A heavy oil hydroprocessing catalyst, its preparation method and application

Abstract

This invention discloses a heavy oil hydrogenation catalyst, its preparation method, and its application. The preparation method includes the following steps: (1) preparing a first material; (2) preparing an acid-modified organic polymer; (3) preparing a second material; (4) preparing a third material; (5) mixing the third material obtained in step (4) with a soluble zirconium salt solution, drying and calcining the mixture to obtain a support, further introducing an active metal component onto the support, and then drying and calcining to obtain the heavy oil hydrogenation catalyst. The catalyst has a non-uniform pore distribution structure, which not only has high impurity removal and containment capacity, but also high asphaltene conversion capacity, making it particularly suitable for use in fluidized bed hydrogenation processes, or composite bed hydrogenation processes combining fluidized beds and fixed beds.

Description

Technical Field

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

[0002] With the continuous extraction of oil, my country's imported oil is becoming increasingly heavy and of lower quality, with the proportion of heavy oil increasing year by year. How to fully utilize heavy oil is key to solving energy problems and improving energy efficiency, and is a major concern for refineries. Currently, the main technologies for heavy oil processing include heavy oil hydrotreating and delayed coking, with hydrotreating technology offering higher economic benefits. The currently industrialized heavy oil hydrotreating technologies mainly include fixed-bed hydrotreating and fluidized-bed hydrotreating. The Dalian Petrochemical Research Institute has proposed a composite-bed hydrotreating technology, which combines fluidized-bed and fixed-bed systems. The fluidized-bed acts as a pre-protective reactor for the fixed-bed system, utilizing its online addition and discharge capabilities to extend the fixed-bed operating cycle to over 30 months, significantly improving the operational lifespan of the fixed-bed unit and bringing considerable economic benefits to refineries. With increasingly stringent fuel standards and environmental emission regulations, higher requirements are being placed on the aforementioned hydrotreating technologies, and improving catalyst activity is crucial to achieving these goals.

[0003] CN201810893969.4 discloses a method for preparing a fluidized bed hydrotreating catalyst. The method includes the following steps: (1) mixing boehmite with basic aluminum ammonium carbonate in a carbon precursor solution and kneading it into a mold, and then drying the molded material; (2) impregnating the material obtained in step (1) with a carbon precursor solution, and then drying and calcining the impregnated material to obtain an alumina support; (3) impregnating the alumina support obtained in step (2) with an impregnation solution containing a hydrogenation active component, and then drying and calcining the impregnated material to obtain the fluidized bed hydrotreating catalyst. The catalyst prepared by the method of the present invention has high strength and wear resistance, and is particularly suitable for the fluidized bed hydrotreating process of heavy oil. However, its carbon precursor has a weak pore-expanding effect, the catalyst's metal-containing capacity needs to be improved, and the interaction between the active metal and the alumina support is strong, resulting in low utilization.

[0004] CN103785400A discloses a method for preparing a highly active hydrodemetallization catalyst for residual oil. The method first involves hydrothermal carbonization of an alumina support, followed by drying and loading with active components Mo and Ni. The catalyst is then calcined under a nitrogen atmosphere followed by calcination under an air atmosphere to finally obtain the catalyst. The carbonization of the alumina support produces a layer of carbon deposits on its surface, resulting in weaker interaction between the active components and the support, more uniform distribution of the active components on the support, and easier complete sulfidation of the active components, significantly improving the demetallization and desulfurization activity of the catalyst. However, the catalyst prepared by this method has a relatively weak interaction between the active components and the support, and its metal-containing capacity needs improvement, both of which directly affect the long-term stability of the catalyst. Summary of the Invention

[0005] This invention provides a heavy oil hydrogenation catalyst, its preparation method, and its application. The provided catalyst has a non-uniform pore distribution structure, which not only has high impurity removal and containment capacity but also high asphaltene conversion capacity. It is particularly suitable for use in fluidized bed hydrogenation processes or composite bed hydrogenation processes combining fluidized and fixed beds, providing high-quality feedstock for downstream units and ensuring long-term stable operation of the units.

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

[0007] (1) Preparation of the first material: Boehmite powder, organic polymer and weak alkaline compound are mixed and stirred to obtain the first material;

[0008] (2) The organic polymer was modified with acid to obtain acid-modified organic polymer.

[0009] (3) Preparation of the second material: The pseudo-boehmite powder, the acid-modified organic polymer obtained in step (2) and the organic polymer aqueous solution after heat treatment are mixed and sphere-shaped to obtain the second material;

[0010] (4) Preparation of the third material: The second material obtained in step (3) is placed in the ball rolling machine, and the first material obtained in step (1) and the organic polymer aqueous solution after heat treatment are added evenly during the rolling process. The material obtained is then heat-treated to obtain the third material.

[0011] (5) The third material obtained in step (4) is mixed with a soluble zirconium salt solution. After the mixture is evenly mixed, it is dried once and calcined once to obtain a support. The active metal component is further introduced onto the support and then dried and calcined twice to obtain a heavy oil hydrogenation catalyst.

[0012] Furthermore, according to a specific embodiment of the present invention, the weakly alkaline compound in step (1) is one or a mixture of two or more of ammonia, ammonium carbonate, and ammonium bicarbonate, preferably ammonia. Even further, the concentration of the ammonia is 1wt% to 20wt%, preferably 5wt% to 15wt%.

[0013] Furthermore, according to a specific embodiment of the present invention, the mass ratio of the organic polymer and the weakly basic compound in step (1) is 1:0.05 to 1:0.5.

[0014] Furthermore, according to a specific embodiment of the present invention, the total amount of organic polymer and weakly basic compound added in step (1) is 5wt% to 25wt% of the dry basis mass of boehmite powder, preferably 10wt% to 20wt%.

[0015] Furthermore, according to a specific embodiment of the present invention, when mixing the organic polymer, the weakly basic compound, and the pseudoboehmite powder in step (1), it is preferable to first mix the organic polymer and the weakly basic compound, and then mix them with the pseudoboehmite powder.

[0016] Furthermore, according to a specific embodiment of the present invention, the organic polymer can be selected from one or more of starch, cellulose ether, and flour, preferably starch. Even further, 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, 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.

[0017] Furthermore, according to a specific embodiment of the present invention, the acid mentioned in step (2) is an inorganic acid or an organic acid; wherein, the inorganic acid is one or a mixture of two or more of hydrochloric acid, sulfuric acid, and nitric acid, preferably hydrochloric 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, preferably citric acid.

[0018] Furthermore, according to a specific embodiment of the present invention, in step (2), the organic polymer is modified by acid, and after the treatment is completed, it is cooled, optionally washed with water, and dried to obtain the acid-modified organic polymer.

[0019] Furthermore, according to a specific embodiment of the present invention, the acid modification treatment temperature for the organic polymer in step (2) is 30-50°C; the modification treatment time is 2-6 hours.

[0020] Furthermore, according to a specific embodiment of the present invention, the concentration of the acidic solution in step (2) is 5wt% to 40wt%; the mass ratio of the organic polymer to the acid is 1:0.1 to 1:5.

[0021] Furthermore, according to a specific embodiment of the present invention, the pseudoboehmite powder, after being calcined at 550–750°C, has the following properties: a specific surface area of ​​260–350 m². 2 / g, with a pore volume of 0.7-1.2 mL / 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.

[0022] Furthermore, according to a specific embodiment of the present invention, the amount of acid-modified organic polymer added in step (3) is 5wt% to 35wt% of the dry basis mass of the pseudoboehmite powder, preferably 10wt% to 30wt%.

[0023] Furthermore, according to a specific embodiment of the present invention, the mass concentration of the organic polymer aqueous solution after heat treatment in step (3) is 0.5wt% to 8.0wt%, preferably 1.0wt% to 5.0wt%. The specific preparation process is as follows: the organic polymer is added to water and heated and mixed at 60 to 100°C for 10 to 40 minutes. After the organic polymer is completely dissolved, the heat-treated organic polymer aqueous solution is obtained.

[0024] Furthermore, according to a specific embodiment of the present invention, the amount of the organic polymer aqueous solution after heat treatment added in step (3) is 0.5 to 1.5 times the mass ratio of the pseudoboehmite powder.

[0025] Furthermore, according to a specific embodiment of the present invention, the spherical forming in step (3) can be any of the existing spherical forming methods in the art, specifically one or more of extrusion ball-throwing forming, rolling forming, and spray drying forming methods.

[0026] Furthermore, according to a specific embodiment of the present invention, the amount of organic polymer aqueous solution added in step (4) is in a mass ratio of 0.5 to 1.2 to the first material.

[0027] Furthermore, according to a specific embodiment of the present invention, the heat treatment temperature in step (4) is 100-300°C, preferably 150-250°C; and the treatment time is 3-12 hours.

[0028] Furthermore, according to a specific embodiment of the present invention, the soluble zirconium salt mentioned in step (5) is one or more of zirconium nitrate, zirconium chloride, zirconium sulfate, etc.

[0029] Furthermore, according to a specific embodiment of the present invention, the primary drying temperature in step (5) is 60-120°C.

[0030] Furthermore, according to a specific embodiment of the present invention, the first calcination in step (5) is carried out under an inert atmosphere, which is one or more of nitrogen, helium, neon, argon, krypton, and xenon, preferably nitrogen; the first calcination temperature is 700-900°C, and the first calcination time is 1-5 hours.

[0031] Furthermore, according to a specific embodiment of the present invention, the introduction of the active metal component in step (5) can be carried out by any one or more of the methods existing in the art, specifically by at least one of the methods such as kneading and impregnation, with impregnation being preferred.

[0032] Furthermore, according to a specific embodiment of the present invention, the active metal component in step (5) 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 is preferably Mo and Ni.

[0033] Furthermore, according to a specific embodiment of the present invention, when introducing the active metal component in step (5), an auxiliary agent P may also be introduced.

[0034] Furthermore, according to a specific embodiment of the present invention, the secondary drying in step (5) is drying at 80-120°C for 4-12 hours.

[0035] Furthermore, according to a specific embodiment of the present invention, the secondary roasting temperature in step (5) is 400-600°C, and the secondary roasting time is 1-5 hours.

[0036] Furthermore, according to a specific embodiment of the present invention, when the active metal component in step (5) is impregnated, 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 hydrogenated 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 and a tungsten-containing compound, and the Group VIII metal-containing compound can be one or more of a nickel-containing compound and 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.

[0037] A second aspect of the present invention provides a heavy oil hydrogenation catalyst prepared by the above-described method.

[0038] Furthermore, in the above-mentioned heavy oil hydrogenation catalyst, the heavy oil hydrogenation catalyst includes a support, an active metal component, an auxiliary metal component, and optional auxiliary agents. The active metal component is one or more of Group VIB metals and / or Group VIII metals, the auxiliary metal component is zirconium oxide, the auxiliary agent is phosphorus pentoxide, and the support is alumina support.

[0039] Furthermore, in the above-mentioned heavy oil hydrogenation catalyst, the support is a core-shell structure, with the core support being mesoporous alumina and the shell support being macroporous alumina; based on the weight of the support, the content of core alumina is 30% to 70%, and the content of shell alumina is 30% to 70%.

[0040] Furthermore, in the above-mentioned heavy oil hydrogenation catalyst, the active metal component exists on the support in the form of oxides.

[0041] Furthermore, in the above-mentioned heavy oil hydrotreating catalyst, based on the weight of the catalyst and calculated as oxides, the content of the Group VIB metal component is 4wt% to 8wt%; the content of the Group VIII metal component is 1.0wt% to 3wt%; and the content of the auxiliary agent phosphorus pentoxide is 0.9wt% to 2.0wt%.

[0042] Furthermore, the properties of the above-mentioned heavy oil hydrotreating catalyst are as follows: specific surface area of ​​140–200 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%–90% of the total pore volume, while macropores with a pore size greater than 50 nm account for 5%–25% of the total pore volume.

[0043] A third aspect of the present invention provides a method for hydrogenating heavy oil, wherein heavy oil and hydrogen are mixed and hydrogenated in the presence of the above-mentioned heavy oil hydrogenation catalyst to carry out a hydrogenation reaction.

[0044] Furthermore, in the above-mentioned heavy oil hydrogenation method, the heavy oil is at least one or more of atmospheric residue, vacuum residue, catalytic slurry, and coal tar.

[0045] Furthermore, in the above-mentioned heavy oil hydrogenation method, the hydrogenation reaction process conditions are as follows: reaction pressure of 10–20 MPa, temperature of 300–500 °C, and liquid hourly space velocity of 0.1–0.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300–800.

[0046] Compared with existing technologies, the heavy oil hydrogenation catalyst, its preparation method, and its application provided by this invention have the following advantages:

[0047] 1. In the preparation method of the heavy oil hydrogenation catalyst of the present invention, organic polymer A is acid-modified, resulting in smaller molecules and weaker adhesion. When mixed with boehmite powder, it can increase the proportion of mesopores in the core layer alumina support. Organic polymer B is heat-treated and decomposes into small molecules in water, giving the aqueous solution high adhesion. This can enhance the interaction force between boehmite powders and improve the strength and wear resistance of the support. Organic polymer C does not change in molecular size after reacting with a weak base compound, but its adhesion deteriorates. When mixed with boehmite powder, it can increase the proportion of macropores in the shell layer alumina support.

[0048] 2. In the preparation method of the heavy oil hydrogenation catalyst of the present invention, the second support precursor is subjected to low-temperature heat treatment. The ammonia in the weak base compound that reacts with the organic polymer C phase will volatilize and be adsorbed by interacting with the strong acid sites on the alumina. The addition of soluble zirconium 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 support alumina and improve the utilization rate of the active metal.

[0049] 3. In the preparation method of the heavy oil hydrogenation catalyst of the present invention, the organic polymer C is calcined under an inert atmosphere or a nitrogen atmosphere to become a macroporous carbon material. Since the macroporous carbon material has a low water absorption rate, its presence reduces the water absorption rate of the outer alumina support. During the impregnation process of the active metal, the outer alumina support adsorbs relatively less active metal, while the core alumina support adsorbs relatively more active metal. The resulting catalyst exhibits a non-uniform distribution of active metal, with a relatively higher concentration of active metal inside and a relatively lower concentration on the outside, resulting in a gradient distribution of the catalyst's hydrogenation activity. The outer layer of the catalyst effectively removes impurities such as metals, sulfur, and nitrogen from the heavy oil, protecting the inner layer, while the inner layer further removes various impurities from the heavy oil.

[0050] 4. In the preparation method of the heavy oil hydrogenation catalyst of the present invention, the catalyst has a core-shell structure with different pore size distribution and activity distribution. The catalyst shell can effectively remove impurities and perform preliminary conversion of asphaltenes in heavy oil, while the catalyst core can further remove impurities and perform further conversion of asphaltenes in heavy oil, reducing the sediment content in the generated oil. This achieves the stepwise removal of impurities and the gradual conversion of asphaltenes in heavy oil, and is particularly suitable for fluidized bed hydrogenation process and composite bed hydrogenation process. Detailed Implementation

[0051] 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.

[0052] 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.

[0053] 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.

[0054] Example 1

[0055] (1) Carrier preparation

[0056] First, mix 42.0g of corn starch with 40g of 10wt% ammonia water, then mix with 600g of pseudoboehmite powder (specific surface area 300m²). 2Mixing (g, pore volume 1.05 mL / g) yields the first material. Mixing 42 g corn starch, 42 g citric acid, and 140 g water, and heating to 40°C for 3 hours, followed by filtration and washing, and drying at 40°C for 24 hours yields the acid-modified organic polymer. Weighing 80 g corn starch and adding it to 2000 g water, heating at 70°C for 20 minutes yields the heat-treated organic polymer aqueous solution. Adding 400 g of pseudoboehmite powder (specific surface area 300 μm)... 2 The first material and 540g of the heated organic polymer aqueous solution were mixed and spherically shaped to obtain the second material. The second material was then placed in a ball rolling mill, and the first material and 540g of the heated organic polymer aqueous solution were uniformly added during the rolling process to form spheres. The resulting material was heat-treated at 200℃ for 4 hours; then mixed with 360mL of an aqueous solution containing 29.3g of zirconium nitrate, dried at 90℃ for 8 hours, and then calcined at 750℃ for 3 hours 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.

[0057] (2) Catalyst preparation

[0058] Dissolve 2.43 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 8.59 g of molybdenum trioxide and 2.91 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and bring the volume to 85 mL to obtain the Mo-Ni-P aqueous solution.

[0059] 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 6.0wt%, the content of NiO was 1.5wt%, and the content of P was 0.6wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0060] (3) Catalyst evaluation

[0061] 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 400℃, 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.

[0062] Example 2

[0063] (1) Carrier preparation

[0064] First, mix 52.5g of corn starch with 50g of 10wt% ammonia solution, then mix with 500g of pseudoboehmite powder (specific surface area 300m²). 2 Mixing (g, pore volume 1.05 mL / g) yields the first material. Mixing 70 g corn starch, 70 g citric acid, and 240 g water, and heating to 40°C for 3 hours, followed by filtration and washing, and drying at 40°C for 24 hours yields the acid-modified organic polymer. Weighing 80 g corn starch and adding it to 2000 g water, heating at 70°C for 20 minutes yields the heat-treated organic polymer aqueous solution. Adding 500 g of pseudoboehmite powder (specific surface area 300 μm)... 2 The first material and 450g of the heated organic polymer aqueous solution were mixed (with a pore volume of 1.05mL / g), acid-modified organic polymer, and 450g of the heated organic polymer aqueous solution. The mixture was then spheroidized to obtain the second material. The second material was placed in a ball rolling mill, and the first material and 450g of the heated organic polymer aqueous solution were uniformly added during the rolling process to form spheres. The resulting material was heat-treated at 200℃ for 4 hours; then mixed with 300mL of an aqueous solution containing 24.4g of zirconium nitrate, dried at 90℃ for 8 hours, and then calcined at 800℃ for 3 hours 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.

[0065] (2) Catalyst preparation

[0066] Dissolve 2.43 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 8.59 g of molybdenum trioxide and 2.91 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and bring the volume to 85 mL to obtain the Mo-Ni-P aqueous solution.

[0067] 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 6.0wt%, the content of NiO was 1.5wt%, and the content of P was 0.6wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0068] (3) Catalyst evaluation

[0069] 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 400℃, 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.

[0070] Example 3

[0071] (1) Carrier preparation

[0072] First, mix 56.0g of corn starch with 54g of 10wt% ammonia solution, then mix with 400g of pseudoboehmite powder (specific surface area 300m²). 2 Mixing (g, pore volume 1.05 mL / g) yields the first material. Mixing 105 g corn starch, 105 g citric acid, and 350 g water, and heating to 40°C for 3 hours, followed by filtration and washing, and drying at 40°C for 24 hours yields the acid-modified organic polymer. Weighing 80 g corn starch and adding it to 2000 g water, heating at 70°C for 20 minutes yields the heat-treated organic polymer aqueous solution. Adding 600 g of pseudoboehmite powder (specific surface area 300 μm)... 2 The first material (containing 19.5 g zirconium nitrate, 1.05 mL / g pore volume), an acid-modified organic polymer, and 540 g of a heat-treated organic polymer aqueous solution were mixed and then spheroidized to obtain the second material. The second material was placed in a ball rolling mill, and the first material and 360 g of the heat-treated organic polymer aqueous solution were uniformly added during the rolling process to form spheres. The resulting material was heat-treated at 200℃ for 4 h; then mixed with 240 mL of an aqueous solution containing 19.5 g zirconium nitrate, dried at 90℃ for 8 h, and then calcined at 800℃ 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.

[0073] (2) Catalyst preparation

[0074] Dissolve 2.43 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 8.59 g of molybdenum trioxide and 2.91 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and bring the volume to 85 mL to obtain the Mo-Ni-P aqueous solution.

[0075] 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 6.0wt%, the content of NiO was 1.5wt%, and the content of P was 0.6wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0076] (3) Catalyst evaluation

[0077] 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 400℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.3 h⁻¹. -1The 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.

[0078] Example 4

[0079] 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 6.0 wt%, the content of NiO was 1.5 wt%, and the content of P was 0.6 wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0080] 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.

[0081] Example 5

[0082] The preparation was essentially the same as in Example 3, except that 56g of corn starch was replaced with 47.19g of methylcellulose, 105g of corn starch with 88.48g of methylcellulose, and 80g of corn starch with 67.41g 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 6.0wt% MoO3, 1.5wt% NiO, and 0.6wt% P. The physicochemical properties of the catalyst are shown in Table 2.

[0083] 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.

[0084] Example 6

[0085] (1) Carrier preparation

[0086] This is essentially the same as Example 3, except that 105g of citric acid and 350g of water are replaced with 350g of a 15% hydrochloric acid aqueous solution, 19.5g of zirconium nitrate is replaced with 16.2g of zirconium sulfate, and the 0.5~0.8mm spherical support is replaced with a 1.2~1.5mm spherical support. The support yield and wear data are shown in Table 1.

[0087] (2) Catalyst preparation

[0088] Dissolve 3.34 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 9.06 g of molybdenum trioxide and 4.01 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and bring the volume to 85 mL to obtain the Mo-Ni-P aqueous solution.

[0089] 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 8.0wt% MoO3, 2.0wt% NiO, and 0.8wt% P. The physicochemical properties of the catalyst are shown in Table 2.

[0090] 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.

[0091] Comparative Example 1

[0092] (1) Carrier preparation

[0093] First, mix 42.0g of corn starch with 40g of 10wt% ammonia water, then mix with 600g of pseudoboehmite powder (specific surface area 300m²). 2 Mixing (g, pore volume 1.05 mL / g) yields the first material. Mixing 42 g corn starch, 42 g citric acid, and 140 g water, and heating to 40°C for 3 hours, followed by filtration and washing, and drying at 40°C for 24 hours yields the acid-modified organic polymer. Adding 400 g of pseudoboehmite powder (specific surface area 300 μm)... 2 A mixture of 14.4 g corn starch and 360 g water (containing a pore volume of 1.05 mL / g), acid-modified organic polymer, and 14.4 g corn starch was then spheroidized to obtain a second material. This second material was placed in a ball-rolling machine, and during the rolling process, the first material, 21.6 g corn starch, and 540 g water were uniformly added to form spheres. The resulting material was then heat-treated at 200℃ for 4 hours; subsequently, it was mixed with 360 mL of an aqueous solution containing 29.3 g zirconium nitrate, dried at 90℃ for 8 hours, and then calcined at 750℃ for 3 hours 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.

[0094] (2) Catalyst preparation

[0095] Dissolve 2.43 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 8.59 g of molybdenum trioxide and 2.91 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and bring the volume to 85 mL to obtain the Mo-Ni-P aqueous solution.

[0096] 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 6.0wt%, the content of NiO was 1.5wt%, and the content of P was 0.6wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0097] (3) Catalyst evaluation

[0098] 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 400℃, 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.

[0099] Comparative Example 2

[0100] (1) Carrier preparation

[0101] Mix 42.0g of corn starch with 600g of pseudoboehmite powder (specific surface area 300m). 2 Mix (g, pore volume 1.05 mL / g) to obtain the first material. 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 400 g of pseudoboehmite powder (specific surface area 300 μm) 2 42g of corn starch and 360g of a heat-treated organic polymer aqueous solution were mixed and then spheroidized to obtain a second material. The second material was placed in a ball rolling machine, and during the rolling process, the first material and 540g of the heat-treated organic polymer aqueous solution were uniformly added to form spheres. The resulting material was heat-treated at 200℃ for 4 hours; then mixed with 360mL of an aqueous solution containing 29.3g of zirconium nitrate, dried at 90℃ for 8 hours, and then calcined at 750℃ for 3 hours 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.

[0102] (2) Catalyst preparation

[0103] Dissolve 2.43 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 8.59 g of molybdenum trioxide and 2.91 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and bring the volume to 85 mL to obtain the Mo-Ni-P aqueous solution.

[0104] 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 6.0wt%, the content of NiO was 1.5wt%, and the content of P was 0.6wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0105] (3) Catalyst evaluation

[0106] 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 400℃, 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.

[0107] Table 1 Carrier yield and wear

[0108]

[0109] Table 2 Physicochemical properties of catalysts

[0110]

[0111] Table 3 Properties of Feed Oil

[0112]

[0113] Table 4 Catalyst Evaluation Results

[0114]

[0115] 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.

Claims

1. A method for preparing a heavy oil hydrotreating catalyst, comprising the following steps: (1) Preparation of the first material: Boehmite powder, organic polymer and weak alkaline compound are mixed and mixed to obtain the first material; the weak alkaline compound is one or more of ammonia water, ammonium carbonate and ammonium bicarbonate. (2) The organic polymer was modified with acid to obtain acid-modified organic polymer. (3) Preparation of the second material: The pseudo-boehmite powder, the acid-modified organic polymer obtained in step (2) and the organic polymer aqueous solution after heat treatment are mixed and sphere-shaped to obtain the second material; (4) Preparation of the third material: The second material obtained in step (3) is placed in the ball rolling machine, and the first material obtained in step (1) and the organic polymer aqueous solution after heat treatment are added evenly during the rolling process. The material obtained is then heat-treated to obtain the third material. (5) The third material obtained in step (4) is mixed with a soluble zirconium salt solution. After mixing evenly, the mixture is dried once and calcined once to obtain a support. The active metal component is further introduced onto the support and then dried and calcined twice to obtain a heavy oil hydrogenation catalyst. The active metal component is one or more of Group VIB metals and / or Group VIII metals. in, The organic polymer is selected from one or more of starch, cellulose ether and flour; the preparation process of the heat-treated organic polymer aqueous solution is as follows: add the organic polymer to water, heat and mix at 60-100℃ for 10-40 minutes, and obtain the heat-treated organic polymer aqueous solution after the organic polymer is completely dissolved.

2. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The weakly alkaline compound in step (1) is ammonia.

3. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The mass ratio of the organic polymer and the weakly basic compound in step (1) is 1:0.05 to 1:0.

5.

4. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The total amount of organic polymer and weakly basic compound added in step (1) is 5 wt% to 25 wt% of the dry basis mass of the pseudoboehmite powder.

5. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The total amount of organic polymer and weakly basic compound added in step (1) is 10 wt% to 20 wt% of the dry basis mass of the pseudoboehmite powder.

6. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, In step (1), when mixing the organic polymer, the weak alkaline compound, and the pseudoboehmite powder, the organic polymer and the weak alkaline compound are mixed first, and then mixed with the pseudoboehmite powder.

7. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The organic polymer is starch.

8. The method for preparing the heavy oil hydrogenation catalyst according to claim 1 or 7, wherein, 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.

9. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The starch is corn starch and / or potato starch; the cellulose ether is methylcellulose.

10. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The acid in step (2) is an inorganic acid or an organic acid; wherein the inorganic acid is one or a mixture of two or more of hydrochloric acid, sulfuric acid and nitric acid; and the organic acid is one or a mixture of two or more of citric acid, acetic acid, lactic acid, malic acid and tartaric acid.

11. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The acid in step (2) is an inorganic acid or an organic acid; the inorganic acid is hydrochloric acid; the organic acid is citric acid.

12. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, In step (2), the acid modification treatment temperature for the organic polymer is 30-50℃, and the modification treatment time is 2-6 hours.

13. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, In step (2), the concentration of acid is 5wt% to 40wt%; the mass ratio of organic polymer to acid is 1:0.1 to 1:

5.

14. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The amount of acid-modified organic polymer added in step (3) is 5 wt% to 35 wt% of the dry basis weight of the pseudoboehmite powder.

15. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The amount of acid-modified organic polymer added in step (3) is 10wt% to 30wt% of the dry basis mass of the pseudoboehmite powder.

16. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The mass concentration of the organic polymer aqueous solution after heat treatment in step (3) is 0.5wt% to 8.0wt%.

17. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The mass concentration of the organic polymer aqueous solution after heat treatment in step (3) is 1.0wt% to 5.0wt%.

18. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The ratio of the amount of the organic polymer aqueous solution after heat treatment in step (3) to the mass ratio of the pseudoboehmite powder is 0.5 to 1.

5.

19. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The ratio of the amount of the heated organic polymer aqueous solution added in step (4) to the mass of the first material is 0.5 to 1.

2.

20. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The heat treatment temperature in step (4) is 100-300℃ and the heat treatment time is 3-12h.

21. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The heat treatment temperature in step (4) is 150-250℃; the heat treatment time is 3-12h.

22. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The soluble zirconium salt mentioned in step (5) is one or more of zirconium nitrate, zirconium chloride, and zirconium sulfate.

23. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The drying temperature in step (5) is 60-120℃.

24. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The first roasting in step (5) is carried out under an inert atmosphere, which is one or more of nitrogen, helium, neon, argon, krypton and xenon; the first roasting temperature is 700-900℃ and the first roasting time is 1-5h.

25. The method for preparing the heavy oil hydrogenation catalyst according to claim 24, wherein, The inert atmosphere is nitrogen.

26. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, Group VIB metals are Mo and / or W, and Group VIII metals are Ni and / or Co.

27. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, In step (5), an auxiliary agent P is introduced when introducing the active metal component.

28. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The secondary drying in step (5) is to dry at 80-120℃ for 4-12 hours; the secondary roasting temperature in step (5) is 400-600℃ and the secondary roasting time is 1-5 hours.

29. A heavy oil hydrogenation catalyst obtained by the preparation method according to any one of claims 1-28.

30. A method for hydrogenating heavy oil, wherein heavy oil and hydrogen are mixed and hydrogenated in the presence of a heavy oil hydrogenation catalyst obtained by any one of the preparation methods described in claims 1-28, and the hydrogenation reaction is carried out.

Images