A heavy oil hydroprocessing catalyst, its preparation method and application

Abstract

The application discloses a heavy distillate oil hydroprocessing catalyst and a preparation method and application thereof. The preparation method comprises the following steps: (1) preparing a first impregnation solution, wherein the first impregnation solution contains gelatin and an active metal component; (2) unsaturatedly impregnating an alumina carrier with the first impregnation solution obtained in the step (1), and performing a cooling solidification treatment after impregnation to obtain a heavy distillate oil hydroprocessing catalyst precursor; (3) preparing a second impregnation solution, wherein the second impregnation solution contains the active metal component; (4) impregnating the heavy distillate oil hydroprocessing catalyst precursor obtained in the step (2) with the second impregnation solution obtained in the step (3), and obtaining a final heavy distillate oil hydroprocessing catalyst after drying and calcination. The hydroprocessing catalyst prepared by the method has high matching degree with a heavy distillate oil hydroprocessing reaction process and high activity.

Description

Technical Field

[0001] This invention relates to a catalyst for the hydrotreating of heavy distillate oil, its preparation method, and its application; more specifically, it relates to a highly active catalyst for the hydrotreating of heavy distillate oil, its preparation method, and its application. Background Technology

[0002] With the increasing weight and quality of crude oil, the proportion of low-quality heavy oil in refinery feedstocks is rising year by year, leading to a corresponding increase in the production of heavy distillate oils such as vacuum gas oil (VGO), coking wax oil (CGO), and deasphalted oil (DAO). Heavy distillate oils contain large amounts of impurities such as sulfur, nitrogen, and metals, which inevitably affect product quality when used as feedstocks in subsequent processing. To address these issues, a relatively effective technical approach is to hydrotreat these feedstocks, and one of the core components of this technology is the hydrotreating catalyst. Hydrotreating catalysts for heavy distillate oils generally refer to supported catalysts containing active components such as Mo, W, Ni, or Co, and the most commonly used preparation method is the impregnation method.

[0003] CN111250103A discloses a method for preparing a supported hydrogenation catalyst, which includes: step 1, preparing a γ-Al2O3 support; step 2, impregnating the γ-Al2O3 support with a solution of an active metal-directed loading agent and drying it; and step 3, impregnating the γ-Al2O3 support obtained in step 2 with an impregnation solution containing an active component, and drying and calcining it to obtain the supported hydrogenation catalyst; wherein the active metal-directed loading agent is one or more of the group consisting of sodium ethylenediaminetetramethylene phosphate, tetrabutylammonium fluoride, and tartaric acid.

[0004] CN114425354A discloses a method for preparing a heavy oil hydrotreating catalyst, the prepared catalyst, and its applications. The preparation method includes: preparing an aqueous solution containing an organic acid, a phosphorus-containing compound, an amine compound, a surfactant, and at least one active metal as an impregnation solution. The impregnation solution is used to impregnate a support to load the active metal component. When the impregnation solution spray volume reaches 90%–98% of the theoretical value, the remaining amount is sprayed with liquid oil. After conditioning, low-temperature drying, and high-temperature calcination, the heavy oil hydrotreating catalyst is obtained.

[0005] CN101927176A discloses a method for preparing a hydrogenation catalyst with a gradient distribution of active metal and acidic additive concentrations. This method involves saturating the carrier by preparing a relatively dilute active metal solution, an acidic additive solution, and deionized water, and gradually adding a more concentrated active metal solution and acidic additive solution during the spraying process; or by preparing active metal solutions and acidic additive solutions of different concentrations and impregnating the carrier in ascending order of active metal and acidic additive concentrations; or by impregnating with a solution of lower acidic additive concentration and deionized water, gradually adding a solution of higher acidic additive concentration to the impregnation solution during the impregnation process; drying and calcining; and then impregnating again with a solution of lower active metal concentration and deionized water, gradually adding a solution of higher active metal concentration to the impregnation solution during the impregnation process, ultimately achieving a gradient distribution of the metal components.

[0006] The reaction process of heavy distillate oils on hydrotreating catalysts is quite complex. During the reaction, reactant molecules diffuse into the pores of the catalyst and undergo catalytic reactions within these pores. The distribution of active metal components within the catalyst pores significantly influences the reaction outcome. However, there is no fully sound theoretical basis for determining how the active metal components should be distributed to favor the hydrotreating of heavy distillate oils. In existing technologies, the hydrotreating activity of hydrotreating catalysts used to treat heavy distillate oils needs further improvement. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a heavy distillate oil hydrotreating catalyst, its preparation method, and its application. The hydrotreating catalyst prepared by the method has a high degree of compatibility with the heavy distillate oil hydrotreating reaction process and exhibits high activity.

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

[0009] (1) Prepare a first impregnation solution containing gelatin and an active metal component;

[0010] (2) The alumina support is unsaturated with the first impregnation liquid obtained in step (1), and then subjected to cooling and solidification treatment to obtain the catalyst precursor for heavy distillate oil hydrotreating.

[0011] (3) Prepare a second impregnation solution, wherein the second impregnation solution contains an active metal component;

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

[0013] In the above-mentioned method for preparing the catalyst for hydrogenation of heavy distillate oil, the gelatin in step (1) is selected from one or more of marine gelatin, pig gelatin, bovine gelatin and chicken gelatin, and the purity level is industrial grade or food grade; the molecular weight of the gelatin is 10,000 to 70,000, preferably 10,000 to 50,000.

[0014] In the above-mentioned method for preparing the catalyst for hydrotreating heavy distillate oil, in step (1), the weight of the first impregnation liquid is used as a basis, and the first impregnation liquid contains 2 to 10 wt% gelatin, preferably 3 to 8 wt% gelatin.

[0015] In the above-mentioned method for preparing heavy distillate oil hydrotreating catalyst, the temperature of the first impregnation solution in step (1) is 40-70°C, preferably 50-60°C.

[0016] In the above-mentioned method for preparing the catalyst for the hydrotreating of heavy distillate oil, the alumina support in step (2) can be a commercially available product or prepared according to existing technology. The alumina support generally has the following properties: pore volume of 0.3–1.5 mL / g and specific surface area of ​​150–450 m². 2 / g.

[0017] In the above-mentioned method for preparing heavy distillate oil hydrotreating catalyst, the alumina support in step (2) may also contain an auxiliary agent, which is 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 oxide) in the alumina support is less than 30 wt%.

[0018] In the above-mentioned method for preparing heavy distillate oil hydrotreating catalyst, the alumina support in step (2) is formed by any one of the forming methods such as drop ball forming, rolling ball granulation, extrusion forming and tablet forming, preferably extrusion forming; the shape of the alumina support can be any one of spherical, strip and sheet shape, preferably spherical and strip shape.

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

[0020] In the above-mentioned method for preparing heavy distillate oil hydrotreating catalyst, the impregnation temperature of the first impregnation liquid for unsaturated impregnation of the alumina support in step (2) is 40-70℃, preferably 50-60℃.

[0021] In the above-mentioned method for preparing heavy distillate oil hydrotreating catalyst, in step (2), the first impregnation solution can be used to impregnate the alumina support in an unsaturated manner using any of the existing technologies that can achieve unsaturated impregnation, such as spray impregnation, and the temperature of the impregnation solution is 40-70°C, preferably 50-60°C.

[0022] In the above-mentioned method for preparing the heavy distillate oil hydrotreating catalyst, the cooling and curing treatment after impregnation in step (2) involves placing the alumina support impregnated with the first impregnation solution in an environment of 2–25°C, preferably 5–20°C, for 1–30 h, preferably 3–20 h. The first impregnation solution contains gelatin, and the cooling and curing treatment can transform the first impregnation solution adsorbed in the alumina support into a gel state. The gel-state first impregnation solution can be enriched in the macropores of the alumina support.

[0023] In the above-mentioned method for preparing heavy distillate oil hydrotreating catalyst, in step (4), the precursor of heavy distillate oil hydrotreating catalyst is impregnated with the second impregnation liquid by saturation impregnation, and the impregnation amount is the difference between the water absorption rate of the alumina support and the solution volume of the first impregnation liquid.

[0024] In the above-mentioned method for preparing heavy distillate oil hydrotreating catalyst, the impregnation temperature in step (4) is 1-30°C, preferably 15-25°C.

[0025] In the above preparation method of heavy distillate oil hydrotreating catalyst, a conditioning treatment can be performed before drying and calcination in step (4); the conditioning temperature is 5-30℃ and the conditioning time is 1-30h, preferably 5-20h.

[0026] In the above-mentioned method for preparing heavy distillate oil hydrotreating catalyst, the drying temperature in step (4) is 80℃~160℃, preferably 100℃~130℃, and the drying time is generally 2h~6h, preferably 3h~4h; the calcination temperature is 80℃~650℃, preferably 100℃~500℃, and the calcination time is 1~10h, preferably 2~6h.

[0027] In the above-mentioned method for preparing the catalyst for hydrotreating heavy distillate oil, the mass ratio of the active metal component (calculated as oxide) introduced by the first impregnation solution in step (1) to the active metal component (calculated as oxide) introduced by the second impregnation solution in step (3) is 0.08 to 0.6, preferably 0.08 to 0.3.

[0028] In the above-mentioned method for preparing the heavy distillate oil hydrotreating catalyst, based on the final weight of the heavy distillate oil hydrotreating catalyst, in step (1), the content of Group VIII metals as oxides in the active metal component introduced by the first impregnation solution is 0.1wt% to 5wt%, preferably 0.1wt% to 2wt%; the content of Group VIB metals as oxides is 0.5wt% to 10wt%, preferably 2wt% to 8wt%; in step (3), the content of Group VIII metals as oxides in the active metal component introduced by the second impregnation solution is 1wt% to 15wt%, preferably 2wt% to 10wt%; the content of Group VIB metals as oxides is 10wt% to 30wt%, preferably 15wt% to 25wt%.

[0029] In the above-mentioned method for preparing the catalyst for hydrotreating heavy distillate oil, 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. Specifically, in this invention, 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 chlorate; and the molybdenum source is selected from one or more of molybdenum oxide, ammonium molybdate, ammonium tetrathiomolybdate, and ammonium paramolybdate.

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

[0031] In the above-mentioned method for preparing the heavy distillate hydrotreating catalyst, the mass ratio of the additive (calculated as oxide) introduced in the first impregnation solution in step (1) to the additive (calculated as oxide) introduced in the second impregnation solution in step (3) is 0 to 1. Specifically, in the method of the present invention, based on the weight of the final heavy distillate hydrotreating catalyst, the weight content of the additive (calculated as oxide) introduced in the first impregnation solution in step (1) is 0% to 2%, preferably 0.5% to 1.5%; the weight content of the additive (calculated as oxide) introduced in the second impregnation solution in step (3) is 0% to 10%, preferably 1% to 5%.

[0032] According to a second aspect of the present invention, a heavy distillate oil hydrotreating catalyst prepared by the above method is provided.

[0033] According to a third aspect of the present invention, the application of the above-described heavy distillate oil hydrotreating catalyst in the heavy distillate oil hydrotreating process is provided.

[0034] In the above applications, the heavy distillate oil has a distillation range of 270–580°C, 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 applications, the operating conditions for the heavy distillate oil hydrogenation process are as follows: reaction temperature of 330–430°C, preferably 350–410°C; reaction pressure of 4–18 MPa, preferably 6–16 MPa; hydrogen-to-oil volume ratio of 400:1–1500:1, preferably 600:1–1200:1; and volume hourly space velocity of 0.5–4.0 h⁻¹. -1 Preferably, it is 0.5 to 2.0 h. -1 .

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

[0037] 1. In the preparation method of the heavy distillate oil hydrotreating catalyst of the present invention, an alumina support is unsaturatedly impregnated with a first impregnation solution containing gelatin and active metal components. Utilizing the low-temperature solidification property of gelatin, the first impregnation solution adsorbed in the alumina support is transformed into a gel state through a cooling and solidification treatment. The gel-state first impregnation solution can be largely concentrated within the macropores of the alumina support. The second impregnation solution, an aqueous solution containing the active metal components, is immiscible with the gel-state first impregnation solution, making it difficult for it to enter the positions occupied by the gel-state first impregnation solution. This allows most of the second impregnation solution to enter the remaining pores of the alumina support. The above operation introduces the active metal components to different positions on the alumina support through the first and second impregnation solutions, regulating the distribution of the active metal components within the catalyst pores, thereby obtaining a highly active heavy distillate oil hydrotreating catalyst.

[0038] 2. In the preparation method of the heavy distillate oil hydrotreating catalyst of the present invention, the first impregnation liquid and / or the second impregnation liquid may also contain an additive. The additive is introduced into different positions of the alumina support by the first impregnation liquid and the second impregnation liquid, thereby controlling the distribution of the additive in the catalyst channel and further improving the activity of the heavy distillate oil hydrotreating catalyst. Attached Figure Description

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

[0040] Wherein, 1 is an alumina support, 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 Implementation

[0041] The present invention will be described in detail below through embodiments, but the present invention is not limited to the following embodiments. Furthermore, unless otherwise specified, all percentages in the present invention refer to weight percentages.

[0042] In this invention, the water absorption rate is calculated as follows: Where: W—water absorption rate (g / g); M0—mass of the dried sample (g); M1—mass of the sample after water saturation (g).

[0043] In this invention, the hydrodesulfurization and denitrification activities of the catalysts in the examples and comparative examples are expressed as hydrodesulfurization and denitrification activities relative to the reference agent (Comparative Example 1), respectively. The relative hydrodesulfurization and relative hydrodenitrification activities of the catalysts are calculated according to Equations (1) and (2), respectively:

[0044]

[0045]

[0046] In the formula, k(S) and k(N) represent the hydrodesulfurization and hydronitrogenation activities of the catalyst, respectively, and k(D) represents the hydrodesulfurization and hydronitrogenation activities of the catalyst. S ), k(D N The numbers ) represent the hydrodesulfurization and hydrodenitrogenation activities of the reference (Comparative Example 1), respectively.

[0047] In the formula, S Sp S represents the mass percentage of sulfur in the reaction products when a catalyst is used. Sf S represents the mass percentage of sulfur in the reaction feedstock when using a catalyst. Dp S represents the mass percentage of sulfur in the reaction product when using a reference reagent. Df This refers to the mass percentage of sulfur in the reaction feedstock when using a reference reagent; N Sp This refers to the mass percentage of nitrogen in the reaction products when a catalyst is used; N Sf This refers to the mass percentage of nitrogen in the reaction feedstock when using a catalyst; N Dp This refers to the mass percentage of nitrogen in the reaction product when using a reference reagent; N Df This refers to the mass percentage of nitrogen in the reaction raw materials when using a reference reagent.

[0048] In this invention, the gelatin used in the examples and comparative examples was purchased from Maclean's, CAS: 9000-70-8. The molecular weight of the gelatin was 10,000 to 50,000.

[0049] In this invention, the alumina support used in the examples and comparative examples has a specific surface area of ​​227 m². 2 / g, pore volume 0.9m 2 / g.

[0050] Example 1

[0051] (1) Preparation of the first impregnation solution: Add gelatin to water at 20°C, stir at 50 r / min and treat at 70°C until the gelatin is completely dissolved to obtain a gelatin solution; prepare an aqueous solution containing active metal components using basic nickel carbonate as the nickel source, molybdenum oxide as the molybdenum source and phosphoric acid as an auxiliary agent, and then mix it with the gelatin solution to obtain the first impregnation solution; the gelatin content in the first impregnation solution is 2 wt%, and the temperature is 50°C;

[0052] (2) Weigh 100g of alumina support with a water absorption rate of 140wt%, impregnate the alumina support with 70mL of the first impregnation solution at 40℃, and then perform a cooling and curing treatment at 2℃ for 3h to obtain a catalyst precursor for heavy distillate oil hydrotreating.

[0053] (3) Preparation of the second impregnation solution: The second impregnation solution is prepared using basic nickel carbonate as the nickel source, molybdenum oxide as the molybdenum source, and phosphoric acid as an auxiliary agent;

[0054] (4) Impregnate the heavy distillate oil hydrotreating catalyst precursor obtained in step (2) with 70 mL of the second impregnation solution at 20 °C, cure at 25 °C for 6 h, dry at 120 °C for 3 h, and calcine at 450 °C for 3 h to obtain heavy distillate oil hydrotreating catalyst C1.

[0055] Example 2

[0056] (1) Prepare the first impregnation solution. The preparation process is the same as in Example 1. The gelatin content of the first impregnation solution is 4 wt%, and the temperature is 50°C.

[0057] (2) Weigh 100g of alumina support with a water absorption rate of 140wt%, impregnate the alumina support with 70mL of the first impregnation solution at 70℃, and then perform a cooling and curing treatment at 25℃ for 3h to obtain a catalyst precursor for heavy distillate oil hydrotreating.

[0058] (3) Prepare the second impregnation solution, the preparation process is the same as in Example 1;

[0059] (4) Impregnate the heavy distillate oil hydrotreating catalyst precursor obtained in step (2) with 70 mL of the second impregnation solution at 25 °C, cure at 25 °C for 6 h, dry at 120 °C for 3 h, and calcine at 450 °C for 3 h to obtain heavy distillate oil hydrotreating catalyst C2.

[0060] Example 3

[0061] (1) Prepare the first impregnation solution. The preparation process is the same as in Example 1. The gelatin content of the first impregnation solution is 5 wt%, and the temperature is 50°C.

[0062] (2) Weigh 100g of alumina support with a water absorption rate of 140wt%, impregnate the alumina support with 42mL of the first impregnation solution at 50℃, and then perform a cooling and curing treatment at 5℃ for 3h to obtain a catalyst precursor for heavy distillate oil hydrotreating.

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

[0064] (4) Impregnate the heavy distillate oil hydrotreating catalyst precursor obtained in step (2) with 98 mL of the second impregnation liquid at 20 °C, cure at 25 °C for 6 h, dry at 120 °C for 3 h, and calcine at 450 °C for 3 h to obtain heavy distillate oil hydrotreating 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 auxiliaries to prepare an aqueous solution containing active metal components. 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) Weigh 100g of alumina support with a water absorption rate of 140wt%, impregnate the alumina support with 84mL of the first impregnation solution at 70℃, and then perform a cooling and curing treatment at 20℃ for 4h to obtain a catalyst precursor for heavy distillate oil hydrotreating.

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

[0069] (4) Impregnate the heavy distillate oil hydrotreating catalyst precursor obtained in step (2) with 56 mL of the second impregnation solution at 20 °C, cure at 25 °C for 6 h, dry at 120 °C for 3 h, and calcine at 450 °C for 3 h to obtain heavy distillate oil hydrotreating catalyst C4.

[0070] Example 5

[0071] (1) Prepare the first impregnation solution. The preparation process is the same as in Example 1, except that: an aqueous solution containing active metal components is prepared using nickel nitrate as the nickel source and ammonium molybdate as the molybdenum source; the gelatin content of the first impregnation solution is 2wt%, and the temperature is 50℃.

[0072] (2) Weigh 100g of alumina support with a water absorption rate of 140wt%, impregnate the alumina support with 84mL of the first impregnation solution at 70℃, and then perform a cooling and curing treatment at 20℃ for 4h to obtain a catalyst precursor for heavy distillate oil hydrotreating.

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

[0074] (4) Impregnate the heavy distillate oil hydrotreating catalyst precursor obtained in step (2) with 56 mL of the second impregnation liquid at 20 °C, cure at 25 °C for 6 h, dry at 120 °C for 3 h, and calcine at 450 °C for 3 h to obtain heavy distillate oil hydrotreating catalyst C5.

[0075] Comparative Example 1

[0076] Compared with Example 2, the first impregnation solution in Comparative Example 1 did not contain gelatin, and the remaining steps were the same as in Example 2, resulting in heavy distillate oil hydrotreating catalyst DC1.

[0077] Comparative Example 2

[0078] The difference from Example 2 is that gelatin is not used in the first impregnation solution; instead, nitrotriacetic acid (NTA) is used. The specific operation process is as follows:

[0079] (1) Prepare the first impregnation solution by using basic nickel carbonate as the nickel source, molybdenum oxide as the molybdenum source, and phosphoric acid as an auxiliary agent to prepare an aqueous solution containing active metal components, and then add nitrotriacetic acid (NTA) to obtain the first impregnation solution; the NTA content in the first impregnation solution is 4 wt%.

[0080] (2) Weigh 100g of alumina support with a water absorption rate of 140wt%, impregnate the alumina support with 70mL of the first impregnation solution at 70℃, and then treat it at 25℃ for 3h to obtain the catalyst precursor for heavy distillate oil hydrotreating.

[0081] (3) Prepare the second impregnation solution, the preparation process is the same as in Example 1;

[0082] (4) Impregnate the heavy distillate oil hydrotreating catalyst precursor obtained in step (2) with 70 mL of the second impregnation solution at 25 °C, cure at 25 °C for 6 h, dry at 120 °C for 3 h, and calcine at 450 °C for 3 h to obtain the heavy distillate oil hydrotreating catalyst DC2.

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

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

[0085]

[0086] Example 6

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

[0088] Table 2 Properties of Crude Oil

[0089] Density (20℃) 0.9235 Distillation range 3, ℃ 282-55 Sulfur, 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, compared with the comparative catalyst, the heavy distillate oil hydrotreating catalyst prepared in this invention has higher hydrodesulfurization and denitrogenation activity, and is particularly suitable for the hydrotreating process of heavy distillate oil.

Claims

1. A method for preparing a catalyst for the hydrotreating of heavy distillate oil, characterized in that: Includes the following steps: (1) Prepare a first impregnation solution containing gelatin and an active metal component; (2) The alumina support is unsaturated with the first impregnation liquid obtained in step (1), and then subjected to cooling and solidification treatment to obtain the catalyst precursor for heavy distillate oil hydrotreating. (3) Prepare a second impregnation solution containing an active metal component; (4) Impregnate the heavy distillate oil hydrotreating catalyst precursor obtained in step (2) with the second impregnation solution obtained in step (3), and obtain the final heavy distillate oil hydrotreating catalyst after drying and calcination. In step (2), the impregnation temperature of the first impregnation solution for unsaturated impregnation of the alumina carrier is 40~70℃; In step (2), the cooling and curing treatment after impregnation involves placing the alumina carrier impregnated with the first impregnation liquid in an environment of 2~25℃ for 1~30h. The immersion temperature in step (4) is 1~30℃; The active metal component comprises at least one metal selected from Group VIII and / or at least one metal selected from Group VIB.

2. The method according to claim 1, characterized in that: The gelatin mentioned in step (1) is selected from one or more of marine gelatin, pig gelatin, bovine gelatin and chicken gelatin, and the purity level is industrial grade or food grade; the molecular weight of the gelatin is 10,000 to 70,000.

3. The method according to claim 2, characterized in that: In step (1), the molecular weight of the gelatin is 10,000 to 50,000.

4. The method according to claim 1, characterized in that: In step (1), the weight of the first impregnation liquid is used as the basis, and the first impregnation liquid contains 2 to 10 wt% gelatin.

5. The method according to claim 4, characterized in that: In step (1), the weight of the first impregnation liquid is used as the basis, and the first impregnation liquid contains 3 to 8 wt% gelatin.

6. The method according to claim 1, characterized in that: In step (1), the temperature of the first impregnation solution is 40~70℃.

7. The method according to claim 6, characterized in that: In step (1), the temperature of the first impregnation solution is 50~60℃.

8. The method according to claim 1, characterized in that: The properties of the alumina support mentioned in step (2) are as follows: pore volume of 0.3~1.5 mL / g, specific surface area of ​​150~450 m². 2 / g.

9. The method according to claim 1, characterized in that: The alumina carrier in step (2) also contains an additive, which is selected from one or more of silicon dioxide, magnesium oxide, zirconium oxide, boron oxide and titanium dioxide, and the content of the additive in the alumina carrier as an oxide is less than 30 wt%.

10. The method according to claim 1, characterized in that: In step (2), the amount of the first impregnation solution used to impregnate the alumina carrier in an unsaturated state is 30 to 60 wt% of the saturated water absorption capacity of the alumina carrier.

11. The method according to claim 1, characterized in that: In step (2), the amount of the first impregnation solution used to impregnate the alumina carrier in an unsaturated state is 40-50 wt% of the saturated water absorption capacity of the alumina carrier.

12. The method according to claim 1, characterized in that: In step (2), the impregnation temperature of the first impregnation solution for unsaturated impregnation of the alumina carrier is 50~60℃.

13. The method according to claim 1, characterized in that: In step (2), the first impregnation solution is used to impregnate the alumina carrier by spraying, and the temperature of the impregnation solution is 40~70℃.

14. The method according to claim 13, characterized in that: In step (2), the first impregnation solution is used to impregnate the alumina carrier by spraying, and the temperature of the impregnation solution is 50~60℃.

15. The method according to claim 1, characterized in that: In step (2), the cooling and curing treatment after impregnation involves placing the alumina carrier impregnated with the first impregnation liquid in an environment of 5~20℃ for 3~20h.

16. The method according to claim 1, characterized in that: In step (4), the heavy distillate oil hydrotreating catalyst precursor is impregnated with the second impregnation solution using saturated impregnation. The impregnation amount is the difference between the water absorption rate of the alumina support and the solution volume of the first impregnation solution. The water absorption rate is calculated as follows: In the formula: W—water absorption rate (g / g); M0—mass of the dried sample (g); M1—mass of the sample after water absorption saturation (g).

17. The method according to claim 1, characterized in that: The immersion temperature in step (4) is 15~25℃.

18. The method according to claim 1, characterized in that: In step (4), a conditioning treatment is performed before drying and roasting; the conditioning temperature is 5~30℃ and the conditioning time is 1~30 h.

19. The method according to claim 18, characterized in that: In step (4), the health preservation time is 5~20 hours.

20. The method according to claim 1, characterized in that: In step (4), the drying temperature is 80℃~160℃ and the drying time is 2h~6h; the calcination temperature is 80℃~650℃ and the calcination time is 1~10h.

21. The method according to claim 20, characterized in that: In step (4), the drying temperature is 100℃~130℃ and the drying time is 3h~4h; the calcination temperature is 100℃~500℃ and the calcination time is 2~6h.

22. The method according to claim 1, characterized in that: The mass ratio of the active metal component introduced by the first impregnation solution in step (1) as oxide to the active metal component introduced by the second impregnation solution in step (3) as oxide is 0.08~0.

6.

23. The method according to claim 22, characterized in that: The mass ratio of the active metal component introduced by the first impregnation solution in step (1) as oxide to the active metal component introduced by the second impregnation solution in step (3) as oxide is 0.08~0.

3.

24. The method according to claim 22, characterized in that: Based on the weight of the final heavy distillate hydrotreating catalyst, the content of Group VIII metals as oxides in the active metal component introduced by the first impregnation solution in step (1) is 0.1 wt%~5 wt%; the content of Group VIB metals as oxides is 0.5 wt%~10 wt%; the content of Group VIII metals as oxides in the active metal component introduced by the second impregnation solution in step (3) is 1 wt%~15 wt%; the content of Group VIB metals as oxides is 10 wt%~30 wt%.

25. The method according to claim 24, characterized in that: Based on the weight of the final heavy distillate hydrotreating catalyst, the content of Group VIII metals as oxides in the active metal component introduced by the first impregnation solution in step (1) is 0.1wt%~2wt%; the content of Group VIB metals as oxides is 2wt%~8wt%; the content of Group VIII metals as oxides in the active metal component introduced by the second impregnation solution in step (3) is 2wt%~10wt%; the content of Group VIB metals as oxides is 15wt%~25wt%.

26. The method according to claim 1, characterized in that: The first impregnation solution in step (1) and / or the second impregnation solution in step (3) further contain an auxiliary agent, which is selected from one or more of phosphorus, titanium, silicon, zinc, magnesium, copper, zirconium, boron, fluorine, lanthanum, cerium and vanadium.

27. The method according to claim 26, characterized in that: The mass ratio of the additive introduced in the first impregnation liquid in step (1) as an oxide to the additive introduced in the second impregnation liquid in step (3) as an oxide is 0~1.

28. A catalyst for hydrotreating heavy distillate oil obtained by the method according to any one of claims 1-27.

29. The application of the heavy distillate oil hydrotreating catalyst according to claim 28 in the heavy distillate oil hydrotreating process.

30. The application according to claim 29, characterized in that: The heavy distillate oil has a boiling range of 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.

31. The application according to claim 29, characterized in that: The operating conditions for the heavy distillate oil hydrogenation process are as follows: reaction temperature 330~430℃, reaction pressure 4~18MPa, hydrogen-to-oil volume ratio 400:1~1500:1, and volume hourly space velocity (VHSV) 0.5~4.0h. -1 .

32. The application according to claim 31, characterized in that: The operating conditions for the heavy distillate oil hydrogenation process are as follows: reaction temperature 350~410℃, reaction pressure 6~16MPa, hydrogen-to-oil volume ratio 600:1~1200:1, and volume hourly space velocity (VHSV) 0.5~2.0h. -1 .

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