Residual oil hydrodesulfurization catalyst and preparation method thereof

Abstract

The invention discloses a catalyst for hydrodesulfurization of residual oil and a preparation method thereof. The preparation method comprises the following steps: dissolving molybdenum salt and nickel salt into an aqueous solution of aminomethylphosphonic acid to obtain an active metal steeping liquor, then adding a dimethylformamide solution of polyacrylonitrile and a high-molecular polymer into the active metal steeping liquor to prepare an electrostatic spinning solution, and then carrying out electrostatic spinning to obtain a nanofiber membrane containing active metal. The preparation method comprises the following steps: carrying out high temperature carbonization and full ball milling to obtain a nano C-coated NiMoO4 precursor, and finally carrying out kneading and strip extrusion on the nano C-coated NiMoO4 precursor, sesbania powder and pseudo-boehmite, and carrying out drying and roasting to obtain the catalyst for residual oil hydrodesulfurization. The catalyst has high catalytic activity, and shows high desulfurization activity and anti-coking stability in a residual oil hydrodesulfurization reaction.

Description

Technical Field

[0001] The present invention belongs to the field of petrochemical industry, and particularly relates to a residue hydrodesulfurization catalyst and a preparation method thereof. Background Art

[0002] The fixed-bed residue hydrotreating technology refers to the removal of impurities such as sulfides, nitrides, metals and asphaltenes in residue under the conditions of hydrogen and catalyst, and at the same time, the hydrogen-carbon ratio of the residue is increased. The hydrogenated residue is used as the feedstock of a fluid catalytic cracking (FCC) unit. On the one hand, the diesel and gasoline yields of the FCC unit can be increased. On the other hand, the properties of diesel and gasoline can be improved, the sulfide content in diesel and gasoline can be reduced, and the operating performance of the FCC catalyst can be improved.

[0003] Due to the advantages of mature process and simple operation, the fixed-bed residue hydrotreating technology will still be the mainstream technology in refineries today and for some time to come. Since the space velocity of the residue hydrotreating catalyst is generally less than 1.0 h -1 -1, the amount of catalyst used during the operation cycle is as high as thousands of tons. On the other hand, the high asphaltene, carbon residue and metal content in the residue make the operation cycle of the residue hydrotreating catalyst generally less than 12 months. As the core of the residue hydrotreating process, reducing the production cost of the catalyst, improving the hydrogenation activity of the catalyst, and improving its long-term stable operation performance have always been the focus of residue hydrotreating technology research. The existing residue hydrotreating catalysts are generally prepared by using alumina as the carrier and loading Co, Mo, Ni and W metals. To improve the performance of the catalyst, the existing literature has carried out research starting from improving the pore structure of the catalyst and increasing the dispersion degree of the active phase, and good research progress has been made. For example, Patent CN 114425353A discloses a preparation method of a residue hydrodemetallization catalyst. First, an alumina carrier with open pores of ten nanometers - one hundred nanometers - micrometer level is prepared, and the pores with a pore diameter greater than 100 nm account for more than 25% of the total pore volume. The catalyst prepared by loading Ni-Mo active metal on this carrier is used in the residue hydrodemetallization reaction, and has the advantages of good anti-coking performance and high demetallization activity. Patent CN 1302849A discloses a preparation method of a hydrogenation protective agent, which uses phosphorus-containing compounds such as phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and the like to be formulated with active metals to prepare a protective agent for desulfurization and denitrification of inferior oil products. To improve the performance of the catalyst, Patent CN 105562117A discloses a preparation method of a phosphorus-containing hydrogenation catalyst, which innovatively uses aminotrimethylenephosphonic acid, carboxyethylenediphosphonic acid, ethylenediaminetetramethylenephosphonic acid, polyol phosphate, polyaminopolyethermethylenephosphonic acid as the phosphorus source, and the prepared hydrogenation catalyst has good desulfurization and denitrification effects.

[0004] In summary, high-performance residue oil hydrogenation catalysts need to have a certain proportion of macroporous structures, and phosphorus plays an important role in the activity of the catalyst. The present invention innovatively uses aminomethylphosphonic acid as an organic phosphorus source to prepare an impregnation solution containing Ni and Mo, and utilizes the amino group in the aminomethylphosphonic acid molecule to have the ability to complex Ni and the phosphonic acid end to generate phosphomolybdic acid with Mo, so that the catalytic synergy between the auxiliary metal Ni and the main active metal Mo can be enhanced; and the polymer semi-gel structure and electrospinning technology are used to make the active metal Ni-Mo highly dispersed on the catalyst surface, so that the prepared catalyst can show higher desulfurization and denitrification activity and stability in the residue oil hydrogenation reaction. Summary of the invention

[0005] In view of the problem that the existing residual oil hydrodesulfurization catalyst has low activity and poor anti-coking performance, the present invention provides a high-activity residual oil hydrodesulfurization catalyst, which uses aminomethylphosphonic acid that has a complexing effect on Ni and can form a phosphomolybdic acid structure with Mo as a phosphorus source, so that the auxiliary agent Ni atom is strengthened to the main active metal Mo; and the active metal impregnation liquid is prepared into nanowires by electrostatic spinning technology to improve the dispersion performance of Ni-Mo metal on the catalyst surface. At the same time, the present invention uses gelatinization technology to expand the prepared catalyst, so that the finally prepared catalyst has a certain macroporous structure, and thus has the advantages of good pore structure penetration and high desulfurization activity.

[0006] To achieve the above object, the present invention adopts the following technical solution: A residual oil hydrodesulfurization catalyst, which is based on Al 2 O 3 The carrier is composed of oxides of active metals Ni and Mo, wherein the content of molybdenum oxide is 4.0~18.0 wt% and the content of nickel oxide is 0.2~6.0 wt%.

[0007] The preparation method of the residue oil hydrodesulfurization catalyst comprises the following steps: 1) Preparation of active metal impregnation solution containing Ni and Mo: under heating conditions, nickel salt and molybdenum salt are added to an aqueous solution of aminomethylphosphonic acid, and stirred until completely dissolved to obtain an active metal impregnation solution; 2) Preparation of electrospinning solution: polyacrylonitrile (PNA) is dissolved in dimethylformamide (DMF) at 50-70 °C, and then added to the active metal impregnation solution obtained in step 1), and then a high molecular polymer is added to adjust the viscosity of the solution to obtain a spinning solution; 3) Nano-C@NiMoO 4 Preparation of precursor: The spinning solution obtained in step 2) is electrospun by electrospinning technology to obtain a nanofiber membrane containing active metals, and then the obtained nanofiber membrane is carbonized at high temperature to obtain C@NiMoO4 After sufficient ball milling, nano-C@NiMoO 4 Precursor; 4) Preparation of catalyst: The obtained nano-C@NiMoO 4 The precursor is fully mixed with sesbania powder and pseudo-boehmite, and then a binder is added to extrude the mixture into strips, which are then dried and calcined to obtain the residual oil hydrodesulfurization catalyst.

[0008] Furthermore, the temperature of the heating condition in step 1) is 60-100°C; Furthermore, in step 1), the nickel salt is nickel nitrate or nickel acetate; and the molybdenum salt is ammonium heptamolybdate, ammonium tetramolybdate or molybdenum oxide.

[0009] Further, the aminomethylphosphonic acid (P 2 O 5 The ratio of the molar amount of the nickel salt (in terms of molar amount) to the total molar amount of Ni and Mo contained in the nickel salt and the molybdenum salt is 1:(4~6).

[0010] Furthermore, the high molecular weight polymer in step 2) is one or more of agar, polyethylene glycol, polyvinyl alcohol, polyethylene oxide, polyacrylamide, polyhydroxyethyl methacrylate, chitosan, alginate and starch.

[0011] Furthermore, the mass ratio of polyacrylonitrile, high molecular polymer and aminomethylphosphonic acid in the active metal impregnation solution used in step 2) is (10-30):(10-30):(40-80).

[0012] Furthermore, the spinning process parameters in step 3) are: positive electrode voltage is 15 kV, negative electrode voltage is -1.5 kV, and the distance between positive and negative electrodes is 20 cm.

[0013] Furthermore, the high temperature carbonization in step 3) is carried out in an inert atmosphere such as nitrogen or argon at a temperature of 600-800°C for 2-6 hours.

[0014] Furthermore, the ball milling speed in step 3) is 500-800 rpm, and the time is 30-180 min.

[0015] Furthermore, the nano C@NiMoO 4 The mass ratio of precursor, sesbania powder, pseudo-boehmite and binder is (5~15):(0.5~5):(35~55):(35~55).

[0016] Furthermore, in step 4), the binder is an aqueous solution of an inorganic acid or an organic acid with a concentration of 0.06-6.0 wt %; the inorganic acid is hydrochloric acid or nitric acid; the organic acid is formic acid, acetic acid or citric acid.

[0017] Furthermore, in step 4), the calcination temperature is 520-650° C. and the calcination time is 2-6 h.

[0018] The beneficial effects of the present invention are: (1) Aminomethylphosphonic acid is used in the preparation of the active metal impregnation solution of the present invention. The amino group in the aminomethylphosphonic acid molecule has the ability to complex metal Ni, and the phosphonic acid end and metal Mo can form a phosphomolybdic acid structure, thereby highly enhancing the catalytic synergy of Ni and Mo metals in the catalyst.

[0019] (2) The nano NiMoO prepared by electrospinning technology 4 The precursor, due to the addition of high molecular weight polymer in the spinning solution, not only makes the prepared catalyst have a certain proportion of macroporous structure, but also makes the active metal highly dispersed, thereby improving the desulfurization activity of the catalyst.

[0020] (3) The catalyst prepared by the present invention can show higher desulfurization activity and long-term stable operation performance when used in residual oil hydrodesulfurization reaction. DETAILED DESCRIPTION

[0021] A residual oil hydrodesulfurization catalyst, the preparation method of which comprises the following steps: 1) Preparation of active metal impregnation solution containing Ni and Mo: Add nickel salt and molybdenum salt to an aqueous solution of aminomethylphosphonic acid under heating conditions of 60-100°C, and stir until completely dissolved to obtain an active metal impregnation solution; 2) Preparation of electrospinning solution: polyacrylonitrile (PNA) is dissolved in dimethylformamide (DMF) at 50-70 °C, and then added to the active metal impregnation solution obtained in step 1), and then a high molecular polymer is added to adjust the viscosity of the solution to obtain a spinning solution; 3) Nano-C@NiMoO 4 Preparation of precursor: The spinning solution obtained in step 2) was electrospun by electrospinning technology (process parameters: positive electrode voltage was 15 kV, negative electrode voltage was -1.5 kV, and the distance between positive and negative electrodes was 20 cm) to obtain a nanofiber membrane containing active metals. The obtained nanofiber membrane was then carbonized in a high-temperature furnace at 600-800 °C and in an inert atmosphere for 2-6 h to obtain C@NiMoO 4 Then, the nano-C@NiMoO was obtained by ball milling at 500-800 rpm for 30-180 min. 4 Precursor; 4) Preparation of catalyst: The obtained nano-C@NiMoO 4The precursor is fully mixed with sesbania powder and pseudo-boehmite, and a binder is added to extrude the mixture into strips, which are then dried and calcined at 520-650 °C for 2-6 h to obtain a residue oil hydrodesulfurization catalyst, in which the content of molybdenum oxide is 4.0-18.0 wt% and the content of nickel oxide is 0.2-6.0 wt%.

[0022] Wherein, the nickel salt in step 1) is nickel nitrate or nickel acetate; the molybdenum salt is ammonium heptamolybdate, ammonium tetramolybdate or molybdenum oxide. 2 O 5 The ratio of the molar amount of Ni (calculated) to the total molar amount of Ni and Mo contained in the nickel salt and molybdenum salt is 1:(4~6).

[0023] The high molecular polymer in step 2) is one or more of agar, polyethylene glycol, polyvinyl alcohol, polyethylene oxide, polyacrylamide, polyhydroxyethyl methacrylate, chitosan, alginate and starch. The mass ratio of polyacrylonitrile, high molecular polymer and aminomethylphosphonic acid in the active metal impregnation solution is (10-30):(10-30):(40-80).

[0024] Nano-C@NiMoO used in step 4) 4 The mass ratio of the precursor, sesbania powder, pseudo-boehmite and binder is (5-15):(0.5-5):(35-55):(35-55). The binder is an aqueous solution of an inorganic acid or an organic acid, and its concentration is 0.06-6.0 wt %; the inorganic acid is hydrochloric acid or nitric acid; the organic acid is formic acid, acetic acid or citric acid.

[0025] In order to make the contents of the present invention easier to understand, the technical solution of the present invention is further described below in conjunction with specific implementation methods, but the present invention is not limited thereto.

[0026] Example 1 (1) Preparation of active metal impregnation solution containing Ni and Mo: 100 g MoO 3 Add to 400 g of 10% aminomethylphosphonic acid aqueous solution, stir until completely dissolved, then add 78.3 g Ni(NO 3 ) 3 6H 2 O, continue stirring and dissolving to obtain an active metal impregnation solution; (2) Preparation of electrospinning solution: At 70 °C, add 10 g of PAN with a degree of polymerization of 56,000 into 100 mL of DMF, and after it is completely dissolved, add it to the active metal impregnation solution obtained in step (1), then add 10 g of corn starch and 10 g of alginate to adjust the liquid viscosity to 180 s (falling ball method) to prepare the spinning solution; (3) Nano-C@NiMoO 4 Preparation of precursor: The spinning solution obtained in step (2) was electrospun by electrospinning technology (the positive electrode voltage was controlled to be 15 kV, the negative electrode voltage was controlled to be -1.5 kV, and the distance between the positive and negative electrodes was 20 cm) to obtain a nanofiber membrane containing active metals; the obtained nanofiber membrane was then carbonized in a high-temperature furnace at 700 °C and a nitrogen atmosphere for 4 h to obtain C@NiMoO 4 Finally, after ball milling at 700 rpm for 120 min, nano-C@NiMoO 4 Precursor; (4) Preparation of catalyst: 1000 g pseudo-boehmite (67 wt% on dry basis), 50 g sesbania powder and 133 g nano-C@NiMO obtained in step (3) were added. 4 The precursor was added to a kneader and mixed. During the kneading process, 1000 g of nitric acid solution (20 g of nitric acid with a mass concentration of 65% was dissolved in 980 g of deionized water) was added. Finally, the catalyst was extruded, dried at 120 °C for 4 h, calcined at 650 °C for 4 h, and then cooled to room temperature to obtain a residue oil hydrodesulfurization catalyst, in which the content of molybdenum oxide was 12.0 wt% and the content of nickel oxide was 2.6 wt%.

[0027] Example 2 In step 2), the amount of corn starch added was changed to 20 g, and no alginate was added. Other operations were the same as in Example 1 to obtain a residue oil hydrodesulfurization catalyst.

[0028] Example 3 In step 2), instead of adding corn starch and alginate, 8 g of poly(hydroxyethyl methacrylate) and 3 g of polyvinyl alcohol were added, and other operations were the same as those in Example 1 to obtain a residue oil hydrodesulfurization catalyst.

[0029] Comparative Example 1 In order to investigate the performance of the catalyst prepared by the present invention in the residual oil hydrodesulfurization reaction, this comparative example uses phosphoric acid as the phosphorus source and adopts the traditional equal volume impregnation method to prepare the residual oil hydrodesulfurization catalyst, and the preparation method thereof is as follows: (1) 1000 g of pseudo-boehmite, 50 g of sesbania powder, and 20 g of polystyrene particles were kneaded in a kneader, and 900 g of nitric acid solution (50 g of nitric acid with a mass concentration of 65% dissolved in 850 g of deionized water) was added during the kneading process; after being stirred into a mass-like mixture, the mixture was kneaded on an extruder for 2-3 times; finally, a clover-shaped sample with a pore size of 1.6 mm was extruded, dried in an oven at 120 °C for 4 h, and calcined at 700 °C for 4 h to obtain Al 2 O 3 Carrier; (2) At 95 °C, 78.3 g Ni(NO 3 ) 3 6H 2 O and 100 g MoO 3 Dissolve in 650 g phosphoric acid solution (50 g of 85% phosphoric acid dissolved in 600 g of deionized water), then add the prepared Al 2 O 3 After impregnation and aging for 12 h, the impregnated sample was placed in a 120 °C oven for 2 h and then calcined in a 500 °C muffle furnace for 4 h to obtain NiMo / Al 2 O 3 The catalyst contains 12.0 wt% of molybdenum oxide and 2.6 wt% of nickel oxide.

[0030] Comparative Example 2 In order to investigate the performance of the catalyst prepared by the present invention in the residual oil hydrodesulfurization reaction, this comparative example uses ammonia water and ethylenediamine as amine sources and adopts the traditional equal volume impregnation method to prepare the residual oil hydrodesulfurization catalyst, and the preparation method is as follows: (1) 1000 g of pseudo-boehmite, 50 g of sesbania powder, and 20 g of polystyrene particles were kneaded in a kneader. During the kneading process, 900 g of nitric acid solution (50 g of nitric acid with a mass concentration of 65% dissolved in 850 g of deionized water) was added. After the mixture was stirred into a mass-like mixture, the mixture was kneaded on an extruder for 2 to 3 times. Finally, a clover-shaped sample with a pore size of 1.6 mm was extruded, dried in an oven at 120 °C for 4 h, and calcined at 700 °C for 4 h to obtain Al 2 O 3 Carrier; (2) At 95 °C, 78.3 g Ni(NO 3 ) 3 6H 2 O and 123.5 g ammonium heptamolybdate were dissolved in ammonia water containing ethylenediamine (25% concentrated ammonia water 300 g + 340 g deionized water + 10 g ethylenediamine). After complete dissolution, 49.8 g diammonium phosphate was added, stirred thoroughly at 60 °C and completely dissolved, and then the prepared Al 2 O 3 After impregnation for 12 h, the impregnated sample was placed in a 120 °C oven for 2 h and then calcined in a 500 °C muffle furnace for 4 h to obtain NiMo / Al 2 O 3 The catalyst contains 12.0 wt% of molybdenum oxide and 2.6 wt% of nickel oxide.

[0031] Comparative Example 3 In order to investigate the performance of the catalyst prepared by the present invention in the residual oil hydrodesulfurization reaction, this comparative example uses aminomethylphosphonic acid as the amine source and adopts the traditional equal volume impregnation method to prepare the residual oil hydrodesulfurization catalyst, and the preparation method is as follows: (1) Preparation of active metal impregnation solution containing Ni and Mo: 100 g MoO 3 Add to 650 g of 10% aminomethylphosphonic acid aqueous solution, stir until completely dissolved, then add 78.3 g Ni(NO 3 ) 3 6H 2 O, continue stirring and dissolving to obtain an active metal impregnation solution; (2) 1000 g of pseudo-boehmite and 50 g of sesbania powder were kneaded evenly in a kneader, and 900 g of nitric acid solution (50 g of nitric acid with a mass concentration of 65% dissolved in 850 g of deionized water) was added during the kneading process; after the mixture was stirred into a mass-like mixture, the mixture was kneaded on an extruder for 2-3 times; finally, a clover-shaped sample with a pore size of 1.6 mm was extruded, dried in an oven at 120 °C for 4 h, and calcined at 700 °C for 4 h to obtain Al 2 O 3 Carrier; (3) The active metal impregnation solution obtained in step (1) was uniformly loaded onto the support obtained in step (2) by an equal volume method, and after aging for 12 h, the impregnated sample was placed in a 120 °C oven for 2 h, and then calcined in a 500 °C muffle furnace for 4 h to obtain NiMo / Al 2 O 3 The catalyst contains 12.0 wt% molybdenum oxide and 2.6 wt% nickel oxide.

[0032] Table 1 gives the specific surface area and pore structure data of the catalysts obtained in the examples and comparative examples.

[0033] Table 1 Pore structure data of catalysts of Examples and Comparative Examples measured by mercury intrusion porosimetry

[0034] As can be seen from Table 1, compared with the comparative example, the catalyst prepared in the embodiment has a larger pore volume, which is mainly due to the fact that the precursor prepared by carbonization has a certain pore expansion effect, so that the catalyst has more macroporous structures of 50-100 nm and 100-200 nm, and these macroporous structures are beneficial to improving the carbon capacity and anti-carbon deposition stability of the catalyst.

[0035] Evaluation of hydrodesulfurization reaction performance The catalyst performance was evaluated in a 100 mL small fixed bed reactor using residual oil with a sulfur content of 4.30%, a nitrogen content of 2980 mg / kg, a residual carbon content of 11.7%, a nickel content of 21 mg / kg, and a vanadium content of 63 mg / kg as raw materials. The specific operation is to take 100 mL of catalyst and fill it into the fixed bed reactor, and pre-sulfurize the catalyst by wet pre-sulfurization, that is, first purge with nitrogen for 30 minutes to replace the air in the pipeline, and then inject the sulfide oil into the reactor through a high-pressure pump to sulfide the catalyst. The sulfidation reaction conditions are: temperature 320 ℃, pressure 2.0 MPa, mass space velocity 1.0 h -1 , hydrogen-oil volume ratio 300:1; after the sulfidation, the residual oil was injected for reaction. The reaction conditions were: reaction temperature 385 °C, hydrogen partial pressure 15 MPa, liquid hourly space velocity 0.23 h -1 , the volume ratio of hydrogen to oil is 760: 1. The sulfur content in the oil before and after the reaction was determined by energy dispersive X-ray fluorescence spectrometry (for specific methods, see GB / T17040-2008), and the results are shown in Table 2.

[0036] Table 2 Performance evaluation results of catalysts of Examples and Comparative Examples

[0037] Table 2 shows the desulfurization rates of the catalysts obtained in the examples and comparative examples at different reaction times. As can be seen from Table 2, compared with the catalyst prepared by phosphoric acid alone in comparative example 1 and the catalyst prepared by organic amine alone in comparative example 2, the catalyst prepared by aminomethylphosphoric acid containing an amine group at one end and phosphorus at the other end in comparative example 3 has higher desulfurization activity, which is mainly due to the fact that aminomethylphosphonic acid can form a complex with Ni and Mo at the same time, so that the catalytic synergistic effect of Ni and Mo is enhanced; the catalyst of the example prepared by adding electrospinning and carbonization pore expansion technology on the basis of comparative example 3 has better anti-carbon deposition stability, which is mainly due to the fact that the macroporous structure has better carbon capacity and anti-carbon deposition stability.

[0038] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made according to the scope of the patent application of the present invention should fall within the scope of the present invention.

Claims

1. A method for preparing a residue hydrodesulfurization catalyst, characterized in that: The steps include: 1) Preparation of active metal impregnation solution containing Ni and Mo: under heating conditions, nickel salt and molybdenum salt are added to an aqueous solution of aminomethylphosphonic acid, and stirred until completely dissolved to obtain an active metal impregnation solution; 2) Preparation of electrospinning solution: dissolving polyacrylonitrile in dimethylformamide at 50-70 °C, then adding it to the active metal impregnation solution obtained in step 1), and then adding a high molecular polymer to obtain a spinning solution; 3) Preparation of nano C@NiMoO4 precursor: The spinning solution obtained in step 2) is spun by electrospinning technology to obtain a nanofiber membrane containing active metals, and then the obtained nanofiber membrane is carbonized at high temperature to obtain C@NiMoO4, and then the nano C@NiMoO4 precursor is obtained after sufficient ball milling; 4) Preparation of catalyst: The obtained nano C@NiMoO4 precursor is fully mixed with sesbania powder and pseudo-boehmite, and then a binder is added to extrude the mixture into strips, which are then dried and calcined to obtain the residual oil hydrodesulfurization catalyst.

2. The method for preparing a residue hydrodesulfurization catalyst according to claim 1, characterized in that: The temperature of the heating condition in step 1) is 60-100°C.

3. The method for preparing a residue hydrodesulfurization catalyst according to claim 1, characterized in that: In step 1), the nickel salt is nickel nitrate or nickel acetate; the molybdenum salt is ammonium heptamolybdate, ammonium tetramolybdate or molybdenum oxide.

4. The method for preparing a residue hydrodesulfurization catalyst according to claim 1, characterized in that: In step 1), the amount of aminomethylphosphonic acid used is calculated based on P2O5, and the ratio of its molar amount to the total molar amount of Ni and Mo contained in the nickel salt and the molybdenum salt is 1:(4-6).

5. The method for preparing a residue hydrodesulfurization catalyst according to claim 1, characterized in that: The mass ratio of polyacrylonitrile, high molecular polymer and aminomethylphosphonic acid in the active metal impregnation solution used in step 2) is (10-30):(10-30):(40-80); The high molecular polymer is one or more of agar, polyethylene glycol, polyvinyl alcohol, polyoxyethylene, polyacrylamide, polyhydroxyethyl methacrylate, chitosan, alginate and starch.

6. The method for preparing a residue hydrodesulfurization catalyst according to claim 1, characterized in that: The process parameters of the electrospinning in step 3) are: the positive electrode voltage is 15 kV, the negative electrode voltage is -1.5 kV, and the distance between the positive and negative electrodes is 20 cm.

7. The method for preparing a residue hydrodesulfurization catalyst according to claim 1, characterized in that: The high temperature carbonization in step 3) is carried out in an inert atmosphere at a temperature of 600-800°C for 2-6 h; the speed of the ball mill is 500-800 rpm for 30-180 min.

8. The method for preparing a residue hydrodesulfurization catalyst according to claim 1, characterized in that: The mass ratio of nano C@NiMoO4 precursor, sesbania powder, pseudo-boehmite and binder used in step 4) is (5-15):(0.5-5):(35-55):(35-55); The binder is an aqueous solution of an inorganic acid or an organic acid, and its concentration is 0.6-6.0 wt %.

9. The method for preparing a residue hydrodesulfurization catalyst according to claim 1, characterized in that: Step 4) The calcination temperature is 520-650°C and the calcination time is 2-6 h.

10. A residue hydrodesulfurization catalyst prepared by the method of any one of claims 1 to 9, characterized in that: The content of molybdenum oxide in the catalyst is 4.0-18.0 wt %, and the content of nickel oxide is 0.2-6.0 wt %.

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