Boiling bed hydroprocessing catalyst, its preparation and application

Abstract

This invention discloses a fluidized bed hydrotreating catalyst, its preparation method, and its application. The hydrotreating catalyst includes a hydrotreating active metal component, a support, and optional auxiliary phosphorus. The support is a carbon-containing alumina composite support. The preparation method includes the following steps: (1) spheroidizing a first pseudoboehmite powder to obtain a first support precursor; (2) treating an aqueous solution of the first support precursor, an additive, and an organic polymer B to obtain a second support precursor; (3) treating the second support precursor, the second pseudoboehmite powder, and an acidic solution to obtain a third support precursor; (4) subjecting the third support precursor to low-temperature heat treatment to obtain a fourth support precursor; (5) mixing the fourth support precursor with an auxiliary solution, drying, and calcining to obtain an auxiliary-modified carbon-containing alumina composite support; (6) introducing a hydrotreating active metal component onto the composite support, followed by drying and calcining to obtain the fluidized bed hydrotreating catalyst.

Description

Technical Field

[0001] This invention belongs to the field of catalytic materials technology, and relates to a hydrogenation catalytic material and its preparation method, particularly to a fluidized bed hydrogenation catalyst and its preparation method. Background Technology

[0002] Residue hydrotreating is the most effective method for solving the deep processing of heavy oil. Among existing residue hydrotreating technologies, fixed-bed hydrotreating technology is the most mature and widely used. However, its poor adaptability to feedstocks is increasingly highlighting its limitations. Eluting-bed residue hydrotreating technology has advantages such as strong adaptability to feedstocks, virtually no pressure drop within the reactor, uniform temperature distribution, good mass and heat transfer, online catalyst addition and removal, high catalyst utilization, long operating cycle, and flexible operation. However, the eluting-bed unit consumes a large amount of catalyst during operation, thus placing higher demands on catalyst performance and cost. Currently, alumina is the most widely used carrier in heavy oil hydrotreating due to its good mechanical properties and low price, but it also has disadvantages such as low specific surface area and strong interaction with active metals. Activated carbon, on the other hand, is increasingly widely used in catalytic reactions due to its low price, stable properties, rich pore structure, large specific surface area, and tunable surface chemical properties. In the residue hydrotreating process, activated carbon can selectively adsorb macromolecules such as asphaltenes, disperse coking precursors, and inhibit coking to a certain extent. Therefore, the composite carrier of alumina and activated carbon has broad application prospects.

[0003] Patent CN201510043976.1 discloses a mesoporous carbon material supported on alumina and its application method, comprising the following steps: dissolving starch and aluminum sulfate in deionized water, ultrasonically mixing, adding colloidal silica dropwise at a rate of 1-2 drops / second under heating and stirring conditions, stirring in an oil bath at 110-150℃ for 20 minutes, naturally cooling, drying, and carbonizing. The carbonized material is stirred in a 20-30wt% sodium hydroxide solution in a water bath, filtered, washed, and dried to obtain the mesoporous carbon material supported on alumina. The specific surface area of ​​the mesoporous carbon is 400-900 μm. 2 / g, average pore size 4-8nm, pore volume 0.5-1.0cm³ 3 / g, the alumina loading is 0.05-0.2g / g mesoporous carbon material. This patent uses carbon as the main component, resulting in a material with a small pore size, which is not suitable for fluidized bed residue hydrotreating processes.

[0004] Patent CN104096584B discloses a residue oil hydrotreating catalyst and its preparation method. The catalyst uses an alumina and activated carbon mixture as a support, with active components being Ni2P, MoO3 and / or WO3, and / or CoO and / or NiO. Introducing a small amount of activated carbon into the alumina reduces the reaction between the Ni2P active component and the alumina during the formation process, while simultaneously improving its dispersibility. This allows for full utilization of the high activity of Ni2P and the support advantages of the alumina-activated carbon mixture, thereby enhancing the catalyst's impurity removal capacity. However, the introduction of activated carbon into the catalyst support reduces the pore size, causing impurities in the feed oil to be removed from the outside of the catalyst. This results in lower utilization of active metals inside the catalyst. During long-term operation, this can lead to uneven distribution of impurity metals on the catalyst, causing pore blockage and catalyst deactivation. Summary of the Invention

[0005] To address several problems existing in the prior art, the main objective of this invention is to provide a fluidized bed hydrotreating catalyst, its preparation method, and its application. The catalyst exhibits a non-uniform pore distribution, making it particularly suitable for heavy oil and residue hydrotreating. The prepared catalyst not only possesses high hydrodemetallization activity and the ability to accommodate metal impurities, but also high hydrodesulfurization activity. Furthermore, the catalyst is not easily clogged by metal impurities, ensuring its stability during long-term operation of the equipment.

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

[0007] (1) The first pseudo-boehmite powder is subjected to spheroidization treatment to obtain the first carrier precursor;

[0008] (2) The first carrier precursor is placed in a ball rolling machine, and an additive and an aqueous solution of organic polymer B after heat treatment are added evenly during the rolling process. After treatment, the second carrier precursor is obtained; wherein the additive is a mixture of organic polymer A and nitrogen-containing weak base compound.

[0009] (3) The second carrier precursor is placed in a ball rolling machine, and the second pseudoboehmite powder and acidic solution are added evenly during the rolling process. After treatment, the third carrier precursor is obtained.

[0010] (4) The third carrier precursor is subjected to low-temperature heat treatment to obtain the fourth carrier precursor;

[0011] (5) The fourth carrier precursor is mixed with a soluble iron salt solution. After the mixture is evenly mixed, it is dried and calcined under an inert atmosphere to obtain a carbon-containing alumina composite carrier modified with additives.

[0012] (6) Introduce hydrogenation active metal components into the composite support obtained in step (5), and further dry and calcine to obtain a fluidized bed hydrogenation catalyst.

[0013] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the properties of the first pseudoboehmite powder after calcination at 550–750 °C are as follows: specific surface area of ​​300–550 m². 2 The first pseudoboehmite powder has a pore volume of 0.4–1.0 mL / g, an average pore diameter of 4–12 nm, and pores with a diameter <10 nm account for 60%–75% of the total pore volume. The first 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.

[0014] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the spheroidizing process in step (1) can be any of the existing spheroidizing methods in the art, specifically one or more of the following: extrusion spheroidizing, rolling molding, and spray drying molding.

[0015] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the particle size of the first support precursor in step (1) is 0.1 to 1.0 mm.

[0016] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the organic polymer A mentioned in step (1) is one or more of starch, sugar, cellulose ether, and flour, preferably starch. More specifically, the starch is one or more of mung bean starch, cassava starch, sweet potato starch, potato starch, wheat starch, water chestnut starch, lotus root starch, and corn starch, preferably corn starch and / or potato starch; the cellulose ether can be at least one of methylcellulose, hydroxyethyl methylcellulose, carboxymethyl cellulose, ethylcellulose, benzylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, cyanoethylcellulose, benzyl cyanoethylcellulose, carboxymethyl hydroxyethyl cellulose, and phenylcellulose, preferably methylcellulose; the sugar is one or more of monosaccharides, disaccharides, and polysaccharides, preferably glucose.

[0017] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the nitrogen-containing weak base compound mentioned in step (2) is one or a mixture of two or more of ammonia, ammonium carbonate, and ammonium bicarbonate, preferably ammonia. Even further, the concentration of ammonia is 1wt% to 20wt%, preferably 3wt% to 12wt%.

[0018] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the mass ratio of the organic polymer and the nitrogen-containing weak base compound in step (2) is 1:0.05 to 1:0.5.

[0019] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the organic polymer B mentioned in step (1) is one or more of starch, sugar, cellulose ether, and flour, preferably starch. Even further, the starch is one or more of mung bean starch, cassava starch, sweet potato starch, potato starch, wheat starch, water chestnut starch, lotus root starch, and corn starch, preferably corn starch and / or potato starch; the cellulose ether can be at least one of methylcellulose, hydroxyethyl methylcellulose, carboxymethyl cellulose, ethylcellulose, benzylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, cyanoethylcellulose, benzyl cyanoethylcellulose, carboxymethyl hydroxyethyl cellulose, and phenylcellulose, preferably methylcellulose; the sugar is one or more of monosaccharides, disaccharides, and polysaccharides, preferably glucose.

[0020] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the concentration of the aqueous solution of the heated organic polymer B in step (2) is 0.5wt% to 5wt%, preferably 1wt% to 3wt%. The preparation method is as follows: add the organic polymer B to water, heat and mix at 60 to 100°C for 10 to 40 minutes, and obtain the aqueous solution of the organic polymer B after the organic polymer is completely dissolved.

[0021] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the second pseudoboehmite powder mentioned in step (3) has the following properties after being calcined at 550-750℃: specific surface area of ​​200-320 μm. 2 The pore volume is 0.8–1.2 mL / g, the average pore diameter is 10–30 nm, and the pore volume of pores with a diameter >10 nm accounts for 60%–75% of the total pore volume. The pseudoboehmite powder B 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, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the acidic solution in step (3) is one or more of acetic acid, nitric acid, and oxalic acid, preferably nitric acid; the concentration of the acidic solution is 0.1wt% to 8wt%, preferably 0.3wt% to 5wt%; and the mass ratio of the amount of acidic solution added to the dry basis of the second pseudoboehmite powder is 0.8 to 1.5.

[0023] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the low-temperature heat treatment temperature in step (4) is 100-300℃, preferably 150-250℃; the treatment time is 1-8h, preferably 3-6h.

[0024] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the soluble iron salt mentioned in step (5) is selected from one or more of ferric nitrate, ferric chloride, and ferric sulfate.

[0025] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the drying temperature in step (5) is 60–90°C.

[0026] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the inert atmosphere described in step (5) is one or more of nitrogen, helium, neon, argon, krypton, and xenon, preferably nitrogen; the calcination temperature is 600-900℃, and the calcination time is 1-5h.

[0027] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the particle size of the carbon-containing alumina composite support in step (5) is 0.2 to 2.0 mm, preferably 0.3 to 1.8 mm, wherein the particle size of the second support is 10% to 90% of the particle size of the composite support.

[0028] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the drying conditions in step (6) are as follows: the drying temperature is 80-120℃ and the drying time is 4-12h.

[0029] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the calcination in step (6) is carried out under an inert atmosphere, which is one or more of nitrogen, helium, neon, argon, krypton, and xenon, preferably nitrogen; the calcination conditions are as follows: calcination temperature is 400-600℃, and calcination time is 1-5h.

[0030] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the introduction of the hydrogenation active metal component in step (6) can be any one or more of the methods existing in the art, specifically at least one of the methods such as mixing and impregnation, with impregnation being preferred.

[0031] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the hydrogenation active metal component mentioned in step (6) is one or more of Group VIB metals and / or Group VIII metals, wherein the Group VIB metals are generally Mo and / or W, and the Group VIII metals are generally Ni and / or Co.

[0032] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, the active metal component in step (6) is preferably Mo and Ni.

[0033] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, P can also be introduced when introducing the hydrogenation active metal component in step (6).

[0034] Furthermore, in the above-mentioned method for preparing the fluidized bed hydrogenation catalyst, when the hydrogenation active metal component is introduced in step (6) by impregnation, the precursor containing the hydrogenation active metal component, water, and optionally a phosphorus-containing compound are first mixed evenly to obtain an aqueous solution containing the hydrogenation metal component and P. Then, after being mixed evenly with the support, the solution is allowed to stand, dried, and calcined to obtain the catalyst. Specifically, the precursor containing the active metal component is a compound containing a Group VIB metal and / or a Group VIII metal. The Group VIB metal-containing compound can be one or more of a molybdenum-containing compound or a tungsten-containing compound, and the Group VIII metal-containing compound can be one or more of a nickel-containing compound or a cobalt-containing compound. The molybdenum-containing compound can be molybdenum oxide and / or ammonium heptamolybdate; the nickel-containing compound is basic nickel carbonate and / or nickel nitrate; and the cobalt-containing compound is basic cobalt carbonate and / or cobalt nitrate. The phosphorus-containing compound can be one or more of phosphoric acid, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate; the concentration of the hydrogenated metal component in the aqueous solution containing the hydrogenated metal component and P is 0.03–0.5 g / mL (calculated as hydrogenated metal oxide), and the concentration of P is 0–0.05 g / mL, preferably 0.002–0.05 g / mL. The standing time is 1–3 h.

[0035] A second aspect of the present invention provides a fluidized bed hydrotreating catalyst obtained by the above preparation method. The hydrotreating catalyst includes a hydrotreating active metal component, a support, an auxiliary metal component, and optionally phosphorus pentoxide. The hydrotreating active metal is one or more of Group VIB metals and / or Group VIII metals; the auxiliary metal is iron; the support is a carbon-containing alumina composite support, wherein the carbon content in the composite support is 5 wt% to 20 wt%; the hydrotreating metal component and the auxiliary metal are distributed on the support in the form of metal oxides.

[0036] Furthermore, in the aforementioned fluidized bed hydrotreating catalyst, based on the catalyst, the concentration and amount of the hydrogenation-active metal compound in the solution are such that the content of Group VIB metal components (calculated as oxides) in the final catalyst is 2 wt% to 15 wt%; the content of Group VIII metal components (calculated as oxides) is 0.5 wt% to 5 wt%. The content of the auxiliary metal components is 0.1 wt% to 2 wt%; and the content of phosphorus pentoxide is 0.4 wt% to 4 wt%.

[0037] Furthermore, in the above-mentioned fluidized bed hydrotreating catalyst, the Group VIB metal is generally Mo and / or W, and the Group VIII metal is generally Ni and / or Co.

[0038] Furthermore, in the above-mentioned fluidized bed hydrogenation catalyst, the hydrogenation metal component is preferably Mo and Ni.

[0039] Furthermore, in the above-mentioned fluidized bed hydrotreating catalyst, the properties of the fluidized bed residue hydrotreating catalyst support are as follows: specific surface area of ​​160–400 m² / g. 2 / g, with a pore volume of 0.65~1.30mL / g, and the proportion of pores with a pore size >50nm to the total pore volume >10%.

[0040] A third aspect of the present invention provides an application of the above-mentioned fluidized bed hydrotreating catalyst in the heavy oil hydrotreating process.

[0041] Furthermore, in the application of the above-mentioned fluidized bed hydrotreating catalyst in the heavy oil hydrotreating process, the heavy oil is at least one or more of atmospheric residue, vacuum residue, catalytic slurry, and coal tar.

[0042] Furthermore, in the application of the above-mentioned fluidized bed hydrotreating catalyst in the heavy oil hydrotreating process, the hydrotreating process conditions are as follows: reaction pressure 10–20 MPa, temperature 300–500 °C, and liquid hourly space velocity 0.1–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300–1000.

[0043] Compared with the prior art, the fluidized bed hydrogenation catalyst and its preparation method provided by the present invention have the following advantages:

[0044] 1. In the preparation method of the fluidized bed hydrogenation catalyst of this invention, additives and an aqueous solution of organic polymer B after heat treatment are introduced during the preparation of the catalyst support, so that a carbon layer is formed in the middle of the support. The organic polymer A in the additive only plays a pore-expanding role after reacting with the ammonia phase. After calcination under an inert or nitrogen atmosphere, it can generate macroporous carbon material. On the other hand, after heat treatment, organic polymer B decomposes into small molecules in the aqueous solution, giving the aqueous solution high adhesiveness. This provides good adhesion during the balling process, allowing organic polymer A to have better interaction and enhancing the interaction force between alumina and the carbon layer. This improves the strength and wear resistance of the support, solving the problem of poor wear when using the rolling ball method to coat the inner alumina layer. Simultaneously, after the organic polymer decomposes into small molecules, calcination under an inert or nitrogen atmosphere generates microporous carbon material, improving the structural stability of the carbon layer. This results in a carbon layer in the support containing both macropores and a certain proportion of micropores.

[0045] 2. In the preparation method of the fluidized bed hydrotreating catalyst of the present invention, the support is divided into a core, a middle carbon layer, and an outer layer. The core is microporous alumina with a relatively high specific surface area and relatively small pore size; the middle carbon layer has both macropores and a certain proportion of micropores; and the outer layer is macroporous alumina with a relatively small specific surface area and relatively large pore size. The catalyst prepared using this support solves the problem of mismatch between hydrodemetallization activity, hydrodesulfurization activity, and the ability to accommodate metal impurities in existing hydrotreating catalysts. The outer layer of the catalyst has a large pore size, allowing for effective deposition of metal impurities. The macropores of the middle carbon layer also allow for effective deposition of metal impurities, protecting the internal microporous alumina. Simultaneously, the abundant pore structure ensures the permeability of reactants. The catalyst core has high hydrodesulfurization activity, enabling effective removal of sulfides from the reactants. The catalyst exhibits a non-uniform pore distribution, making it less prone to clogging by metal impurities, ensuring the stability of the catalyst during long-term operation of the unit, and is particularly suitable for heavy oil hydrotreating.

[0046] 3. In the preparation method of the fluidized bed hydrogenation catalyst of the present invention, the support precursor B is treated at low temperature, and the ammonia in the additive will volatilize and interact with the acidic sites on the alumina to undergo adsorption. After the addition of the auxiliary agent, it will interact with the ammonia on the alumina and adsorb on the acidic sites of the alumina. After calcination, the auxiliary agent will occupy the acidic 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.

[0047] 4. After the fluidized bed hydrogenation catalyst of this invention is in operation, a large amount of metallic impurities are deposited on the outer layer of the catalyst, while only impurities such as carbon and sulfur are deposited on the inner layer of the catalyst. During the regeneration process, the carbon layer in the middle of the catalyst is completely burned off, the outer layer of the catalyst will fall off, and the carbon and sulfur impurities in the inner layer of the catalyst will also be completely burned off. Its properties and activity will be well restored, and it can continue to be used as the inner layer of the catalyst to prepare new catalysts, which reduces the cost of catalyst use and simplifies the treatment process of waste catalysts. Detailed Implementation

[0048] 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.

[0049] 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.

[0050] In this invention, the wear index of microsphere carriers >0.8mm is measured by the drum method using a KM-ZV wear meter.

[0051] Example 1

[0052] (1) Carrier preparation

[0053] The first pseudoboehmite powder (specific surface area 330m²) 2 A first carrier precursor of 0.4–0.5 mm was obtained by rolling and forming a ball in a ball rolling machine with a pore volume of 0.8 mL / g. 258.5 g of corn starch was mixed with 120 g of 5 wt% ammonia water to obtain an additive. 12.9 g of corn starch was added to 100 g of water and heated at 70 °C for 20 min to obtain an aqueous solution of organic polymer B. 500 g of the first carrier precursor was placed in the ball rolling machine, and during the rolling process, the additive and the aqueous solution of organic polymer B were evenly sprinkled in. The ball rolling machine rotated at 30 rpm. After ball formation, a second carrier precursor of 0.5–0.6 mm was obtained. 300 g of the second carrier precursor was placed in the ball rolling machine, and during the rolling process, 750 g of second pseudoboehmite powder (specific surface area 290 m²) was evenly sprinkled in. 2 The sample was prepared by mixing 800 mL of a 0.5 wt% nitric acid aqueous solution with a pore volume of 1.08 mL / g and a ball-rolling machine at 30 rpm. After ball formation, a third carrier precursor with a particle size of 0.8–0.9 mm was obtained. The third carrier precursor was subjected to low-temperature heat treatment at 200 °C for 4 h to obtain a fourth carrier precursor. 100 mL of an aqueous solution containing 5.38 g of ferric nitrate was added to 200 g of the fourth carrier precursor, and the mixture was dried at 90 °C for 8 h. Then, it was calcined at 750 °C for 3 h under a nitrogen atmosphere to obtain a spherical carrier with a particle size of 0.8–0.9 mm. The carrier yield and wear data are shown in Table 1, and the physicochemical properties of the carrier are shown in Table 2.

[0054] (2) Catalyst preparation

[0055] Dissolve 1.57g of phosphoric acid H3PO4 (concentration 85wt%) in 50mL of water, then add 4.27g of molybdenum trioxide and 1.88g of basic nickel carbonate, heat to 100℃ and stir under reflux for 2.0h, filter and make up to 85mL to obtain Mo-Ni-P aqueous solution.

[0056] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed evenly, and allowed to stand for 3h. Then it was dried at 110℃ for 4h and calcined at 450℃ for 3h under a nitrogen atmosphere to obtain the catalyst, in which the content of MoO3 was 4.0wt%, the content of NiO was 1.0wt%, and the content of P was 0.4wt%.

[0057] (3) Catalyst evaluation

[0058] The catalyst was evaluated over a long period using a small-scale hydrogenation unit, with an operating time of 1500 hours. The evaluation conditions were: reaction temperature 410℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.3 h⁻¹. -1 The hydrogen-to-oil volume ratio was 500:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0059] Example 2

[0060] (1) Carrier preparation

[0061] The first pseudoboehmite powder (specific surface area 330m²) 2 A first carrier precursor of 0.4–0.5 mm was obtained by rolling and forming a ball in a ball rolling machine with a pore volume of 0.8 mL / g. 619.3 g of corn starch was mixed with 287.5 g of 5 wt% ammonia water to obtain an additive. 30.9 g of corn starch was added to 250 g of water and heated at 70 °C for 20 min to obtain an aqueous solution of organic polymer B. 500 g of the first carrier precursor was placed in a ball rolling machine, and during the rolling process, the additive and the aqueous solution of organic polymer B were evenly sprinkled in. The ball rolling machine rotated at 30 rpm. After ball formation, a second carrier precursor of 0.6–0.7 mm was obtained. 300 g of the second carrier precursor was placed in a ball rolling machine, and during the rolling process, 563 g of second pseudoboehmite powder (specific surface area 290 m²) was evenly sprinkled in. 2 The sample was prepared by mixing 600 mL of a 0.5 wt% nitric acid aqueous solution with a pore volume of 1.08 mL / g and a ball-rolling machine at 30 rpm. After ball formation, a third carrier precursor with a particle size of 0.8–0.9 mm was obtained. The third carrier precursor was subjected to low-temperature heat treatment at 200 °C for 4 h to obtain a fourth carrier precursor. 100 mL of an aqueous solution containing 2.02 g of ferric chloride was added to 200 g of the fourth carrier precursor, and the mixture was dried at 90 °C for 8 h. Then, it was calcined at 800 °C for 3 h under a nitrogen atmosphere to obtain a spherical carrier with a particle size of 0.8–0.9 mm. The carrier yield and wear data are shown in Table 1, and the physicochemical properties of the carrier are shown in Table 2.

[0062] (2) Catalyst preparation

[0063] Dissolve 2.43 g of phosphoric acid H3PO4 (concentration 85 wt%) in 50 mL of water, then add 6.59 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.

[0064] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed evenly, and allowed to stand for 3h. Then it was dried at 110℃ for 4h and calcined at 450℃ for 3h under a nitrogen atmosphere to obtain the catalyst, in which the MoO3 content was 6.0wt%, the NiO content was 1.5wt%, and the P content was 0.6wt%.

[0065] (3) Catalyst evaluation

[0066] The catalyst was evaluated over a long period using a small-scale hydrogenation unit, with an operating time of 1500 hours. The evaluation conditions were: reaction temperature 410℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.3 h⁻¹. -1 The hydrogen-to-oil volume ratio was 500:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0067] Example 3

[0068] (1) Carrier preparation

[0069] The first pseudoboehmite powder (specific surface area 330m²) 2 A first carrier precursor of 0.4–0.5 mm was obtained by rolling and forming particles (0.8 mL / g, pore volume 0.8 mL / g) in a ball rolling machine. 456.3 g of corn starch was mixed with 508 g of 5 wt% ammonia water to obtain an additive. 22.8 g of corn starch was added to 100 g of water and heated at 70 °C for 20 min to obtain an aqueous solution of organic polymer B. 500 g of the first carrier precursor was placed in the ball rolling machine, and during rolling, the additive and the aqueous solution of organic polymer B were evenly sprinkled in. The ball rolling machine rotated at 30 rpm. After ball formation, a second carrier precursor of 0.7–0.8 mm was obtained. 300 g of the second carrier precursor was placed in the ball rolling machine, and during rolling, 500 g of second pseudoboehmite powder (specific surface area 290 m²) was evenly sprinkled in. 2 The sample was prepared by mixing 500 mL of 0.5 wt% nitric acid aqueous solution with a sphere mill speed of 30 rpm. After sphere formation, a third carrier precursor with a particle size of 0.8–0.9 mm was obtained. The third carrier precursor was subjected to low-temperature heat treatment at 200 °C for 4 h to obtain a fourth carrier precursor. 100 mL of an aqueous solution containing 2.19 g of ferric sulfate was added to 200 g of the fourth carrier precursor, dried at 90 °C for 8 h, and then calcined at 850 °C for 3 h under a nitrogen atmosphere to obtain a spherical carrier with a particle size of 0.8–0.9 mm. The carrier yield and wear data are shown in Table 1, and the physicochemical properties of the carrier are shown in Table 2.

[0070] (2) Catalyst preparation

[0071] Dissolve 4.30 g of phosphoric acid H3PO4 (concentration 85 wt%) in 50 mL of water, then add 11.68 g of molybdenum trioxide and 5.16 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and make up to 85 mL to obtain Mo-Ni-P aqueous solution.

[0072] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed evenly, and allowed to stand for 3h. Then it was dried at 110℃ for 4h and calcined at 450℃ for 3h under a nitrogen atmosphere to obtain the catalyst, in which the content of MoO3 was 10.0wt%, the content of NiO was 2.5wt%, and the content of P was 1.0wt%.

[0073] (3) Catalyst evaluation

[0074] The catalyst was evaluated over a long period using a small-scale hydrogenation unit, with an operating time of 1500 hours. The evaluation conditions were: reaction temperature 410℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.3 h⁻¹. -1 The hydrogen-to-oil volume ratio was 500:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0075] Example 4

[0076] (1) Carrier preparation

[0077] The first pseudoboehmite powder (specific surface area 330m²) 2 A first carrier precursor of 0.5–0.6 mm was obtained by rolling and forming a ball in a ball rolling machine with a pore volume of 0.8 mL / g. 1448.7 g of corn starch was mixed with 672.5 g of 5 wt% ammonia water to obtain an additive. 72.3 g of corn starch was added to 560 g of water and heated at 70 °C for 20 min to obtain an aqueous solution of organic polymer B. 500 g of the first carrier precursor was placed in a ball rolling machine, and during the rolling process, the additive and the aqueous solution of organic polymer B were evenly sprinkled in. The ball rolling machine rotated at 30 rpm. After ball formation, a second carrier precursor of 0.8–0.9 mm was obtained. 300 g of the second carrier precursor was placed in a ball rolling machine, and during the rolling process, 390 g of second pseudoboehmite powder (specific surface area 290 m²) was evenly sprinkled in. 2The sample was prepared by mixing 400 mL of a 0.5 wt% nitric acid aqueous solution with a pore volume of 1.08 mL / g and a ball-rolling machine at 30 rpm. After ball formation, a third carrier precursor with a particle size of 1.1–1.2 mm was obtained. The third carrier precursor was subjected to low-temperature heat treatment at 200 °C for 4 h to obtain a fourth carrier precursor. 100 mL of an aqueous solution containing 5.38 g of ferric nitrate was added to 200 g of the fourth carrier precursor, and the mixture was dried at 90 °C for 8 h. Then, it was calcined at 850 °C for 3 h under a nitrogen atmosphere to obtain a spherical carrier with a particle size of 1.1–1.2 mm. The carrier yield and wear data are shown in Table 1, and the physicochemical properties of the carrier are shown in Table 2.

[0078] (2) Catalyst preparation

[0079] Dissolve 4.30 g of phosphoric acid H3PO4 (concentration 85 wt%) in 50 mL of water, then add 11.68 g of molybdenum trioxide and 5.16 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and make up to 85 mL to obtain Mo-Ni-P aqueous solution.

[0080] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed evenly, and allowed to stand for 3h. Then it was dried at 110℃ for 4h and calcined at 450℃ for 3h under a nitrogen atmosphere to obtain the catalyst, in which the content of MoO3 was 10.0wt%, the content of NiO was 2.5wt%, and the content of P was 1.0wt%.

[0081] (3) Catalyst evaluation

[0082] The catalyst was evaluated over a long period using a small-scale hydrogenation unit, with an operating time of 1500 hours. The evaluation conditions were: reaction temperature 410℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.3 h⁻¹. -1 The hydrogen-to-oil volume ratio was 500:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0083] Example 5

[0084] The preparation was essentially the same as in Example 3, except that 456.3g of corn starch was replaced with 456.3g of potato starch, 22.8g of corn starch was replaced with 22.8g of potato starch, and 2.19g of ferric sulfate was replaced with 5.38g of ferric nitrate. Spherical supports with a particle size of 0.8–0.9 mm were obtained. The support yield and wear data are shown in Table 1, and the physicochemical properties of the support are shown in Table 2. A catalyst was prepared, containing 10.0 wt% MoO3, 2.5 wt% NiO, and 1.0 wt% P.

[0085] 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.

[0086] Example 6

[0087] The preparation was essentially the same as in Example 3, except that 456.3g of corn starch was replaced with 384.0g of methylcellulose, and 22.8g of corn starch was replaced with 19.2g of methylcellulose. Spherical supports with a particle size of 0.8–0.9 mm were obtained. The support yield and wear data are shown in Table 1, and the physicochemical properties of the support are shown in Table 2. A catalyst was prepared, containing 10.0 wt% MoO3, 2.5 wt% NiO, and 1.0 wt% P.

[0088] 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.

[0089] Comparative Example 1

[0090] (1) Carrier preparation

[0091] The first pseudoboehmite powder (specific surface area 330m²) 2 A first carrier precursor of 0.4–0.5 mm was obtained by rolling and forming a ball in a ball rolling machine with 258.5 g of corn starch and 220 g of 5% ammonia water to obtain an additive. 500 g of the first carrier precursor was weighed and placed into the ball rolling machine. During rolling, the additive, 12.9 g of corn starch, and water were evenly sprinkled in. The ball rolling machine was rotated at 30 rpm. After ball formation, a second carrier precursor of 0.5–0.6 mm was obtained. 300 g of the second carrier precursor was weighed and placed into the ball rolling machine. During rolling, 750 g of second pseudoboehmite powder (specific surface area 290 m²) was evenly sprinkled in. 2 The sample was prepared by mixing 800 mL of a 0.5 wt% nitric acid aqueous solution with a pore volume of 1.08 mL / g and a ball-rolling machine at 30 rpm. After ball formation, a third carrier precursor with a particle size of 0.8–0.9 mm was obtained. The third carrier precursor was subjected to low-temperature heat treatment at 200 °C for 4 h to obtain a fourth carrier precursor. 100 mL of an aqueous solution containing 5.38 g of ferric nitrate was added to 200 g of the fourth carrier precursor, and the mixture was dried at 90 °C for 8 h. Then, it was calcined at 750 °C for 3 h under a nitrogen atmosphere to obtain a spherical carrier with a particle size of 0.8–0.9 mm. The carrier yield and wear data are shown in Table 1, and the physicochemical properties of the carrier are shown in Table 2.

[0092] (2) Catalyst preparation

[0093] Dissolve 1.57g of phosphoric acid H3PO4 (concentration 85wt%) in 50mL of water, then add 4.27g of molybdenum trioxide and 1.88g of basic nickel carbonate, heat to 100℃ and stir under reflux for 2.0h, filter and make up to 85mL to obtain Mo-Ni-P aqueous solution.

[0094] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed evenly, and allowed to stand for 3h. Then it was dried at 110℃ for 4h and calcined at 450℃ for 3h under a nitrogen atmosphere to obtain the catalyst, in which the content of MoO3 was 4.0wt%, the content of NiO was 1.0wt%, and the content of P was 0.4wt%.

[0095] (3) Catalyst evaluation

[0096] The catalyst was evaluated over a long period using a small-scale hydrogenation unit, with an operating time of 1500 hours. The evaluation conditions were: reaction temperature 410℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.3 h⁻¹. -1 The hydrogen-to-oil volume ratio was 500:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0097] Comparative Example 2

[0098] (1) Carrier preparation

[0099] The first pseudoboehmite powder (specific surface area 330m²) 2 A first carrier precursor of 0.4–0.5 mm was obtained by rolling and forming a ball in a ball rolling machine with a pore volume of 0.8 mL / g. 12.9 g of corn starch was added to 150 g of water and heated at 70 °C for 20 min to obtain an aqueous solution of organic polymer B. 500 g of the first carrier precursor was placed in the ball rolling machine, and during the rolling process, 258.5 g of corn starch and the aqueous solution of organic polymer B were evenly sprinkled in. The ball rolling machine was rotated at 30 rpm. After ball formation, a second carrier precursor of 0.5–0.6 mm was obtained. 300 g of the second carrier precursor was placed in the ball rolling machine, and during the rolling process, 750 g of second pseudoboehmite powder (specific surface area 290 m²) was evenly sprinkled in. 2 The sample was prepared by mixing 800 mL of a 0.5 wt% nitric acid aqueous solution with a pore volume of 1.08 mL / g and a ball-rolling machine at 30 rpm. After ball formation, a third carrier precursor with a particle size of 0.8–0.9 mm was obtained. The third carrier precursor was dried at 120 °C for 4 h to obtain a fourth carrier precursor. 100 mL of an aqueous solution containing 5.38 g of ferric nitrate was added to 200 g of the fourth carrier precursor, and the mixture was dried at 90 °C for 8 h. Then, it was calcined at 750 °C for 3 h under a nitrogen atmosphere to obtain a spherical carrier with a particle size of 0.8–0.9 mm. The carrier yield and wear data are shown in Table 1, and the physicochemical properties of the carrier are shown in Table 2.

[0100] (2) Catalyst preparation

[0101] Dissolve 1.57g of phosphoric acid H3PO4 (concentration 85wt%) in 50mL of water, then add 4.27g of molybdenum trioxide and 1.88g of basic nickel carbonate, heat to 100℃ and stir under reflux for 2.0h, filter and make up to 85mL to obtain Mo-Ni-P aqueous solution.

[0102] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed evenly, and allowed to stand for 3h. Then it was dried at 110℃ for 4h and calcined at 450℃ for 3h under a nitrogen atmosphere to obtain the catalyst, in which the content of MoO3 was 4.0wt%, the content of NiO was 1.0wt%, and the content of P was 0.4wt%.

[0103] (3) Catalyst evaluation

[0104] The catalyst was evaluated over a long period using a small-scale hydrogenation unit, with an operating time of 1500 hours. The evaluation conditions were: reaction temperature 410℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.3 h⁻¹. -1 The hydrogen-to-oil volume ratio was 500:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0105] Table 1 Carrier yield and wear

[0106]

[0107] Table 2 Physicochemical properties of the carrier

[0108]

[0109] Table 3 Properties of Feed Oil

[0110]

[0111] Table 4 Catalyst Evaluation Results

[0112]

[0113] 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 fluidized bed hydrotreating catalyst, the method comprising the following steps: (1) The first pseudo-boehmite powder is subjected to spheroidization treatment to obtain the first carrier precursor; (2) The first carrier precursor is placed in a ball rolling machine, and additives and an aqueous solution of organic polymer B after heat treatment are added evenly during the rolling process. After treatment, the second carrier precursor is obtained. The additive is a mixture of organic polymer A and a nitrogen-containing weak base compound. Organic polymer A is one or more of starch, cellulose ether and flour. The nitrogen-containing weak base compound is one or more of ammonia, ammonium carbonate and ammonium bicarbonate. Organic polymer B is one or more of starch, cellulose ether and flour. Organic polymer B is added to water and heated and mixed at 60-100°C for 10-40 minutes. After organic polymer B is completely dissolved, an aqueous solution of organic polymer B after heat treatment is obtained. (3) The second carrier precursor is placed in a ball rolling machine, and the second pseudoboehmite powder and acidic solution are added evenly during the rolling process. After treatment, the third carrier precursor is obtained. (4) The third carrier precursor is subjected to low-temperature heat treatment to obtain the fourth carrier precursor; the low-temperature heat treatment temperature is 100-300℃. (5) The fourth carrier precursor is mixed with a soluble iron salt solution. After the mixture is evenly mixed, it is dried and calcined under an inert atmosphere to obtain a carbon-containing alumina composite carrier modified with auxiliary metal components. (6) Introduce a hydrogenation active metal component onto the composite support obtained in step (5). The hydrogenation active metal component is one or more of Group VIB metals and / or Group VIII metals. P is introduced when introducing the hydrogenation active metal component. The catalyst is further dried and calcined to obtain a fluidized bed hydrogenation treatment catalyst.

2. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The properties of the first pseudoboehmite powder after calcination at 550–750℃ are as follows: specific surface area is 300–550 m². 2 / g, pore volume is 0.4~1.0mL / g, average pore diameter is 4~12nm, and pore volume with a diameter <10nm accounts for 60%~75% of the total pore volume.

3. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The spherical forming process in step (1) adopts one or more of the following methods: extrusion ball forming, rolling forming, and spray drying forming.

4. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The particle size of the first carrier precursor in step (1) is 0.1 to 1.0 mm.

5. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The organic polymer A in step (2) is starch.

6. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The starch is one or more of the following: 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 the following: methylcellulose, hydroxyethyl methylcellulose, carboxymethylcellulose, ethylcellulose, benzylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, cyanoethylcellulose, benzyl cyanoethylcellulose, carboxymethyl hydroxyethylcellulose, and phenylcellulose.

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

8. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The nitrogen-containing weak base compound in step (2) is ammonia.

9. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: In step (2), the mass ratio of organic polymer A to nitrogen-containing weak base compound is 1:0.05 to 1:0.

5.

10. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The organic polymer B in step (1) is starch.

11. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The concentration of the aqueous solution of organic polymer B after heat treatment in step (2) is 0.5wt% to 5wt%.

12. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The concentration of the aqueous solution of organic polymer B after heat treatment in step (2) is 1wt% to 3wt%.

13. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The properties of the second pseudoboehmite powder in step (3) after calcination at 550–750℃ are as follows: specific surface area is 200–320 m². 2 / g, pore volume is 0.8~1.2mL / g, average pore diameter is 10~30nm, and pore volume of pores with diameter >10nm accounts for 60%~75% of the total pore volume.

14. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The acidic solution in step (3) is one or more of acetic acid solution, nitric acid solution and oxalic acid solution; the concentration of the acidic solution is 0.1wt% to 8wt%; the mass ratio of the amount of acidic solution added to the dry basis of the second pseudoboehmite powder is 0.8 to 1.

5.

15. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The acidic solution in step (3) is a nitric acid solution; the concentration of the acidic solution is 0.3wt% to 5wt%; the mass ratio of the amount of acidic solution added to the dry basis of the second pseudoboehmite powder is 0.8 to 1.

5.

16. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The low-temperature heat treatment temperature in step (4) is 150-250℃; the low-temperature heat treatment time is 1-8h.

17. The method for preparing the fluidized bed hydrotreating catalyst according to claim 16, characterized in that: The low-temperature heat treatment time is 3 to 6 hours.

18. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The soluble iron salt in step (5) is one or more of ferric nitrate, ferric chloride and ferric sulfate.

19. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The drying temperature in step (5) is 60-90℃.

20. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: In step (5), the calcination is carried out under an inert atmosphere, which is one or more of nitrogen, helium, neon, argon, krypton and xenon; the calcination temperature is 600-900℃ and the calcination time is 1-5h.

21. The method for preparing the fluidized bed hydrogenation catalyst according to claim 20, characterized in that: The inert atmosphere is nitrogen.

22. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The particle size of the carbon-containing alumina composite carrier in step (5) is 0.2 to 2.0 mm.

23. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The particle size of the carbon-containing alumina composite carrier in step (5) is 0.3 to 1.8 mm.

24. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The drying conditions in step (6) are as follows: the drying temperature is 80-120℃ and the drying time is 4-12h.

25. The method for preparing the fluidized bed hydrogenation catalyst according to claim 1, characterized in that: The roasting in step (6) is carried out under an inert atmosphere, which is one or more of nitrogen, helium, neon, argon, krypton and xenon. The roasting conditions are as follows: the roasting temperature is 400-600℃ and the roasting time is 1-5h.

26. The method for preparing the fluidized bed hydrogenation catalyst according to claim 25, characterized in that: The inert atmosphere is nitrogen.

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

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

29. A fluidized bed hydrotreating catalyst obtained by the preparation method according to any one of claims 1-28, the fluidized bed hydrotreating catalyst comprising a hydrotreating active metal component, a support, an auxiliary metal component, and phosphorus pentoxide, wherein the hydrotreating active metal component is one or more of Group VIB metals and / or Group VIII metals; the auxiliary metal component is iron; and the support is a carbon-containing alumina composite support, wherein the carbon content in the composite support is 5wt% to 20wt%.

30. The fluidized bed hydrotreating catalyst according to claim 29, characterized in that: The properties of the catalyst support for fluidized bed hydrotreating are as follows: specific surface area of ​​160–400 m². 2 / g, with a pore volume of 0.65~1.30mL / g, and the proportion of pores with a pore size >50nm to the total pore volume >10%.

31. The application of the fluidized bed hydrotreating catalyst of claim 29 or 30 in the heavy oil hydrotreating process.

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

33. The application according to claim 31, characterized in that: The process conditions for heavy oil hydrotreating are as follows: reaction pressure 10–20 MPa, temperature 300–500 °C, and liquid hourly space velocity (LHSV) 0.1–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300–1000.

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