatment process described in step (2) is: heat treatment at 300-400° C. for 1-72 hours in a closed container.

8. The method according to claim 1, characterized in that: The closed heat treatment process described in step (2) is: in a closed container, heating at 50-250°C for 1-8 hours, heating to 250-300°C for 1-72 hours, and then heating to 300-400°C for 1-72 hours.

9. The method according to claim 1, characterized in that: The closed heat treatment process described in step (2) is as follows: the drying conditions described in step (2) are: drying at 100-120° C. for 1-5 hours; the roasting conditions are: roasting at 300-350° C. for 3-4 hours; the vulcanization treatment process adopts the vulcanization treatment method in step (1).

10. A hydrodesulfurization catalyst prepared by the method according to any one of claims 1 to 9, characterized in that: Based on the total weight of the catalyst, MoS2 is 2.0%~30.0%, preferably 2.0%~25.0%, Co9S8 is 0.1%~7.0%, preferably 0.1%~6.0%, the carbon content is 0.5%~18.0%, preferably 5%~18.0%, and the carrier content is the balance; the carrier is an inorganic refractory oxide selected from one or more of alumina, silicon oxide, zirconium oxide, titanium oxide or magnesium oxide, preferably alumina.

11. The catalyst according to claim 10, characterized in that: The pore volume of the hydrodesulfurization catalyst is 0.3~1.3mL / g, and the specific surface area is 150~400m 2 / g, strength 100~250N / cm, bulk density 0.65~0.90g / mL.

12. Use of a hydrodesulfurization catalyst prepared by the method according to any one of claims 1 to 9 in the selective hydrodesulfurization of gasoline.