Hydrotreating catalyst as well as preparation method and application thereof

Abstract

The invention provides a hydrotreating catalyst and a preparation method and application thereof, the preparation method comprises the following steps: (1) preparing a first impregnation liquid containing gelatin, then carrying out unsaturated impregnation on an alumina carrier, and then carrying out cooling curing treatment to obtain a hydrotreating catalyst precursor; (2) preparing a second impregnation liquid containing an active metal component, then impregnating the hydrotreating catalyst precursor obtained in the step (1), and then curing, drying and roasting to obtain a hydrotreating catalyst intermediate; and (3) preparing a third impregnation liquid containing gelatin and active metal components, carrying out unsaturated impregnation on the hydrotreating catalyst intermediate obtained in the step (2), carrying out cooling curing treatment, and drying to obtain the final hydrotreating catalyst. The hydrotreating catalyst has good catalytic activity and stability, and is especially suitable for catalyzing the hydrotreating process of secondary processing oil products such as diesel oil and coker diesel oil.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of petroleum chemical industry, and particularly relates to a hydroprocessing catalyst and a preparation method and application thereof. BACKGROUND

[0002] In recent years, with the enhancement of people's environmental protection consciousness, the market puts forward higher requirements for oil quality, and at the same time, the quality of crude oil in the world is deteriorating, and a large amount of sulfur and nitrogen impurities are contained in catalytic diesel oil, coking diesel oil and other secondary processing oil products, which increases the processing difficulty. Hydroprocessing technology is one of the main means for producing clean oil products in a refinery, and the research and development of a hydroprocessing catalyst is one of the cores of the hydroprocessing technology.

[0003] CN111151270A discloses a distillate oil hydroprocessing catalyst and a preparation method thereof. The weight content of the hydroactive metal in the form of sulfide is 14% to 50% based on the weight of the catalyst, the average flake length of MoS2 is 4 to 7 nm, the average number of flake layers in a single stack is 1 to 4 layers, and the proportion of the stack with 3 to 5 layers is 40% to 90%. The preparation method is as follows: (1) preparing an impregnation solution, wherein the solution contains a hydroactive metal, an organic additive, methylene bisnaphthalene sulfonic acid sodium and an aluminum salt; (2) mixing and kneading the macroporous alumina powder and the impregnation solution, shaping, drying and calcining to obtain an oxidation state hydroprocessing catalyst; and (3) sulfidizing the oxidation state catalyst to obtain the catalyst.

[0004] The reaction process of the secondary processing oil products such as catalytic diesel oil and coking diesel oil on the hydroprocessing catalyst is relatively complex. In the reaction process, the reactant molecules diffuse into the pores of the catalyst, and the catalytic reaction is carried out in the pores of the catalyst. The distribution of the active phase in the pores of the catalyst has an important influence on the reaction result. However, how different types of active phases are distributed in the pores of the catalyst to be more conducive to the hydroprocessing process of the secondary processing oil products such as catalytic diesel oil and coking diesel oil has not been determined. In the prior art, the catalytic activity and stability of the catalyst applied to the hydroprocessing of the secondary processing oil products need to be improved. SUMMARY

[0005] In view of the deficiencies in the prior art, the present application provides a hydroprocessing catalyst and a preparation method and application thereof. The hydroprocessing catalyst has good catalytic activity and stability, and is particularly suitable for the hydroprocessing process of the secondary processing oil products such as catalytic diesel oil and coking diesel oil.

[0006] According to a first aspect of the present application, the present application provides a preparation method of a hydroprocessing catalyst, comprising the following steps:

[0007] (1) preparing a first impregnation solution containing gelatin, then unsaturatedly impregnating an alumina carrier, and then performing a cooling solidification treatment to obtain a hydroprocessing catalyst precursor;

[0008] (2) preparing a second impregnation solution containing active metal components, then impregnating the hydroprocessing catalyst precursor obtained in step (1), and then aging, drying and calcining to obtain a hydroprocessing catalyst intermediate;

[0009] (3) preparing a third impregnation solution containing gelatin and active metal components, unsaturatedly impregnating the hydroprocessing catalyst intermediate obtained in step (2), and then drying after temperature reduction and solidification treatment to obtain a final hydroprocessing catalyst.

[0010] In the above method, in step (1), the gelatin content in the first impregnation solution containing gelatin is 4wt% to 20wt%; the gelatin 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; and the molecular weight of the gelatin is 10000 to 70000, preferably 10000 to 50000.

[0011] In the above method, in step (1), the temperature of the first impregnation solution containing gelatin is 40 to 70°C, preferably 50 to 60°C.

[0012] In the above method, in step (1), the first impregnation solution containing gelatin is prepared by adding gelatin to water at 5 to 20°C, and then treating at a temperature of 40 to 70°C, preferably 50 to 60°C, until the gelatin is completely dissolved.

[0013] In the above method, in step (1), the first impregnation solution containing gelatin can also contain a modification aid selected from one or more of phosphorus, titanium, silicon, zinc, copper, magnesium, zirconium, boron, fluorine, lanthanum, cerium and vanadium.

[0014] In the above method, in step (1), the properties of the alumina carrier are generally required as follows: pore volume is 0.3 to 1.5 mL / g, specific surface area is 150 to 450 m 2 / g; preferably, the alumina carrier has a bimodal pore structure, the pore volume of pores with a diameter of 2 to 15 nm accounts for 40 to 80%, preferably 55 to 75%, of the total pore volume; and the pore volume of pores with a diameter greater than 15 nm accounts for 20 to 60%, preferably 30 to 50%, of the total pore volume.

[0015] In the above method, in step (1), the impregnation amount of the first impregnation solution containing gelatin for unsaturated impregnation of the alumina carrier is 30 to 60wt%, preferably 40 to 50wt%, of the saturated water absorption amount of the alumina carrier.

[0016] In the above method, in step (1), the impregnation temperature of the first impregnation solution containing gelatin for unsaturated impregnation of the alumina carrier is 40 to 70°C, preferably 50 to 60°C.

[0017] In the above method, in step (1), the first impregnation solution unsaturated impregnation of alumina carrier can use any one of the ways that can achieve unsaturated impregnation in the prior art, such as spray impregnation; the temperature of the impregnation solution is 40-70℃, preferably 50-60℃.

[0018] In the above method, in step (1), the specific operation process of the cooling solidification treatment is that the alumina carrier impregnated with the first impregnation solution containing gelatin is placed in an environment of 2-25℃, preferably 5-20℃, and the placement time is 1-30h, preferably 3-20h. The first impregnation solution contains gelatin, and the cooling 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.

[0019] In the above method, the active metal component includes at least one metal selected from Group VIII and 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.

[0020] In the above method, in step (2), the content of the Group VIII metal in the active metal component introduced by impregnation is 0.2wt%-5wt% as calculated as the oxide, preferably 1wt%-3wt%, and the content of the Group VIB metal is 1wt%-15wt% as calculated as the oxide, preferably 5wt%-10wt%, based on the weight of the final hydroprocessing catalyst.

[0021] In the above method, in step (2), the hydroprocessing catalyst precursor obtained in step (1) is saturated impregnated, 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.

[0022] In the above method, in step (2), the impregnation temperature is 1-30℃, preferably 15-25℃.

[0023] In the above method, in step (2), the aging time is 1-30h, preferably 5-20h, and the temperature is 0-30℃, preferably 5-25℃.

[0024] In the above method, in step (2), the drying and calcination conditions are as follows: the drying time is generally 2h-6h, preferably 3h-4h, the drying temperature is 80℃-160℃, preferably 100℃-130℃; the calcination temperature is 80℃-650℃, preferably 100℃-500℃, and the calcination time is 1-10h, preferably 2-6h.

[0025] In the above method, the content of the gelatin in the third impregnation solution is 3wt% to 10wt% based on the mass of the third impregnation solution containing the gelatin and the active metal component.

[0026] In the above method, the mass ratio of the active metal component (calculated as oxide) introduced in step (3) to the active metal component (calculated as oxide) introduced in step (2) is 1:(0.25 to 4), preferably 1:(0.5 to 2).

[0027] In the above method, the third impregnation solution in step (3) can further contain an acidic additive, and the acidic additive is at least one of phosphoric acid, citric acid and EDTA.

[0028] In the above method, the temperature of the third impregnation solution containing the gelatin and the active metal component in step (3) is 40 to 70°C, preferably 50 to 60°C.

[0029] In the above method, the impregnation amount of the third impregnation solution to the unsaturated impregnated hydroprocessing catalyst intermediate in step (3) is 30 to 60wt% of the saturated water absorption amount of the alumina carrier, preferably equal to the impregnation amount of the first impregnation solution to the unsaturated impregnated alumina carrier.

[0030] In the above method, the impregnation temperature of the third impregnation solution to the unsaturated impregnated hydroprocessing catalyst intermediate in step (3) is 40 to 60°C.

[0031] In the above method, the third impregnation solution to the unsaturated impregnated hydroprocessing catalyst intermediate in step (3) can use any one of the methods capable of achieving unsaturated impregnation in the prior art, such as spray impregnation; the temperature of the impregnation solution is 40 to 70°C, preferably 50 to 60°C.

[0032] In the above method, the specific operation process of the cooling solidification treatment in step (3) is that the material obtained after the unsaturated impregnation is placed in an environment of 2 to 25°C, preferably 5 to 20°C, and the placement time is 1 to 30h, preferably 3 to 20h. The cooling solidification treatment can convert the third impregnation solution adsorbed in the alumina carrier into a gel state, and the third impregnation solution in the gel state can be enriched in the macropores of the alumina carrier.

[0033] In the above method, the drying time in step (3) is 2h to 6h, preferably 3h to 4h; the drying temperature is 80°C to 180°C, preferably 100°C to 160°C. The drying can be single-temperature drying or multi-temperature gradual heating drying.

[0034] According to the second aspect of the present application, a hydroprocessing catalyst obtained by the above preparation method is provided.

[0035] In the catalyst, the hydrotreating catalyst contains a carrier and an active metal component; the carrier is alumina, and the active metal component is a Group VIII metal and / or a Group VIB metal, the Group VIII metal is preferably Ni and / or Co, and the Group VIB metal is preferably Mo. The content of the carrier is 57-86% by weight, and the content of the active metal component is 11-35% by weight in terms of oxides, based on the weight of the hydrotreating catalyst.

[0036] In the catalyst, the hydrotreating catalyst has a pore volume of 0.3-1.3 mL / g and a specific surface area of 100-250 m 2 / g.

[0037] According to a third aspect of the present application, the present application provides the use of the above hydrotreating catalyst in a hydrotreating process of secondary processing oil products.

[0038] In the use, the hydrotreating catalyst needs to be pre-sulfided before reaction. The pre-sulfidation can be performed according to the prior art, for example, the pre-sulfidation is divided into two temperature stages, the first stage: 120-160℃, the sulfidation time is 2-8 hours, and the second stage: 160-350℃, the sulfidation time is 1-6 hours.

[0039] In the use, the secondary processing oil products are one or more of catalytic diesel, coking diesel and coking wax oil.

[0040] In the use, the operating conditions of the hydrotreating process of the secondary processing oil products are as follows: the reaction temperature is 300-380℃, preferably 330-375℃, the reaction pressure is 4-12 MPa, preferably 5-10 MPa, the hydrogen to oil ratio is 600:1-1200:1, preferably 750:1-1000:1, and the volume space velocity is 0.5-4.0 h -1 , preferably 0.5-2.0 h -1 .

[0041] Compared with the prior art, the present application has the following advantages:

[0042] In the preparation method of the hydroprocessing catalyst, firstly, the alumina carrier is impregnated with a first impregnation solution containing gelatin, and the first impregnation solution adsorbed in the alumina carrier is converted into a gel state through a cooling solidification treatment by utilizing the low-temperature solidification property of the gelatin, and can be mostly enriched in the macropores of the alumina carrier; then, a second impregnation solution containing an active metal component is used for impregnation, and since the second impregnation solution is an aqueous solution, it is not miscible with the first impregnation solution in the gel state, so that the active metal component is mostly enriched in the micropores which are not occupied by the first impregnation solution in the gel state, and after drying and calcination treatment, type I active centers are formed. Then, a third impregnation solution containing gelatin and the active metal component is introduced, and the third impregnation solution is converted into a gel state through a cooling solidification treatment by utilizing the low-temperature solidification property of the gelatin, and can be mostly enriched in the macropores of the alumina carrier, so as to introduce the active metal component to the specific position, and after drying treatment, type II active centers with higher activity are formed. Through the above-mentioned mode, the distribution of type I active centers and type II active centers in the pores of the catalyst is regulated, and the obtained hydroprocessing catalyst exhibits good activity and stability in the hydroprocessing process of catalytic diesel, coking diesel and other secondary processed oil products. BRIEF DESCRIPTION OF DRAWINGS

[0043] Figure 1 SEM image of the hydroprocessing catalyst prepared in Example 1.

[0044] Figure 2 SEM image of the hydroprocessing catalyst prepared in Comparative Example 1.

[0045] Figure 3 SEM image of the hydroprocessing catalyst prepared in Comparative Example 2. DETAILED DESCRIPTION

[0046] The present application will be described in detail below by way of examples, but the present application is not limited to the following examples. In addition, in the present application, unless otherwise specified, all percentages are by weight.

[0047] In the present application, the calculation method of the water absorption rate is as follows:

[0048] In the formula, W represents the water absorption rate (g / g), M0 represents the mass of the dried sample (g), and M1 represents the mass of the sample after water absorption saturation (g).

[0049] In the present application, the active phase is tested by transmission electron microscopy (TEM) to obtain the micro-morphology of the active metal active phase. 20 TEM photos randomly selected from each sample are counted by using Digital Micrograph software to obtain the average stacking number of molybdenum disulfide crystal sheets in the photos, and the stacking number of 1-2 layers is classified as type I active phase, and the stacking number of 3-8 layers is classified as type II active phase.

[0050] 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.

[0051] In the present application, the properties of the alumina carrier used in the examples and comparative examples are as follows: the pore volume is 0.85 mL / g, the specific surface area is 213 m 2 / g, the pore volume corresponding to 2-15 nm mesopores is 0.5 mL / g, and the pore volume corresponding to mesopores greater than 15 nm is 0.35 mL / g.

[0052] In the present application, the preparation process of the first impregnation solution is as follows: the gelatin is added to cold water at 20℃, stirred at 50 r / min, and treated at low temperature of 70℃ until completely dissolved.

[0053] In the present application, the preparation process of the third impregnation solution is as follows: (1) an aqueous solution of active metal components is prepared by using basic nickel carbonate, molybdenum oxide and phosphoric acid; (2) the gelatin is added to water at 20℃, and treated at 70℃ under the condition of stirring at 50 r / min until the gelatin is completely dissolved to obtain a gelatin solution; (3) the gelatin solution is added to the aqueous solution of active metal components to obtain the third impregnation solution.

[0054] Example 1

[0055] (1) 50 mL of the first impregnation solution with a gelatin content of 4 wt% is prepared, and the temperature of the first impregnation solution is 50℃; 100 g of the alumina carrier with a water absorption rate of 100% at 50℃ is unsaturatedly impregnated with the first impregnation solution, and the temperature is reduced to 10℃ for solidification treatment for 3 h to obtain a hydrotreating catalyst precursor;

[0056] (2) 50 mL of the second impregnation solution is prepared, and the active metal components contained in the second impregnation solution are Mo and Ni; based on the weight of the final hydrotreating catalyst, the Mo content of the active metal components (calculated as oxides) is 5 wt%, and the Ni content is 1 wt%. The hydrotreating catalyst precursor obtained in step (1) is impregnated with the second impregnation solution at 15℃, and after incubation at room temperature 25℃ for 6 h, drying at 120℃ for 3 h, and calcination at 450℃ for 3 h, a hydrotreating catalyst intermediate is obtained.

[0057] (3) Preparation of 50 mL of a third impregnation solution containing gelatin, active metals Mo and Ni, and additives phosphoric acid and citric acid; the gelatin content is 5 wt% based on the weight of the third impregnation solution; the active metal Mo content is 15 wt% based on the weight of the final hydroprocessing catalyst, the Ni content is 3 wt% based on the weight of the final hydroprocessing catalyst, the phosphoric acid content is 2 wt%, and the citric acid content is 1 wt%. The third impregnation solution has a temperature of 50 °C; the hydroprocessing catalyst intermediate obtained in step (2) is impregnated with the third impregnation solution at 40 °C, and is then solidified at room temperature (20 °C) for 6 h, and is dried at 160 °C for 2 h to obtain the final hydroprocessing catalyst Cat-1.

[0058] Example 2

[0059] (1) Preparation of 60 mL of a first impregnation solution containing gelatin at a content of 10 wt%, and the first impregnation solution has a temperature of 55 °C; 100 g of the alumina support having a water absorption rate of 100% is impregnated with the first impregnation solution at 40 °C, and is then solidified at 5 °C for 1 h to obtain a hydroprocessing catalyst precursor.

[0060] (2) Preparation of 40 mL of a second impregnation solution containing active metal components Mo and Ni; the active metal component (calculated as oxides) Mo content is 10 wt% based on the weight of the final hydroprocessing catalyst, and the Ni content is 2 wt% based on the weight of the final hydroprocessing catalyst; the hydroprocessing catalyst precursor obtained in step (1) is impregnated with the second impregnation solution at 20 °C, and is then incubated at room temperature (20 °C) for 6 h, and is dried at 120 °C for 3 h, and is calcined at 450 °C for 3 h to obtain a hydroprocessing catalyst intermediate.

[0061] (3) Preparation of 60 mL of a third impregnation solution containing gelatin, active metals Mo and Ni, and additives phosphoric acid and citric acid; the gelatin content is 5 wt% based on the weight of the third impregnation solution; the active metal Mo content is 15 wt% based on the weight of the final hydroprocessing catalyst, the Ni content is 3 wt% based on the weight of the final hydroprocessing catalyst, the phosphoric acid content is 3 wt%, and the citric acid content is 3 wt%. The third impregnation solution has a temperature of 55 °C; the hydroprocessing catalyst intermediate obtained in step (2) is impregnated with the third impregnation solution at 50 °C, and is then solidified at room temperature (20 °C) for 6 h, and is dried at 160 °C for 2 h to obtain the final hydroprocessing catalyst Cat-2.

[0062] Example 3

[0063] (1) Preparation of 30 mL of a first impregnation solution containing gelatin at a content of 15 wt%, and the first impregnation solution has a temperature of 60 °C; 100 g of the alumina support having a water absorption rate of 100% is impregnated with the first impregnation solution at 60 °C, and is then solidified at 20 °C for 5 h to obtain a hydroprocessing catalyst precursor.

[0064] (2) Preparation of a second impregnation solution 70 mL, the active metal components in the second impregnation solution are Mo and Ni, the Mo content of the active metal components (calculated as oxides) is 5 wt% and the Ni content is 1 wt% based on the weight of the final hydrotreating catalyst. The hydrotreating catalyst precursor obtained in step (1) is impregnated with the second impregnation solution at 25 °C, and after aging at room temperature 20 °C for 6 h, drying at 120 °C for 3 h, and calcination at 450 °C for 3 h, a hydrotreating catalyst intermediate is obtained.

[0065] (3) Preparation of a third impregnation solution 30 mL, the third impregnation solution contains gelatin, active metals Mo and Ni, and additives phosphoric acid and citric acid; the gelatin content is 5 wt% based on the weight of the third impregnation solution; the Mo content of the active metal components calculated as oxides is 20 wt% and the Ni content calculated as oxides is 4 wt%, the phosphoric acid content is 3 wt%, and the citric acid content is 2 wt% based on the weight of the final hydrotreating catalyst. The temperature of the third impregnation solution is 60 °C; the hydrotreating catalyst intermediate obtained in step (2) is impregnated with the third impregnation solution at 60 °C, and after temperature reduction and solidification treatment at room temperature 20 °C for 6 h, drying at 160 °C for 2 h, a final hydrotreating catalyst Cat-3 is obtained.

[0066] Example 4

[0067] (1) Preparation of a first impregnation solution 50 mL with a gelatin content of 20 wt%, the temperature of the first impregnation solution is 50 °C; 100 g of an alumina carrier with a water absorption rate of 100% is impregnated with the first impregnation solution at 50 °C, and after temperature reduction and solidification treatment at 15 °C for 10 h, a hydrotreating catalyst precursor is obtained.

[0068] (2) Preparation of a second impregnation solution 50 mL, the active metal components in the second impregnation solution are Mo and Ni; the Mo content of the active metal components (calculated as oxides) is 10 wt% and the Ni content is 2 wt% based on the weight of the final hydrotreating catalyst. The hydrotreating catalyst precursor obtained in step (1) is impregnated with the second impregnation solution at 15 °C, and after aging at room temperature 20 °C for 6 h, drying at 120 °C for 3 h, and calcination at 450 °C for 3 h, a hydrotreating catalyst intermediate is obtained.

[0069] (3) Preparation of a third impregnation solution 50 mL, the third impregnation solution containing gelatin, active metals Mo and Ni, and additives phosphoric acid and citric acid; the content of gelatin being 5 wt% based on the weight of the third impregnation solution; the content of active metal Mo being 10 wt% based on the weight of the final hydroprocessing catalyst, the content of Ni being 2 wt% based on the weight of the final hydroprocessing catalyst, the content of phosphoric acid being 2 wt%, and the content of citric acid being 2 wt%. The temperature of the third impregnation solution is 60 °C; the hydroprocessing catalyst intermediate obtained in step (2) is impregnated with the third impregnation solution at 50 °C, and the impregnated catalyst is solidified at room temperature 20 °C for 6 h, and then dried at 160 °C for 2 h to obtain the final hydroprocessing catalyst Cat-4.

[0070] Comparative Example 1

[0071] An impregnation solution having the same total content of active metal components and additives as in Example 2 (without gelatin) is prepared, and the support is impregnated with the impregnation solution in an equal volume. After incubation at room temperature 20 °C for 6 h, the impregnated support is dried at 120 °C for 3 h, and then dried at 160 °C for 2 h to obtain the hydroprocessing catalyst DC-1.

[0072] Comparative Example 2

[0073] An impregnation solution having the same total content of active metal components and additives as in Example 2 (without gelatin) is prepared, and the support is impregnated with the impregnation solution in an equal volume. After incubation at room temperature 20 °C for 6 h, the impregnated support is dried at 120 °C for 3 h, and then calcined at 450 °C for 3 h to obtain the hydroprocessing catalyst DC-2.

[0074] Comparative Example 3

[0075] Comparative to Example 2, steps (1) and (2) in Example 2 are absent. Specifically as follows:

[0076] (1) Preparation of a first impregnation solution 40 mL, the first impregnation solution containing active metal components Mo and Ni; the content of active metal components (as oxides) Mo being 10 wt% and the content of Ni being 2 wt% based on the weight of the final hydroprocessing catalyst. The alumina support is impregnated with the first impregnation solution at 20 °C, and the impregnated support is incubated at room temperature 20 °C for 6 h, dried at 120 °C for 3 h, and calcined at 450 °C for 3 h to obtain the hydroprocessing catalyst intermediate.

[0077] (2) Preparation of a second impregnation solution 60 mL containing active metals Mo and Ni, and additives phosphoric acid and citric acid; based on the weight of the final hydroprocessing catalyst, the content of Mo as an active metal component (as an oxide) is 15 wt%, the content of Ni as an active metal component (as an oxide) is 3 wt%, the content of phosphoric acid is 3 wt%, and the content of citric acid is 3 wt%. The temperature of the second impregnation solution is 55°C; the hydroprocessing catalyst intermediate obtained in step (1) is impregnated with the second impregnation solution at 50°C, and after solidification treatment at room temperature 20°C for 6 h, the final hydroprocessing catalyst DC-3 is obtained by drying at 160°C for 2 h.

[0078] Comparative Example 4

[0079] Compared with Example 2, steps (1) and (2) in Example 2 are absent, and the third impregnation solution does not contain gelatin. The specific operation process is as follows.

[0080] (1) Preparation of a first impregnation solution 40 mL containing active metal components Mo and Ni; based on the weight of the final hydroprocessing catalyst, the content of Mo as an active metal component (as an oxide) is 10 wt%, and the content of Ni is 2 wt%. The alumina carrier is impregnated with the first impregnation solution at 20°C, and after incubation at room temperature 20°C for 6 h, the hydroprocessing catalyst intermediate is obtained by drying at 120°C for 3 h and calcination at 450°C for 3 h.

[0081] (2) Preparation of a second impregnation solution 60 mL containing active metals Mo and Ni, and additives phosphoric acid and citric acid; based on the weight of the final hydroprocessing catalyst, the content of Mo as an active metal component (as an oxide) is 15 wt%, the content of Ni as an active metal component (as an oxide) is 3 wt%, the content of phosphoric acid is 3 wt%, and the content of citric acid is 3 wt%. The temperature of the second impregnation solution is 50°C; the hydroprocessing catalyst intermediate obtained in step (1) is impregnated with the second impregnation solution at 50°C, and after solidification treatment at room temperature 20°C for 6 h, the final hydroprocessing catalyst DC-4 is obtained by drying at 160°C for 2 h.

[0082] Comparative Example 5

[0083] Compared with Example 2, gelatin is not used in the first impregnation solution in step (1), but nitrilotriacetic acid (NTA) is used. The specific operation process is as follows.

[0084] (1) Preparation of a first impregnation solution 60 mL containing nitrilotriacetic acid (NTA) at a content of 10 wt%, and the temperature of the first impregnation solution is 60°C; the alumina carrier 100 g with a water absorption rate of 100% is impregnated with the first impregnation solution at 40°C, and after treatment at 5°C for 1 h, the hydroprocessing catalyst precursor is obtained;

[0085] (2) Preparation of a second impregnation solution 40 mL, the active metal components contained in the second impregnation solution are Mo and Ni; the Mo content of the active metal components (calculated as oxides) is 10 wt%, and the Ni content is 2 wt% based on the weight of the final hydroprocessing catalyst. The hydroprocessing catalyst precursor obtained in step (1) is impregnated with the second impregnation solution at 20 °C, and after aging at room temperature 20 °C for 6 h, dried at 120 °C for 3 h, and calcined at 450 °C for 3 h, a hydroprocessing catalyst intermediate is obtained.

[0086] (3) Preparation of a third impregnation solution 60 mL, the third impregnation solution contains NTA, active metals Mo and Ni, and additives phosphoric acid and citric acid; the NTA content is 5 wt% based on the weight of the third impregnation solution; the Mo content of the active metals, calculated as oxides, is 15 wt%, the Ni content, calculated as oxides, is 3 wt%, the phosphoric acid content is 3 wt%, and the citric acid content is 3 wt% based on the weight of the final hydroprocessing catalyst. The temperature of the third impregnation solution is 50 °C; the hydroprocessing catalyst intermediate obtained in step (2) is impregnated with the third impregnation solution at 50 °C, and after aging at room temperature 20 °C for 6 h, dried at 160 °C for 2 h, a final hydroprocessing catalyst DC-5 is obtained.

[0087] The properties of the catalysts obtained in the examples and comparative examples are shown in Table 1.

[0088]

[0089] Example 5

[0090] Evaluation of the catalytic performance of the catalysts: before evaluation, the catalysts are sulfided by using a cyclohexane solution of CS2, and the concentration of the cyclohexane solution of CS2 is 4 wt%; the operating conditions are as follows: the hydrogen pressure is 3.0 MPa, the sulfiding process is divided into two temperature stages, the first stage starts from 120 °C, the heating rate is 1.0 °C / min, and after reaching 160 °C, the temperature is kept constant for 4.0 h; the second stage starts from 160 °C, the heating rate is 1.0 °C / min, and after reaching 350 °C, the temperature is kept constant for 3.0 h. After the sulfiding is completed, the temperature is cooled to below 100 °C, and then the raw oil is introduced for reaction.

[0091] The catalytic cracking diesel is used as the raw material, and the properties of the raw material are shown in Table 2. The activity of the catalyst is evaluated in a micro-reactor device with a catalyst loading of 20 mL, the reaction temperature is 358 °C, the reaction pressure is 6 MPa, the volume space velocity is 2.0 h-1, and the hydrogen / oil volume ratio is 550. The evaluation results of the catalysts obtained in the examples and comparative examples are shown in Table 3. -1

[0092] Table 2 Properties of the raw material oil

[0093] Density (20°C), g-cm -3 ]] 0.9395 Distillation range, °C 191～349 [S, pg g -1 ]] 2800 [N, pg g -1 ]] 292

[0094] ​Table 1 Catalyst properties obtained from the examples and comparative examples

[0095] Table 3 Evaluation results

[0096]

[0097]

[0098] The relative activity is based on Comparative Example DC-1.

[0099] As can be seen from Table 3, the hydroprocessing catalyst prepared according to the present application has higher hydrodesulfurization and hydrodenitrogenation activity and stability compared with the catalyst of the comparative examples, and is particularly suitable for the hydrofining process of secondary processing oil.

Claims

1. A process for the preparation of a hydroprocessing catalyst, characterized by: The method comprises the following steps: (1) preparing a first impregnation solution containing gelatin, then unsaturatedly impregnating an alumina carrier, and then performing a temperature reduction solidification treatment to obtain a hydrotreating catalyst precursor; (2) preparing a second impregnation solution containing an active metal component, then impregnating the hydrotreating catalyst precursor obtained in step (1), and then performing a curing, drying and calcination to obtain a hydrotreating catalyst intermediate; (3) preparing a third impregnation solution containing gelatin and the active metal component, then unsaturatedly impregnating the hydrotreating catalyst intermediate obtained in step (2), and then performing a temperature reduction solidification treatment and drying to obtain a final hydrotreating catalyst.

2. The method of claim 1, wherein: The content of gelatin in the first impregnation solution containing gelatin is 4wt%-20wt%; the gelatin 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; the molecular weight of the gelatin is 10000-70000, preferably 10000-50000.

3. The method of claim 1, wherein: In step (1), the temperature of the first impregnation solution containing gelatin is 40-70℃, preferably 50-60℃.

4. The method of claim 1, wherein: In step (1), the first impregnation solution containing gelatin is prepared by adding gelatin to water at 5-20℃, and then performing a treatment at a temperature of 40-70℃, preferably 50-60℃, until the gelatin is completely dissolved.

5. The method of claim 1, wherein: In step (1), the first impregnation solution containing gelatin further contains a modification aid selected from one or more of phosphorus, titanium, silicon, zinc, copper, magnesium, zirconium, boron, fluorine, lanthanum, cerium and vanadium.

6. The method of claim 1, wherein: In step (1), the alumina support has the following properties: pore volume of 0.3 to 1.5 mL / g, specific surface area of 150 to 450 m 2 / g; preferably, the alumina support has a bimodal pore structure, the pore volume of pores having a diameter of 2 to 15 nm accounts for 40 to 80%, preferably 55 to 75%, of the total pore volume; the pore volume of pores having a diameter greater than 15 nm accounts for 20 to 60%, preferably 30 to 50%, of the total pore volume.

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

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

9. The method of claim 1, wherein: In step (1), the first impregnation solution is used for spray impregnation of the alumina carrier; the temperature of the impregnation solution is 40-70℃, preferably 50-60℃.

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

11. The method of claim 1, wherein: The active metal component comprises at least one metal selected from Group VIII and at least one metal selected from Group ⅥB; the metal of Group VIII is preferably Ni and / or Co, and the metal of Group ⅥB is preferably Mo.

12. The method of claim 1, wherein: In step (2), the content of the metal of Group VIII in the active metal component introduced by impregnation is 0.2wt%-5wt%, preferably 1wt%-3wt%, as calculated in terms of the oxide content of the final hydrotreating catalyst; the content of the metal of Group ⅥB is 1wt%-15wt%, preferably 5wt%-10wt%.

13. The method of claim 1, wherein: In step (2), the hydrotreating catalyst precursor obtained in step (1) is saturatedly impregnated, 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.

14. The method of claim 1, wherein: In step (2), the temperature of the impregnation is 1-30°C, preferably 15-25°C.

15. The method of claim 1, wherein: In step (2), the time of the aging is 1-30h, preferably 5-20h; the temperature is 0-30°C, preferably 5-25°C.

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

17. The method of claim 1, wherein: In step (3), the content of the gelatin in the third impregnation solution is 3-10wt% based on the mass of the third impregnation solution containing the gelatin and the active metal component.

18. The method of making according to claim 1 or 17, wherein: In step (3), the mass ratio of the active metal component (calculated as oxide) introduced in the third impregnation to the active metal component (calculated as oxide) introduced in step (2) is 1:(0.25-4), preferably 1:(0.5-2).

19. The method of claim 1, wherein: In step (3), the third impregnation solution further contains an acidic additive, which is at least one of phosphoric acid, citric acid and EDTA.

20. The method of claim 1, wherein: In step (3), the temperature of the third impregnation solution containing the gelatin and the active metal component is 40-70°C, preferably 50-60°C.

21. The method of claim 1, wherein: In step (3), the impregnation amount of the third impregnation solution to the unsaturated impregnated hydroprocessing catalyst intermediate is 30-60wt% of the saturated water absorption of the alumina carrier, preferably equal to the impregnation amount of the first impregnation solution to the unsaturated impregnated alumina carrier.

22. The method of claim 1, wherein: In step (3), the impregnation temperature of the third impregnation solution to the unsaturated impregnated hydroprocessing catalyst intermediate is 40-60°C.

23. The method of claim 1, wherein: In step (3), the third impregnation solution is used to unsaturatedly impregnate the hydroprocessing catalyst intermediate by spraying impregnation; the temperature of the impregnation solution is 40-70°C, preferably 50-60°C.

24. The method of claim 1, wherein: In step (3), the specific operation process of the cooling and solidification treatment is as follows: the material obtained after the unsaturated impregnation is placed in an environment with a temperature of 2-25°C, preferably 5-20°C, and the placing time is 1-30h, preferably 3-20h.

25. The method of claim 1, wherein: In step (3), the drying time is 2-6h, preferably 3-4h; the drying temperature is 80-180°C, preferably 100-160°C.

26. A hydroprocessing catalyst prepared by the method of any one of claims 1-25.

27. The catalyst of claim 26, wherein: The hydroprocessing catalyst has a pore volume of 0.3 to 1.3 mL / g and a specific surface area of 100 to 250 m 2 / g.

28. The use of the hydroprocessing catalyst of claim 26 or 27 in the hydroprocessing of secondary processed oil products.

29. The use according to claim 28, characterized in that: The hydroprocessing catalyst needs to be pre-sulfided before reaction, and the pre-sulfiding is divided into two temperature stages: the first stage is 120-160°C, and the sulfiding time is 2-8h; the second stage is 160-350°C, and the sulfiding time is 1-6h.

30. The use of claim 28, wherein: The secondary processed oil products are one or more of catalytic diesel, coking diesel and coking wax oil. The hydroprocessing catalyst needs to be pre-sulfided before reaction, and the pre-sulfiding is divided into two temperature stages: the first stage is 120-160°C, and the sulfiding time is 2-8h; the second stage is 160-350°C, and the sulfiding time is 1-6h. The secondary processed oil products are one or more of catalytic diesel, coking diesel and coking wax oil.

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