A heavy oil hydrotreating catalyst and its preparation method and application

Abstract

The present invention discloses a heavy oil hydroprocessing catalyst, its preparation method, and its application. The catalyst comprises a carrier and an active metal component; the carrier comprises macroporous alumina and modified diatomaceous earth; the modified diatomaceous earth is diatomaceous earth coated with a modified metal component; the modified metal component is at least one of alumina and titanium dioxide. When used in heavy oil hydrogenation reactions, this catalyst can reduce the diffusion resistance of asphaltene macromolecules within the catalyst pores, enhance the accessibility of macromolecules to active centers, thereby improving the hydrogenation conversion capacity of asphaltene macromolecules and mitigating the negative effects of coking.

Description

Technical Field

[0001] The present invention relates to a heavy oil hydroprocessing catalyst and a preparation method and application thereof, in particular to a residual oil hydroprocessing catalyst for removing asphaltene and colloid macromolecules and a preparation method and application thereof. Background Art

[0002] Heavy oil, especially residual oil, contains significant amounts of impurities such as sulfur, nitrogen, and metals, as well as undesirable components such as condensed aromatics, resins, and asphaltenes. The primary purpose of heavy oil hydrotreating, particularly residual oil hydrotreating, is to remove these impurities, improve oil quality, and ensure further processing.

[0003] Fixed-bed residue hydrotreating is a commonly used heavy oil deep processing technology. In a fixed-bed reactor loaded with a specific catalyst, atmospheric or vacuum residues are desulfurized, denitrogenated, and demetallized under high-temperature, high-pressure hydrogenation conditions to maximize the production of lightweight products. This technology is a key method for lightweighting residues. Its advantages, such as high liquid product yields and high product quality, have led to its increasing application.

[0004] Despite its numerous advantages, fixed-bed residue oil hydrotreating technology is prone to experiencing increased pressure drop in individual reactors during actual industrial operation, leading to unstable plant operation. This is primarily due to the high viscosity and high concentrations of metallic impurities and asphaltenes found in heavy oil products. During the hydrogenation process, these metals and coke gradually deposit on the catalyst, causing rapid catalyst deactivation, bed clogging, and increased pressure. In particular, the asphaltenes and colloidal macromolecules in the residue oil are enriched with large amounts of metals and coking precursors, which directly affect catalyst deactivation. This ultimately leads to plant shutdowns and catalyst replacements due to pressure drop reaching the design value or insufficient catalyst reactivity, shortening the catalyst's online lifespan.

[0005] Therefore, how to effectively hydrogenate asphaltene and resin macromolecules and slow down the rapid deactivation of catalysts caused by their coking remains a very important research topic in the heavy oil hydrotreating process. Summary of the Invention

[0006] To address the shortcomings of existing technologies in hydrogenating heavy components in residual oil, particularly the insufficient hydrogenation conversion capacity of asphaltene and resin macromolecules, a hydroprocessing catalyst, its preparation method, and its application are provided. This catalyst, when applied to heavy oil hydrogenation reactions, can reduce the diffusion resistance of asphaltene macromolecules within the catalyst pores, enhance the accessibility of macromolecules to active centers, thereby improving the hydrogenation conversion capacity of asphaltene macromolecules and mitigating the negative effects of coking.

[0007] The first aspect of the present invention is to provide a heavy oil hydroprocessing catalyst, which includes a carrier and an active metal component; the carrier includes macroporous alumina and modified diatomaceous earth; the modified diatomaceous earth is diatomaceous earth with a modified metal component coated on its surface; the modified metal component is at least one of alumina and titanium dioxide.

[0008] In the above technical solution, the modified metal components are titanium dioxide and aluminum oxide; preferably, the weight ratio of titanium dioxide to aluminum oxide is 1:1 to 10, more preferably 1:1 to 6.

[0009] In the above technical solution, in the modified diatomaceous earth, the content of the modified metal component in the modified diatomaceous earth is 2 wt% to 20 wt%.

[0010] In the above technical solution, the active metals include at least one metal from Group VIII and at least one metal from Group VIB. The Group VIII metal is preferably nickel and / or cobalt. The Group VIB metal is preferably molybdenum and / or tungsten, more preferably molybdenum. Based on the mass of the catalyst, the Group VIB metal content, calculated as oxide, is 5% to 15%, preferably 8.0% to 14.0%; and the Group VIII metal content, calculated as oxide, is 1.0% to 4.0%, preferably 1.5% to 3.0%.

[0011] In the above technical solution, the weight ratio of macroporous alumina to modified diatomaceous earth in the carrier is 15-65:70-150.

[0012] In the above technical solution, the properties of the carrier are as follows: the specific surface area is 80 to 200 m 2 / g, preferably 100-170m 2 / g. Pore volume is 0.80~0.95cm 3 / g, preferably 0.82 to 0.90 cm 3 / g. The water absorption rate is 1.00 to 1.30, preferably 1.10 to 1.25.

[0013] In the above technical solution, the carrier is in granular form, the cross-section of the granules is a clover-shaped shape, and the diameter of the circumscribed circle of the granules is 1.3 to 4.0 mm, preferably 1.8 to 3.0 mm.

[0014] In the above technical solution, the void ratio of the catalyst when packed in the bag is greater than 48.0%, preferably the void ratio is 49% to 53%, and more preferably the void ratio is 50% to 52%.

[0015] In the above technical solution, the catalyst is in granular form, the cross-section of the particles is a clover-shaped particle, and the diameter of the circumscribed circle of the particles is 1.3 to 4.0 mm, preferably 1.8 to 3.0 mm.

[0016] In the above technical solution, the specific surface area of the catalyst is 60 to 160 m 2 / g, preferably 60 to 140 m 2 / g; pore volume is 0.65~0.90cm 3 / g, preferably 0.70 to 0.85 cm 3 / g.

[0017] The second aspect of the present invention is to provide a method for preparing the above-mentioned hydroprocessing catalyst, comprising the following steps:

[0018] (1) taking modified diatomite and macroporous pseudo-boehmite, adding an extrusion aid, a pore-enlarging agent, an adhesive, and water, kneading and forming, drying, and calcining to obtain a catalyst carrier;

[0019] (2) preparing an impregnation solution containing an organic acid and an active metal;

[0020] (3) The carrier of step (1) is impregnated with the impregnation solution of step (2), and the carrier is dried and calcined to obtain a hydroprocessing catalyst.

[0021] In the above technical solution, the modified diatomaceous earth in step (1) is diatomaceous earth with a modified metal component on its surface; the modified metal component is at least one of aluminum oxide and titanium dioxide.

[0022] In the above technical solution, the modified metal components in the modified diatomaceous earth in step (1) are titanium dioxide and aluminum oxide; preferably, the weight ratio of titanium dioxide to aluminum oxide is 1:1 to 10, preferably 1:1 to 6.

[0023] In the above technical solution, the preparation method of the modified diatomaceous earth in step (1) is: mixing diatomaceous earth and a modified metal source, adding ammonia water for treatment, and drying the filter cake obtained by solid-liquid separation to obtain modified diatomaceous earth, that is, diatomaceous earth with a modified metal component on its surface.

[0024] In the above technical solution, the modified metal source in the preparation method of modified diatomite is at least one of a titanium source and an aluminum source, preferably a titanium source and an aluminum source. More preferably, the weight ratio of the titanium source to the aluminum source, calculated as oxides, is 1:1 to 10, preferably 1:1 to 6. The titanium source is at least one of titanium tetrachloride and titanyl sulfate, preferably titanyl sulfate. The aluminum source is at least one of aluminum chloride and aluminum hydroxide, preferably aluminum chloride. The raw material feed ratio is: 150 to 300 parts diatomite; 20 to 80 parts modified metal source; 300 to 600 parts ammonia solution, by weight. The concentration of the ammonia solution is 2 wt% to 20 wt%.

[0025] In the above technical solution, the addition of aqueous ammonia to the modified diatomaceous earth is performed with stirring; the treatment temperature is 40-60°C, and the treatment time is 50-90 minutes. The solid-liquid separation is performed using conventional methods. Preferably, washing is performed after solid-liquid separation until the filtrate has a pH of 5-6. The resulting filter cake is dried and pulverized before use. The drying process is preferably performed at 120-130°C for 100-160 minutes.

[0026] In the above technical solution, the macroporous pseudo-boehmite in step (1) is preferably produced by the aluminum sulfate method, and the pore volume is greater than or equal to 1.08 cm 3 / g, preferably 1.15 to 1.50 cm 3 / g. In step (1), the pore-enlarging agent is one or more of carbon black, ammonium bicarbonate, urea, starch, etc., preferably one or two of ammonium bicarbonate and urea. The adhesive is hydroxypropyl methylcellulose. The extrusion aid is sesbania powder. The water is deionized water. The raw materials in step (1) are fed in a ratio of 70 to 150 parts by weight of modified diatomaceous earth, 20 to 90 parts of macroporous pseudo-boehmite, 1 to 7 parts of adhesive, 1 to 7 parts of pore-enlarging agent, 1 to 5 parts of extrusion aid, and 250 to 350 parts of water.

[0027] In the above technical solution, the kneading process in step (1) can be performed by rolling or kneading, preferably kneading. The kneading time is 10 to 80 minutes, preferably 15 to 40 minutes. The forming is performed to form a granular material, the cross-sectional shape of the granules is a clover-shaped shape, and the diameter of the circumscribed circle of the granules is 1.3 to 4.0 mm, preferably 1.8 to 3.0 mm.

[0028] In the above technical solution, the drying in step (1) is performed at 90-140°C for 40-360 minutes, preferably at 100-135°C for 60-240 minutes. The calcination is performed at a heating rate of 3.5-10°C / min, preferably 3.5-6°C / min, and a constant temperature of 700-950°C, preferably 740-900°C, for 1.5-5 hours.

[0029] In the above technical solution, the active metal in step (2) includes at least one metal selected from Group VIII and at least one metal selected from Group VIB. The Group VIII metal is preferably nickel and / or cobalt. The Group VIB metal is preferably molybdenum and / or tungsten, and more preferably molybdenum. The active metal content in the impregnation solution is calculated as oxide, wherein the Group VIB metal is preferably molybdenum, with a content of 40 to 200 g / L, preferably 60 to 160 g / L, and more preferably 60 to 130 g / L; the Group VIII metal is preferably nickel and / or cobalt, with a content of 10 to 50 g / L, preferably 15 to 40 g / L, and more preferably 18 to 30 g / L.

[0030] In the above technical solution, the impregnation liquid in step (2) further contains a surfactant; the surfactant is one or more of Tween-20, Tween-30, Tween-40, Tween-60, Tween-80 and Tween-85, preferably Tween-60 and / or Tween-80; the content of the surfactant in the impregnation liquid is 5 to 100 g / L, preferably 10 to 30 g / L.

[0031] In the above technical solution, the organic acid in the impregnation solution in step (2) is one or more of fumaric acid, adipic acid, tartaric acid, citric acid, oxalic acid, acetic acid, salicylic acid, and malic acid, preferably citric acid. The content of the organic acid in the impregnation solution is 5 to 120 g / L, preferably 10 to 40 g / L.

[0032] In the above technical solution, the ratio of the impregnation liquid to the carrier in step (3) is (1-1.4) mL:1 g. In other words, 1-1.4 mL of impregnation liquid is required for every gram of carrier.

[0033] In the above technical solution, the drying in step (3) is performed at a temperature of 110-140° C. for 2.0-5.0 h. The calcination is performed at a temperature of 400-600° C. for 2.0-5.0 h.

[0034] The third aspect of the present invention is to provide the use of the above catalyst or the catalyst prepared by the above method in heavy oil hydroprocessing reaction.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) In the present invention, the heavy oil hydroprocessing catalyst comprises a support and an active metal component; the support comprises macroporous alumina and modified diatomaceous earth; the modified diatomaceous earth is diatomaceous earth coated with alumina and / or titanium dioxide. The catalyst prepared by the present invention is particularly suitable for the hydrogenation conversion of asphaltene and colloidal macromolecules in the feedstock during heavy oil hydroprocessing. The preparation process of the present invention is simple and environmentally friendly and safe.

[0037] (2) In the present invention, in the preparation method of the catalyst, the carrier raw material diatomaceous earth is chemically modified, and the surface of the diatomaceous earth is covered with alumina and / or titanium dioxide, especially alumina and titanium dioxide. The modified diatomaceous earth and macroporous pseudo-boehmite are selected as the main raw materials to prepare the carrier. In addition to having a large pore size distribution, the prepared carrier has a pore internal surface covered with alumina and / or titanium dioxide. The catalyst has suitable surface acid properties and has strong resistance to carbon deposition. In particular, when diatomaceous earth is modified with alumina and titanium dioxide, since the polarity of the Ti-O bond in titanium dioxide is relatively large, it is polarized and dissociated after the surface adsorbed water, and surface hydroxyl groups are easily generated. After titanium dioxide is compounded with alumina, tetrahedral Al 3+The hydroxyl groups on the catalyst are replaced by titanium to form new Al-O-Ti bonds, and Si-O-Al-O-Ti bonds may also exist. After these surface hydroxyl groups react with the active metal precursor to shrink, the catalyst has suitable surface acid properties, and the catalyst has strong resistance to carbon deposition. In addition, the use of organic acids, especially mixtures used in combination with surfactants, to form special complexes with the active metal ions (nickel ions or cobalt ions) in the solution can adjust the structure of the phosphomolybdate formed in the solution, and reduce the adsorption heat generated during the contact between the solution and the modified carrier surface during the impregnation process, reduce the interaction between the active metal and the aluminum oxide and / or titanium dioxide on the carrier surface, and facilitate the formation of a higher quality active phase, thereby improving the hydrogenation performance of the catalyst. In addition, the catalyst of the present invention has a large bed porosity, which can effectively reduce the diffusion resistance of asphaltene and colloid macromolecules in the catalyst pores and improve the hydrogenation conversion efficiency. A higher bed porosity can effectively alleviate the rapid increase in pressure drop caused by coking between catalyst particles.

[0038] The catalyst carrier for the hydroprocessing process provided by the present invention preferably adopts a material rich in macropores. A non-acidic adhesive and a pore-enlarging agent are used in the carrier preparation process to further prepare a catalyst with a larger pore volume and pore diameter.

[0039] (3) The hydroprocessing catalyst of the present invention is suitable for heavy oil hydroprocessing reactions, and is particularly suitable for the hydroconversion of asphaltene and colloid macromolecules in the feedstock during heavy oil hydroprocessing. In such applications, the catalyst of the present invention reduces the diffusion resistance of asphaltene macromolecules within the catalyst pores, enhances the accessibility of the macromolecules to the active centers, thereby improving the hydroconversion capacity of asphaltene macromolecules and alleviating the negative effects of coking. DETAILED DESCRIPTION

[0040] The technical solution of the present invention is further described in detail below with reference to the embodiments, but the protection scope of the present invention is not limited thereto.

[0041] In the present invention, the pore volume, pore diameter and specific surface area are measured using a physical adsorption instrument ASAP2420 from Micromeritics Instruments, Inc. The sample was pre-treated at 300°C for 4 hours under vacuum, and then an isothermal N2 adsorption-desorption experiment was performed at 77K.

[0042] In the present invention, the catalyst porosity is measured by the measuring cylinder method. The specific method is as follows: (1) Measure the catalyst water absorption rate λ. Accurately weigh 50g of catalyst and place the catalyst in medium water. After 60 minutes, no bubbles are generated on the catalyst surface. After wiping the water on the surface of the catalyst particles with wet gauze, accurately weigh the water-containing catalyst to obtain M1. The catalyst water absorption rate λ = (M1-50) / 50. (2) Select a measuring cylinder with a volume of 2000mL and accurately weigh M2. The catalyst is densely packed to obtain a density of d1g / mL. According to the dense packing method, 1000mL of catalyst is weighed, and the catalyst weight M3 = d1×1000g. Moisten and saturate M3g of catalyst with water. After no bubbles are generated on the catalyst surface, transfer all of it into a 2000mL measuring cylinder and add water to 1800mL. The total weight of the measuring cylinder + catalyst + water in the catalyst pores + water in the catalyst pores + 800mL of water is measured to be M4. The weight of water in the catalyst interstices of 1000 mL is M5 = M4 - 800 - M3 × λ × 1.0 - M3 - M2, and the volume of water in the catalyst interstices is V1 = M5 / 1.0. (3) Catalyst void ratio = V1 / 1000.

[0043] In the present invention, the content of the modified metal in the modified diatomaceous earth is measured by colorimetry.

[0044] In the present invention, the alumina content in the pseudo-boehmite of the examples and comparative examples is 70 wt%.

[0045] Example 1

[0046] Weigh 200g of commercially available refined diatomaceous earth and 25g of aluminum chloride and put them into a beaker, weigh 500g of ammonia water with a mass concentration of 5% and slowly add it to the beaker and start stirring. Heat to 40°C and maintain stirring for 75 minutes before stopping stirring. Filter the reacted material and wash with deionized water until the pH value of the filtrate is 5.5. The obtained filter cake is dried at 120°C for 120 minutes and then set aside. The surface of the modified diatomaceous earth is covered with aluminum oxide. In the modified diatomaceous earth, the content of modified metal aluminum oxide in the modified diatomaceous earth is 4.8wt%.

[0047] Weigh 190 g of modified diatomite and 160 g of commercially available pseudo-boehmite (pore volume 1.16 cm 3 / g), 7g hydroxypropyl methylcellulose, 7g sesbania powder, 14g urea, and 640g deionized water. The above materials were mixed and added to a kneader. After a kneading operation unit for 30 minutes, a plastic body was formed. A clover-shaped granular material was obtained by extrusion molding. The granular material after molding was dried at 135°C for 180 minutes. The dried sample was placed in a muffle furnace. The carrier S-1 was obtained by calcining at a constant temperature of 740°C for 3.3 hours at a heating rate of 4.0°C / min.

[0048] The cross-sectional shape of the obtained carrier S-1 particles is a clover leaf shape, and the diameter of the particle circumscribed circle is 2.0 mm. The properties of the carrier are as follows: the specific surface area is 159 m 2 / g, pore volume is 0.86cm 3 / g. Water absorption rate is 1.17.

[0049] Accurately weigh 22.3g of molybdenum trioxide (containing 99wt% molybdenum oxide), 8.3g of basic nickel carbonate (containing 52wt% nickel oxide), and 7.5g of phosphoric acid solution (containing 26.7wt% phosphorus). Add clean water and react at room temperature for 30 minutes. Then add 3.5g of citric acid and continue the reaction for 20 minutes. Then, heat and boil until all the raw materials are dissolved. Maintain the temperature for 60 minutes, then cool to 25°C for later use. Slowly add 3.8g of Tween-40 to the above solution while stirring, stir until the solution becomes clear, maintain stirring for 30 minutes, and then adjust the volume to 176mL for later use.

[0050] Weigh 150 g of the S-1 support and thoroughly mix the impregnation solution with the support by spraying. The thoroughly homogenized sample was placed in a sealed container at room temperature for 5 hours, dried at 130°C for 2.5 hours, and finally calcined at 520°C for 3.5 hours to produce catalyst SC-1. Catalyst composition and properties are shown in Table 1.

[0051] Example 2

[0052] Weigh 250g of commercially available refined diatomaceous earth and 20g of aluminum chloride and put them into a beaker, weigh 375g of ammonia water with a mass concentration of 8.5% and slowly add it to the beaker and start stirring. Heat to 50°C and maintain stirring for 60 minutes before stopping stirring. Filter the reacted material and wash with deionized water until the pH value of the filtrate is 5.2. The obtained filter cake is dried at 125°C for 110 minutes and set aside. The surface of the modified diatomaceous earth is covered with alumina. In the modified diatomaceous earth, the content of modified metal alumina in the modified diatomaceous earth is 3.1wt%.

[0053] Weigh 240 g of modified diatomite and 80 g of commercially available pseudo-boehmite (pore volume 1.21 cm 3 / g), 6g of hydroxypropyl methylcellulose, 8g of sesbania powder, 6g of ammonium bicarbonate, and 670g of deionized water. The above materials were mixed and added to a kneader. After a kneading operation unit for 30 minutes, a plastic body was formed. A clover-shaped granular material was obtained by extrusion molding. The granular material after molding was dried at 125°C for 200 minutes. The dried sample was placed in a muffle furnace. The carrier S-2 was obtained by calcining at a constant temperature of 800°C for 2.7 hours at a heating rate of 3.5°C / min.

[0054] The cross-sectional shape of the obtained carrier S-2 particles is a clover leaf shape, and the diameter of the particle circumscribed circle is 1.9 mm. The properties of the carrier are as follows: the specific surface area is 131 m 2 / g, pore volume is 0.88cm 3 / g. Water absorption rate is 1.19.

[0055] Accurately weigh 18.4g of molybdenum trioxide (containing 99wt% molybdenum oxide), 6.4g of basic nickel carbonate (containing 52wt% nickel oxide), and 6.6g of phosphoric acid solution (containing 26.7wt% phosphorus) in a certain order. Place them in a beaker, add clean water, and react at room temperature for 40 minutes. Then add 4.6g of tartaric acid and continue the reaction for 30 minutes. Then, heat and boil until all the raw materials are dissolved. Keep the temperature constant for 50 minutes, then cool to 25°C for use. Slowly add 3.0g of Tween-60 to the above solution while stirring, stir until the solution becomes clear, maintain the stirring state for 30 minutes, and then adjust the volume to 179mL for use.

[0056] Weigh 150 g of the S-2 support and thoroughly mix the impregnation solution with the support by spraying. The thoroughly homogenized sample was placed in a sealed container at room temperature for 4 hours, dried at 120°C for 3.5 hours, and finally calcined at 540°C for 3 hours to produce catalyst SC-2. Catalyst composition and properties are shown in Table 1.

[0057] Example 3

[0058] 300g of commercially available purified diatomaceous earth and 80g of aluminum chloride were weighed and placed in a beaker. 550g of 15% aqueous ammonia was slowly added to the beaker with stirring. The mixture was heated to 45°C and stirred for 80 minutes before stopping. The reaction mixture was filtered and washed with deionized water until the filtrate reached a pH of 5.5. The resulting filter cake was dried at 120°C for 130 minutes and then set aside. The modified diatomaceous earth contained 10.2wt% of the modified metal aluminum oxide.

[0059] Weigh 280 g of modified diatomite and 50 g of commercially available pseudo-boehmite (pore volume 1.09 cm 3 / g), 6g of hydroxypropyl methylcellulose, 7g of sesbania powder, 6.9g of carbon black, and 650g of deionized water. The above materials were mixed and added to a kneader. After a kneading operation unit for 30 minutes, a plastic body was formed. A clover-shaped granular material was obtained by extrusion molding. The granular material after molding was dried at 120°C for 200 minutes. The dried sample was placed in a muffle furnace. The carrier S-3 was obtained by calcining at a constant temperature of 780°C for 3.5 hours at a heating rate of 3.5°C / min.

[0060] The cross-sectional shape of the obtained carrier S-3 particles is a clover leaf shape, and the diameter of the particle circumscribed circle is 2.0 mm. The properties of the carrier are as follows: the specific surface area is 86 m 2 / g, pore volume is 0.92cm 3 / g. Water absorption rate is 1.27.

[0061] Accurately weigh 15.6g of molybdenum trioxide (containing 99wt% molybdenum oxide), 5.6g of basic nickel carbonate (containing 52wt% nickel oxide), and 5.8g of phosphoric acid solution (containing 26.7wt% phosphorus) in a certain order. Place them in a beaker, add clean water, and react at room temperature for 35 minutes. Then add 2.6g of salicylic acid and continue the reaction for 30 minutes. Then, heat and boil until all the raw materials are dissolved. Keep the temperature constant for 70 minutes, then cool to 25°C for use. Slowly add 2.9g of Tween-30 to the above solution while stirring, stir until the solution becomes clear, maintain the stirring state for 25 minutes, and then add 191mL of fixed volume for use.

[0062] Weigh 150 g of the S-3 support and thoroughly mix the impregnation solution with the S-3 support by spraying. The thoroughly homogenized sample was placed in a sealed container at room temperature for 7 hours, dried at 125°C for 3.5 hours, and finally calcined at 510°C for 3 hours to produce catalyst SC-3. Catalyst composition and properties are shown in Table 1.

[0063] Example 4

[0064] Weigh 160g of commercially available purified diatomaceous earth and 70g of aluminum chloride into a beaker. Weigh 350g of 20% aqueous ammonia and slowly add it to the beaker with stirring. Heat to 45°C and maintain stirring for 70 minutes before ceasing stirring. The reaction mixture is filtered and washed with deionized water until the filtrate has a pH of 5.5. The resulting filter cake is dried at 120°C for 150 minutes and then set aside. The modified diatomaceous earth contains 16.7wt% of the modified metal aluminum oxide.

[0065] Weigh 150g of modified diatomite and 180g of commercially available pseudo-boehmite (pore volume 1.26cm 3 / g), 12g hydroxypropyl methylcellulose, 9g sesbania powder, 9g ammonium bicarbonate, and 640g deionized water. The above materials were mixed and added to a kneader. After a kneading operation unit for 30 minutes, a plastic body was formed. A clover-shaped granular material was obtained by extrusion molding. The granular material after molding was dried at 120°C for 180 minutes. The dried sample was placed in a muffle furnace. The carrier S-4 was calcined at a constant temperature of 810°C for 2.5 hours at a heating rate of 3.5°C / min to obtain the carrier S-4.

[0066] The cross-sectional shape of the obtained carrier S-4 particles is a clover leaf shape, and the diameter of the particle circumscribed circle is 3.0 mm. The properties of the carrier are as follows: the specific surface area is 89 m 2 / g, pore volume is 0.85cm 3 / g. Water absorption rate is 1.15.

[0067] Accurately weigh 14.0g of molybdenum trioxide (containing 99wt% molybdenum oxide), 5.2g of basic nickel carbonate (containing 54wt% nickel oxide), and 5.1g of phosphoric acid solution (containing 26.7wt% phosphorus) in a certain order. Place them in a beaker, add clean water, and react at room temperature for 40 minutes. Then add 4.9g of citric acid and continue the reaction for 35 minutes. Then, heat and boil until all the raw materials are dissolved. Keep the temperature constant for 50 minutes, then cool to 25°C for use. Slowly add 4.3g of Tween-80 to the above solution while stirring, stir until the solution becomes clear, maintain the stirring state for 40 minutes, and then stop. The volume is 173mL for use.

[0068] Weigh 150 g of the S-4 support and thoroughly mix the impregnation solution with the S-4 support by spraying. The thoroughly homogenized sample was placed in a sealed container at room temperature for 7 hours, dried at 130°C for 3 hours, and finally calcined at 545°C for 3 hours to produce catalyst SC-4. Catalyst composition and properties are shown in Table 1.

[0069] Example 5

[0070] Weigh 200g of commercially available refined diatomaceous earth and 25g of aluminum chloride and put them into a beaker, weigh 500g of ammonia water with a mass concentration of 5% and slowly add it to the beaker and start stirring. Heat to 40°C and maintain stirring for 75 minutes before stopping stirring. Filter the reacted material and wash with deionized water until the pH value of the filtrate is 5.5. The obtained filter cake is dried at 120°C for 120 minutes and then set aside. The surface of the modified diatomaceous earth is covered with aluminum oxide. In the modified diatomaceous earth, the content of modified metal aluminum oxide in the modified diatomaceous earth is 4.8wt%.

[0071] Weigh 190 g of modified diatomite and 160 g of commercially available pseudo-boehmite (pore volume 1.16 cm 3 / g), 7g hydroxypropyl methylcellulose, 7g sesbania powder, 14g urea, and 640g deionized water. The above materials were mixed and added to a kneader. After a kneading operation unit for 30 minutes, a plastic body was formed. A clover-shaped granular material was obtained by extrusion molding. The granular material after molding was dried at 135°C for 180 minutes. The dried sample was placed in a muffle furnace. The carrier S-5 was calcined at a constant temperature of 740°C for 3.3 hours at a heating rate of 4.0°C / min to obtain the carrier S-5.

[0072] The cross-sectional shape of the obtained carrier S-5 particles is a clover leaf shape, and the diameter of the particle circumscribed circle is 2.0 mm. The properties of the carrier are as follows: the specific surface area is 159 m 2 / g, pore volume is 0.86cm 3 / g. Water absorption rate is 1.17.

[0073] Accurately weigh 22.3g of molybdenum trioxide (containing 99wt% molybdenum oxide), 8.3g of basic nickel carbonate (containing 52wt% nickel oxide), and 7.5g of phosphoric acid solution (containing 26.7wt% phosphorus). Add clean water and react at room temperature for 30 minutes. Add 3.5g of oxalic acid and continue the reaction for 20 minutes. Then, heat and boil until all the raw materials are dissolved. Maintain the temperature for 60 minutes, then cool to 25°C for later use. Slowly add 3.8g of Tween-40 to the above solution while stirring, stir until the solution becomes clear, maintain stirring for 30 minutes, and then adjust the volume to 176mL for later use.

[0074] Weigh 150g of the S-5 carrier and thoroughly mix the impregnation solution with the carrier by spraying. The thoroughly homogenized sample was placed in a sealed container at room temperature for 5 hours, dried at 130°C for 2.5 hours, and finally calcined at 520°C for 3.5 hours to produce the catalyst SC-5. Catalyst composition and properties are shown in Table 1.

[0075] Example 6

[0076] Weigh 160g of commercially available refined diatomaceous earth and 54g of titanium oxysulfate and place them in a beaker. Weigh 350g of 20% ammonia water and slowly add it to the beaker with stirring. Heat to 45°C and maintain stirring for 70 minutes before stopping stirring. The reacted material is filtered and washed with deionized water until the filtrate has a pH of 5.5. The resulting filter cake is dried at 120°C for 150 minutes and then set aside. The content of modified metal titanium dioxide in the modified diatomaceous earth is 16.7wt%.

[0077] Weigh 150g of modified diatomite and 180g of commercially available pseudo-boehmite (pore volume 1.26cm 3 / g), 12g hydroxypropyl methylcellulose, 9g sesbania powder, 9g ammonium bicarbonate, and 640g deionized water. The above materials were mixed and added to a kneader. After a kneading operation unit for 30 minutes, a plastic body was formed. A clover-shaped granular material was obtained by extrusion molding. The granular material after molding was dried at 120°C for 180 minutes. The dried sample was placed in a muffle furnace. The carrier S-6 was obtained by calcining at a constant temperature of 810°C for 2.5 hours at a heating rate of 3.5°C / min.

[0078] The cross-sectional shape of the obtained carrier S-6 particles is a clover leaf shape, and the diameter of the particle circumscribed circle is 3.0 mm. The properties of the carrier are as follows: the specific surface area is 91 m 2 / g, pore volume is 0.84cm 3 / g. Water absorption rate is 1.15.

[0079] Accurately weigh 14.0g of molybdenum trioxide (containing 99wt% molybdenum oxide), 5.2g of basic nickel carbonate (containing 54wt% nickel oxide), and 5.1g of phosphoric acid solution (containing 26.7wt% phosphorus) in a certain order. Place them in a beaker, add clean water, and react at room temperature for 40 minutes. Then add 4.9g of citric acid and continue the reaction for 35 minutes. Then, heat and boil until all the raw materials are dissolved. Keep the temperature constant for 50 minutes, then cool to 25°C for use. Slowly add 4.3g of Tween-80 to the above solution while stirring, stir until the solution becomes clear, maintain the stirring state for 40 minutes, and then stop. The volume is 173mL for use.

[0080] Weigh 150 g of the S-6 carrier and thoroughly mix the impregnation solution with the carrier by spraying. The thoroughly homogenized sample was placed in a sealed container at room temperature for 7 hours, dried at 130°C for 3 hours, and finally calcined at 545°C for 3 hours to produce catalyst SC-6. Catalyst composition and properties are shown in Table 1.

[0081] Example 7

[0082] Weigh 160g of commercially available refined diatomaceous earth, 27g of titanium oxysulfate, and 35g of aluminum chloride and place them in a beaker. Weigh 350g of 20% ammonia water and slowly add it to the beaker while stirring. Heat to 45°C and maintain stirring for 70 minutes before stopping stirring. The reacted material is filtered and washed with deionized water until the pH value of the filtrate reaches 5.5. The resulting filter cake is dried at 120°C for 150 minutes and then set aside. The content of the modified metal in the modified diatomaceous earth is: TiO2 content is 8.4wt% and Al2O3 content is 8.4wt%.

[0083] Weigh 150g of modified diatomite and 180g of commercially available pseudo-boehmite (pore volume 1.26cm 3 / g), 12g hydroxypropyl methylcellulose, 9g sesbania powder, 9g ammonium bicarbonate, and 640g deionized water. The above materials were mixed and added to a kneader. After a kneading operation unit for 30 minutes, a plastic body was formed. A clover-shaped granular material was obtained by extrusion molding. The granular material after molding was dried at 120°C for 180 minutes. The dried sample was placed in a muffle furnace. The carrier S-7 was obtained by calcining at a constant temperature of 810°C for 2.5 hours at a heating rate of 3.5°C / min.

[0084] The cross-sectional shape of the obtained carrier S-7 particles is a clover leaf shape, and the diameter of the particle circumscribed circle is 3.0 mm. The properties of the carrier are as follows: the specific surface area is 90 m 2 / g, pore volume is 0.85cm 3 / g. Water absorption rate is 1.15.

[0085] Accurately weigh 14.0g of molybdenum trioxide (containing 99wt% molybdenum oxide), 5.2g of basic nickel carbonate (containing 54wt% nickel oxide), and 5.1g of phosphoric acid solution (containing 26.7wt% phosphorus) in a certain order. Place them in a beaker, add clean water, and react at room temperature for 40 minutes. Then add 4.9g of citric acid and continue the reaction for 35 minutes. Then, heat and boil until all the raw materials are dissolved. Keep the temperature constant for 50 minutes, then cool to 25°C for use. Slowly add 4.3g of Tween-80 to the above solution while stirring, stir until the solution becomes clear, maintain the stirring state for 40 minutes, and then stop. The volume is 173mL for use.

[0086] Weigh 150 g of the S-7 support and thoroughly mix the impregnation solution with the S-7 support by spraying. The thoroughly homogenized sample was placed in a sealed container at room temperature for 7 hours, dried at 130°C for 3 hours, and finally calcined at 545°C for 3 hours to produce the SC-7 catalyst. Catalyst composition and properties are shown in Table 1.

[0087] Example 8

[0088] Weigh 160g of commercially available refined diatomaceous earth, 8.9g of titanyl sulfate, and 58.3g of aluminum chloride into a beaker. Weigh 350g of 20% ammonia water and slowly add it to the beaker with stirring. Heat to 45°C, maintain stirring for 70 minutes, and then stop stirring. The reacted material is filtered and washed with deionized water until the filtrate has a pH of 5.5. The resulting filter cake is dried at 120°C for 150 minutes and then set aside. The modified diatomaceous earth contains 2.8% TiO2 and 13.9% Al2O3 of the modified metal.

[0089] Weigh 150g of modified diatomite and 180g of commercially available pseudo-boehmite (pore volume 1.26cm 3 / g), 12g hydroxypropyl methylcellulose, 9g sesbania powder, 9g ammonium bicarbonate, and 640g deionized water. The above materials were mixed and added to a kneader. After a kneading operation unit for 30 minutes, a plastic body was formed. A clover-shaped granular material was obtained by extrusion molding. The granular material after molding was dried at 120°C for 180 minutes. The dried sample was placed in a muffle furnace. The carrier S-8 was obtained by calcining at a constant temperature of 810°C for 2.5 hours at a heating rate of 3.5°C / min.

[0090] The cross-sectional shape of the obtained carrier S-8 particles is a clover leaf shape, and the diameter of the particle circumscribed circle is 3.0 mm. The properties of the carrier are as follows: the specific surface area is 91 m 2 / g, pore volume is 0.84cm 3 / g. Water absorption rate is 1.15.

[0091] Accurately weigh 14.0g of molybdenum trioxide (containing 99wt% molybdenum oxide), 5.2g of basic nickel carbonate (containing 54wt% nickel oxide), and 5.1g of phosphoric acid solution (containing 26.7wt% phosphorus) in a certain order. Place them in a beaker, add clean water, and react at room temperature for 40 minutes. Then add 4.9g of citric acid and continue the reaction for 35 minutes. Then, heat and boil until all the raw materials are dissolved. Keep the temperature constant for 50 minutes, then cool to 25°C for use. Slowly add 4.3g of Tween-80 to the above solution while stirring, stir until the solution becomes clear, maintain the stirring state for 40 minutes, and then stop. The volume is 173mL for use.

[0092] Weigh 150 g of the S-8 carrier and thoroughly mix the impregnation solution with the carrier by spraying. The thoroughly homogenized sample was placed in a sealed container at room temperature for 7 hours, dried at 130°C for 3 hours, and finally calcined at 545°C for 3 hours to produce the catalyst SC-8. Catalyst composition and properties are shown in Table 1.

[0093] Example 9

[0094] Weigh 200g of commercially available refined diatomaceous earth and 25g of aluminum chloride and put them into a beaker, weigh 500g of ammonia water with a mass concentration of 5% and slowly add it to the beaker and start stirring. Heat to 40°C and maintain stirring for 75 minutes before stopping stirring. Filter the reacted material and wash with deionized water until the pH value of the filtrate is 5.5. The obtained filter cake is dried at 120°C for 120 minutes and then set aside. The surface of the modified diatomaceous earth is covered with aluminum oxide. In the modified diatomaceous earth, the content of modified metal aluminum oxide in the modified diatomaceous earth is 4.8wt%.

[0095] Weigh 190 g of modified diatomite and 160 g of commercially available pseudo-boehmite (pore volume 1.16 cm 3 / g), 7g hydroxypropyl methylcellulose, 7g sesbania powder, 14g urea, and 640g deionized water. The above materials were mixed and added to a kneader. After a kneading operation unit for 30 minutes, a plastic body was formed. A clover-shaped granular material was obtained by extrusion molding. The granular material after molding was dried at 135°C for 180 minutes. The dried sample was placed in a muffle furnace. The carrier S-9 was obtained by calcining at a constant temperature of 740°C for 3.3 hours at a heating rate of 4.0°C / min.

[0096] The cross-sectional shape of the obtained carrier S-9 particles is a clover leaf shape, and the diameter of the particle circumscribed circle is 2.0 mm. The properties of the carrier are as follows: the specific surface area is 159 m 2 / g, pore volume is 0.86cm 3 / g. Water absorption rate is 1.17.

[0097] Accurately weigh 22.3g of molybdenum trioxide (containing 99wt% molybdenum oxide), 8.3g of basic nickel carbonate (containing 52wt% nickel oxide), and 7.5g of phosphoric acid solution (containing 26.7wt% phosphorus). Add clean water and react at room temperature for 30 minutes. Add 3.5g of citric acid and continue to react for 20 minutes. Then, heat and boil until all the ingredients are dissolved. Maintain the temperature for 60 minutes, then cool to 25°C and adjust the volume to 176mL for later use.

[0098] Weigh 150g of the S-9 support and thoroughly mix the impregnation solution with the S-9 support by spraying. The thoroughly homogenized sample was placed in a sealed container at room temperature for 5 hours, dried at 130°C for 2.5 hours, and finally calcined at 520°C for 3.5 hours to produce the SC-9 catalyst. Catalyst composition and properties are shown in Table 1.

[0099] Comparative Example 1

[0100] Weigh 190 g of diatomaceous earth and 160 g of commercially available pseudo-boehmite (pore volume 1.16 cm 3 / g), 7g hydroxypropyl methylcellulose, 7g sesbania powder, 14g urea, and 640g deionized water. The above materials were mixed and added to a kneader. After kneading for 30 minutes, a plastic body was formed. A clover-shaped granular material was obtained by extrusion molding. The granular material after molding was dried at 135°C for 180 minutes. The dried sample was placed in a muffle furnace. The carrier S-10 was calcined at a constant temperature of 740°C for 3.3 hours at a heating rate of 4.0°C / min to obtain the carrier S-10.

[0101] The cross-sectional shape of the obtained carrier S-10 particles is a clover leaf shape, and the diameter of the particle circumscribed circle is 2.0 mm. The properties of the carrier are as follows: the specific surface area is 143 m 2 / g, pore volume is 0.80cm 3 / g. Water absorption rate is 1.09.

[0102] Accurately weigh 22.3g of molybdenum trioxide (containing 99wt% molybdenum oxide), 8.3g of basic nickel carbonate (containing 52wt% nickel oxide), and 7.5g of phosphoric acid solution (containing 26.7wt% phosphorus). Add clean water and react at room temperature for 30 minutes. Then add 3.5g of citric acid and continue the reaction for 20 minutes. Then, heat and boil until all the raw materials are dissolved. Maintain the temperature for 60 minutes, then cool to 25°C for later use. Slowly add 3.8g of Tween-40 to the above solution while stirring, stir until the solution becomes clear, maintain stirring for 30 minutes, and then adjust the volume to 164mL for later use.

[0103] Weigh 150g of the S-10 carrier and thoroughly mix the impregnation solution with the carrier by spraying. The thoroughly homogenized sample was placed in a sealed container at room temperature for 5 hours, dried at 130°C for 2.5 hours, and finally calcined at 520°C for 3.5 hours to produce the SC-10 catalyst. Catalyst composition and properties are shown in Table 1.

[0104] Table 1 Composition and properties of catalysts in Examples and Comparative Examples

[0105]

[0106] Table 2 Comparison of hydrogenation performance between the embodiment and the comparative example

[0107]

[0108]

[0109] *Note: HDAs in Table 2 are relative asphaltene removal rates.

[0110] Gums and asphaltenes are the primary coke precursors in the residue hydrogenation process. Although they constitute a relatively small proportion of the residue, they pose a significant risk. Nickel and vanadium compounds in the residue are primarily found in gums and asphaltenes. During the hydrogenation process, nickel and vanadium can only be removed after the three-dimensional structure of the gums and asphaltenes macromolecules is disrupted. The relatively large molecular size of gums and asphaltenes creates a high diffusion resistance within the catalyst pores, leading to reactions occurring on or near the catalyst particle surface. As the reaction time increases, significant carbon deposits and metal deposition build up on the catalyst surface, ultimately leading to catalyst inactivity due to pore blockage and surface coating.

[0111] The catalyst prepared by the present invention has a high bed porosity and pore size, which can effectively alleviate the rapid increase in pressure drop caused by coking between catalyst particles. The catalyst prepared by the method provided by the present invention focuses on the hydrogenation conversion of macromolecules, especially the conversion of asphaltene macromolecules. The reason is that in the catalyst preparation process in the embodiment, after being treated with an impregnation solution of a specific composition (especially an impregnation solution composed of citric acid, surfactants, and active metals), there are significant differences in the surface chemical properties and pore properties of the catalysts in the embodiment and the comparative example. It is mainly reflected in that the pore structure of the catalyst carrier in the embodiment is more suitable for the diffusion of residual oil macromolecules in the catalyst pores, and the accessibility of the reactants to the active center is greater. At the same time, after the catalyst carrier in the embodiment is modified with alumina and / or titanium dioxide, the acidic properties of the catalyst surface are conducive to the cracking of asphaltene and colloid macromolecules into small molecules, and its hydrogenation apparent activity is higher. At the same time, a larger catalyst bed porosity is conducive to improving the anti-coking performance of the catalyst bed, ensuring that the bed porosity is at a high level during operation, and alleviating the negative impact of the unplanned shutdown of the device caused by the rapid increase in bed pressure drop.

Claims

1. Application of a heavy oil hydrotreating catalyst in a heavy oil hydrotreating reaction, characterized in that: The application is to be used in the hydrogenation conversion process of asphaltene and colloid macromolecules in the raw material during the heavy oil hydroprocessing process; the catalyst comprises a carrier and an active metal component; the carrier comprises macroporous alumina and modified diatomaceous earth; The modified diatomaceous earth is diatomaceous earth with a modified metal component on its surface; the modified metal component is titanium dioxide or titanium dioxide and aluminum oxide; The weight ratio of macroporous alumina to modified diatomaceous earth in the carrier is 15-65:70-150; the content of the modified metal component in the modified diatomaceous earth is 2wt%-20wt%; The preparation method of the modified diatomaceous earth comprises the following steps: mixing diatomaceous earth and a modified metal source, adding ammonia water for treatment, and drying a filter cake obtained by solid-liquid separation to obtain the modified diatomaceous earth.

2. The application according to claim 1, characterized in that The modified metal components are titanium dioxide and aluminum oxide, and the weight ratio of titanium dioxide to aluminum oxide is 1:1-10.

3. The application according to claim 1, characterized in that The modified metal components are titanium dioxide and aluminum oxide, and the weight ratio of titanium dioxide to aluminum oxide is 1:1-6.

4. The application according to claim 1, characterized in that The active metals include at least one metal selected from Group VIII and at least one metal selected from Group VIB.

5. The application according to claim 4, characterized in that: The Group VIII metal is nickel and / or cobalt, and the Group VIB metal is molybdenum and / or tungsten.

6. The application according to claim 4, characterized in that: The Group VIII metal is nickel and / or cobalt, and the Group VIB metal is molybdenum.

7. The use according to claim 4, characterized in that Based on the mass of the catalyst, the content of the Group VIB metal in terms of oxide is 5% to 15%; the content of the Group VIII metal in terms of oxide is 1.0% to 4.0%.

8. The use according to claim 4, characterized in that: Based on the mass of the catalyst, the content of Group VIB metals in terms of oxides is 8.0% to 14.0%; the content of Group VIII metals in terms of oxides is 1.5% to 3.0%.

9. The use according to claim 1, characterized in that: The preparation method of the catalyst comprises the following steps: (1) Take modified diatomite and macroporous pseudo-boehmite, add extrusion aid, pore enlarging agent, adhesive and water, mix and knead, dry and calcine to obtain a catalyst carrier; (2) preparing an impregnation solution containing an organic acid and an active metal; (3) The carrier of step (1) is impregnated with the impregnation solution of step (2), and the carrier is dried and calcined to obtain a hydroprocessing catalyst.

10. The use according to claim 9, characterized in that: In the preparation method of the modified diatomite, the modified metal source is a titanium source or a titanium source and an aluminum source; the aluminum source is at least one of aluminum chloride and aluminum hydroxide; and the titanium source is at least one of titanium tetrachloride and titanyl sulfate.

11. The application according to claim 10, characterized in that: The aluminum source is aluminum chloride; the titanium source is titanyl sulfate.

12. The use according to claim 9, characterized in that: The raw material feeding ratio of the modified diatomaceous earth preparation method is: by weight, 150-300 parts of diatomaceous earth; 20-80 parts of modified metal source; 300-600 parts of ammonia water; wherein the concentration of the ammonia water is 2wt%-20wt%.

13. The use according to claim 9, characterized in that: The raw material feeding ratio in step (1) is: by weight, 70-150 parts of modified diatomite, 20-90 parts of macroporous pseudo-boehmite, 1-7 parts of adhesive, 1-7 parts of pore expanding agent, 1-5 parts of extrusion aid and 250-350 parts of water.

14. The use according to claim 9, characterized in that The impregnation liquid in step (2) contains a surfactant; the surfactant is one or more of Tween-20, Tween-30, Tween-40, Tween-60, Tween-80 and Tween-85; the content of the surfactant in the impregnation liquid is 5-100 g / L.

15. The use according to claim 14, characterized in that: The impregnation liquid in step (2) contains a surfactant; the surfactant is Tween-60 and / or Tween-80; and the content of the surfactant in the impregnation liquid is 10-30 g / L.

16. The use according to claim 9, characterized in that The organic acid in the impregnation solution of step (2) is one or more of fumaric acid, adipic acid, tartaric acid, citric acid, oxalic acid, acetic acid, salicylic acid and malic acid; and the content of the organic acid in the impregnation solution is 10-40 g / L.

17. The use according to claim 9, characterized in that The drying in step (3) is carried out at a temperature of 110-140°C for 2.0-5.0 hours; and the calcination is carried out at a temperature of 400-600°C for 2.0-5.0 hours.

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