Hydrodemetallization catalyst as well as preparation method and application thereof

Abstract

The invention provides a hydrodemetallization catalyst and a preparation method and application thereof, and the preparation method comprises the following steps: step 1, mixing an alumina precursor, polyvinyl butyral resin, an adhesive and a solvent, kneading, molding, and roasting to obtain an alumina carrier; the solvent comprises an organic solvent and water; and 2, impregnating the alumina carrier in a metal impregnation liquid, curing, and roasting to obtain the hydrodemetallization catalyst. According to the invention, polyvinyl butyral resin is used as a pore-enlarging agent and is partially dissolved under the action of an organic solvent, and after extension crosslinking, a macroporous diffusion channel of more than 100nm is formed in the alumina carrier, and the volume of macropores accounts for more than 10% of the total pore volume, so that a channel can be provided for diffusion of macromolecular reaction substances; and impurities can be promoted to be diffused and deposited into internal pore channels of the catalyst, so that the catalyst has high demetallization activity and high impurity capacity.

Description

Technical Field

[0001] This invention relates to the field of heavy and inferior residual oil treatment, specifically to a hydrodemetallization catalyst, its preparation method, and its application. Background Technology

[0002] Currently, the global oil refining industry is facing the severe challenge of increasingly heavy and inferior crude oil resources. Residue oil typically accounts for 45% to 75% of crude oil, and its properties are significantly inferior to fractions such as gas oil with lower boiling ranges. Therefore, the key to maximizing the production of light products and chemical feedstocks in crude oil deep processing lies in the efficient conversion and utilization of residue oil.

[0003] Residue hydrotreating is the most effective processing technology for heavy and residual oil feedstocks. Hydrotreating removes most of the metals, sulfur, and nitrogen impurities from the residue, reducing its carbon residue and facilitating further efficient processing and conversion. The combination of residue hydrotreating and residue catalytic cracking (RFCC) has become a key technological path for refining enterprises processing low-quality crude oil to improve economic efficiency. This combination not only maximizes the conversion of low-value, environmentally polluting residue, significantly increasing the yield of light oil, but also yields high-value, high-quality clean oil products. In a sense, it achieves 100% conversion of crude oil, realizing the goal of fully utilizing crude oil in the refining process. This technological combination has become a core technology for refining enterprises processing sulfur-containing crude oil to improve economic efficiency.

[0004] Catalysts are the core of residue hydrotreating technology and play a decisive role in the stable and efficient operation of residue hydrotreating units. The residue hydrotreating process differs from distillate hydrotreating; its operating space velocity and operating cycle are much shorter, and the catalyst loading is large and deactivation is rapid.

[0005] Residue oil is the heaviest and lowest-quality component of petroleum, containing large amounts of gums and asphaltenes. It has a large molecular weight, high density, high viscosity, strong polarity, and high sulfur and carbon content, enriching it with almost all the metallic impurities found in petroleum. During the hydrotreating of residue oil, the deposition of metals such as Na, Ca, Ni, and V on the hydrotreating catalyst can cause permanent poisoning, a core factor to consider in the hydrotreating process of heavy and low-quality residue oil. Hydrodemetallization (HDM) catalysts are one of the key technologies in the hydrotreating process of heavy oil. Their main function is to remove most of the Ni and V metallic impurities from the feedstock, protecting downstream desulfurization (HDS) and denitrification (HDN) catalysts, while also possessing a certain desulfurization capacity. These catalysts not only need good metal removal capabilities but also a high capacity to accommodate metallic impurities. Since most metallic impurities in residue oil are located in gums and asphaltenes, diffusion resistance is high. The demetallization agent is limited by the mass transfer and diffusion efficiency of the carrier, easily leading to pore blockage, severely uneven deposition of removed impurities, and limited metal-accepting capacity. All of the above result in a significant waste of the catalyst's internal space, preventing the catalyst from reaching its maximum efficiency. Therefore, such catalysts must possess large pore volume, pore size, and good pore permeability to facilitate the diffusion, reaction, and deposition of large molecules such as asphaltene containing metallic impurities in the residual oil feedstock. One solution is to employ a bimodal pore structure support. During the reaction, the large pores provide channels for the diffusion of large molecular reactants, promoting the diffusion and deposition of impurities into the catalyst's internal pores; while the smaller pore diameter provides the reaction surface and deposition site for impurities. The synergistic effect of these two types of pores results in a catalyst with high demetallization activity and high impurity tolerance.

[0006] In existing alumina support preparation technologies, acidic substances such as nitric acid, acetic acid, and aluminum nitrate are often added as binders during alumina molding. However, the addition of these acidic substances can damage the particle structure of alumina, reducing the pore volume and pore size of the support. Using organic binders instead of peptizing acids for support molding can increase the pore volume and pore size to some extent, but the effect is limited. Existing methods that increase the proportion of macropores in the support simply by adding pore-expanding agents face problems such as increased cost, molding difficulties, and decreased strength when preparing supports and catalysts with a high macropore ratio and bimodal pore structure.

[0007] Patent CN1103009A discloses a method for preparing a dual-pore alumina carrier. This method involves mixing two types of alumina or their precursors with different pore sizes, carbon black powder, a surfactant, a binder, and water, followed by drying and calcination. When carbon black powder is used as a pore-expanding agent, carrier formation is difficult, the pore-expanding effect is poor, and the carrier strength is low. Furthermore, the addition of the binder reduces the pore volume and pore size of the carrier.

[0008] Patent CN105983443B discloses a method for preparing a bimodal porous alumina carrier. This method involves mixing an organic binder, a chemical pore expander, and a physical pore expander, followed by molding and calcination to obtain a macroporous bimodal porous alumina carrier. However, this method results in limited pore size increase, a large pore ratio significantly affected by the amount of pore expander added, difficulty in extrusion molding, low carrier strength, high calcination temperature, and high production costs.

[0009] On the other hand, in addition to good hydrotreating and impurity removal activity, operational stability is crucial for residue hydrotreating catalysts. The activity and stability of residue hydrotreating catalysts are closely related to their active phase structure; the active metal needs to be highly dispersed on the support surface. Generally, the shorter the active metal lamellar size and the fewer the number of layers, the better the dispersion and the superior the catalyst's activity and stability. By developing novel active metal solution systems that are simple to operate, environmentally friendly, and exhibit excellent stability, the interaction between the support and the active metal can be reduced, improving the dispersion of the active metal in the residue hydrotreating catalyst, decreasing the length and number of MoS2 lamellar layers, and generating a greater proportion of 1-2 layer MoS2 lamellae. This enhances the catalyst's activity and stability, improves its adaptability to processing inferior feedstocks during hydrotreating reactions, extends the operating cycle, and increases operational efficiency.

[0010] Traditional catalysts are produced using an ammonia-containing metal solution system, which generates large amounts of ammonia gas during solution preparation, impregnation, drying, and calcination. This poses a health risk to workers and pollutes the atmosphere. To address ammonia pollution, existing technologies use phosphoric acid to prepare active metal impregnation solutions. However, catalysts prepared with phosphoric acid exhibit poor active metal dispersion, and excessively high phosphorus content leads to overly acidic catalysts. This results in catalysts prone to coking and rapid deactivation during hydrotreating, exhibiting insufficient stability and failing to meet the requirements for hydrotreating low-quality heavy residue oil.

[0011] Patent CN1230491C discloses a method for preparing a catalyst impregnation solution. The method involves using 12-24 wt% ammonia water to dissolve salts containing Group VIB or Group VIII metals, or mixtures thereof, and then treating the solution with ultrasound during and / or after dissolution. This method uses a large amount of ammonia water during solution preparation, leading to significant ammonia gas release during impregnation, drying, and calcination. This results in a harsh operating environment, difficult exhaust gas treatment, and severe environmental pollution. Furthermore, the need for ultrasound makes large-scale production a costly undertaking with poor operability.

[0012] Patent CN114425354B discloses a method for preparing a heavy oil hydrogenation catalyst. This method involves preparing an aqueous solution containing citric acid, phosphoric acid, amine compounds, a surfactant, and at least one active metal as an impregnation solution. In preparing the solution, a compound containing molybdenum and nickel is first dissolved under heating conditions using phosphoric acid and citric acid. Then, the amine compound and surfactant are added to obtain the active metal impregnation solution. This invention provides a stable impregnation solution, does not use volatile ammonia, and is environmentally friendly. However, the use of phosphoric acid in the metal solution increases the acidity of the catalyst, resulting in the metal component existing in the form of heteropolyacids or isopolyacid salts. The active phase structure exhibits a high relative content of two-dimensional aggregated octahedral molybdenum, leading to poor metal dispersion. When processing low-quality residual oil feedstock, the catalyst is prone to coking, resulting in insufficient hydrogenation activity and stability.

[0013] Patent CN103007949B discloses a method for preparing a hydrogenation catalyst, comprising the following steps: dissolving salts of Group VIB and Group VIII metals in a 10-45 wt%, preferably 30 wt%, hydrogen peroxide aqueous solution to obtain an impregnation solution; simultaneously adding a dicarboxylic acid or tricarboxylic acid (including citric acid, tartaric acid, and oxalic acid) containing 2-12 carbons as a dispersant to impregnate a support; and then drying and calcining to obtain a hydrogenation catalyst with a bimetallic component. This method effectively reduces the interaction between the active component and the support, improves the dispersion of the active component on the support, and exhibits good hydrogenation performance. However, this method uses high-concentration hydrogen peroxide to dissolve the metal salts, posing certain safety hazards during the drying and calcination stages; furthermore, the solution has poor stability, and the metal component is prone to decomposition and precipitation during impregnation and drying processes, which is detrimental to the efficient utilization of the active metal.

[0014] Therefore, further research is needed in this field on hydrogenation demetallization catalysts. Summary of the Invention

[0015] The main objective of this invention is to provide a hydrogenation demetallization catalyst, its preparation method, and its application, so as to overcome the defects of existing technologies such as weak demetallization ability, weak metal impurity tolerance, and poor catalyst activity stability.

[0016] To achieve the above objectives, the present invention provides a method for preparing a hydrogenation demetallization catalyst, comprising the following steps:

[0017] Step 1: Mix the alumina precursor, polyvinyl butyral resin, binder and solvent, knead, shape and calcine to obtain the alumina carrier; the solvent includes organic solvent and water.

[0018] Step 2: Impregnate the alumina support with a metal impregnation solution, allow it to cure, and then calcine to obtain a hydrogenation demetallization catalyst.

[0019] The method for preparing the hydrogenation demetallization catalyst of the present invention, wherein the polyvinyl butyral resin has an average weight-average molecular weight of 1.0 × 10⁻⁶. 4 -15.0×10 4 ; and / or, the viscosity of the polyvinyl butyral resin in a 5% ethanol solution at 20°C is 5.0-200.0 mPa·s; and / or, the particle size of the polyvinyl butyral resin is 80-3000 mesh.

[0020] The method for preparing the hydrogenation demetallization catalyst of the present invention includes alumina precursor comprising 100% by mass and polyvinyl butyral resin comprising 2.0%-25.0% by amount.

[0021] The method for preparing the hydrogenation demetallization catalyst of the present invention includes the following: the alumina precursor is hydrated alumina, the binder is synthetic cellulose, the mass of alumina in the alumina precursor is 100%, the amount of binder added is 1%-5%, and the amount of organic solvent added is 2.0%-10.0%.

[0022] The preparation method of the hydrodemetallization catalyst of the present invention includes:

[0023] Step A: Mix the active metal precursor, organic acid, and hydrogen peroxide to form a metal solution;

[0024] Step B: Mix the metal solution with the composite complexing agent to obtain a metal impregnation solution;

[0025] The composite complexing agent is a polycarboxylic acid scale inhibitor and an organic phosphorus compound.

[0026] The method for preparing the hydrogenation demetallization catalyst of the present invention comprises the following: the polycarboxylic acid scale inhibitor is selected from at least one of polyepoxysuccinic acid, polyacrylic acid, hydrolyzed polymaleic anhydride, maleic acid-acrylic acid copolymer, polyaspartic acid, acrylate-hydroxypropyl acrylate copolymer, and acrylate-2-acrylamide-2-methylpropanesulfonic acid copolymer; the organic phosphorus-containing compound is selected from at least one of aminotrimethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, hydroxyethylidene diphosphonic acid, and ethylenediaminetetramethylenephosphonic acid; and / or, the amount of the polycarboxylic acid scale inhibitor added to the metal impregnation solution is 0.5-15.0 g / 100 cm³. 3 The amount of the organic phosphorus-containing compound added is 0.5-10.0 g / 100 cm³. 3 .

[0027] The method for preparing the hydrogenation demetallization catalyst of the present invention comprises, wherein the active metal precursor includes at least one Group VIII metal compound and at least one Group VIB metal compound; the organic acid is selected from at least one of tartaric acid, oxalic acid, malic acid, citric acid, succinic acid, and maleic acid; and the amount of the Group VIII metal compound added to the metal impregnation solution, calculated as metal oxide, is 0.5-5.0 g / 100 cm³. 3 The amount of Group VIB metal compounds added, calculated as metal oxides, is 2.0-18.0 g / 100 cm³. 3 In the metal impregnation solution, the amount of organic acid added is 1.0-12.0 g / 100 cm³. 3 ; and / or, in the metal impregnation solution, the amount of hydrogen peroxide added, calculated as H2O2, is 0.1-4.0 g / 100 cm³. 3 .

[0028] The preparation method of the hydrogenation demetallization catalyst of the present invention, wherein step A includes the following steps:

[0029] Step A1: Mix the Group VIB metal compound, organic acid, and water to completely dissolve the Group VIB metal compound;

[0030] Step A2: Mix the mixture obtained in step A1 with a Group VIII metal compound to obtain a metal mixture solution;

[0031] Step A3: Mix the metal mixture solution obtained in step A2 with hydrogen peroxide to form a metal solution.

[0032] The preparation method of the hydrogenation demetallization catalyst of the present invention includes a calcination temperature of 500-1200℃ in step 1 and a calcination temperature of 400-700℃ in step 2.

[0033] To achieve the above objectives, the present invention also provides a hydrodemetallization catalyst, comprising an alumina support and an active metal, wherein the active metal is supported on the alumina support, and the specific surface area of ​​the alumina support is 80-240 m². 2 / g, pore volume 0.5-1.5cm³ 3 / g, with a bimodal pore distribution, the sum of the pore volumes of channels with a pore diameter greater than 100nm accounts for ≥10% of the total pore volume of the alumina carrier; the lateral compressive strength of the alumina carrier is ≥14.5N / mm.

[0034] To achieve the above objectives, the present invention also provides the application of the above-mentioned hydrodemetallization catalyst in the hydrodemetallization of residue oil.

[0035] The beneficial effects of this invention are:

[0036] (1) In this invention, polyvinyl butyral resin is used as a pore expander. It is partially dissolved under the action of organic solvent. After extension and cross-linking, it forms a macroporous diffusion channel of more than 100 nm in the alumina support. The macroporous volume accounts for more than 10% of the total pore volume. It can provide a channel for the diffusion of macromolecular reactants and promote the diffusion and deposition of impurities into the internal pores of the catalyst, so that the catalyst has high demetallization activity and high impurity tolerance.

[0037] (2) The catalyst support prepared by the present invention is inexpensive, easy to form, and, more importantly, has high strength, which can meet the requirements of hydrogenation demetallization catalyst. Attached Figure Description

[0038] Figure 1 The images show the laser Raman spectra of the metal impregnation solutions prepared in Examples 2, 1, and 2 of this invention.

[0039] Figure 2 This is a TEM transmission electron microscope image of catalyst B prepared in Example 2 of the present invention.

[0040] Figure 3 This is a TEM transmission electron microscope image of catalyst D prepared in Example 4 of the present invention.

[0041] Figure 4 This is a TEM transmission electron microscope image of catalyst G prepared in Comparative Example 1 of the present invention.

[0042] Figure 5 This is a mercury porosimetry pore size distribution diagram of the carrier a prepared in Example 1 of the present invention. Detailed Implementation

[0043] The technical solution of the present invention will be described in detail below. The following embodiments are implemented under the premise of the technical solution of the present invention and a detailed implementation process is given. However, the protection scope of the present invention is not limited to the following embodiments. Structures or experimental methods that do not specify specific conditions in the following embodiments are generally performed under conventional conditions.

[0044] This invention provides a method for preparing a hydrogenation demetallization catalyst, comprising the following steps:

[0045] Step 1: Mix the alumina precursor, polyvinyl butyral resin, binder and solvent, knead, shape and calcine to obtain the alumina carrier; the solvent includes organic solvent and water.

[0046] Step 2: Impregnate the alumina support with a metal impregnation solution, allow it to cure, and then calcine to obtain a hydrogenation demetallization catalyst.

[0047] This invention uses polyvinyl butyral resin as a pore-expanding agent. It partially dissolves in an organic solvent, and after extension and cross-linking, forms macroporous diffusion channels larger than 100 nm in an alumina support. The macropore volume accounts for more than 10% of the total pore volume, thus enabling the catalyst to possess high demetallization activity and high impurity tolerance. Furthermore, the addition of the pore-expanding agent does not affect the catalyst strength; that is, the resulting catalyst still possesses high strength, is easy to mold, and has low preparation cost.

[0048] The catalyst prepared by the method of the present invention has a bimodal pore structure, good activity stability, and high metal tolerance, and is suitable for the hydrotreating process of heavy and inferior residue oil with high metal content.

[0049] Step 1 of this invention involves mixing an alumina precursor, polyvinyl butyral resin, an adhesive, and a solvent, kneading, molding, and calcining to obtain an alumina carrier; the solvent includes organic solvents and water.

[0050] In one embodiment, the alumina precursor is hydrated alumina, such as at least one selected from gibbsite, boehmite, pseudoboehmite, and amorphous aluminum hydroxide, preferably pseudoboehmite. The alumina precursor of this invention can be a commercially available product or prepared according to methods in the prior art, such as pseudoboehmite prepared using the aluminum sulfate-sodium aluminate method.

[0051] In one embodiment, the average weight-average molecular weight of the polyvinyl butyral resin is 1.0 × 10⁻⁶. 4 -15.0×10 4 Preferred size: 1.5×10 4 -10.0×10 4 The viscosity of polyvinyl butyral resin at 20°C in a 5wt% ethanol solution is 5.0-200.0 mPa·s, preferably 10.0-150.0 mPa·s, wherein the 5wt% ethanol solution refers to a solution containing 5wt% polyvinyl butyral resin, and the solvent is ethanol; the particle size is 80-3000 mesh, preferably 100-2000 mesh.

[0052] In another embodiment, the amount of polyvinyl butyral resin added is 2.0%-25.0%, based on the mass of alumina in the alumina precursor being 100%.

[0053] In one embodiment, the binder is synthetic cellulose, the viscosity of a 2 wt% aqueous solution of which is not less than 50,000 mPa·s at 20°C. For example, it is selected from one or more of methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, and hydroxyethyl methylcellulose, preferably hydroxypropyl methylcellulose. In another embodiment, the amount of binder added is 1%-5%, based on 100% of the mass of alumina in the alumina precursor.

[0054] In this invention, the solvent includes an organic solvent and water. The organic solvent is selected from alcohols, ketones, esters, halogenated hydrocarbons, etc., and more specifically, for example, one or more of methanol, ethanol, butanol, acetone, methyl ethyl ketone, cyclohexanone, dichloromethane, chloroform, methyl acetate, ethyl acetate, and butyl acetate. Based on the mass of alumina in the alumina precursor as 100%, the amount of organic solvent added is 2.0%-10.0%.

[0055] In one embodiment, the solvent is at a temperature of 30-100°C, preferably 40-80°C, before being mixed with other substances.

[0056] The alumina carrier of this invention can be supplemented with various additives as needed, including but not limited to one or more elements such as silicon, phosphorus, boron, titanium, zirconium, chlorine, and fluorine. Various molecular sieves can also be added as needed, including but not limited to one or more of X, Y, ZSM-5, β, phosphorus aluminum, titanium silicon, ZSM-41, and SBA-15 molecular sieves.

[0057] The present invention does not specifically limit the shape of the alumina carrier, and can be changed as needed, including but not limited to strips, spheres, Raschig rings, toothed balls, honeycombs, impellers, etc., wherein the strip shape includes but is not limited to cylinders, clover, four-leaf clover, butterfly, etc.

[0058] In one embodiment, the carrier formed in step 1 is dried at a temperature of 100-180°C, preferably 120-160°C, and then calcined at a temperature of 500-1200°C, preferably 700-1000°C, for a time of 1-4 hours.

[0059] The catalyst support prepared by the method of this invention has a specific surface area of ​​80-240 m². 2 / g, preferably 100-200m 2 / g, pore volume 0.5-1.5cm³ 3 / g, preferably 0.6-1.2cm 3 / g, the sum of the pore volumes of channels with a pore diameter greater than 100nm accounts for ≥10% of the total pore volume.

[0060] Step 2 of this invention involves impregnating an alumina support with a metal impregnation solution, curing it, and calcining it to obtain a hydrogenation demetallization catalyst.

[0061] The metal impregnation solution is a liquid containing an active metal precursor. The metal impregnation solution of the present invention can be prepared using conventional methods in the art, such as mixing the active metal precursor with water.

[0062] In one embodiment, the method for preparing the metal impregnation solution of the present invention includes:

[0063] Step A: Mix the active metal precursor, organic acid, and hydrogen peroxide to form a metal solution;

[0064] Step B: Mix the metal solution with the composite complexing agent to obtain a metal impregnation solution;

[0065] The composite complexing agent is a polycarboxylic acid scale inhibitor and an organic phosphorus compound.

[0066] This invention utilizes organic acids to prepare the metal solution system. The organic acid anions possess coordination sites capable of forming coordinate bonds with metal ions. Through coordination with active metal ions, the organic acid anions can form stable complexes. Furthermore, the weak acidity of the organic acid reduces corrosion and loss of the support. Hydrogen peroxide undergoes a redox reaction under acidic conditions, promoting the formation of more stable oxidation products from the active metal and weakening the interaction between the active component and the alumina support. This positively impacts the activity and stability of the final residue hydrotreating catalyst. The metal impregnation solution preparation process does not use volatile ammonia, making the solution system green and environmentally friendly, and the production process environmentally friendly.

[0067] The composite complexing agent used in this invention has strong complexing ability and good solution stability. Through efficient complexation, the length of the metal active phase lamellae can be shortened, the number of lamellar layers can be reduced, and a higher proportion of 1-2 lamellar structures can be generated, achieving high dispersion loading of the active metal and improving catalyst activity and stability. In addition, the use of organic phosphorus compounds in the composite complexing agent introduces an appropriate amount of phosphorus into the acidic active metal solution system, which can effectively weaken the strong interaction between the active component and the support, optimize the structure of the metal active phase, and further improve the dispersion of active metal in the residue hydrotreating catalyst; at the same time, it avoids problems such as excessive phosphorus, excessive acidity, and metal component aggregation caused by using phosphoric acid to prepare the active metal solution, prevents the increase in the number and length of the catalyst active phase lamellar layers, and avoids the decrease in stability of the catalyst during the hydrogenation reaction.

[0068] In this invention, the active metal precursor is used to provide the active metal for the hydrodemetallization catalyst. Any metal suitable for use as a hydrodemetallization catalyst in the art can be used as the active metal in this invention. In one embodiment, the active metal precursor includes at least one Group VIII metal compound and at least one Group VIB metal compound. The Group VIII metal compound is preferably a nickel compound and / or a cobalt compound, most preferably a nickel compound; the Group VIB metal compound is preferably a molybdenum compound and / or a tungsten compound, most preferably a molybdenum compound. The active metal precursor is a metal oxide, a metal salt, etc., and the metal salt is, for example, a basic carbonate, sulfate, nitrate, acetate, chloride, etc. of a metal. Specifically, the nickel compound can be basic nickel carbonate, nickel sulfate, nickel nitrate, nickel acetate, nickel chloride, etc., preferably nickel nitrate and nickel acetate; the molybdenum compound can be molybdenum trioxide, ammonium heptamolybdate (ammonium molybdate tetrahydrate), ammonium tetramolybdate, ammonium orthomolybdate, ammonium octamolybdate, ammonium dodecamolybdate, etc., preferably molybdenum trioxide and ammonium heptamolybdate.

[0069] In another embodiment, the amount of Group VIII metal compound added to the active metal impregnation solution, calculated as metal oxide, is 0.5-5.0 g / 100 cm³. 3 The amount of Group VIB metal compounds added, calculated as metal oxides, is 2.0-18.0 g / 100 cm³. 3 .

[0070] The organic acid of this invention can form coordination bonds with metal ions, and through coordination with active metal ions, it can form stable complexes. This invention does not particularly limit the organic acid; for example, it can be at least one selected from tartaric acid, oxalic acid, malic acid, citric acid, succinic acid, and maleic acid, preferably oxalic acid. The amount of organic acid added to the active metal impregnation solution is 1.0-12.0 g / 100 cm³. 3 .

[0071] This invention does not impose a particular limitation on the concentration of hydrogen peroxide. In one embodiment, the amount of hydrogen peroxide added to the metal impregnation solution, calculated as H2O2, is 0.1-4.0 g / 100 cm³. 3 Hydrogen peroxide can undergo redox reactions under acidic conditions, promoting the formation of more stable oxidation products from active metals and weakening the interaction between the active component and the support. This can have a positive effect on the activity and stability of the final residue hydrodemetallization catalyst. Moreover, the amount of hydrogen peroxide added in this invention is low, so there are no safety issues.

[0072] In one embodiment, step A of the present invention includes the following steps:

[0073] Step A1: Mix the Group VIB metal compound, organic acid, and water to completely dissolve the Group VIB metal compound;

[0074] Step A2: Mix the mixture obtained in step A1 with a Group VIII metal compound to obtain a metal mixture solution;

[0075] Step A3: Mix the metal mixture solution obtained in step A2 with hydrogen peroxide to form a metal solution.

[0076] In another embodiment, during the mixing of the Group VIB metal compound, organic acid, and water in step A1, heating and stirring may be performed to completely dissolve the Group VIB metal compound. The heating temperature may be, for example, 60-100°C.

[0077] In another embodiment, the mixture obtained in step A1 may also be heated and stirred during the mixing process with the Group VIII metal compound to obtain a metal mixture solution.

[0078] This invention uses a composite complexing agent, a polycarboxylic acid scale inhibitor, and an organic phosphorus-containing compound, which has strong complexing ability and good solution stability.

[0079] In one embodiment, the polycarboxylic acid scale inhibitor is selected from at least one of polyepoxysuccinic acid, polyacrylic acid, hydrolyzed polymaleic anhydride, maleic acid-acrylic acid copolymer, polyaspartic acid, acrylate-hydroxypropyl acrylate copolymer (T-225), and acrylate-2-acrylamide-2-methylpropanesulfonic acid copolymer. The organic phosphorus-containing compound is selected from at least one of aminotrimethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, hydroxyethylidene diphosphonic acid, and ethylenediaminetetramethylenephosphonic acid. The amount of polycarboxylic acid scale inhibitor added to the metal impregnation solution is 0.5-15.0 g / 100 cm³. 3 The amount of organic phosphorus compounds added is 0.5-10.0 g / 100 cm³. 3 .

[0080] The present invention does not impose any particular limitation on the method of impregnating the carrier with the metal impregnation liquid, and can be an equal volume impregnation method or a supersaturated impregnation method, etc.; the metal impregnation liquid can be sprayed onto the surface of the carrier, or the carrier can be immersed in the metal impregnation liquid; the impregnation process can be carried out by vacuuming the carrier or by direct impregnation; the impregnation process can be carried out by heating the carrier or by carrying it out at room temperature; the impregnation process can be carried out by auxiliary technologies such as ultrasound or microwave.

[0081] After impregnation, the samples are cured under sealed conditions at a temperature of 20-100℃, preferably 20-60℃, for 0.5-6 hours, preferably 1.0-4 hours. Then, they are dried at 80-180℃, preferably 100-140℃, for 1-6 hours, preferably 2-4 hours. Next, they are calcined at 400-700℃, preferably 420-600℃, for 0.5-6 hours, preferably 1-4 hours.

[0082] The hydrodemetallization catalyst obtained by the method of this invention has a specific surface area of ​​80-180 m². 2 / g, pore volume 0.5-1.1cm³ 3 / g, the sum of the pore volumes corresponding to channels with a pore diameter greater than 100nm accounts for ≥10% of the total pore volume.

[0083] This invention also provides a hydrodemetallization catalyst, which can be prepared by the above method. The hydrodemetallization catalyst of this invention comprises an alumina support and an active metal, wherein the active metal is supported on the alumina support, and the specific surface area of ​​the alumina support is 80-240 m². 2 / g, pore volume 0.5-1.5cm³ 3 / g, with a bimodal pore distribution, the sum of the pore volumes of channels with a pore diameter greater than 100nm accounts for ≥10% of the total pore volume of the alumina carrier, and the lateral compressive strength of the alumina carrier is ≥14.5N / mm.

[0084] Furthermore, the average MoS2 lamellar length of the hydrogenation demetallization catalyst of the present invention is ≤4.7nm, and the proportion of monolayer and bilayer MoS2 lamellars is ≥60%, and further ≥65%.

[0085] The macroporous alumina support with a bimodal pore structure of this invention can solve the diffusion problem of macromolecular metal compounds and asphaltenes in inferior residual oil. Furthermore, by improving the active metal impregnation solution, the emission of pollutants such as ammonia during the production process is effectively reduced, making catalyst production cleaner. At the same time, it achieves high dispersion loading of active metal with a good state of low stacking and short crystal lamellars, resulting in a high-performance residual oil hydrodemetallization catalyst.

[0086] The present invention will be specifically described below through embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description.

[0087] Example 1:

[0088] Weigh out 500g of PN-2 type macroporous pseudoboehmite dry adhesive powder (aluminum sulfate-sodium aluminate method, dry basis content 71.5wt%) produced by Binzhou Juchuang New Materials Co., Ltd., and add 2.5×10 435.8g of polyvinyl butyral resin powder with a viscosity of 40 mPa·s (referring to the viscosity of a 5% ethanol solution at 20℃, the same below) and a particle size of 160 mesh was mixed with 17.9g of hydroxypropyl methylcellulose with a viscosity of 150,000 mPa·s (referring to the viscosity of a 2% aqueous solution at 20℃, the same below), and the mixture was homogeneous. 17.9g of ethanol was dissolved in 607.8g of purified water, heated to 60℃, and slowly added to the aforementioned materials. The mixture was kneaded into a plastic body, and then extruded into a clover shape with a diameter of 1.6mm on a single-screw extruder. The mixture was dried at 140℃ for 2 hours, and then placed in a high-temperature calcination furnace and kept at 900℃ for 3 hours to obtain carrier a. The physicochemical properties of carrier a are shown in Table 1.

[0089] Weigh 2.0g of molybdenum trioxide and 1.0g of oxalic acid, place them in a beaker, add 60g of deionized water, and heat and stir at 95℃ to dissolve. Weigh 2.08g of nickel nitrate and add it, stirring to dissolve. Cool the solution to room temperature, and add 0.5g of 20wt% hydrogen peroxide gradually while stirring. Add 0.5g of DR-001 type polyacrylic acid produced by Dongrun Chemical Technology Co., Ltd. and 0.5g of diethylenetriaminepentamethylenephosphonic acid produced by Shandong Weiyuan Environmental Protection Technology Co., Ltd., stir to dissolve, and then standardize to 100cm. 3 An active metal impregnation solution was obtained. 50 g of carrier a was weighed and impregnated onto carrier a using an equal-volume impregnation method via spraying. The impregnated sample was then cured at 20°C under sealed conditions for 1 hour; dried at 110°C for 2 hours; and calcined at 550°C for 4 hours to obtain catalyst A for residue hydrotreating. The transmission electron microscopy (TEM) analysis results of the active phase after sulfidation are shown in Table 2.

[0090] Example 2:

[0091] Weigh 500g of the aforementioned pseudoboehmite dry adhesive powder, and add a molecular weight of 1.5×10 4 71.5g of polyvinyl butyral resin powder with a viscosity of 10 mPa·s and a particle size of 2000 mesh was mixed with 10.7g of hydroxypropyl methylcellulose with a viscosity of 100,000 mPa·s. 17.9g of methanol and 17.9g of acetone were dissolved in 600.0g of purified water, heated to 40°C, and slowly added to the aforementioned materials. The mixture was kneaded into a plastic body and then extruded into a clover shape with a diameter of 1.6mm on a single-screw extruder. The mixture was dried at 120°C for 3 hours and then placed in a high-temperature calcination furnace and kept at 700°C for 4 hours to obtain carrier b. The physicochemical properties of carrier b are shown in Table 1.

[0092] Weigh 7.68g of molybdenum trioxide and 4.0g of oxalic acid, place them in a beaker, add 60g of deionized water, and heat and stir at 60℃ to dissolve. Weigh 5.54g of nickel nitrate and add it, stirring to dissolve. Cool the solution to room temperature, and add 6.0g of 20wt% hydrogen peroxide gradually while stirring. While stirring, add 4.0g of epoxysuccinic acid produced by Runyang Chemical Co., Ltd. and 3.0g of aminotrimethylenephosphonic acid produced by Zibo Yueyang Chemical Technology Co., Ltd., and stir to dissolve at room temperature. Standardize the solution to 100cm³. 3 50g of carrier b was weighed and impregnated onto the alumina carrier b by spraying using an equal-volume impregnation method. The impregnated sample was cured at 40℃ for 4 hours under sealed conditions; dried at 100℃ for 4 hours; and calcined at 500℃ for 2 hours to obtain catalyst B for residue hydrotreating. The transmission electron microscopy (TEM) analysis results of the active phase after sulfidation are shown in Table 2.

[0093] Example 3:

[0094] Weigh 500g of the aforementioned pseudoboehmite dry adhesive powder, and add a 10.0×10⁻⁶ molecular weight compound. 4 17.9g of polyvinyl butyral resin powder with a viscosity of 150mPa·s and a particle size of 100 mesh was mixed with 3.6g of hydroxypropyl methylcellulose with a viscosity of 200,000mPa·s. 3.6g of ethanol and 3.6g of chloroform were dissolved in 605.0g of purified water, heated to 80℃, and slowly added to the aforementioned materials. The mixture was kneaded into a plastic body and then extruded into a clover shape with a diameter of 1.6mm on a single-screw extruder. The mixture was dried at 160℃ for 1 hour and then placed in a high-temperature calcination furnace and kept at 1000℃ for 1 hour to obtain carrier c. The physicochemical properties of carrier c are shown in Table 1.

[0095] Weigh 11.53 g of ammonium heptamolybdate and 6.0 g of oxalic acid, place them in a beaker, add 60 g of deionized water, and heat and stir at 98 °C to dissolve. Weigh 6.47 g of nickel acetate and add it, stirring to dissolve. Cool the solution to room temperature, and add 7.5 g of 20 wt% hydrogen peroxide gradually while stirring. While stirring, add 4.0 g of hydrolyzed polymaleic anhydride produced by Kathon Chemical Co., Ltd. and 10.0 g of HEDP60 type hydroxyethylidene diphosphonic acid produced by Runyang Chemical Co., Ltd., and stir to dissolve at room temperature. Standardize the solution to 100 cm⁻¹. 3 50g of carrier c was weighed and impregnated onto the alumina carrier c by spraying using an equal-volume impregnation method. The impregnated sample was cured at 45℃ for 2 hours under sealed conditions; dried at 120℃ for 2 hours; and calcined at 600℃ for 1 hour to obtain catalyst C for residue hydrotreating. The transmission electron microscopy (TEM) analysis results of the active phase after sulfidation are shown in Table 2.

[0096] Example 4:

[0097] Weigh 500g of the aforementioned pseudoboehmite dry adhesive powder, and add 4.5×10 4 53.6 g of polyvinyl butyral resin powder with a viscosity of 65 mPa·s and a particle size of 300 mesh was mixed with 10.7 g of hydroxypropyl methylcellulose with a viscosity of 150,000 mPa·s. 14.3 g of ethanol and 14.3 g of ethyl acetate were dissolved in 600.0 g of purified water, heated to 50 °C, and slowly added to the aforementioned materials. The mixture was kneaded into a plastic body and then extruded into a clover shape with a diameter of 1.6 mm on a single-screw extruder. The mixture was dried at 130 °C for 3 hours and then placed in a high-temperature calcination furnace and kept at 800 °C for 2 hours to obtain carrier d. The physicochemical properties of carrier d are shown in Table 1.

[0098] Weigh 11.81 g of molybdenum trioxide and 8.0 g of oxalic acid, place them in a beaker, add 65 g of deionized water, and heat and stir at 100 °C to dissolve. Weigh 8.33 g of nickel nitrate and add it, stirring to dissolve. Cool the solution to room temperature, and gradually add 9.0 g of 20% hydrogen peroxide while stirring. Add 6.0 g of hydrolyzed polymaleic anhydride and 4.0 g of ethylenediaminetetramethylenephosphonic acid (produced by Jiangsu Haolong Chemical Co., Ltd.) while stirring, and dissolve at room temperature. Standardize the solution to 100 cm⁻¹. 3 50g of carrier d was weighed and impregnated onto the alumina carrier d by spraying using an equal-volume impregnation method. The impregnated sample was cured at 60℃ in a closed environment for 3 hours; dried at 140℃ for 2 hours; and calcined at 480℃ for 2 hours to obtain catalyst D for residue hydrotreating. The transmission electron microscopy (TEM) analysis results of the active phase after sulfidation are shown in Table 2.

[0099] Example 5:

[0100] Weigh 500g of the aforementioned pseudoboehmite dry adhesive powder, and add 3.5×10 4 25.0g of polyvinyl butyral resin powder with a viscosity of 50mPa·s and a particle size of 600 mesh was mixed with 10.7g of hydroxypropyl methylcellulose with a viscosity of 150,000mPa·s. 14.3g of ethanol and 7.2g of methyl ethyl ketone were dissolved in 603.0g of purified water, heated to 50℃, and slowly added to the aforementioned materials. The mixture was kneaded into a plastic body and then extruded into a clover shape with a diameter of 1.6mm on a single-screw extruder. The mixture was dried at 130℃ for 3 hours and then placed in a high-temperature calcination furnace and kept at 950℃ for 3 hours to obtain carrier e. The physicochemical properties of carrier e are shown in Table 1.

[0101] Weigh 14.31 g of molybdenum trioxide and 11.0 g of oxalic acid, place them in a beaker, add 65 g of deionized water, and heat and stir at 85 °C to dissolve. Weigh 8.73 g of nickel nitrate and add it, stirring to dissolve. Cool the solution to room temperature, and gradually add 12.0 g of 20 wt% hydrogen peroxide while stirring. Add 15.0 g of polyacrylic acid and 6.0 g of ethylenediaminetetramethylenephosphonic acid while stirring, and dissolve at room temperature. Standardize the solution to 100 cm⁻¹. 3 50g of carrier e was weighed and impregnated onto the alumina carrier e by spraying using an equal-volume impregnation method. The impregnated sample was cured at 40℃ for 4 hours under sealed conditions; dried at 120℃ for 3 hours; and calcined at 460℃ for 3 hours to obtain the residue hydrotreating catalyst E. The transmission electron microscopy (TEM) analysis results of the active phase after sulfidation are shown in Table 2.

[0102] Example 6:

[0103] Weigh 500g of the aforementioned pseudoboehmite dry adhesive powder, and add 2.0×10 4 28.6g of polyvinyl butyral resin powder with a viscosity of 25 mPa·s and a particle size of 200 mesh was mixed with 10.7g of hydroxypropyl methylcellulose with a viscosity of 150,000 mPa·s. 14.3g of butanol and 7.2g of methyl acetate were dissolved in 600.0g of purified water, heated to 55℃, and slowly added to the aforementioned materials. The mixture was kneaded into a plastic body and then extruded into a clover shape with a diameter of 1.6mm on a single-screw extruder. The mixture was dried at 120℃ for 3 hours and then placed in a high-temperature calcination furnace and kept at 850℃ for 3 hours to obtain carrier f. The physicochemical properties of carrier f are shown in Table 1.

[0104] Weigh 18.0 g of molybdenum trioxide and 12.0 g of oxalic acid, place them in a beaker, add 60 g of deionized water, and heat and stir at 90 °C to dissolve. Weigh 20.83 g of nickel nitrate and add it, stirring to dissolve. Cool the solution to room temperature, and add 15.0 g of 20% hydrogen peroxide gradually while stirring. Add 8.0 g of epoxysuccinic acid and 5.0 g of hydroxyethylidene diphosphonic acid while stirring, and dissolve while stirring at room temperature. Standardize the solution to 100 cm⁻¹. 3 50g of carrier f was weighed and impregnated onto the alumina carrier f by spraying using an equal-volume impregnation method. The impregnated sample was cured at 55℃ for 2 hours under sealed conditions; dried at 110℃ for 3 hours; and calcined at 420℃ for 3 hours to obtain the residue hydrotreating catalyst F. The transmission electron microscopy (TEM) analysis results of the active phase after sulfidation are shown in Table 2.

[0105] Comparative Examples 1-3 are residue oil hydrotreating catalysts prepared according to existing technical solutions.

[0106] Comparative Example 1:

[0107] Comparative Example 1 was prepared by using the method described in patent CN105983443B to prepare the alumina support and the method provided in patent CN114425354B to prepare the metal impregnation solution. The catalyst metal loading was the same as in Example 2.

[0108] Weigh 500g of macroporous pseudoboehmite dry adhesive powder (dry basis content 71.5wt%) produced by Yantai Heng Hui Chemical Co., Ltd., add 10.7g of hydroxypropyl methylcellulose with a viscosity of 150,000 mPa·s and 17.9g of polyvinyl alcohol powder with a particle diameter of 90-150μm, and mix evenly; dissolve 14.3g of boric acid in 390g of purified water, slowly add it to the above materials, knead into a plastic body, and then extrude it into a clover shape with a diameter of 1.6mm on a front-extrusion single-screw extruder. Dry at 120℃ for 2.0 hours, and then place it in a calcination furnace and keep it at 850℃ for 3 hours to obtain a carrier g, the physicochemical properties of which are shown in Table 1.

[0109] Weigh 7.68g of molybdenum trioxide and 2.61g of basic nickel carbonate, place them in a beaker, add water and stir. Weigh 3.76g of phosphoric acid, dilute it with water, and slowly add it to the beaker. React at room temperature for 15 minutes. Increase the temperature to 95℃ and heat for 35 minutes. Weigh 3.0g of citric acid and add it, continue heating at a constant temperature for 25 minutes until all the raw materials are dissolved. Turn off the heating and let it cool to room temperature. While stirring, add 10.0g of triethanolamine and 3g of Tween-80, stir to dissolve, and then standardize to 100cm. 3 The above impregnation solution was applied to the carrier g using a spray method. After drying, the sample was kept at 500℃ for 2 hours to obtain catalyst G. The transmission electron microscopy (TEM) analysis results of the active phase after sulfidation are shown in Table 2.

[0110] Comparative Example 2:

[0111] Comparative Example 2 prepared an alumina support according to the method described in patent CN1103009A, and prepared a metal impregnation solution according to the method disclosed in patent CN103007949B. The catalyst metal loading was the same as in Example 2.

[0112] 34.1g of aluminum hydroxide dry adhesive powder (containing 75% alkyl aluminum hydrolysis product of aluminum oxide) and 39.3g of aluminum hydroxide powder obtained by aluminum sulfate method were mixed, and then 4.7g of high wear-resistant carbon black, 3.5g of surfactant SA-20, 2.1g of aluminum nitrate, and 66ml of water were added and thoroughly mixed. The mixture was then extruded into a clover shape with a diameter of 1.8mm on an extruder, dried at 120℃, and calcined at 800℃ for 4 hours to obtain carrier h. Its physicochemical properties are shown in Table 1.

[0113] Take 30wt% hydrogen peroxide and add it dropwise to 9.48g of ammonium heptamolybdate, stirring to dissolve; add 5.54g of nickel nitrate, stirring to dissolve; add 1.5g of terephthalic acid, and titrate to 100cm. 3 The solution was added dropwise to the support h, impregnated at room temperature for 6 hours, dried at 110℃ for 2 hours, and calcined at 500℃ for 4 hours to obtain catalyst H. The transmission electron microscopy (TEM) analysis results of the active phase after sulfidation are shown in Table 2.

[0114] Comparative Example 3:

[0115] Comparative Example 3 prepared an alumina support according to the method described in patent CN1647857A, and prepared a metal impregnation solution according to the method disclosed in patent CN1230491C. The catalyst metal loading was the same as in Example 2.

[0116] 500g of PN-2 type macroporous pseudoboehmite dry adhesive powder (aluminum sulfate-sodium aluminate method, dry basis content 71.5wt%) produced by Binzhou Juchuang New Materials Co., Ltd. was weighed, and 10.7g of polyethylene glycol with a molecular weight of 2000 was added. Water was added and the mixture was slurried to obtain 6 liters of slurry. The slurry was then spray-dried at an inlet temperature of 580℃ and an outlet temperature of 180℃. The resulting composition was extruded and dried, and then calcined at 800℃ for 3 hours to obtain carrier i. Its physicochemical properties are shown in Table 1.

[0117] Take 75cm 3 Ammonia solution with a concentration of 18 wt% was placed in an ultrasonic transducer, with the transmission power controlled at 350 W and the frequency at 25 kHz. 9.48 g of ammonium heptamolybdate was added and dissolved, followed by 5.54 g of nickel nitrate. After the metal salt was completely dissolved, the ultrasonic transducer was turned off, and the solution volume was adjusted to 100 cm³ using ammonia solution. 3 The solution was added dropwise to support I, impregnated at room temperature for 4 hours, dried at 120°C for 2 hours, and calcined at 500°C for 3 hours to obtain catalyst I. The transmission electron microscopy (TEM) analysis results of the active phase after sulfidation are shown in Table 2.

[0118] Figure 1 The images show the laser Raman spectra of the metal impregnation solutions prepared in Examples 2, 1, and 2 of this invention. Raman spectroscopy reflects the state of metal ions in solution, especially their complexed state, which is directly related to the final loading state of the metal on the catalyst, thus affecting the catalyst's reaction performance.

[0119] Figure 5 This is a mercury intrusion porosimetry pore size distribution diagram of the carrier a prepared in Example 1 of the present invention. Figure 5 A clear macropore structure with a diameter of over 100 nm can be observed, i.e., a bimodal pore structure.

[0120] Catalysts B, G, H, and I were tested using the same feedstock and process conditions on a fixed-bed residue hydrotreating evaluation unit. The feedstock properties and process conditions are shown in Table 3, and the evaluation results are shown in Table 4.

[0121] Table 1 Physical and chemical properties of the carrier

[0122]

[0123] Table 2. TEM characterization results of the catalyst

[0124]

[0125]

[0126] Table 3. Feedstock and Process Conditions for Evaluation Tests

[0127] properties of crude oil Middle Eastern residual oil <![CDATA[Density (20 °C) / g·cm -3 > 0.9884 Sulfur content, w% 4.478 Carbon residue value, w% 13.20 <![CDATA[Metal (Ni + V), μg·g -1 > 79.44 Process conditions Reaction temperature, °C 380 Hydrogen partial pressure, MPa 16.0 <![CDATA[Space velocity, h -1 > 1.0 Hydrogen / oil ratio, V / V 700

[0128] Table 4 Catalyst Evaluation Results

[0129]

[0130]

[0131] As shown in Table 1, compared with Comparative Examples 1-3, the carrier obtained by the present invention has the characteristics of large pore volume and pore size, high proportion of macropores above 100 nm and good strength, and can better adapt to the hydrodemetallization process of inferior residue oil.

[0132] As shown in Table 2, the catalyst for hydrotreating residual oil obtained by the present invention has fewer lamellar layers, mainly consisting of single-layer and double-layer MoS2, with short lamellar length and good dispersion of the active phase. It exhibits obvious characteristics of high dispersion, low stacking, and short lamellar structure, making it more suitable for hydrotreating heavy and inferior residual oil. In contrast, the catalyst obtained in the comparative example has a high proportion of lamellar structures with more than 3 layers, large lamellar length, and poor dispersion of active components.

[0133] As shown in Table 4, compared with the comparative catalyst, the catalyst prepared in this invention has better desulfurization, decarbonization and demetallization activity, better activity stability, and stronger adaptability to the processing of inferior raw materials, which is conducive to extending the operating cycle of the equipment and improving economic efficiency.

[0134] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing a hydrogenation demetallization catalyst, characterized in that, Includes the following steps: Step 1: Mix the alumina precursor, polyvinyl butyral resin, binder and solvent, knead, shape and calcine to obtain the alumina carrier; the solvent includes organic solvent and water. Step 2: Impregnate the alumina support with a metal impregnation solution, allow it to cure, and then calcine to obtain a hydrogenation demetallization catalyst.

2. The method for preparing the hydrogenation demetallization catalyst according to claim 1, characterized in that, The average weight-average molecular weight of the polyvinyl butyral resin is 1.0 × 10⁻⁶. 4 -15.0×10 4 ; and / or, the viscosity of the polyvinyl butyral resin in a 5wt% ethanol solution at 20°C is 5.0-200.0 mPa·s; and / or, the particle size of the polyvinyl butyral resin is 80-3000 mesh.

3. The method for preparing the hydrogenation demetallization catalyst according to claim 1, characterized in that, The alumina precursor contains 100% alumina by mass, and the amount of polyvinyl butyral resin added is 2.0%-25.0%.

4. The method for preparing the hydrogenation demetallization catalyst according to claim 1, characterized in that, The alumina precursor is hydrated alumina, the binder is synthetic cellulose, the mass of alumina in the alumina precursor is 100%, the amount of binder added is 1%-5%, and the amount of organic solvent added is 2.0%-10.0%.

5. The method for preparing the hydrogenation demetallization catalyst according to claim 1, characterized in that, The method for preparing the metal impregnation solution includes: Step A: Mix the active metal precursor, organic acid, and hydrogen peroxide to form a metal solution; Step B: Mix the metal solution with the composite complexing agent to obtain a metal impregnation solution; The composite complexing agent is a polycarboxylic acid scale inhibitor and an organic phosphorus compound.

6. The method for preparing the hydrogenation demetallization catalyst according to claim 5, characterized in that, The polycarboxylic acid scale inhibitor is selected from at least one of polyepoxysuccinic acid, polyacrylic acid, hydrolyzed polymaleic anhydride, maleic acid-acrylic acid copolymer, polyaspartic acid, acrylate-hydroxypropyl acrylate copolymer, and acrylate-2-acrylamide-2-methylpropanesulfonic acid copolymer; the organic phosphorus-containing compound is selected from at least one of aminotrimethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, hydroxyethylidene diphosphonic acid, and ethylenediaminetetramethylenephosphonic acid; and / or, in the metal impregnation solution, the amount of the polycarboxylic acid scale inhibitor added is 0.5-15.0 g / 100 cm³. 3 The amount of the organic phosphorus-containing compound added is 0.5-10.0 g / 100 cm³. 3 .

7. The method for preparing the hydrogenation demetallization catalyst according to claim 5, characterized in that, The active metal precursor comprises at least one Group VIII metal compound and at least one Group VIB metal compound; the organic acid is selected from at least one of tartaric acid, oxalic acid, malic acid, citric acid, succinic acid, and maleic acid; in the metal impregnation solution, the amount of the Group VIII metal compound added, calculated as metal oxide, is 0.5-5.0 g / 100 cm³. 3 The amount of Group VIB metal compounds added, calculated as metal oxides, is 2.0-18.0 g / 100 cm³. 3 In the metal impregnation solution, the amount of organic acid added is 1.0-12.0 g / 100 cm³. 3 ; and / or, in the metal impregnation solution, the amount of hydrogen peroxide added, calculated as H2O2, is 0.1-4.0 g / 100 cm³. 3 .

8. The method for preparing the hydrogenation demetallization catalyst according to claim 7, characterized in that, Step A includes the following steps: Step A1: Mix the Group VIB metal compound, organic acid, and water to completely dissolve the Group VIB metal compound; Step A2: Mix the mixture obtained in step A1 with a Group VIII metal compound to obtain a metal mixture solution; Step A3: Mix the metal mixture solution obtained in step A2 with hydrogen peroxide to form a metal solution.

9. The method for preparing the hydrogenation demetallization catalyst according to claim 1, characterized in that, The roasting temperature for step 1 is 500-1200℃, and the roasting temperature for step 2 is 400-700℃.

10. A hydrogenation demetallization catalyst, characterized in that, It comprises an alumina support and an active metal, wherein the active metal is supported on the alumina support, and the specific surface area of ​​the alumina support is 80-240 m². 2 / g, pore volume 0.5-1.5cm³ 3 / g, with a bimodal pore distribution, the sum of the pore volumes of channels with a pore diameter greater than 100nm accounts for ≥10% of the total pore volume of the alumina carrier; the lateral compressive strength of the alumina carrier is ≥14.5N / mm.

11. The application of the hydrodemetallization catalyst obtained by the preparation method according to any one of claims 1-9 or the hydrodemetallization catalyst according to claim 10 in the hydrodemetallization of residue oil.

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