Residue oil hydrodesulfurization catalyst and its preparation method and application

Abstract

The present invention discloses a residue oil hydrodesulfurization catalyst, its preparation method, and application. The catalyst comprises a core layer, a carbon film layer coated on the surface of the core layer, and a second active metal component supported within and on the surface of the carbon film layer. The core layer comprises a carrier and a first active metal component, the carbon film layer has a thickness of 20 to 450 μm, and the ratio of tetrahedral molybdenum to octahedral molybdenum in the catalyst, calculated as Mo atoms, is 0.12 to 0.48. The catalyst has strong resistance to carbon deposition and high active metal utilization. When used in residue oil hydrodesulfurization reactions, it exhibits high desulfurization performance and stability.

Description

Technical Field

[0001] The present invention relates to a hydrogenation catalyst and a preparation method thereof, and in particular to a residue oil hydrodesulfurization catalyst and a preparation method and application thereof. Background Art

[0002] As crude oil continues to become increasingly heavier and inferior in quality worldwide, the need for lighter and more efficient heavy oil processing is becoming a growing concern for refineries. Fixed-bed residue hydrotreating technology, with its catalyst grading system, effectively removes impurities such as metals, sulfur, nitrogen, and carbon residue from residue, demonstrating promising industrial performance. However, to further improve refinery economics, the proportion of inferior residue oil in the feedstock of residue hydrotreating units is constantly increasing, placing higher demands on residue hydrotreating catalysts. Furthermore, increasingly stringent environmental standards are placing even higher performance demands on residue hydrodesulfurization catalysts.

[0003] At present, due to the worsening deterioration of feed in residue oil hydrotreating units, a large amount of aromatic fused-ring compounds in the raw materials are deposited on the catalyst, forming carbon-rich organic deposits that block the pores, cover the active centers of the catalyst, affect the catalyst activity, and cause the bed pressure drop to gradually increase, thereby affecting the operation cycle of the unit.

[0004] CN101618326A discloses a heavy oil hydrotreating catalyst and a preparation method thereof. The catalyst comprises a carrier, at least one metal component selected from Group VIII and at least one metal component selected from Group VIB. The pore volume of the carrier is 0.6 to 1.2 ml / g, and the specific surface area is 200 to 380 m 2 / g, an average pore diameter of 11 to 14 nm, and pores with a diameter of 9 to 15 nm accounting for 80 to 95% of the total pore volume. The preparation method of the carrier comprises shaping, drying, and calcining an alumina precursor, wherein the calcination conditions are: calcining at a temperature of 350 to 400°C for 0.5 to 2 hours, and then calcining at a temperature of 600 to 800°C for 1 to 6 hours.

[0005] CN110201691A discloses a residual oil hydrodemetallization desulfurization catalyst and its preparation method. The catalyst is prepared by using two pseudo-boehmite with different crystal sizes as precursors to form an alumina carrier, and at least one VIB group metal component and at least one VIII group metal component as a hydrogenation active metal component to prepare the residual oil hydrodemetallization desulfurization catalyst. The catalyst has a pore volume of 0.4 to 0.8 mL / g and a specific surface area of ​​100 to 200 m 2 / g, with an average mesopore diameter of 12 to 20 nm, and can be used for hydrodemetallization and desulfurization of heavy oils such as residual oil.

[0006] In summary, as the deterioration of feed in the residue oil hydrotreating unit worsens, the catalysts prepared by the prior art have failed to effectively improve the problem of carbon deposition on the catalyst surface. Summary of the Invention

[0007] To address the problems of high surface active metal content, easy carbon deposition, low active site utilization, and short catalyst service life in existing residual oil hydrodesulfurization catalysts, the present invention provides a residual oil hydrodesulfurization catalyst, its preparation method, and its application. The catalyst exhibits strong resistance to carbon deposition, high active metal utilization, and high desulfurization performance and stability when used in residual oil hydrodesulfurization reactions.

[0008] In one aspect, the present invention provides a residue oil hydrodesulfurization catalyst comprising a core layer composed of a carrier and a first active metal component supported on the carrier, a carbon film layer coated on the surface of the core layer, and a second active metal component, wherein the first active metal component comprises molybdenum and nickel, and the second active metal component comprises molybdenum and nickel; the carbon film layer has a thickness of 20 to 450 μm, preferably 50 to 150 μm, and further preferably 100 to 140 μm. The catalyst comprises a content ratio of tetrahedral molybdenum to octahedral molybdenum, calculated as Mo atoms, of 0.12 to 0.48.

[0009] In the present invention, the pore volume of the carbon film layer is 0.80 to 1.50 cm 3 / g, preferably 1.0 to 1.4 cm 3 / g, and the average pore diameter is 35 to 85 nm, preferably 50 to 75 nm.

[0010] In the present invention, the carrier can be an alumina-based carrier with a pore volume of 0.65 to 0.95 cm 3 / g, with a specific surface area of ​​185 to 345 m 2 / g.

[0011] In the present invention, in the catalyst, based on the mass of the catalyst, the content of molybdenum oxide is 4.0% to 26.0%, and the content of nickel oxide is 2.0% to 12.0%.

[0012] In the present invention, based on the mass of the total molybdenum oxide in the catalyst, the content of molybdenum oxide in the first active metal component is 25% to 60%, and the content of molybdenum oxide in the second active metal component is 40% to 75%.

[0013] In the present invention, based on the mass of the total nickel oxide in the catalyst, the content of nickel oxide in the first active metal component is 25% to 60%, and the content of nickel oxide in the second active metal component is 40% to 75%.

[0014] A second aspect of the present invention provides a method for preparing the above-mentioned residue hydrodesulfurization catalyst, comprising the following steps:

[0015] (1) spraying a first active metal impregnation solution onto a support in an unsaturated impregnation manner, followed by drying and a first calcination to obtain a catalyst intermediate A;

[0016] (2) soaking the intermediate A obtained in step (1) in a carbohydrate aqueous solution, drying, and then carbonizing to obtain intermediate B;

[0017] (3) Spraying the second active metal impregnation solution onto the intermediate B obtained in step (2) in a saturated impregnation manner, and obtaining the residual oil hydrodesulfurization catalyst after drying and a second calcination.

[0018] In the method of the present invention, the carrier in step (1) can be an alumina-based carrier with a pore volume of 0.65 to 0.95 cm 3 / g, with a specific surface area of ​​185 to 345 m 2 / g.

[0019] In the method of the present invention, the active metals in the first active metal impregnation solution in step (1) are preferably molybdenum and nickel. The content of MoO3 in the first active metal impregnation solution is 12.0 to 60.0 g / 100 ml, and the content of NiO is 2.0 to 16.0 g / 100 ml. The mass of molybdenum oxide introduced into the catalyst by the first active metal impregnation solution accounts for 25% to 60% of the total molybdenum oxide loading in the catalyst, and the mass of nickel oxide introduced into the catalyst by the first active metal impregnation solution accounts for 25% to 60% of the total nickel oxide loading in the catalyst.

[0020] In the method of the present invention, the amount of the first impregnation liquid used in step (1) is 30% to 60% of the saturated water absorption rate of the carrier.

[0021] In the method of the present invention, the drying condition in step (1) is drying at 80-180° C. for 4-12 hours.

[0022] In the method of the present invention, the first calcination condition in step (1) is calcination at 550-650° C. for 2-8 hours, and the calcination atmosphere is one or more of air, water vapor, and nitrogen, preferably air.

[0023] In the method of the present invention, the carbohydrate solution described in step (2) is preferably an aqueous solution of starch and / or monosaccharides, and the mass concentration of starch and / or monosaccharides in the solution is 8.0% to 48.0%; the monosaccharides include one or more of glucose, ribose, fructose, and maltose.

[0024] In the method of the present invention, ammonium bicarbonate is added to the carbohydrate solution in step (2) as a pore-enlarging agent, the mass concentration of ammonium bicarbonate in the carbohydrate solution is 5.0% to 45.0%, and the soaking time is 0.5 min to 10 min, preferably 3.0 min to 8.0 min.

[0025] In the method of the present invention, the drying condition in step (2) is drying at 120-200° C. for 3-8 hours.

[0026] In the method of the present invention, the carbonization conditions described in step (2) are: pre-oxidation for 4 to 20 hours, preferably 3 to 16 hours, under an air atmosphere at a temperature of 160 to 320°C, preferably at 180 to 340°C; then carbonization for 2 to 10 hours under a nitrogen atmosphere at a temperature of 400 to 700°C, preferably 450 to 650°C, to form the carbon film layer on the surface of the intermediate A after carbonization.

[0027] In the method of the present invention, the active metals in the second active metal impregnation solution in step (2) are preferably molybdenum and nickel. The content of MoO3 in the second active metal impregnation solution is 2.0 to 36.0 g / 100 ml, and the content of NiO is 1.0 to 18.0 g / 100 ml. The mass of molybdenum oxide introduced into the catalyst by the second active metal impregnation solution accounts for 40% to 75% of the total molybdenum oxide loading in the catalyst, and the mass of nickel oxide introduced into the catalyst by the second active metal impregnation solution accounts for 40% to 75% of the total nickel oxide loading in the catalyst.

[0028] In the method of the present invention, the second calcination method in step (3) adopts programmed temperature rise, the heating rate is 1°C / min to 3°C / min, the calcination temperature is 450 to 550°C, the calcination time is 3 to 6 hours, and the calcination atmosphere is one or more of air, water vapor, and nitrogen, preferably air.

[0029] In the method of the present invention, the temperature of the second calcination is 50 to 200° C. lower than the temperature of the first calcination.

[0030] The third aspect of the present invention provides the use of the above-mentioned residue oil hydrodesulfurization catalyst in a residue oil hydrotreating process.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] The residue oil hydrodesulfurization catalyst of the present invention comprises a core layer, a carbon film layer coated on the surface of the core layer, and a second active metal component with a uniform distribution and a rational active phase structure supported within and on the surface of the carbon film layer. The core layer comprises a support and a first active metal component, and the carbon film layer comprises a carbon structure with unobstructed pores and a well-structured structure. This catalyst exhibits high desulfurization performance and stability when used in residue oil hydrodesulfurization reactions.

[0033] 2. The residual oil hydrodesulfurization catalyst of the present invention adopts two impregnations and two calcinations, which can effectively regulate the relative content of tetrahedral molybdenum and octahedral molybdenum in the final catalyst; wherein the surface of the catalyst after the first impregnation is coated with a carbon film with a more unobstructed pore structure, which not only avoids the deposition of residual oil macromolecules on the catalyst surface in the early stage of the reaction, but also provides a better loading site for the active metal of the second impregnation, so that the active metal is more dispersed, and the utilization rate of the active metal on the catalyst is effectively improved. During the reaction process, the residual oil macromolecules first undergo partial hydrogenation reaction and thermal cracking. Even if coke is produced, it is first deposited in the pores of the carbon film layer. The carbon film layer has good structural permeability, and the produced carbon deposits will not block the pores. The molecules after the reaction can enter the core layer for further hydrogenation reaction. In summary, through the comprehensive coordination of various steps, the method of the present invention not only improves the utilization rate of the active metal, but also significantly improves the desulfurization performance and stability of the catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is a Raman spectrum of the catalyst surface obtained in Example 1;

[0035] Figure 2 This is a Raman spectrum of the catalyst surface obtained in Example 2;

[0036] Figure 3 This is a Raman spectrum of the catalyst surface obtained in Comparative Example 1;

[0037] Figure 4 This is the Raman spectrum of the catalyst surface obtained in Comparative Example 2. DETAILED DESCRIPTION

[0038] In the present invention, the Raman spectroscopic characterization of the catalyst was performed using a DXR Microscope type DXR micro Raman spectrometer from Thermo Scientific. 1 The peak near it is the peak of tetrahedral molybdenum, at 960cm- 1 The nearby peak is the peak of octahedral molybdenum. The contents of tetrahedral molybdenum and octahedral molybdenum are calculated based on the area under the same baseline.

[0039] In the present invention, the pore structure (SVD) and specific surface area of ​​the catalyst were characterized using a Michael ASAP-2420 physical adsorption instrument. The pore volume and pore diameter of the outer layer of the carbon membrane involved were obtained by mercury intrusion testing.

[0040] The technical solutions and effects of the present invention are further described below with reference to the following embodiments, but are not limited to the following embodiments.

[0041] Example 1

[0042] (1) Prepare 180 g of residual oil hydrodesulfurization alumina support (the pore volume of the support is 0.75 cm 3 / g, specific surface area of ​​285m 2 / g), dried at 140°C for 6 hours and set aside. Prepare a first active metal impregnation solution with a volume of 64.08ml, wherein the content of MoO3 is 21.68g / 100ml and the content of NiO is 4.58g / 100ml. The above-mentioned carrier is impregnated with the prepared first active metal impregnation solution (the amount of molybdenum oxide introduced into the catalyst by the first active metal impregnation solution accounts for 45% of the total molybdenum oxide loading in the catalyst, and the amount of nickel oxide introduced into the catalyst by the first active metal impregnation solution accounts for 45% of the total nickel oxide loading in the catalyst). The amount used is 40% of the saturated water absorption rate of the carrier. After the impregnation, it is dried at 140°C for 6 hours and then subjected to a first calcination. The first calcination process adopts a programmed temperature rising method, and the temperature is raised to 650°C at a heating rate of 3.0°C / min and calcined for 3 hours to obtain catalyst intermediate A.

[0043] (2) The catalyst intermediate A was soaked in an aqueous solution containing 28.0% by mass of ammonium bicarbonate and 42.0% by mass of glucose for 5 minutes, then taken out and pre-oxidized at 320° C. in an air atmosphere for 8 hours, and then carbonized at 450° C. in a nitrogen atmosphere for 6 hours to obtain the residue oil hydrodemetallization catalyst intermediate B.

[0044] (3) A second active metal impregnation solution was prepared with a volume of 163.04 ml, wherein the content of MoO3 was 10.41 g / 100 ml and the content of NiO was 3.72 g / 100 ml. The second active metal impregnation solution was sprayed onto the catalyst intermediate B by saturation impregnation (the amount of molybdenum oxide introduced into the catalyst by the second active metal impregnation solution accounted for 55% of the total molybdenum oxide loading in the catalyst, and the amount of nickel oxide introduced into the catalyst by the second active metal impregnation solution accounted for 55% of the total nickel oxide loading in the catalyst). After impregnation, the catalyst was dried at 140°C for 6 hours and then subjected to a second calcination process. The second calcination process was performed by programmed temperature rise, with the temperature rising to 500°C at a rate of 1.0°C / min and calcination for 6 hours. Thus, the residue hydrodesulfurization catalyst CAT-1 was obtained.

[0045] The pore volume of the core layer (catalyst intermediate A) of catalyst CAT-1 is 0.59 cm 3 / g, the thickness of the carbon film layer is 138 μm, and the pore volume is 1.23 cm 3 / g, the average pore size is 62nm, and the ratio of tetrahedral molybdenum to octahedral molybdenum is 0.12.

[0046] Example 2

[0047] Compared with Example 1, the difference is that in step (2), the catalyst is immersed in an aqueous solution containing 25.0% by mass of ammonium bicarbonate and 36.0% by mass of starch for 4.5 minutes, then removed and pre-oxidized at 300°C in an air atmosphere for 7 hours, and then carbonized at 500°C in a nitrogen atmosphere for 7 hours. Thus, the residue oil hydrodesulfurization catalyst CAT-2 is obtained.

[0048] The core layer pore volume of catalyst CAT-2 is 0.57 cm 3 / g, the thickness of the carbon film layer is 131 μm, and the pore volume is 1.21 cm 3 / g, the average pore size is 58nm, and the ratio of tetrahedral molybdenum to octahedral molybdenum is 0.27.

[0049] Example 3

[0050] Compared with Example 1, the difference is that in step (2), the mixture is immersed in an aqueous solution containing 22.0% by mass of ammonium bicarbonate and 32.0% by mass of starch for 4.0 minutes, then taken out, pre-oxidized at 280°C in an air atmosphere for 6 hours, and then carbonized at 550°C in a nitrogen atmosphere for 8 hours. In step (1), the first roasting process adopts a programmed temperature rising method, heating the temperature to 600°C at a heating rate of 2.5°C / min and roasting for 4 hours. In step (3), the second roasting process adopts a programmed temperature rising method, heating the temperature to 450°C at a heating rate of 1.5°C / min and roasting for 5 hours. Thus, the residue oil hydrodesulfurization catalyst CAT-3 is obtained.

[0051] The core layer pore volume of catalyst CAT-3 is 0.56 cm 3 / g, the thickness of the carbon film layer is 126 μm, and the pore volume is 1.20 cm 3 / g, the average pore size is 56nm, and the ratio of tetrahedral molybdenum to octahedral molybdenum is 0.35.

[0052] Example 4

[0053] Compared with Example 1, the difference is that in the first active metal impregnation solution in step (1), the content of MoO3 is 23.12 g / 100 ml, and the content of NiO is 4.89 g / 100 ml (the amount of molybdenum oxide introduced into the catalyst by the first active metal impregnation solution accounts for 48% of the total molybdenum oxide loading in the catalyst, and the amount of nickel oxide introduced into the catalyst by the first active metal impregnation solution accounts for 48% of the total nickel oxide loading in the catalyst). In step (2), the catalyst is immersed in an aqueous solution containing 20.0% by mass of ammonium bicarbonate and 30.0% by mass of starch for 3.5 minutes, then removed, pre-oxidized at 260°C in an air atmosphere for 5 hours, and then carbonized at 600°C in a nitrogen atmosphere for 9 hours. Meanwhile, the volume of the second active metal impregnation solution in step (3) was 163.04 ml, wherein the MoO3 content was 9.85 g / 100 ml and the NiO content was 3.71 g / 100 ml (the amount of molybdenum oxide introduced into the catalyst by the second active metal impregnation solution accounted for 52% of the total molybdenum oxide loading in the catalyst, and the amount of nickel oxide introduced into the catalyst by the second active metal impregnation solution accounted for 52% of the total nickel oxide loading in the catalyst). Residue oil hydrodesulfurization catalyst CAT-4 was obtained.

[0054] The pore volume of the core layer of catalyst CAT-4 is 0.53 cm 3 / g, the thickness of the carbon film layer is 121 μm, and the pore volume is 1.19 cm 3 / g, the average pore size is 54nm, and the ratio of tetrahedral molybdenum to octahedral molybdenum is 0.42.

[0055] Example 5

[0056] Compared with Example 1, the difference is that in step (2), the catalyst is immersed in an aqueous solution containing 16.0% by mass of ammonium bicarbonate and 25.0% by mass of starch for 3.0 minutes, then taken out, pre-oxidized at 240°C in an air atmosphere for 4 hours, and then carbonized at 650°C in a nitrogen atmosphere for 10 hours. Thus, the residue oil hydrodesulfurization catalyst CAT-5 is obtained.

[0057] The pore volume of the core layer of catalyst CAT-5 is 0.51 cm 3 / g, the thickness of the carbon film layer is 102 μm, and the pore volume is 1.08 cm 3 / g, the average pore diameter is 53nm, and the ratio of tetrahedral molybdenum to octahedral molybdenum is 0.48.

[0058] Comparative Example 1

[0059] Compared with Example 1, the difference is that only one impregnation process is performed, that is, in step (1), a first active metal impregnation solution is prepared with a volume of 160.2 ml, wherein the MoO3 content is 19.27 g / 100 ml and the NiO content is 4.07 g / 100 ml. The residue oil hydrodesulfurization catalyst DCAT-1 is obtained.

[0060] The core layer pore volume of catalyst DCAT-1 is 0.53 cm 3 / g, the thickness of the carbon film layer is 123 μm, and the pore volume is 1.17 cm 3 / g, the average pore size is 67nm, and the ratio of tetrahedral molybdenum to octahedral molybdenum is 2.31.

[0061] Comparative Example 2

[0062] Compared with Example 1, the difference is that steps (2) and (3) are omitted, and a first active metal impregnation solution with a volume of 160.2 ml is directly prepared. The MoO3 content is 19.27 g / 100 ml, and the NiO content is 4.07 g / 100 ml. The alumina support is impregnated with the solution, and then a first calcination is performed (the process is the same as in Example 1). This yields the residue oil hydrodesulfurization catalyst DCAT-2.

[0063] The pore volume of catalyst DCAT-2 is 0.51 cm 3 / g, and the ratio of tetrahedral molybdenum to octahedral molybdenum is 2.40.

[0064] Comparative Example 3

[0065] Compared with Example 1, the difference is that no ammonium bicarbonate is added in step (2), and no pre-oxidation is performed in air, but carbonization is directly performed at 650° C. for 10 hours in a nitrogen atmosphere to obtain the residue hydrodesulfurization catalyst DCAT-3.

[0066] The core layer pore volume of catalyst DCAT-3 is 0.50 cm 3 / g, the thickness of the carbon film layer is 132 μm, and the pore volume is 1.04 cm 3 / g, the average pore diameter is 51nm, and the ratio of tetrahedral molybdenum to octahedral molybdenum is 2.48.

[0067] Evaluation test

[0068] The activity and stability of Example Catalysts CAT-1-5 and Comparative Example Catalysts DCAT-1-3 were evaluated in a 200 ml fixed-bed hydrogenation test apparatus. The feedstock used was atmospheric residue (sulfur content 4.42%). The experimental process conditions are shown in Table 1. The desulfurization efficiency of Catalyst CAT-1 after 100 hours of operation was used as a benchmark to determine the relative desulfurization efficiency of the other catalysts. The catalyst evaluation results are shown in Table 2.

[0069] Table 1 Experimental process conditions

[0070] Reaction temperature, °C 390 Reaction pressure, MPa 15.7 <![CDATA[Space velocity, h- 1 > 0.5 Hydrogen to oil ratio, V / V 800

[0071] Table 2 Evaluation results of various catalysts

[0072]

[0073] It can be seen from Table 1 and Table 2 that the hydrodesulfurization catalyst prepared by the present invention has better hydrodesulfurization activity than that of the comparative example, and has better stability during the long-term operation of the catalyst.

Claims

1. A residue oil hydrodesulfurization catalyst, comprising a core layer consisting of a carrier and a first active metal component supported on the carrier, a carbon film layer and a second active metal component coated on the surface of the core layer, wherein the first active metal component comprises molybdenum and nickel, and the second active metal component comprises molybdenum and nickel; the carbon film layer has a thickness of 100 to 140 μm; the catalyst has a content ratio of tetrahedral molybdenum to octahedral molybdenum, calculated as Mo atoms, of 0.12 to 0.48; and the carbon film layer has a pore volume of 0.80 to 1.50 cm 3 / g, average pore size is 35~85nm; The preparation method of the catalyst comprises the following steps: (1) spraying a first active metal impregnation solution onto a support in an unsaturated impregnation manner, followed by drying and a first calcination to obtain a catalyst intermediate A; (2) soaking the intermediate A obtained in step (1) in a carbohydrate aqueous solution, drying, and then carbonizing to obtain intermediate B; (3) spraying the second active metal impregnation solution onto the intermediate B obtained in step (2) in a saturated impregnation manner, and drying and second calcining to obtain the residual oil hydrodesulfurization catalyst; In step (1), the first roasting temperature is 550-650°C, and in step (3), the second roasting temperature is 450-500°C, and the second roasting temperature is 50-200°C lower than the first roasting temperature.

2. The catalyst according to claim 1, characterized in that The pore volume of the carbon film layer is 1.0~1.4cm 3 / g, and the average pore size is 50~75nm.

3. The catalyst according to claim 1, characterized in that The carrier is an alumina-based carrier with a pore volume of 0.65 to 0.95 cm 3 / g, with a specific surface area of ​​185~345m 2 / g.

4. The catalyst according to claim 1, characterized in that In the catalyst, based on the mass of the catalyst, the mass content of molybdenum oxide is 4.0% to 26.0%, and the mass content of nickel oxide is 2.0% to 12.0%.

5. The catalyst according to claim 1, characterized in that The pore volume of the core layer is 0.45~65cm 3 / g.

6. The catalyst according to claim 1, characterized in that Based on the mass of the total molybdenum oxide in the catalyst, the content of molybdenum oxide in the first active metal component is 25%~60%, and the content of molybdenum oxide in the second active metal component is 40%~75%; based on the mass of the total nickel oxide in the catalyst, the content of nickel oxide in the first active metal component is 25%~60%, and the content of nickel oxide in the second active metal component is 40%~75%.

7. A method for preparing the catalyst according to any one of claims 1 to 6, comprising the steps of: (1) spraying a first active metal impregnation solution onto a support in an unsaturated impregnation manner, followed by drying and a first calcination to obtain a catalyst intermediate A; (2) soaking the intermediate A obtained in step (1) in a carbohydrate aqueous solution, drying, and then carbonizing to obtain intermediate B; (3) Spraying the second active metal impregnation solution onto the intermediate B obtained in step (2) in a saturated impregnation manner, and obtaining the residual oil hydrodesulfurization catalyst after drying and a second calcination.

8. The preparation method according to claim 7, characterized in that The amount of the first active metal impregnation solution used in step (1) is 30% to 60% of the saturated water absorption capacity of the carrier.

9. The preparation method according to claim 7, characterized in that The first calcination condition in step (1) is calcination at 550-650° C. for 2-8 hours, and the calcination atmosphere is one or more of air, water vapor, and nitrogen.

10. The preparation method according to claim 7, characterized in that In step (1), the first calcination atmosphere is air.

11. The preparation method according to claim 7, characterized in that The carbohydrate aqueous solution described in step (2) is an aqueous solution of starch and / or monosaccharides, and the mass concentration of starch and / or monosaccharides in the solution is 8.0% to 48.0%; the monosaccharides include one or more of glucose, ribose, and fructose.

12. The preparation method according to claim 7, characterized in that Ammonium bicarbonate is added to the carbohydrate aqueous solution in step (2) as a pore-enlarging agent, the mass concentration of ammonium bicarbonate in the carbohydrate aqueous solution is 5.0% to 45.0%, and the immersion time is 0.5 min to 10 min.

13. The preparation method according to claim 12, characterized in that The mass concentration of ammonium bicarbonate in the carbohydrate aqueous solution is 15% to 30%, and the soaking time is 3.0 min to 8.0 min.

14. The preparation method according to claim 7, characterized in that The carbonization conditions described in step (2) are: pre-oxidation at a temperature of 160-320°C in an air atmosphere for 4-20 hours; and then carbonization at a temperature of 400-700°C in a nitrogen atmosphere for 2-10 hours.

15. The preparation method according to claim 7, characterized in that The carbonization conditions described in step (2) are: pre-oxidation at a temperature of 180-340°C in an air atmosphere for 3-16 hours; and then carbonization at a temperature of 450-650°C in a nitrogen atmosphere for 2-10 hours.

16. The preparation method according to claim 7, characterized in that The second calcination method in step (3) adopts programmed temperature rise, the heating rate is 1°C / min~3°C / min, the calcination temperature is 450~500°C, the calcination time is 3~6 hours, and the calcination atmosphere is one or more of air, water vapor, and nitrogen.

17. The preparation method according to claim 7, characterized in that The second calcination atmosphere in step (3) is air.

18. The preparation method according to claim 7, characterized in that The temperature of the second calcination is 50-200° C. lower than the temperature of the first calcination.

19. Use of the catalyst according to any one of claims 1 to 6 in a residue oil hydrotreating process.

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