Heavy distillate oil hydrotreating catalyst as well as preparation method and application thereof

Abstract

The invention discloses a heavy distillate oil hydrotreating catalyst and a preparation method and application thereof, the preparation method comprises the following steps: (1) preparing a first impregnation liquid which contains gelatin and active metal components; (2) carrying out unsaturated impregnation on an alumina carrier by using the first impregnation liquid obtained in the step (1), and carrying out cooling and curing treatment after impregnation to obtain a heavy distillate oil hydrotreating catalyst precursor; (3) preparing a second impregnation liquid, wherein the second impregnation liquid contains an active metal component; and (4) impregnating the heavy distillate hydrotreating catalyst precursor obtained in the step (2) with the second impregnation liquid obtained in the step (3), and drying and roasting to obtain the final heavy distillate hydrotreating catalyst. The hydrotreating catalyst prepared by the method has high matching degree with the hydrotreating reaction process of heavy distillate oil, and has high activity.

Description

TECHNICAL FIELD

[0001] The present application relates to a heavy distillate oil hydroprocessing catalyst, a preparation method and application thereof, in particular to a high-activity heavy distillate oil hydroprocessing catalyst, a preparation method and application thereof. BACKGROUND

[0002] With the continuous increase of the heavy and poor quality of crude oil, the proportion of poor quality heavy oil in the refinery processing raw materials increases year by year, and the production of heavy distillate oil such as vacuum gas oil (VGO), coking gas oil (CGO) and deasphalted oil (DAO) also increases. Heavy distillate oil contains a large amount of sulfur, nitrogen, metal and other impurities, which will inevitably affect the product quality when used as raw materials for subsequent processing. To solve the above problems, a relatively effective technical route is to carry out hydroprocessing on the above-mentioned raw materials, and one of the cores of the technology is the hydroprocessing catalyst. The heavy distillate oil hydroprocessing catalyst generally refers to a supported catalyst containing Mo, W, Ni or Co active components, and the commonly used preparation method is impregnation method.

[0003] CN111250103A discloses a preparation method of a supported hydrogenation catalyst, which comprises the following steps: step 1, preparing a γ-Al2O3 carrier; step 2, impregnating the γ-Al2O3 carrier with a solution of an active metal positioning load directing agent and drying; and step 3, impregnating the γ-Al2O3 carrier obtained in step 2 with an impregnating solution containing active components, drying and calcining to obtain a supported hydrogenation catalyst; wherein the active metal positioning load directing agent is one or several selected from the group consisting of ethylenediamine tetramethylene phosphonic acid sodium, tetrabutylammonium fluoride and tartaric acid.

[0004] CN114425354A discloses a preparation method of a heavy oil hydrogenation catalyst, the prepared catalyst and application. The preparation method comprises: preparing an aqueous solution containing organic acid, phosphorus compound, amine compound, surfactant and at least one active metal as impregnating solution. The impregnating solution is used to impregnate the carrier to load the active metal component, and the remaining amount is sprayed with liquid oil when the spraying amount of the impregnating solution reaches 90% to 98% of the theoretical value. After the treatment of growth, low-temperature drying and high-temperature calcination, the heavy oil hydroprocessing catalyst is obtained.

[0005] CN101927176A discloses a preparation method of a hydrogenation catalyst with a gradient increase of active metal and acidic additive concentration. The method saturates the carrier by preparing a relatively dilute active metal solution and an acidic additive solution and deionized water, gradually adding a relatively concentrated active metal solution and an acidic additive solution during the spraying process, or by preparing active metal solutions and acidic additive solutions with different concentrations, impregnating the carrier in the order of active metal impregnation solution and acidic additive solution concentration from low to high, or impregnating with a solution with a lower acidic additive concentration and deionized water, gradually adding a solution with a higher acidic additive concentration to the impregnation solution during the impregnation process, drying and calcining, then impregnating with a solution with a lower active metal concentration and deionized water, gradually adding a solution with a higher active metal concentration to the impregnation solution during the impregnation process, and finally achieving a gradient distribution of metal components.

[0006] The reaction process of heavy distillate oil on a hydrotreating catalyst is relatively complex. During the reaction process, reactant molecules diffuse into the pores of the catalyst, and catalytic reactions are carried out in the pores of the catalyst. The distribution of active metal components in the pores of the catalyst has an important influence on the reaction results. However, there is no perfect theoretical basis for how the distribution of active metal components is beneficial to the hydrotreatment of heavy distillate oil. In the prior art, the hydrogenation activity of the hydrotreating catalyst needs to be further improved when the hydrotreating catalyst is used to treat heavy distillate oil. SUMMARY

[0007] In view of the deficiencies in the prior art, the present application provides a heavy distillate oil hydrotreating catalyst, a preparation method and application thereof. The hydrotreating catalyst prepared by the method has a high matching degree with the heavy distillate oil hydrotreatment reaction process and high activity.

[0008] According to a first aspect of the present application, the present application provides a preparation method of a heavy distillate oil hydrotreating catalyst, comprising the following steps:

[0009] (1) preparing a first impregnation solution containing gelatin and active metal components;

[0010] (2) unsaturatedly impregnating an alumina carrier with the first impregnation solution obtained in step (1), and performing a cooling solidification treatment after impregnation to obtain a heavy distillate oil hydrotreating catalyst precursor;

[0011] (3) preparing a second impregnation solution containing active metal components;

[0012] (4) impregnating the heavy distillate oil hydrotreating catalyst precursor obtained in step (2) with the second impregnation solution obtained in step (3), and obtaining a final heavy distillate oil hydrotreating catalyst after drying and calcination.

[0013] In the preparation method of the heavy oil hydroprocessing catalyst, the gelatin in step (1) is selected from one or more of marine gelatin, pig gelatin, cow gelatin and chicken gelatin, and has an industrial grade or food grade purity level; the molecular weight of the gelatin is 10,000-70,000, preferably 10,000-50,000.

[0014] In the preparation method of the heavy oil hydroprocessing catalyst, the first impregnation solution in step (1) contains 2-10 wt% of gelatin, preferably 3-8 wt% of gelatin, based on the weight of the first impregnation solution.

[0015] In the preparation method of the heavy oil hydroprocessing catalyst, the temperature of the first impregnation solution in step (1) is 40-70°C, preferably 50-60°C.

[0016] In the preparation method of the heavy oil hydroprocessing catalyst, the alumina carrier in step (2) can be a commercially available product or prepared according to the prior art. The properties of the alumina carrier are generally required as follows: pore volume is 0.3-1.5 mL / g, specific surface area is 150-450 m 2 / g.

[0017] In the preparation method of the heavy oil hydroprocessing catalyst, the alumina carrier in step (2) can also contain an auxiliary agent selected from one or more of silicon dioxide, magnesium oxide, zirconium oxide, boron oxide and titanium dioxide, and the content of the auxiliary agent (calculated as an oxide) in the alumina carrier is below 30 wt%.

[0018] In the preparation method of the heavy oil hydroprocessing catalyst, the alumina carrier in step (2) is formed by any one of molding means such as drop ball molding, rolling ball granulation, extrusion molding and tablet molding, and is preferably formed by extrusion molding; the shape of the alumina carrier can be any one of a spherical shape, a strip shape and a sheet shape, and is preferably any one of a spherical shape and a strip shape.

[0019] In the preparation method of the heavy oil hydroprocessing catalyst, the impregnation amount of the first impregnation solution for unsaturated impregnation of the alumina carrier in step (2) is 30-60 wt%, preferably 40-50 wt%, of the saturated water absorption amount of the alumina carrier.

[0020] In the preparation method of the heavy oil hydroprocessing catalyst, the impregnation temperature of the first impregnation solution for unsaturated impregnation of the alumina carrier in step (2) is 40-70°C, preferably 50-60°C.

[0021] In the preparation method of the heavy oil hydroprocessing catalyst, the unsaturated impregnation of the alumina carrier in step (2) can be performed by any of the methods known in the art, such as spray impregnation. The temperature of the impregnation solution is 40-70°C, preferably 50-60°C.

[0022] In the preparation method of the heavy oil hydroprocessing catalyst, the temperature reduction and solidification treatment after impregnation in step (2) is placing the alumina carrier impregnated with the first impregnation solution in an environment with a temperature of 2-25°C, preferably 5-20°C, for 1-30h, preferably 3-20h. The first impregnation solution contains gelatin. The temperature reduction and solidification treatment can convert the first impregnation solution adsorbed in the alumina carrier into a gel state, and the gel state of the first impregnation solution can be enriched in the macropores of the alumina carrier.

[0023] In the preparation method of the heavy oil hydroprocessing catalyst, the impregnation of the heavy oil hydroprocessing catalyst precursor with the second impregnation solution in step (4) is saturated impregnation, and the impregnation amount is the difference between the water absorption rate of the alumina carrier and the solution amount of the first impregnation solution.

[0024] In the preparation method of the heavy oil hydroprocessing catalyst, the impregnation temperature in step (4) is 1-30°C, preferably 15-25°C.

[0025] In the preparation method of the heavy oil hydroprocessing catalyst, the aging treatment can be performed before drying and calcination in step (4). The aging temperature is 5-30°C, and the aging time is 1-30h, preferably 5-20h.

[0026] In the preparation method of the heavy oil hydroprocessing catalyst, the drying temperature in step (4) is 80-160°C, preferably 100-130°C, and the drying time is generally 2-6h, preferably 3-4h. The calcination temperature is 80-650°C, preferably 100-500°C, and the calcination time is 1-10h, preferably 2-6h.

[0027] In the preparation method of the heavy oil hydroprocessing catalyst, the mass ratio of the active metal components (calculated as oxides) introduced by the first impregnation solution in step (1) to the active metal components (calculated as oxides) introduced by the second impregnation solution in step (3) is 0.08-0.6, preferably 0.08-0.3.

[0028] In the above process for preparing a heavy distillate hydroprocessing catalyst, the content of the Group VIII metal in the active metal component introduced by the first impregnation solution in step (1) is 0.1 wt% to 5 wt% as oxide, preferably 0.1 wt% to 2 wt%; the content of the Group VIB metal in the active metal component introduced by the first impregnation solution is 0.5 wt% to 10 wt% as oxide, preferably 2 wt% to 8 wt%; the content of the Group VIII metal in the active metal component introduced by the second impregnation solution in step (3) is 1 wt% to 15 wt% as oxide, preferably 2 wt% to 10 wt%; the content of the Group VIB metal in the active metal component introduced by the second impregnation solution is 10 wt% to 30 wt% as oxide, preferably 15 wt% to 25 wt%.

[0029] In the above process for preparing a heavy distillate hydroprocessing catalyst, the active metal component comprises at least one metal selected from Group VIII and / or at least one metal selected from Group VIB; the Group VIII metal is preferably Ni and / or Co, and the Group VIB metal is preferably Mo. In the present application, the nickel source is selected from one or more of nickel nitrate, basic nickel carbonate, nickel oxalate, nickel chloride and nickel acetate; the cobalt source is selected from one or more of cobalt nitrate, cobalt oxalate, basic cobalt carbonate and cobalt chloride; and the molybdenum source is selected from one or more of molybdenum oxide, ammonium molybdate, ammonium tetrathiomolybdate and ammonium dimolybdate.

[0030] In the above process for preparing a heavy distillate hydroprocessing catalyst, the first impregnation solution in step (1) and / or the second impregnation solution in step (3) can also contain an auxiliary agent selected from one or more of phosphorus, titanium, silicon, zinc, magnesium, copper, zirconium, boron, fluorine, lanthanum, cerium and vanadium.

[0031] In the above process for preparing a heavy distillate hydroprocessing catalyst, the mass ratio of the auxiliary agent (as oxide) introduced by the first impregnation solution in step (1) to the auxiliary agent (as oxide) introduced by the second impregnation solution in step (3) is 0 to 1. In the present application, the weight content of the auxiliary agent (as oxide) introduced by the first impregnation solution in step (1) is 0% to 2%, preferably 0.5% to 1.5%, and the weight content of the auxiliary agent (as oxide) introduced by the second impregnation solution in step (3) is 0% to 10%, preferably 1% to 5%, based on the weight of the final heavy distillate hydroprocessing catalyst.

[0032] According to a second aspect of the present application, there is provided a heavy distillate hydroprocessing catalyst prepared by the above process.

[0033] According to a third aspect of the present application, there is provided the use of the above heavy distillate hydroprocessing catalyst in a heavy distillate hydroprocessing process.

[0034] In the above application, the distillation range of the heavy distillate oil is 270-580℃, and the heavy distillate oil is at least one of vacuum gas oil, deasphalted oil, catalytic cracking cycle oil, shale oil and coal tar.

[0035] In the above application, the operating conditions of the heavy distillate oil hydrogenation process are as follows: the reaction temperature is 330-430℃, preferably 350-410℃, the reaction pressure is 4-18 MPa, preferably 6-16 MPa, the hydrogen / oil volume ratio is 400:1-1500:1, preferably 600:1-1200:1, and the volume space velocity is 0.5-4.0 h -1 , preferably 0.5-2.0 h -1 .

[0036] Compared with the prior art, the present application has the following advantages:

[0037] 1. In the preparation method of the heavy distillate oil hydrotreating catalyst, after the alumina carrier is unsaturatedly impregnated with the first impregnation solution containing gelatin and active metal components, the first impregnation solution adsorbed in the alumina carrier is converted into a gel state by a solidification treatment using the low-temperature solidification characteristics of gelatin, and the gel state of the first impregnation solution can be mostly enriched in the macropores of the alumina carrier; the second impregnation solution is an aqueous solution containing active metal components, which is not miscible with the gel state of the first impregnation solution and is difficult to enter the positions occupied by the gel state of the first impregnation solution, so that most of the second impregnation solution enters the remaining channels of the alumina carrier. The above operation introduces the active metal components in the first impregnation solution and the second impregnation solution into different positions of the alumina carrier, respectively, so as to regulate the distribution of the active metal components in the channels of the catalyst, thereby obtaining a high-activity heavy distillate oil hydrotreating catalyst.

[0038] 2. In the preparation method of the heavy distillate oil hydrotreating catalyst, the first impregnation solution and / or the second impregnation solution can also contain an additive, which is introduced into different positions of the alumina carrier by the first impregnation solution and the second impregnation solution, so as to regulate the distribution of the additive in the channels of the catalyst, thereby further improving the activity of the heavy distillate oil hydrotreating catalyst. BRIEF DESCRIPTION OF DRAWINGS

[0039] Figure 1 The figure shows the pore size distribution of the alumina carrier and the catalyst.

[0040] In the figure, 1 is the alumina carrier, 2 is the heavy distillate oil hydrotreating catalyst obtained in Comparative Example 1, and 3 is the heavy distillate oil hydrotreating catalyst obtained in Example 2. DETAILED DESCRIPTION

[0041] The present application is described in detail below by way of examples, but the present application is not limited to the following examples. In addition, the percentages in the present application are percentages by weight unless otherwise specified.

[0042] In the present application, the water absorption is calculated by the following formula: In the formula, W represents the water absorption (g / g); M0 represents the mass of the dry sample (g); and M1 represents the mass of the sample after water absorption (g).

[0043] In the present application, the hydrogen desulfurization and denitrification activities of the catalysts in the examples and comparative examples are represented by the hydrogen desulfurization and denitrification activities relative to the reference agent (Comparative Example 1), and the relative hydrogen desulfurization and relative hydrogen denitrification activities of the catalysts are calculated according to Formulas (1) and (2), respectively:

[0044]

[0045]

[0046] In the formula, k(S) and k(N) represent the hydrogen desulfurization and hydrogen denitrification activities of the catalyst, respectively; k(D S ) and k(D N ) represent the hydrogen desulfurization and hydrogen denitrification activities of the reference agent (Comparative Example 1), respectively.

[0047] In the formula, S Sp represents the mass percentage of sulfur in the reaction product when the catalyst is used; S Sf represents the mass percentage of sulfur in the reaction raw material when the catalyst is used; S Dp represents the mass percentage of sulfur in the reaction product when the reference agent is used; S Df represents the mass percentage of sulfur in the reaction raw material when the reference agent is used; N Sp represents the mass percentage of nitrogen in the reaction product when the catalyst is used; N Sf represents the mass percentage of nitrogen in the reaction raw material when the catalyst is used; N Dp represents the mass percentage of nitrogen in the reaction product when the reference agent is used; N Df represents the mass percentage of nitrogen in the reaction raw material when the reference agent is used.

[0048] In the present application, the gelatin used in the examples and comparative examples is purchased from McKin, CAS: 9000-70-8. The molecular weight of the gelatin is 10000-50000.

[0049] In the present application, the specific surface area of the alumina carrier used in the examples and comparative examples is 227 m 2 / g, and the pore volume is 0.9 m 2 / g.

[0050] Example 1

[0051] (1) preparing the first impregnation solution: adding gelatin into water at 20℃, stirring at 50r / min, treating at 70℃ until the gelatin is completely dissolved to obtain a gelatin solution; preparing an aqueous solution containing active metal components with basic nickel carbonate as nickel source, molybdenum oxide as molybdenum source and phosphoric acid as additive, and then mixing with the gelatin solution to obtain the first impregnation solution; the gelatin content in the first impregnation solution is 2wt%, and the temperature is 50℃;

[0052] (2) taking 100g of alumina carrier with a water absorption rate of 140wt%, impregnating the alumina carrier with 70mL of the first impregnation solution at 40℃, and then performing cooling solidification treatment at 2℃ for 3h to obtain a heavy distillate oil hydroprocessing catalyst precursor;

[0053] (3) preparing the second impregnation solution: preparing the second impregnation solution with basic nickel carbonate as nickel source, molybdenum oxide as molybdenum source and phosphoric acid as additive;

[0054] (4) impregnating the heavy distillate oil hydroprocessing catalyst precursor obtained in step (2) with 70mL of the second impregnation solution at 20℃, and then performing maintenance at 25℃ for 6h, drying at 120℃ for 3h and calcining at 450℃ for 3h to obtain a heavy distillate oil hydroprocessing catalyst C1.

[0055] Example 2

[0056] (1) preparing the first impregnation solution: the preparation process is the same as that in Example 1; the gelatin content in the first impregnation solution is 4wt%, and the temperature is 50℃;

[0057] (2) taking 100g of alumina carrier with a water absorption rate of 140wt%, impregnating the alumina carrier with 70mL of the first impregnation solution at 70℃, and then performing cooling solidification treatment at 25℃ for 3h to obtain a heavy distillate oil hydroprocessing catalyst precursor;

[0058] (3) preparing the second impregnation solution: the preparation process is the same as that in Example 1;

[0059] (4) impregnating the heavy distillate oil hydroprocessing catalyst precursor obtained in step (2) with 70mL of the second impregnation solution at 25℃, and then performing maintenance at 25℃ for 6h, drying at 120℃ for 3h and calcining at 450℃ for 3h to obtain a heavy distillate oil hydroprocessing catalyst C2.

[0060] Example 3

[0061] (1) preparing the first impregnation solution: the preparation process is the same as that in Example 1; the gelatin content in the first impregnation solution is 5wt%, and the temperature is 50℃;

[0062] (2) Take 100 g of the alumina carrier with a water absorption of 140 wt%, and impregnate the alumina carrier with 42 mL of the first impregnation solution at 50°C, and then perform a temperature reduction solidification treatment at 5°C for 3 h to obtain a heavy distillate oil hydroprocessing catalyst precursor;

[0063] (3) Prepare the second impregnation solution by the same process as in Example 1;

[0064] (4) Impregnate the heavy distillate oil hydroprocessing catalyst precursor obtained in step (2) with 98 mL of the second impregnation solution at 20°C, and then perform a 6 h incubation at 25°C, a 3 h drying at 120°C, and a 3 h calcination at 450°C to obtain a heavy distillate oil hydroprocessing catalyst C3.

[0065] Example 4

[0066] (1) Prepare the first impregnation solution by using basic nickel carbonate as the nickel source, molybdenum oxide as the molybdenum source, and phosphoric acid and magnesium acetate as the auxiliary agents to prepare an aqueous solution containing active metal components, and the rest of the preparation process is the same as in Example 1; the gelatin content of the first impregnation solution is 2 wt%, and the temperature is 50°C;

[0067] (2) Take 100 g of the alumina carrier with a water absorption of 140 wt%, and impregnate the alumina carrier with 84 mL of the first impregnation solution at 70°C, and then perform a temperature reduction solidification treatment at 20°C for 4 h to obtain a heavy distillate oil hydroprocessing catalyst precursor;

[0068] (3) Prepare the second impregnation solution by the same process as in Example 1;

[0069] (4) Impregnate the heavy distillate oil hydroprocessing catalyst precursor obtained in step (2) with 56 mL of the second impregnation solution at 20°C, and then perform a 6 h incubation at 25°C, a 3 h drying at 120°C, and a 3 h calcination at 450°C to obtain a heavy distillate oil hydroprocessing catalyst C4.

[0070] Example 5

[0071] (1) Prepare the first impregnation solution by the same process as in Example 1, except that nickel nitrate is used as the nickel source and ammonium molybdate is used as the molybdenum source to prepare an aqueous solution containing active metal components; the gelatin content of the first impregnation solution is 2 wt%, and the temperature is 50°C;

[0072] (2) Take 100 g of the alumina carrier with a water absorption of 140 wt%, and impregnate the alumina carrier with 84 mL of the first impregnation solution at 70°C, and then perform a temperature reduction solidification treatment at 20°C for 4 h to obtain a heavy distillate oil hydroprocessing catalyst precursor;

[0073] (3) Prepare the second impregnation solution by using nickel nitrate as the nickel source and ammonium molybdate as the molybdenum source;

[0074] (4) The heavy distillate oil hydroprocessing catalyst precursor obtained in step (2) was impregnated with 56 mL of the second impregnation solution at 20 °C, and then aged at 25 °C for 6 h, dried at 120 °C for 3 h, and calcined at 450 °C for 3 h to obtain the heavy distillate oil hydroprocessing catalyst C5.

[0075] Comparative Example 1

[0076] Comparative Example 1 was the same as Example 2 except that the first impregnation solution did not contain gelatin, and a heavy distillate oil hydroprocessing catalyst DC1 was obtained.

[0077] Comparative Example 2

[0078] Comparative Example 2 was the same as Example 2 except that the first impregnation solution did not contain gelatin, and a heavy distillate oil hydroprocessing catalyst DC1 was obtained.

[0079] (1) The first impregnation solution was prepared by dissolving the active metal components in an aqueous solution using basic nickel carbonate as the nickel source, molybdenum oxide as the molybdenum source, and phosphoric acid as the additive, and then adding nitrilotriacetic acid (NTA) to obtain the first impregnation solution. The content of NTA in the first impregnation solution was 4 wt%.

[0080] (2) 100 g of alumina carrier with a water absorption rate of 140 wt% was impregnated with 70 mL of the first impregnation solution at 70 °C, and then treated at 25 °C for 3 h to obtain the heavy distillate oil hydroprocessing catalyst precursor.

[0081] (3) The second impregnation solution was prepared by the same method as in Example 1.

[0082] (4) The heavy distillate oil hydroprocessing catalyst precursor obtained in step (2) was impregnated with 70 mL of the second impregnation solution at 25 °C, and then aged at 25 °C for 6 h, dried at 120 °C for 3 h, and calcined at 450 °C for 3 h to obtain the heavy distillate oil hydroprocessing catalyst DC2.

[0083] The preparation conditions of the examples and comparative examples are shown in Table 1.

[0084] Table 1 Preparation conditions of examples and comparative examples

[0085]

[0086] Example 6

[0087] The catalysts of the above examples and comparative examples were evaluated in a micro-reactor. The feedstock oil was Iranian VGO, and its properties are shown in Table 2. The operating conditions were as follows: the reaction temperature was 380 °C, the reaction pressure was 12.0 MPa, the hydrogen to oil volume ratio was 1000:1, and the volume space velocity was 1.0 h -1 .

[0088] Table 2 Properties of raw oil

[0089] Density (20°C), 0.9235 Distillation range, °C 282-55 Sulphur, mg / kg 19110 Nitrogen, mg / kg 1574

[0090] The evaluation results of the catalysts prepared in the examples and comparative examples are shown in Table 3.

[0091] Table 3 Evaluation results

[0092]

[0093] As can be seen from Table 4, the heavy distillate oil hydroprocessing catalyst prepared according to the present application has higher hydrodesulfurization and hydrodenitrogenation activities compared with the comparative catalyst, and is particularly suitable for the hydroprocessing of heavy distillate oil.

Claims

1. A process for the preparation of a heavy oil hydroprocessing catalyst characterized by: The method comprises the following steps: (1) preparing a first impregnation solution containing gelatin and active metal components; (2) unsaturatedly impregnating the alumina carrier with the first impregnation solution obtained in step (1), and then performing a cooling solidification treatment after impregnation to obtain a heavy oil hydroprocessing catalyst precursor; (3) preparing a second impregnation solution containing active metal components; (4) impregnating the heavy oil hydroprocessing catalyst precursor obtained in step (2) with the second impregnation solution obtained in step (3), and then performing drying and calcination to obtain a final heavy oil hydroprocessing catalyst.

2. The method of claim 1, wherein: The gelatin in step (1) is selected from one or more of marine gelatin, pig gelatin, cow gelatin and chicken gelatin, and has an industrial grade or food grade purity level; the gelatin has a molecular weight of 10,000-70,000, preferably 10,000-50,000.

3. The method of claim 1, wherein: In step (1), the first impregnation solution contains 2-10 wt% of gelatin, preferably 3-8 wt% of gelatin, based on the weight of the first impregnation solution.

4. The method of claim 1, wherein: The temperature of the first impregnation solution in step (1) is 40-70°C, preferably 50-60°C.

5. The method of claim 1, wherein: The alumina support in step (2) has the following properties: pore volume of 0.3 to 1.5 mL / g, specific surface area of 150 to 450 m 2 / g.

6. The method of claim 1, wherein: The alumina carrier in step (2) further contains an additive selected from one or more of silicon dioxide, magnesium oxide, zirconium oxide, boron oxide and titanium dioxide, and the additive (calculated as oxide) is contained in the alumina carrier in an amount of less than 30 wt%.

7. The method of claim 1, wherein: In step (2), the impregnation amount of the first impregnation solution for unsaturatedly impregnating the alumina carrier is 30-60 wt%, preferably 40-50 wt%, of the saturated water absorption amount of the alumina carrier.

8. The method of claim 1, wherein: In step (2), the impregnation temperature of the first impregnation solution for unsaturatedly impregnating the alumina carrier is 40-70°C, preferably 50-60°C.

9. The method of claim 1, wherein: In step (2), the first impregnation solution is unsaturatedly impregnated by spraying, and the temperature of the impregnation solution is 40-70°C, preferably 50-60°C.

10. The method of claim 1, wherein: In step (2), the cooling solidification treatment after impregnation is performed by placing the alumina carrier impregnated with the first impregnation solution in an environment with a temperature of 2-25°C, preferably 5-20°C, for 1-30 h, preferably 3-20 h.

11. The method of claim 1, wherein: In step (4), the impregnation of the heavy oil hydroprocessing catalyst precursor with the second impregnation solution is performed by saturated impregnation, and the impregnation amount is the difference between the water absorption rate of the alumina carrier and the solution amount of the first impregnation solution.

12. The method of claim 1, wherein: In step (4), the impregnation temperature is 1-30°C, preferably 15-25°C.

13. The method of claim 1, wherein: In step (4), a curing treatment can be performed before drying and calcination; the curing temperature is 5-30°C, and the curing time is 1-30 h, preferably 5-20 h.

14. The method of claim 1, wherein: In step (4), the drying temperature is 80-160°C, preferably 100-130°C, and the drying time is 2-6 h, preferably 3-4 h; the calcination temperature is 80-650°C, preferably 100-500°C, and the calcination time is 1-10 h, preferably 2-6 h.

15. The method of claim 1, wherein: In step (1), the mass ratio of the active metal components (calculated as oxide) introduced by the first impregnation solution to the active metal components (calculated as oxide) introduced by the second impregnation solution in step (3) is 0.08-0.6, preferably 0.08-0.

3.

16. The method of claim 15, wherein: The content of the Group VIII metal in the active metal component introduced by the first impregnation solution in step (1) is 0.1 wt% to 5 wt% as oxide, preferably 0.1 wt% to 2 wt%; the content of the Group VIB metal is 0.5 wt% to 10 wt% as oxide, preferably 2 wt% to 8 wt%; the content of the Group VIII metal in the active metal component introduced by the second impregnation solution in step (3) is 1 wt% to 15 wt% as oxide, preferably 2 wt% to 10 wt%; the content of the Group VIB metal is 10 wt% to 30 wt% as oxide, preferably 15 wt% to 25 wt%.

17. The method of claim 1, wherein: The first impregnation solution in step (1) and / or the second impregnation solution in step (3) further contains an auxiliary agent selected from one or more of phosphorus, titanium, silicon, zinc, magnesium, copper, zirconium, boron, fluorine, lanthanum, cerium and vanadium.

18. The method of claim 17, wherein: The mass ratio of the auxiliary agent (as oxide) introduced by the first impregnation solution in step (1) to the auxiliary agent (as oxide) introduced by the second impregnation solution in step (3) is 0 to 1.

19. A heavy distillate hydroprocessing catalyst obtained by the method of any one of claims 1 to 18.

20. Use of the heavy distillate hydroprocessing catalyst of claim 19 in a heavy distillate hydroprocessing process.

21. The use according to claim 20, characterized in that: The heavy distillate has a distillation range of 270 to 580°C, and is at least one of vacuum gas oil, deasphalted oil, catalytic cracking cycle oil, shale oil and coal tar. The heavy distillate has a distillation range of 270 to 580°C, and is at least one of vacuum gas oil, deasphalted oil, catalytic cracking cycle oil, shale oil and coal tar.

22. The use according to claim 20, characterized in that: The operating conditions for the heavy oil hydroprocessing are as follows: reaction temperature is 330-430°C, preferably 350-410°C, reaction pressure is 4-18 MPa, preferably 6-16 MPa, hydrogen to oil volume ratio is 400:1-1500:1, preferably 600:1-1200:1, and volume space velocity is 0.5-4.0 h -1 , preferably 0.5-2.0 h -1 .

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