Hydrodesulfurization catalyst, method for preparing the same, and use thereof

Abstract

This invention discloses a hydrodesulfurization catalyst and its preparation method and application. The steps are as follows: (1) an organic polymer is modified with acid and then mixed with boehmite powder to obtain a first mixture; (2) an aqueous solution of amorphous silica-alumina and a heated organic polymer is mixed and spheroidized to obtain a first precursor; (3) a second precursor is prepared; (4) a second mixture is prepared; (5) a third precursor is prepared; (6) a support is prepared, and after introducing a hydrogenation active metal component, it is dried and calcined to obtain the hydrodesulfurization catalyst. The prepared catalyst has a non-uniform pore distribution structure, which not only gives it high impurity removal capacity, containment capacity and asphaltenes conversion capacity, but also reduces the sediment content in the generated oil. It is particularly suitable for the hydrotreating process of directly producing low-sulfur marine fuel oil from fluidized bed heavy oil.

Description

Technical Field

[0001] This invention belongs to the field of petroleum refining technology, and relates to a hydrogenation catalyst and its preparation method, particularly to a hydrodesulfurization catalyst and its preparation method. Background Technology

[0002] Since January 1, 2020, the sulfur content of fuel oil used in ships worldwide must not exceed 0.5%. Currently, low-sulfur marine fuel oil is mainly produced using fixed-bed residue hydrotreating technology. The resulting oil can be directly used as low-sulfur heavy marine fuel oil or a blending component. However, this technology has high requirements for the quality of the feedstock and has high processing costs. In recent years, fluidized bed hydrotreating technology has developed rapidly. It can use low-quality, inexpensive heavy oil as feedstock, producing hydrotreated heavy oil that can be used as low-sulfur marine fuel oil or a blending component. This results in lower production costs and significant economic benefits. However, a problem remains: the sulfur content of the hydrotreated heavy oil needs to be further reduced to increase the blending ratio. To enable both fixed-bed and fluidized bed hydrotreating technologies to produce low-sulfur marine fuel oil or blending components at low cost, higher requirements are placed on the hydrodesulfurization activity and asphaltenes conversion capacity of the catalysts. Therefore, there is an urgent need to develop a new generation of highly active desulfurization hydrotreating catalysts.

[0003] CN105772005A discloses a hydrogenation catalyst, its preparation method, and a method for hydrodesulfurization of heavy oil. The hydrogenation catalyst comprises a support and an active metal component, wherein the active metal component is distributed in a double layer along the radial direction of the support. The core layer's active metal component is CoO and MoO3, and the shell layer's active metal component is NiO, MoO3, and / or WO3. The hydrogenation catalyst provided by this invention exhibits high activity for hydrodemetallization, desulfurization, residual carbon removal, and denitrification. However, the catalyst's ability to convert macromolecules such as asphaltene still needs further improvement.

[0004] CN104646008A discloses a low-quality heavy oil hydrodesulfurization and demetallization catalyst and its preparation method. The catalyst uses alumina as a support and Ni-Mo as the active component. The average pore diameter of the catalyst particles gradually increases radially from the center to the outer surface. The catalyst preparation method involves treating the shaped and calcined support particles with an acid solution of continuously increasing concentration. The catalyst of this invention has large pores and open channels, exhibiting excellent diffusion performance, high hydrodesulfurization and demetallization activity, and high activity stability. However, the active metal in this catalyst is still loaded using a conventional impregnation method, resulting in a strong interaction between the active metal and the alumina support. This leads to low utilization of the active metal, limiting further improvement in catalyst activity. Summary of the Invention

[0005] The main objective of this invention is to provide a hydrodesulfurization catalyst, its preparation method, and its application. The prepared catalyst has a non-uniform pore distribution structure, which not only gives it high impurity removal capacity, containment capacity, and asphaltenes conversion capacity, but also reduces the sediment content in the generated oil. It is particularly suitable for hydrotreating processes that directly produce low-sulfur marine fuel oil from fluidized bed heavy oil.

[0006] The first aspect of this invention provides a method for preparing a hydrodesulfurization catalyst, comprising the following steps:

[0007] (1) The organic polymer was modified with acid, and the acid-modified organic polymer was further mixed with boehmite powder to obtain the first mixture.

[0008] (2) Mix an aqueous solution of amorphous silica-alumina and a heat-treated organic polymer, and then perform a pelletizing process to obtain the first precursor;

[0009] (3) The first precursor obtained in step (2) is placed in a ball rolling machine, and the first mixture obtained in step (1) and the heated organic polymer aqueous solution are added evenly during the rolling process. The second precursor is obtained after treatment.

[0010] (4) Mix the organic polymer, the weakly basic compound, and the pseudoboehmite powder to obtain a second mixture;

[0011] (5) The second precursor obtained in step (3) is placed in a ball rolling machine, and the second mixture obtained in step (4) and the heated organic polymer aqueous solution are added evenly during the rolling process. After treatment, the third precursor is obtained.

[0012] (6) The third precursor obtained in step (5) is subjected to heat treatment. The material obtained after heat treatment is mixed with a soluble zinc salt solution, and then dried and calcined to obtain a carrier.

[0013] (7) The support obtained in step (6) is introduced into the hydrogenation active metal component and then dried and calcined to obtain the hydrogenation desulfurization catalyst.

[0014] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the organic polymer is modified by acid in step (1), and after the modification is completed, it is cooled, optionally washed with water, and dried to obtain the acid-modified organic polymer.

[0015] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the acid modification treatment temperature of the organic polymer in step (1) is 30-50℃; the modification treatment time is 2-6 hours.

[0016] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the concentration of the acidic solution in step (1) is 5wt% to 40wt%; the mass ratio of organic polymer to acid is 1:0.1 to 1:5.

[0017] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the acid in step (1) can be an inorganic acid or an organic acid; more specifically, the organic acid is one or a mixture of two or more of citric acid, acetic acid, lactic acid, malic acid, and tartaric acid, preferably citric acid; the inorganic acid is one or a mixture of two or more of hydrochloric acid, sulfuric acid, and nitric acid, preferably hydrochloric acid.

[0018] In the above-mentioned method for preparing the hydrodesulfurization catalyst, as a preferred embodiment, the organic polymer is one or more of starch, cellulose ether, and flour, preferably starch. Furthermore, the starch is one or more of mung bean starch, cassava starch, sweet potato starch, potato starch, wheat starch, water chestnut starch, lotus root starch, and corn starch, preferably corn starch and / or potato starch; the cellulose ether can be at least one of methylcellulose, hydroxyethyl methylcellulose, carboxymethyl cellulose, ethylcellulose, benzylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, cyanoethylcellulose, benzyl cyanoethylcellulose, carboxymethyl hydroxyethyl cellulose, and phenylcellulose, preferably methylcellulose.

[0019] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the pseudoboehmite powder in step (1) has the following properties after calcination at 550-750℃: specific surface area of ​​280-320 m². 2 / g, with a pore volume of 0.9-1.2mL / g, the pseudoboehmite powder can be a commercially available product that meets the product properties, or it can be prepared using methods disclosed in existing patents or literature.

[0020] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the boehmite powder in step (1) and step (4) can be the same or different.

[0021] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the amount of acid-modified organic polymer added in step (1) is 5wt% to 35wt% of the dry basis mass of boehmite powder, preferably 10wt% to 30wt%.

[0022] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the amorphous silicon-aluminum in step (2) has the following properties: specific surface area of ​​250-320 m². 2 / g, with a pore volume of 0.7 to 1.0 mL / g and a silica content of 10% to 50% by mass.

[0023] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the amorphous silicon-aluminum particle size in step (2) is above 200 mesh. Specifically, the amorphous silicon-aluminum can be processed in a grinding equipment with crushing function, such as a ball mill, to obtain an amorphous silicon-aluminum sample with the required particle size.

[0024] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the amorphous silicon-aluminum in step (2) can be prepared by purchasing commercially available products or by using existing methods.

[0025] In the above-mentioned method for preparing the hydrodesulfurization catalyst, as a preferred embodiment, the concentration of the aqueous solution of the heat-treated organic polymer in step (2) is 0.5wt% to 8.0wt%, preferably 1.0wt% to 5.0wt%. The method for preparing the aqueous solution of the heat-treated organic polymer is as follows: the organic polymer is added to water, heated and mixed at 60 to 100°C for 10 to 40 minutes, and the aqueous solution of the heat-treated organic polymer is obtained after the organic polymer is completely dissolved.

[0026] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the mass ratio of the amount of aqueous solution of organic polymer added in step (2) to that of amorphous silicon and aluminum is 0.5 to 1.5.

[0027] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the spherical forming in step (2) can be any of the existing spherical forming methods in the art, specifically one or more of the following methods: extrusion spherical forming, rolling forming, and spray drying forming.

[0028] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the mass ratio of the amount of the organic polymer aqueous solution added in step (3) to the mass of the first mixture is 0.5 to 1.2.

[0029] In the above-mentioned method for preparing the hydrodesulfurization catalyst, as a preferred embodiment, the weakly basic compound in step (4) is one or a mixture of two or more of ammonia, ammonium carbonate, and ammonium bicarbonate, preferably ammonia. Furthermore, the concentration of the aqueous solution of the nitrogen-containing weakly basic compound is 2wt% to 40wt%, preferably 5wt% to 35wt%.

[0030] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the mass ratio of organic polymer and weakly basic compound in step (4) is 1:0.05 to 1:0.5.

[0031] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the total amount of organic polymer and weakly basic compound added in step (4) (by mass) is 5wt% to 25wt% of the dry basis mass of boehmite powder, preferably 10wt% to 20wt%.

[0032] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, when mixing the organic polymer, weak basic compound and pseudoboehmite powder in step (4), it is preferable to first mix the organic polymer and weak basic compound, and then mix them with pseudoboehmite powder.

[0033] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the mass ratio of the amount of the aqueous solution of the heated organic polymer in step (5) to the mass ratio of the second mixture is 0.5 to 1.2.

[0034] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the heat treatment temperature in step (6) is 100-300℃, preferably 150-250℃; the treatment time is 3-12h.

[0035] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the soluble zinc salt in step (6) is one or more of zinc nitrate, zinc acetate, zinc chloride, zinc sulfate, etc.

[0036] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the drying temperature in step (6) is 60-120℃; the calcination in step (6) is carried out under an inert atmosphere, which is one or more of nitrogen, helium, neon, argon, krypton, and xenon, preferably nitrogen; the calcination temperature is 600-800℃, and the calcination time is 1-5h.

[0037] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the introduction of hydrogenation active metal component in step (7) can be any one or more of the methods existing in the art, specifically at least one of the methods such as mixing and impregnation, with impregnation being preferred.

[0038] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the active metal component in step (7) is one or more of Group VIB metals and / or Group VIII metals, wherein the Group VIB metal is generally Mo and / or W, and the Group VIII metal is generally Ni and / or Co; the active metal component for hydrodesulfurization is preferably Mo and Ni.

[0039] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, an auxiliary agent P may also be introduced when introducing the active metal component in step (7).

[0040] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the drying in step (7) is performed at 80-120°C for 4-12 hours.

[0041] In the above-mentioned method for preparing hydrodesulfurization catalyst, as a preferred embodiment, the calcination temperature in step (7) is 400-600℃ and the calcination time is 1-5h.

[0042] In the above-mentioned method for preparing the hydrodesulfurization catalyst, as a preferred embodiment, when the hydrogenation active metal component in step (7) is prepared by impregnation, the precursor containing the active metal component, water, and optionally a phosphorus-containing compound are first mixed uniformly to obtain an aqueous solution containing the hydrogenation metal component and P. Then, after uniform mixing with the support, the solution is allowed to stand, dried, and calcined to obtain the catalyst. Specifically, the precursor containing the active metal component is a compound containing a Group VIB metal and / or a Group VIII metal. The Group VIB metal-containing compound can be one or more of a molybdenum-containing compound or a tungsten-containing compound, and the Group VIII metal-containing compound can be one or more of a nickel-containing compound or a cobalt-containing compound. The molybdenum-containing compound can be molybdenum oxide and / or ammonium heptamolybdate; the nickel-containing compound is basic nickel carbonate and / or nickel nitrate; and the cobalt-containing compound is basic cobalt carbonate and / or cobalt nitrate. The phosphorus-containing compound can be one or more of phosphoric acid, ammonium dihydrogen phosphate, and ammonium monohydrogen phosphate; the concentration of the hydrogenated metal component in the aqueous solution containing the hydrogenated metal component and P is 0.05–1.0 g / mL (calculated as hydrogenated metal oxide), and the concentration of P is 0–0.1 g / mL, preferably 0.002–0.1 g / mL. The standing time is 1–3 h.

[0043] A second aspect of the present invention provides a hydrodesulfurization catalyst obtained by the above preparation method.

[0044] In the above-mentioned hydrodesulfurization catalyst, as a preferred embodiment, the fluidized bed heavy oil hydrotreating catalyst includes an active metal component, an auxiliary metal component, optional auxiliary agents, and a support. The active metal component is one or more of Group VIB metals and / or Group VIII metals, the auxiliary metal component is zinc oxide, the auxiliary agent is phosphorus pentoxide, and the support is an amorphous silica-alumina and alumina composite support, wherein the active metal and the auxiliary metal exist on the support in the form of oxides.

[0045] In the aforementioned hydrodesulfurization catalyst, as a preferred embodiment, the composite support comprises a core layer, an intermediate layer, and an outer layer, wherein the core layer is amorphous silica-alumina, the intermediate layer is alumina with mesopores, and the outer layer is alumina with macropores. Based on the weight of the support, the content of amorphous silica-alumina in the core layer is 20%–40%, the content of alumina in the intermediate layer is 30%–50%, and the content of alumina in the outer layer is 10%–40%.

[0046] In the above-mentioned hydrodesulfurization catalyst, as a preferred embodiment, based on the weight of the catalyst and calculated as oxides, the content of the Group VIB metal component is 8 wt% to 15 wt%; the content of the Group VIII metal component is 2 wt% to 5 wt%; and the content of phosphorus pentoxide is 1.5 wt% to 4.0 wt%. The content of the auxiliary metal component zinc oxide is 0.1 wt% to 3.0 wt% of the support.

[0047] In the above-mentioned hydrodesulfurization catalyst, as a preferred embodiment, the properties of the hydrodesulfurization catalyst are as follows: specific surface area of ​​150-240 m² / g. 2 / g, with a pore volume of 0.40–0.80 mL / g. Mesopores with a pore size of 10–50 nm account for 70%–93% of the total pore volume, while macropores with a pore size greater than 50 nm account for 5%–15% of the total pore volume.

[0048] A third aspect of the present invention provides an application of the above-mentioned hydrodesulfurization catalyst in the heavy oil hydrotreating process.

[0049] Furthermore, in the above applications, the heavy oil is at least one or more of atmospheric residue, vacuum residue, catalytic slurry, and coal tar.

[0050] Furthermore, in the above applications, the process conditions for hydrogenation are as follows: reaction pressure of 10–20 MPa, temperature of 300–500 °C, and liquid hourly space velocity of 0.1–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300–1000.

[0051] A fourth aspect of the present invention provides an application of the above-mentioned hydrodesulfurization catalyst in the production of low-sulfur marine fuel oil.

[0052] Furthermore, in the above applications, the process conditions for producing low-sulfur marine fuel are as follows: reaction pressure of 15–20 MPa, temperature of 400–430 °C, and liquid hourly space velocity of 0.1–0.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 500–1000.

[0053] The hydrodesulfurization catalyst and its preparation method provided by this invention have the following advantages compared with the prior art:

[0054] 1. In the hydrodesulfurization catalyst of the present invention, the core support layer is amorphous silica-alumina, which has large pore volume, high specific surface area and high acid content; the middle layer alumina support has a high proportion of mesopores, while the outer layer alumina support has a high proportion of macropores. The catalyst pores gradually increase from the inside to the outside, which can effectively remove impurities from heavy oil and gradually convert asphaltenes, reduce the sediment content in the generated oil, and is especially suitable for the fluidized bed hydrotreating process for direct production of low-sulfur marine feedstock oil from heavy oil.

[0055] 2. In the preparation method of the hydrodesulfurization catalyst of the present invention, the organic polymer is decomposed into small molecules in water after being heated, so that the aqueous solution has high adhesion, which can enhance the interaction between amorphous silicon and aluminum materials, and at the same time enhance the interaction force between pseudoboehmite powder and amorphous silicon and aluminum, thereby improving the strength and wear resistance of the carrier.

[0056] 3. In the preparation method of the hydrodesulfurization catalyst of the present invention, the organic polymer is modified by acid, the molecules become smaller and the adhesion is weakened. When mixed with pseudoboehmite powder, it can increase the proportion of mesopores in the intermediate support. However, after the organic polymer reacts with the weak base compound, the molecular size does not change, but the adhesion becomes worse. When mixed with pseudoboehmite powder, it only plays a pore-expanding role and can increase the proportion of macropores in the outer support.

[0057] 4. In the preparation method of the hydrodesulfurization catalyst of the present invention, the ammonia in the weak base compound that reacts with the organic polymer after heat treatment will volatilize and be adsorbed by interacting with the strong acid sites on the alumina. The addition of soluble zinc salt will interact with the ammonia on the alumina and be adsorbed on the strong acid sites of the alumina. After calcination, it will occupy the strong acid sites of the alumina, which can weaken the interaction between the active metal and the alumina support and improve the utilization rate of the active metal.

[0058] 5. In the preparation method of the hydrodesulfurization catalyst of this invention, the acid-modified organic polymer is calcined under an inert atmosphere to become a mesoporous carbon material, while the organic polymer is calcined under an inert atmosphere to become a macroporous carbon material. Since the water absorption rate of mesoporous and macroporous carbon materials is lower than that of alumina, the presence of carbon materials reduces the water absorption rate of the middle and outer alumina supports. During the impregnation process of active metals, relatively less active metal is adsorbed on the middle and outer alumina supports, while a relatively larger amount of active metal is adsorbed on the inner amorphous silica-alumina supports. The resulting catalyst exhibits an uneven distribution of active metals, with a relatively larger distribution inside the catalyst and a relatively smaller distribution on the outer surface, resulting in a gradient distribution of the catalyst's hydrodesulfurization activity. The middle and outer layers of the catalyst can effectively remove impurities such as metals, sulfur, and nitrogen from the residual oil and effectively convert asphaltenes, protecting the inner amorphous silica-alumina layers. The inner layer of the catalyst can further achieve deep desulfurization of the residual oil, thereby meeting the sulfur content and sediment requirements for the direct production of low-sulfur marine fuel oil from residual oil. Attached Figure Description

[0059] Figure 1 This is an electron probe microanalysis image of the catalyst cross-section in Example 3 of the present invention.

[0060] Figure 2 This is an electron probe scanning diagram of the catalyst cross-section MoO3 distribution in Example 3 of the present invention. Detailed Implementation

[0061] The technical solution and effects of the present invention are further illustrated below through specific embodiments. In the present invention, wt% is the mass fraction.

[0062] In this invention, the specific surface area and pore volume were measured using a cryogenic liquid nitrogen physical adsorption method, specifically using a Micron ASAP2420 cryogenic nitrogen adsorption instrument. The procedure involved: a small sample was vacuum-treated at 300°C for 3–4 hours, and finally, the product was placed under liquid nitrogen cryogenic (-200°C) conditions for nitrogen adsorption-desorption testing. The surface area was obtained using the BET equation, and the pore size distribution was obtained using the BJH model.

[0063] The wear index of microsphere carriers <0.8 mm was tested using the high-speed air jet method (see ASTM D5757-00), and the wear index of microsphere carriers >0.8 mm was measured using the drum method with a KM-ZV wear meter.

[0064] The distribution of active metals in the catalyst was detected using a JXA-8230 electron probe microanalyzer from NEC Corporation.

[0065] The sediments in the generated oil were determined according to the SHT0702-2001 method for determining total sediments in residual fuel oil (aging method) using an FDR-1431 residual fuel oil total sediment analyzer.

[0066] Example 1

[0067] (1) Carrier preparation

[0068] 42g corn starch, 42g citric acid, and 140g water were mixed and heated to 40℃ for 3 hours. The mixture was then filtered, washed with water, and dried at 40℃ for 24 hours to obtain an acid-modified organic polymer. This polymer was then mixed with 400g of pseudoboehmite powder (specific surface area 290 μm). 2 Mix (g, pore volume 1.05 mL / g) to obtain the first mixture; weigh 80 g of corn starch and add it to 2000 g of water, heat at 70 °C for 20 min to obtain a heat-treated organic polymer aqueous solution; add 300 g of amorphous silica-alumina (specific surface area 285 μm) 2 270g of a heated organic polymer aqueous solution (with a pore volume of 0.90mL / g) and 21.0g of corn starch (with a pore volume of 0.90mL / g) were mixed and then spheroidized to obtain the first precursor. The first precursor was placed in a ball rolling machine, and during the rolling process, the first mixture and 360g of the heated organic polymer aqueous solution were added evenly. After spheroidization, the second precursor was obtained. 21.0g of corn starch was first mixed with 20g of 10wt% ammonia water, and then mixed with 300g of pseudoboehmite powder (with a specific surface area of ​​290m²). 2 The second precursor was mixed with 15.4 g of zinc nitrate (1.05 mL / g pore volume) to obtain a second mixture. The second precursor was placed in a ball rolling mill, and during the rolling process, the second mixture and 270 g of heated organic polymer aqueous solution were added evenly. After ball forming, a third precursor was obtained. The third precursor was heat-treated at 200 °C for 4 h. Then it was mixed with 270 mL of aqueous solution containing 15.4 g of zinc nitrate, dried at 90 °C for 8 h, and then calcined at 650 °C for 3 h under a nitrogen atmosphere to obtain spherical carriers with a particle size of 0.5~0.8 mm. The carrier yield and wear data are shown in Table 1.

[0069] (2) Catalyst preparation

[0070] Dissolve 4.30 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 11.68 g of molybdenum trioxide and 5.16 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and make up to 85 mL to obtain Mo-Ni-P aqueous solution.

[0071] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 550℃ for 3h to obtain the catalyst, in which the content of MoO3 was 10.0wt%, the content of NiO was 2.5wt%, and the content of P was 1.0wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0072] (3) Catalyst evaluation

[0073] The catalyst was evaluated over a long period using a CSTR hydrogenation evaluation system, with an operating time of 1500 hours. The evaluation conditions were: reaction temperature 420℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.3 h⁻¹. -1 The hydrogen-to-oil volume ratio was 600:1. The properties of the feedstock oil are shown in Table 3, and the evaluation results are shown in Table 4. The generated oil was also fractionated, and the sulfur content and sediment content of the >400℃ fraction were analyzed; the results are shown in Table 5.

[0074] Example 2

[0075] (1) Carrier preparation

[0076] 70g corn starch, 70g citric acid, and 235g water were mixed thoroughly and heated to 40℃ for 3 hours. The mixture was then filtered, washed with water, and dried at 40℃ for 24 hours to obtain an acid-modified organic polymer. This polymer was then mixed with 500g of pseudoboehmite powder (specific surface area 290 μm). 2 Mix (g, pore volume 1.05 mL / g) to obtain the first mixture; weigh 80 g of corn starch and add it to 2000 g of water, heat at 70 °C for 20 min to obtain a heat-treated organic polymer aqueous solution; add 300 g of amorphous silica-alumina (specific surface area 285 μm) 2 270g of a heated organic polymer aqueous solution (with a pore volume of 0.90mL / g) and 21.0g of corn starch (with a pore volume of 0.90mL / g) were mixed and then spheroidized to obtain the first precursor. The first precursor was placed in a ball rolling machine, and during the rolling process, the first mixture and 450g of the heated organic polymer aqueous solution were added evenly. After spheroidization, the second precursor was obtained. 20g of corn starch (with a pore volume of 0.90mL / g) was first mixed with 20g of 10wt% ammonia water, and then mixed with 200g of pseudoboehmite powder (with a specific surface area of ​​290m²). 2The second precursor was mixed with 180g of a heated organic polymer aqueous solution (1.05mL / g) to obtain a second mixture. The second precursor was placed in a ball rolling mill, and the second mixture and 180g of heated organic polymer aqueous solution were added evenly during the rolling process. After ball forming, a third precursor was obtained. The third precursor was heat-treated at 200℃ for 4h. Then it was mixed with 180mL of an aqueous solution containing 10.3g of zinc nitrate, dried at 90℃ for 8h, and then calcined at 700℃ for 3h under a nitrogen atmosphere to obtain spherical carriers with a particle size of 0.5~0.8mm. The carrier yield and wear data are shown in Table 1.

[0077] (2) Catalyst preparation

[0078] Dissolve 4.30 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 11.68 g of molybdenum trioxide and 5.16 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and make up to 85 mL to obtain Mo-Ni-P aqueous solution.

[0079] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 550℃ for 3h to obtain the catalyst, in which the content of MoO3 was 10.0wt%, the content of NiO was 2.5wt%, and the content of P was 1.0wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0080] (3) Catalyst evaluation

[0081] The catalyst was evaluated over a long period using a CSTR hydrogenation evaluation system, with an operating time of 1500 hours. The evaluation conditions were: reaction temperature 420℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.3 h⁻¹. -1 The hydrogen-to-oil volume ratio was 600:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0082] Example 3

[0083] (1) Carrier preparation

[0084] 52.5g corn starch, 52.5g citric acid, and 175g water were mixed and heated to 40℃ for 3 hours. The mixture was then filtered, washed with water, and dried at 40℃ for 24 hours to obtain an acid-modified organic polymer. This polymer was then mixed with 300g of pseudoboehmite powder (specific surface area 290 μm). 2 Mix (g, pore volume 1.05 mL / g) to obtain the first mixture; weigh 80 g of corn starch and add it to 2000 g of water, heat at 70 °C for 20 min to obtain a heat-treated organic polymer aqueous solution; add 300 g of amorphous silica-alumina (specific surface area 285 μm) 256.0 g of corn starch (0.90 mL / g pore volume) and 270 g of a heat-treated organic polymer aqueous solution were mixed and then spheroidized to obtain the first precursor. The first precursor was then placed in a ball rolling machine, and during the rolling process, the first mixture and 270 g of the heat-treated organic polymer aqueous solution were uniformly added. After spheroidization, the second precursor was obtained. 56.0 g of corn starch was first mixed with 55 g of 10 wt% ammonia water, and then mixed with 400 g of pseudoboehmite powder (specific surface area 290 μm). 2 The second precursor was mixed with 1.05 mL / g of zinc nitrate (with a pore volume of 1.05 mL / g) to obtain a second mixture. The second precursor was placed in a ball rolling mill, and during the rolling process, the second mixture and 360 g of a heated organic polymer aqueous solution were added evenly. After ball forming, a third precursor was obtained. The third precursor was heat-treated at 200 °C for 4 h. Then it was mixed with 360 mL of an aqueous solution containing 20.5 g of zinc nitrate, dried at 90 °C for 8 h, and then calcined at 750 °C for 3 h under a nitrogen atmosphere to obtain a spherical carrier with a particle size of 0.5~0.8 mm. The carrier yield and wear data are shown in Table 1.

[0085] (2) Catalyst preparation

[0086] Dissolve 4.30 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 11.68 g of molybdenum trioxide and 5.16 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and make up to 85 mL to obtain Mo-Ni-P aqueous solution.

[0087] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 550℃ for 3h to obtain the catalyst, which contained 10.0wt% MoO3, 2.5wt% NiO, and 1.0wt% P. The physicochemical properties of the catalyst are shown in Table 2, and the distribution of MoO3 on the catalyst is shown in [Table 2]. Figure 1 and Figure 2 .

[0088] (3) Catalyst evaluation

[0089] The catalyst was evaluated over a long period using a CSTR hydrogenation evaluation system, with an operating time of 1500 hours. The evaluation conditions were: reaction temperature 420℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.3 h⁻¹. -1 The hydrogen-to-oil volume ratio was 600:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0090] Example 4

[0091] The preparation was essentially the same as in Example 3, except that corn starch was replaced with potato starch to obtain a spherical support with a particle size of 0.5~0.8 mm. The support yield and wear data are shown in Table 1. A catalyst was prepared, in which the content of MoO3 was 10.0 wt%, the content of NiO was 2.5 wt%, and the content of P was 1.0 wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0092] The catalyst was evaluated in the same way as in Example 3. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0093] Example 5

[0094] The preparation was essentially the same as in Example 3, except that 52.5g of corn starch was replaced with 44.24g of methylcellulose, 80g of corn starch with 67.41g of methylcellulose, and 56g of corn starch with 47.19g of methylcellulose, to obtain spherical supports with a particle size of 0.5~0.8mm. The support yield and wear data are shown in Table 1. A catalyst was prepared, containing 10.0wt% MoO3, 2.5wt% NiO, and 1.0wt% P. The physicochemical properties of the catalyst are shown in Table 2.

[0095] The catalyst was evaluated in the same way as in Example 3. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0096] Example 6

[0097] (1) Carrier preparation

[0098] This is essentially the same as Example 3, except that 52.5g of citric acid and 175g of water are replaced with 175g of a 15% hydrochloric acid aqueous solution, 20.5g of zinc nitrate is replaced with 17.7g of zinc acetate, and the 0.5~0.8mm spherical carrier is replaced with a 1.2~1.5mm spherical carrier. The carrier yield and wear data are shown in Table 1.

[0099] (2) Catalyst preparation

[0100] Dissolve 6.99 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 19.00 g of molybdenum trioxide and 8.39 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and make up to 85 mL to obtain Mo-Ni-P aqueous solution.

[0101] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 550℃ for 3h to obtain the catalyst, which contained 15.0wt% MoO3, 3.75wt% NiO, and 1.5wt% P. The physicochemical properties of the catalyst are shown in Table 2.

[0102] The catalyst was evaluated in the same way as in Example 3. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0103] Comparative Example 1

[0104] (1) Carrier preparation

[0105] 42g corn starch, 42g citric acid, and 140g water were mixed and heated to 40℃ for 3 hours. The mixture was then filtered, washed with water, and dried at 40℃ for 24 hours to obtain an acid-modified organic polymer. This polymer was then mixed with 400g of pseudoboehmite powder (specific surface area 290 μm). 2 The first mixture was obtained by mixing 300g of amorphous aluminum silica (specific surface area 285 μm / g, pore volume 1.05 mL / g); 2 10.8g of corn starch and 270g of water were mixed and then spheroidized to obtain the first precursor. The first precursor was then placed in a ball-rolling machine, and during the rolling process, the first mixture, 14.4g of corn starch, and 360g of water were added evenly. After spheroidizing, the second precursor was obtained. 21.0g of corn starch was first mixed with 20g of 10wt% ammonia water, and then mixed with 300g of pseudoboehmite powder (specific surface area 290m²). 2 The second precursor was mixed with a pore volume of 1.05 mL / g to obtain a second mixture. The second precursor was placed in a ball rolling machine, and during the rolling process, the second mixture, 10.8 g of corn starch and 270 g of water were added evenly. After ball forming, a third precursor was obtained. The third precursor was heat-treated at 200 °C for 4 h. Then it was mixed with 270 mL of an aqueous solution containing 15.4 g of zinc nitrate, dried at 90 °C for 8 h, and then calcined at 650 °C for 3 h under a nitrogen atmosphere to obtain a spherical carrier with a particle size of 0.5~0.8 mm. The carrier yield and wear data are shown in Table 1.

[0106] (2) Catalyst preparation

[0107] Dissolve 4.30 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 11.68 g of molybdenum trioxide and 5.16 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and make up to 85 mL to obtain Mo-Ni-P aqueous solution.

[0108] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 550℃ for 3h to obtain the catalyst, in which the content of MoO3 was 10.0wt%, the content of NiO was 2.5wt%, and the content of P was 1.0wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0109] (3) Catalyst evaluation

[0110] The catalyst was evaluated over a long period using a CSTR hydrogenation evaluation system, with an operating time of 1500 hours. The evaluation conditions were: reaction temperature 420℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.3 h⁻¹. -1 The hydrogen-to-oil volume ratio was 600:1. The properties of the feedstock oil are shown in Table 3, and the evaluation results are shown in Table 4. The generated oil was also fractionated, and the sulfur content and sediment content of the >400℃ fraction were analyzed; the results are shown in Table 5.

[0111] Comparative Example 2

[0112] (1) Carrier preparation

[0113] Mix 42g corn starch and 140g water, heat to 40℃ for 3 hours, then filter and wash with water. Dry at 40℃ for 24 hours. Finally, mix with 400g of pseudoboehmite powder (specific surface area 290m²). 2 Mix (g, pore volume 1.05 mL / g) to obtain the first mixture; weigh 80 g of corn starch and add it to 2000 g of water, heat at 70 °C for 20 min to obtain a heat-treated organic polymer aqueous solution; add 300 g of amorphous silica-alumina (specific surface area 285 μm) 2 270g of a heat-treated organic polymer aqueous solution (with a pore volume of 0.90mL / g) and 21.0g of corn starch (with a pore volume of 0.90mL / g) were mixed with 300g of pseudoboehmite powder (with a specific surface area of ​​290m² / g). After uniform mixing, the mixture was spherically formed to obtain the first precursor. The first precursor was then placed in a ball rolling machine, and during the rolling process, the first mixture and 360g of the heat-treated organic polymer aqueous solution were uniformly added. After spherical forming, the second precursor was obtained. 2 The second precursor was mixed with 15.4 g of zinc nitrate (1.05 mL / g pore volume) to obtain a second mixture. The second precursor was placed in a ball rolling mill, and during the rolling process, the second mixture and 270 g of heated organic polymer aqueous solution were added evenly. After ball forming, a third precursor was obtained. The third precursor was heat-treated at 200 °C for 4 h. Then it was mixed with 270 mL of aqueous solution containing 15.4 g of zinc nitrate, dried at 90 °C for 8 h, and then calcined at 650 °C for 3 h under a nitrogen atmosphere to obtain spherical carriers with a particle size of 0.5~0.8 mm. The carrier yield and wear data are shown in Table 1.

[0114] (2) Catalyst preparation

[0115] Dissolve 4.30 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 11.68 g of molybdenum trioxide and 5.16 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and make up to 85 mL to obtain Mo-Ni-P aqueous solution.

[0116] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 550℃ for 3h to obtain the catalyst, in which the content of MoO3 was 10.0wt%, the content of NiO was 2.5wt%, and the content of P was 1.0wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0117] (3) Catalyst evaluation

[0118] The catalyst was evaluated over a long period using a CSTR hydrogenation evaluation system, with an operating time of 1500 hours. The evaluation conditions were: reaction temperature 420℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.3 h⁻¹. -1 The hydrogen-to-oil volume ratio was 600:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0119] Comparative Example 3

[0120] (1) Carrier preparation

[0121] 42g corn starch, 42g citric acid, and 140g water were mixed and heated to 40℃ for 3 hours. The mixture was then filtered, washed with water, and dried at 40℃ for 24 hours to obtain an acid-modified organic polymer. This polymer was then mixed with 400g of pseudoboehmite powder (specific surface area 290 μm). 2 Mix (g, pore volume 1.05 mL / g) to obtain the first mixture; weigh 80 g of corn starch and add it to 2000 g of water, heat at 70 °C for 20 min to obtain a heat-treated organic polymer aqueous solution; add 300 g of amorphous silica-alumina (specific surface area 285 μm) 2 270g of a heated organic polymer aqueous solution (with a pore volume of 0.90mL / g) and 21.0g of corn starch (with a pore volume of 0.90mL / g) were mixed and then spheroidized to obtain the first precursor. The first precursor was placed in a ball rolling machine, and during the rolling process, the first mixture and 360g of the heated organic polymer aqueous solution were added evenly. After spheroidization, the second precursor was obtained. 21.0g of corn starch was first mixed with 20g of 10wt% ammonia water, and then mixed with 300g of pseudoboehmite powder (with a specific surface area of ​​290m²). 2 The second precursor was mixed with 1.05 mL / g of organic polymer (with a pore volume of 1.05 mL / g) to obtain a second mixture. The second precursor was placed in a ball rolling mill, and during the rolling process, the second mixture and 270 g of heated organic polymer aqueous solution were added evenly. After ball forming, a third precursor was obtained. The third precursor was heat-treated at 200 °C for 4 h. Then, it was calcined at 650 °C for 3 h under a nitrogen atmosphere to obtain spherical carriers with a particle size of 0.5~0.8 mm. The carrier yield and wear data are shown in Table 1.

[0122] (2) Catalyst preparation

[0123] Dissolve 4.30 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 11.68 g of molybdenum trioxide and 5.16 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and make up to 85 mL to obtain Mo-Ni-P aqueous solution.

[0124] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 550℃ for 3h to obtain the catalyst, in which the content of MoO3 was 10.0wt%, the content of NiO was 2.5wt%, and the content of P was 1.0wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0125] (3) Catalyst evaluation

[0126] The catalyst was evaluated over a long period using a CSTR hydrogenation evaluation system, with an operating time of 1500 hours. The evaluation conditions were: reaction temperature 420℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.3 h⁻¹. -1 The hydrogen-to-oil volume ratio was 600:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0127] Table 1 Carrier yield and wear

[0128]

[0129] Table 2 Physicochemical properties of catalysts

[0130]

[0131] Table 3 Properties of Feed Oil

[0132]

[0133] Table 4 Catalyst Evaluation Results

[0134]

[0135] With the activity of Comparative Example 1 as 100, the evaluation results of the other activities compared with the Comparative Example are shown in Table 4.

[0136] Table 5. Sulfur and sediment content of the >400℃ fraction

[0137]

[0138] After cutting the oil produced in Example 1, the sulfur and sediment content of the >400℃ fraction both meet the requirements for low-sulfur marine fuel oil.

Claims

1. A method for preparing a hydrodesulfurization catalyst, comprising the following steps: (1) The organic polymer was modified with acid, and the acid-modified organic polymer was further mixed with boehmite powder to obtain the first mixture. (2) Mix an aqueous solution of amorphous silica-alumina and a heat-treated organic polymer, and then perform a pelletizing process to obtain the first precursor; (3) The first precursor obtained in step (2) is placed in a ball rolling machine, and the first mixture obtained in step (1) and the heated organic polymer aqueous solution are added evenly during the rolling process. The second precursor is obtained after treatment. (4) Mix the organic polymer, the weakly basic compound and the pseudoboehmite powder to obtain a second mixture; the weakly basic compound is one or more of ammonia, ammonium carbonate and ammonium bicarbonate. (5) The second precursor obtained in step (3) is placed in a ball rolling machine, and the second mixture obtained in step (4) and the heated organic polymer aqueous solution are added evenly during the rolling process. After treatment, the third precursor is obtained. (6) The third precursor obtained in step (5) is subjected to heat treatment. The material obtained after heat treatment is mixed with a soluble zinc salt solution, and then dried and calcined to obtain a carrier. (7) The support obtained in step (6) is introduced with hydrogenation active metal component and then dried and calcined to obtain hydrogenation desulfurization catalyst; the hydrogenation active metal component is one or more of Group VIB metals and / or Group VIII metals; the auxiliary agent P is introduced when introducing the active metal component; in, The organic polymer is one or more of starch, cellulose ether, and flour; The method for preparing an aqueous solution of heat-treated organic polymer is as follows: add the organic polymer to water, heat and mix at 60-100℃ for 10-40 minutes, and obtain an aqueous solution of heat-treated organic polymer after the organic polymer has completely dissolved.

2. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: In step (1), the organic polymer is modified with acid. After the modification is completed, the polymer is cooled, optionally washed with water, and dried to obtain the acid-modified organic polymer.

3. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: In step (1), the temperature for acid modification of the organic polymer is 30-50℃ and the modification time is 2-6 hours.

4. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The acid in step (1) is an inorganic acid or an organic acid; the organic acid is one or a mixture of two or more of citric acid, acetic acid, lactic acid, malic acid and tartaric acid; the inorganic acid is one or a mixture of two or more of hydrochloric acid, sulfuric acid and nitric acid.

5. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The acid in step (1) is an inorganic acid or an organic acid; the organic acid is citric acid; the inorganic acid is hydrochloric acid.

6. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The organic polymer is starch.

7. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The starch is one or more of mung bean starch, tapioca starch, sweet potato starch, potato starch, wheat starch, water chestnut starch, lotus root starch, and corn starch; the cellulose ether is at least one of methylcellulose, hydroxyethyl methylcellulose, carboxymethylcellulose, ethylcellulose, benzylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, cyanoethylcellulose, benzyl cyanoethylcellulose, carboxymethyl hydroxyethylcellulose, and phenylcellulose.

8. The method for preparing the hydrodesulfurization catalyst according to claim 1 or 7, characterized in that: The starch is corn starch and / or potato starch; the cellulose ether is methylcellulose.

9. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The properties of the pseudoboehmite powder in step (1) after calcination at 550–750℃ are as follows: specific surface area is 280–320 m². 2 / g, with a pore volume of 0.9~1.2mL / g.

10. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The pseudoboehmite powder in step (1) may be the same as or different from that in step (4).

11. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The amount of acid-modified organic polymer added in step (1) is 5 wt% to 35 wt% of the dry basis mass of the pseudoboehmite powder.

12. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The amount of acid-modified organic polymer added in step (1) is 10wt% to 30wt% of the dry basis mass of the pseudoboehmite powder.

13. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The properties of the amorphous silicon-aluminum in step (2) are as follows: specific surface area is 250-320 m². 2 / g, with a pore volume of 0.7 to 1.0 mL / g and a silica content of 10% to 50% by mass.

14. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The concentration of the aqueous solution of the organic polymer in step (2) is 0.5wt% to 8.0wt%.

15. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The concentration of the aqueous solution of the organic polymer in step (2) is 1.0wt% to 5.0wt%.

16. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The weakly alkaline compound in step (4) is ammonia.

17. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The concentration of the weakly alkaline compound aqueous solution in step (4) is 2wt% to 40wt%.

18. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The concentration of the weakly alkaline compound aqueous solution in step (4) is 5wt% to 35wt%.

19. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The total amount of organic polymer and weakly basic compound added in step (4) is 5 wt% to 25 wt% of the dry basis weight of the pseudoboehmite powder.

20. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The total amount of organic polymer and weakly basic compound added in step (4) is 10 wt% to 20 wt% of the dry basis mass of the pseudoboehmite powder.

21. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The heat treatment temperature in step (6) is 100 to 300°C.

22. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The heat treatment temperature in step (6) is 150 to 250°C.

23. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The soluble zinc salt in step (6) is one or more of zinc nitrate, zinc acetate, zinc chloride, and zinc sulfate.

24. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The drying temperature in step (6) is 60-120℃; the calcination in step (6) is carried out under an inert atmosphere, which is one or more of nitrogen, helium, neon, argon, krypton and xenon; the calcination temperature is 600-800℃.

25. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: Group VIB metals are Mo and / or W, and Group VIII metals are Ni and / or Co.

26. The method for preparing the hydrodesulfurization catalyst according to claim 1, characterized in that: The active metal components for hydrogenation are Mo and Ni.

27. A hydrodesulfurization catalyst obtained by the preparation method according to any one of claims 1-26.

28. The hydrodesulfurization catalyst according to claim 27, characterized in that: The catalyst comprises an active metal component, an auxiliary metal component, a support, and an auxiliary agent. The auxiliary metal component is zinc oxide, and the auxiliary agent is phosphorus pentoxide. The active metal component and the auxiliary metal component exist on the support in the form of oxides.

29. The hydrodesulfurization catalyst according to claim 28, characterized in that: The carrier is an amorphous silicon-aluminum and alumina composite carrier, which includes a core layer, an intermediate layer and an outer layer. The core layer is amorphous silicon-aluminum, the intermediate layer is alumina with mesopores, and the outer layer is alumina with macropores. Based on the weight of the carrier, the amorphous silicon-aluminum content of the core layer is 20% to 40%, the alumina content of the intermediate layer is 30% to 50%, and the alumina content of the outer layer is 10% to 40%.

30. The hydrodesulfurization catalyst according to claim 27, characterized in that: The catalyst has the following properties: specific surface area of ​​150–240 m². 2 / g, with a pore volume of 0.40 to 0.80 mL / g, the proportion of mesopores with a pore size of 10 to 50 nm to the total pore volume is 70% to 93%, and the proportion of macropores with a pore size greater than 50 nm to the total pore volume is 5% to 15%.

31. The application of the hydrodesulfurization catalyst according to any one of claims 27-30 in the heavy oil hydrotreating process.

32. The application according to claim 31, characterized in that: The heavy oil is at least one or more of atmospheric residue, vacuum residue, catalytic slurry, and coal tar.

33. The use of the hydrodesulfurization catalyst according to any one of claims 27-30 in the production of low-sulfur marine fuel oil.

Images