Hydrodesulfurization and demetalization catalyst with defects on surface and preparation method of hydrodesulfurization and demetalization catalyst

Abstract

The invention provides a hydrodesulfurization and demetalization catalyst with defects on the surface and a preparation method of the hydrodesulfurization and demetalization catalyst, and is suitable for the field of catalyst preparation. The preparation method comprises the following steps: preparing a phosphorus-modified aluminum oxide compound; preparing the phosphorus-modified aluminum oxide compound into phosphorus-modified unit cell distortion pseudo-boehmite; the preparation method comprises the following steps: dipping phosphorus-modified cell-distorted pseudo-boehmite in a solution A containing an active metal component, carrying out second drying on the material, uniformly mixing the material obtained after second drying, pseudo-boehmite C and sesbania powder, adding a peptizing agent, carrying out kneading molding, and carrying out third drying and second roasting to obtain an alumina carrier; impregnating the alumina carrier with a solution B containing an active metal component, and carrying out fourth drying and third roasting to obtain a catalyst precursor; adding a second urea solution, carrying out third hydrothermal treatment, filtering, washing, fifth drying and fourth roasting to obtain the hydrodesulfurization and demetalization catalyst, the catalyst has the beneficial effects of high surface defect content and high activity.

Description

Technical Field

[0001] The present application relates to the technical field of catalyst preparation, and in particular to a hydrodesulfurization and demetallization catalyst with surface defects and a preparation method thereof. Background Art

[0002] As oil becomes heavier and its quality deteriorates, oil processing becomes increasingly difficult. Heavy oil contains a large amount of sulfur, most of which is found in asphaltenes, making it a very difficult component to remove. Hydrodesulfurization, as a key process in oil refining and the production of synthetic ammonia using oil as a raw material, has always been of great importance. Due to the limitations of the properties of existing residue oil hydrodesulfurization catalysts, residue oil hydrodesulfurization catalysts generally only have a desulfurization function and a weak demetallization function. Demetallization reactions can only be carried out on the outer surface of the catalyst, and metal precipitates are deposited in the gaps. Therefore, in the residue oil hydrodesulfurization series catalysts, the demetallization agent must remove the metal to the greatest extent possible during desulfurization, so that the metal content is as low as possible when entering the desulfurization agent bed, so as to achieve long-term operation of the desulfurization agent.

[0003] The surface pores of conventional hydrodesulfurization and demetallization catalysts are typically formed by the accumulation of spherical particles. This pore structure hinders the diffusion of macromolecular reactants into the catalyst. Furthermore, conventional catalysts often have a relatively small number of surface defects, which hinders the catalytic activity. Summary of the Invention

[0004] In order to solve one of the above technical defects, the present application provides a hydrodesulfurization and demetallization catalyst with surface defects and a preparation method thereof.

[0005] According to a first aspect of the present application, a method for preparing a hydrodesulfurization and demetallization catalyst having surface defects is provided, comprising: Preparation of phosphorus-modified aluminum oxide compounds; The prepared phosphorus-modified aluminum oxide compound is added with a first urea solution, stirred evenly, and then placed in a closed kettle for a first hydrothermal treatment and a second hydrothermal treatment, and then filtered, washed, and dried for a first time to obtain phosphorus-modified unit cell distorted pseudo-boehmite; The phosphorus-modified unit cell distorted pseudo-boehmite is impregnated with a solution A containing an active metal component in a saturated impregnation manner, and then the material is subjected to a second drying. The material obtained after the second drying, the pseudo-boehmite C, and the sesbania powder are uniformly mixed, a peptizing agent is added, and kneading is performed. The alumina support is then obtained after a third drying and a second calcination. The alumina support is impregnated with the solution B containing the active metal component in a saturated impregnation manner, and then subjected to a fourth drying and a third calcination to obtain a catalyst precursor; The catalyst precursor is added with a second urea solution, and subjected to a third hydrothermal treatment in a closed kettle, and then filtered, washed, dried for a fifth time, and calcined for a fourth time to obtain a hydrodesulfurization and demetallization catalyst with surface defects.

[0006] Preferably, the preparation of the phosphorus-modified aluminum oxide compound specifically comprises: Weigh aluminum nitrate and a phosphorus-containing compound, mix them evenly, and grind them to obtain a paste; The paste is first calcined and pulverized to obtain a phosphorus-modified aluminum oxide compound.

[0007] More preferably, the phosphorus-containing compound is one or more of ammonium phosphate, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate.

[0008] More preferably, the mass ratio of aluminum nitrate to the phosphorus-containing compound is 60:1-30:1.

[0009] Preferably, the first hydrothermal treatment temperature is 90-130° C., and the first hydrothermal treatment time is 1-4 hours; the second hydrothermal treatment temperature is 150-200° C., and the second hydrothermal treatment time is 4-8 hours.

[0010] More preferably, the microscopic morphology of the phosphorus-modified unit cell distorted pseudo-boehmite is curved lamellar, and the curved lamellar particle size is 100-500 nm; compared with SB powder, the (020) crystal plane spacing of the phosphorus-modified unit cell distorted pseudo-boehmite is reduced by a percentage δ of 0.3%-1.7%.

[0011] Preferably, the active metal component-containing solution A and the active metal component-containing solution B both include Group VIB metals and Group VIII metals.

[0012] More preferably, the active metal component-containing solution A contains 2.5-5.5 g / 100 mL of Group VIB metal in terms of oxide content, and 0.6-1.5 g / 100 mL of Group VIII metal in terms of oxide content.

[0013] More preferably, the content of Group VIB metal in the solution B containing active metal components is 10-20 g / 100 mL in terms of oxide content, and the content of Group VIII metal in the solution B containing active metal components is 2.5-5 g / 100 mL in terms of oxide content.

[0014] According to a second aspect of the present application, there is provided a hydrodesulfurization and demetallization catalyst containing surface defects prepared by the method for preparing a hydrodesulfurization and demetallization catalyst containing surface defects as described in any one of the above items.

[0015] In the present application, phosphorus-modified unit cell distorted pseudo-boehmite is used as raw material, and the pseudo-boehmite is transformed into an alumina support containing defect structures after calcination, which increases the surface defect structure content of the alumina support and the catalyst prepared subsequently, and promotes the activity of the catalyst. In addition, the phosphorus-modified unit cell distorted pseudo-boehmite has a curved lamellar morphology, and the special structure of the particles effectively regulates the pore structure of the catalyst and increases the content of large pores. When the phosphorus-containing compound is calcined with the aluminum salt, the elemental phosphorus is embedded in the interior of the aluminum oxide compound grains to form a phosphorus-modified aluminum oxide compound. The Lewis acid content of the phosphorus-containing micro-region is significantly improved. At the same time, the active metal components of the micro-region are Mo, W, Ni, and Co multi-component components, which greatly improves the catalytic activity of the large pore micro-region. When the catalyst precursor is immersed in the second urea solution for the third hydrothermal treatment, the interaction between the metal component and the alumina carrier is improved, so that the active metal and the catalyst interact appropriately. At the same time, flaky particles are formed on the outer surface of the catalyst. The flaky particles accumulate to form open channels that utilize the diffusion of macromolecular reactants, allowing the reactants to quickly enter the interior of the catalyst to participate in the reaction, thereby improving the overall activity of the catalyst.

[0016] Other features and advantages of the present application will be described in the following description, and in part will become apparent from the description, or will be understood by practicing the present application. The purpose and other advantages of the present application can be realized and obtained by the contents indicated in the written description and the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The drawings described herein are used to provide a further understanding of the present application and constitute a part of the present application. The illustrative embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings: Figure 1 This is an SEM image of the phosphorus-modified unit cell distorted pseudo-boehmite provided in Example 1 of the present application; Figure 2 This is an SEM image of the outer surface of the hydrodesulfurization and demetallization catalyst with surface defects provided in Example 1 of the present application; Figure 3 This is the XRD spectrum of the phosphorus-modified unit cell distorted pseudo-boehmite and SB powder provided in Example 1 of the present application. DETAILED DESCRIPTION

[0018] In order to make the technical solutions and advantages of the embodiments of the present application more clearly understood, the exemplary embodiments of the present application are further described in detail below with reference to the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present application, and are not an exhaustive list of all the embodiments. It should be noted that the embodiments and features in the embodiments of the present application can be combined with each other unless they conflict.

[0019] To address the above problems, the present invention provides a method for preparing a hydrodesulfurization and demetallization catalyst having surface defects, comprising: S10, preparing a phosphorus-modified aluminum oxide compound, specifically comprising: Aluminum nitrate and a phosphorus-containing compound are weighed in a mass ratio of 60:1-30:1, mixed evenly, and then ground to obtain a paste; the phosphorus-containing compound is one or more of ammonium phosphate, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate; The paste is subjected to a first calcination and pulverization to obtain a phosphorus-modified aluminum oxide compound; the first calcination temperature is 450-600°C, and the first calcination time is 4-8 hours; the powder is pulverized into a powder with a particle size of less than 20 μm, more preferably, the powder is pulverized into a powder with a particle size of less than 10 μm. The smaller the particle size, the better the effect.

[0020] S20, adding a first urea solution with a concentration of 5.5wt%-10.5wt% to the prepared phosphorus-modified aluminum oxide compound, wherein the mass ratio of the phosphorus-modified aluminum oxide compound to the first urea solution is 1:3.5-1:6; magnetic stirring for 10 minutes, after uniform stirring, placing in a closed kettle for a first hydrothermal treatment and a second hydrothermal treatment, the closed kettle is an autoclave, and then filtering, washing, and first drying to obtain phosphorus-modified unit cell distorted pseudo-boehmite; the first hydrothermal treatment temperature is 90-130°C, and the first hydrothermal treatment time is 1-4h; the second hydrothermal treatment temperature is 150-200°C, and the second hydrothermal treatment time is 4-8h; the first drying temperature is 100-160°C, and the first drying time is 6-10h.

[0021] During the first hydrothermal treatment, the treatment temperature is low and the treatment time is short, and the phosphorus-modified aluminum oxide compound first slowly forms unit cell distorted pseudo-boehmite nuclei in the system; during the second hydrothermal treatment, the unit cell distorted pseudo-boehmite nuclei continue to grow with amorphous aluminum oxide as raw material, facilitating the subsequent formation of the final unit cell distorted pseudo-boehmite; the morphology of the prepared phosphorus-modified unit cell distorted pseudo-boehmite is curved lamellar and has abundant macropore channels.

[0022] The microscopic morphology of the phosphorus-modified unit cell distorted pseudo-boehmite is curved lamellar, and the curved lamellar particle size is 100-500nm; compared with SB powder, the (020) crystal plane spacing of the phosphorus-modified unit cell distorted pseudo-boehmite is reduced by 0.3%-1.7%.

[0023] S30, impregnating the phosphorus-modified unit cell distorted pseudo-boehmite by saturated impregnation with a solution A containing an active metal component, then subjecting the material to a second drying, uniformly mixing the material obtained after the second drying, pseudo-boehmite C, and sesbania powder, adding a peptizing agent and kneading to form, wherein the amount of pseudo-boehmite C added is the same as the amount of the aluminum-modified aluminum oxide compound added; the amount of sesbania powder added is 0.5% to 1.5% of the total mass of the material obtained after the second drying and the pseudo-boehmite C; the peptizing agent is an acetic acid solution with a concentration of 1%, and the amount of the peptizing agent added is 0.8% to 1.2% of the total mass of the material obtained after the second drying and the pseudo-boehmite C; and then subjecting the material to a third drying and a second calcination to obtain an alumina support. The most probable pore size of pseudo-boehmite C is 10-20 nm, and the proportion of the most probable pore size of pseudo-boehmite C to the total pore size is 30%-60%. Pseudo-boehmite C can be prepared by any one of acid precipitation method, alkali precipitation method and alcohol aluminum hydrolysis method.

[0024] S40, impregnating the alumina support with a solution B containing active metal components by saturation impregnation, and then obtaining a catalyst precursor after a fourth drying and a third calcination; the fourth drying temperature is 100-180°C, and the fourth drying time is 1-10 hours; the third calcination temperature is 400-500°C, and the third calcination time is 2-8 hours.

[0025] S50, adding a second urea solution with a concentration of 11.5wt%-18.5wt% to the catalyst precursor, with a mass ratio of the catalyst precursor to the second urea solution being 1:3.5-1:6, and performing a third hydrothermal treatment in a closed kettle, wherein the third hydrothermal treatment temperature is 150-200°C and the third hydrothermal treatment time is 10-16h, followed by filtration, washing, a fifth drying, and a fourth calcination to obtain a hydrodesulfurization and demetallization catalyst containing surface defects; the fifth drying temperature is 100-160°C, the fifth drying time is 6-10h; the fourth calcination temperature is 450-550°C, and the fourth calcination time is 4-6h.

[0026] In this application, phosphorus-modified unit cell distorted pseudo-boehmite is used as the raw material. After calcination, the pseudo-boehmite is transformed into an alumina support containing a defective structure, which increases the surface defect structure content of the alumina support and the subsequently prepared catalyst, thereby promoting the activity of the catalyst. In addition, the phosphorus-modified unit cell distorted pseudo-boehmite has a curved lamellar morphology. The special structure of the particles effectively regulates the pore structure of the catalyst and increases the content of large pores. When the phosphorus-containing compound is calcined with the aluminum salt, the elemental phosphorus is embedded in the interior of the aluminum oxide compound grains to form a phosphorus-modified aluminum oxide compound. The Lewis acid content of the phosphorus-containing micro-region is significantly improved. At the same time, the active metal components of the micro-region are molybdenum (Mo), tungsten (W), nickel (Ni), and cobalt (Co) multi-components, which greatly improves the catalytic activity of the large pore micro-region. When the catalyst precursor is immersed in the second urea solution for the third hydrothermal treatment, the interaction between the metal component and the alumina carrier is improved, so that the active metal and the catalyst interact appropriately. At the same time, flaky particles are formed on the outer surface of the catalyst. The flaky particles accumulate to form open channels that utilize the diffusion of macromolecular reactants, allowing the reactants to quickly enter the interior of the catalyst to participate in the reaction, thereby improving the overall activity of the catalyst.

[0027] Furthermore, the solution A containing active metal components and the solution B containing active metal components both include Group VIB metals and Group VIII metals.

[0028] Furthermore, in the solution A containing active metal components, the content of Group VIB metal in terms of oxide is 2.5-5.5 g / 100 mL, and the content of Group VIII metal in terms of oxide is 0.6-1.5 g / 100 mL.

[0029] Specifically, in solution A containing active metal components, the Group VIB metal is tungsten (W), and the Group VIB metal oxide is tungsten oxide (WO3); the Group VIII metal is cobalt (Co), and the Group VIII metal oxide is cobalt oxide (CoO).

[0030] Furthermore, in the solution B containing the active metal components, the content of the Group VIB metal in terms of oxide is 10-20 g / 100 mL, and the content of the Group VIII metal in terms of oxide is 2.5-5 g / 100 mL.

[0031] Specifically, in solution B containing active metal components, the Group VIB metal is molybdenum (Mo), and the Group VIB metal oxide is molybdenum oxide (MoO3); the Group VIII metal is nickel (Ni), and the Group VIII metal oxide is nickel oxide (NiO).

[0032] In the present application, the active metals used are Group VIB metals W, Mo and Group VIII metals Co, Ni. Solution A containing active metal components prepared therefrom is used to impregnate phosphorus-modified unit cell distorted pseudo-boehmite, thereby enabling the phosphorus-modified unit cell distorted pseudo-boehmite to be modified with active metals; solution B containing active metal components prepared therefrom is used to impregnate an alumina support, thereby enabling the alumina support to be prepared as an active metal-modified catalyst precursor, thereby enabling the surface metal deposition resistance and activity of the prepared surface-defective hydrodesulfurization and demetallization catalyst to be improved.

[0033] In order to demonstrate the beneficial effects of the surface-defective hydrodesulfurization and demetallization catalysts prepared in the present application, the present application provides Examples 1 to 4, and Comparative Examples 1 to 5, wherein the reaction conditions of all Examples and Comparative Examples are shown in Table 1 below.

[0034] This application also provides a blank control, which is a high-quality high-purity pseudo-boehmite developed by Sasol, Germany, produced with high-purity aluminum and higher alcohols as raw materials, hereinafter referred to as SB (Sasol boehmite) powder.

[0035] In this application, scanning electron microscopy is used to characterize the microstructure of the products obtained in the examples, comparative examples, and blank controls, and corresponding scanning electron microscope images (SEM images) can be obtained. For the purpose of simplicity and clarity, this application takes Example 1 as an example and provides SEM images of the phosphorus-modified unit cell distorted pseudo-boehmite and the surface defective hydrodesulfurization and demetallization catalyst prepared in Example 1, which are respectively Figure 1 and Figure 2 ; Depend on Figure 1 It can be seen that the microscopic morphology of the phosphorus-modified unit cell distorted pseudo-boehmite prepared in Example 1 is curved lamellar. The special curved lamellar structure can effectively adjust the pore structure of the catalyst and increase the macropore content.

[0036] Since the first urea solution in Comparative Example 1 was replaced by an ammonia solution and the first urea solution in Comparative Example 2 was replaced by an ammonium carbonate solution, the morphology of the products prepared therefrom was different from that of the phosphorus-modified unit cell distorted pseudo-boehmite prepared in the present application.

[0037] In this application, an X-ray diffractometer is used to characterize the physical structure of the products obtained in the examples, comparative examples and blank controls, and the corresponding XRD spectra are obtained. For the purpose of simplicity, this application uses Example 1 as an example to provide the XRD spectra of SB powder and the phosphorus-modified unit cell distorted pseudo-boehmite P1 prepared in Example 1, as shown in FIG. Figure 3 shown.

[0038] Depend on Figure 3As shown, the phosphorus-modified unit cell distorted pseudo-boehmite prepared in Example 1 of the present application has a smaller (020) crystal plane spacing than that of SB powder.

[0039] The reduction percentage of the (020) interplanar spacing of Examples 1 to 4 compared to the blank control was calculated based on the XRD spectra of the phosphorus-modified unit cell distorted pseudo-boehmite prepared in Examples 1 to 4 and the XRD spectra of the SB powder in the blank control, specifically including: The crystal plane corresponding to the characteristic peak of 11.1°-17.5° at 2θ in the XRD spectrum is the (020) crystal plane; By Bragg's law , , respectively calculate the interplanar spacing of the blank control and the phosphorus-modified unit cell distorted pseudo-boehmite prepared in Examples 1 to 4 ; Where n represents the diffraction order, n is an integer, λ represents the wavelength of the incident X-ray, and θ represents the diffraction angle, that is, the angle between the incident beam and the (020) crystal plane. represents the (020) interplanar spacing of SB powder, Respectively represent the (020) crystal plane spacing of the phosphorus-modified unit cell distorted pseudo-boehmite prepared in Example 1 to Example 4; The percentage reduction of the (020) interplanar spacing of Examples 1 to 4 compared to the blank control was calculated using the following formula: , ; Where, Respectively represent the percentage reduction of the (020) interplanar spacing of Examples 1 to 4 compared with the blank control.

[0040] The metal-modified unit cell distorted pseudo-boehmite prepared by the preparation method provided in the present application has a (020) crystal plane spacing reduction percentage δ of 0.3%-1.7% compared to the blank control.

[0041] Table 1 Reaction conditions

[0042] It should be noted that, in comparative example three, in step S30, the pre-impregnation loading is not performed by solution A containing active metal components, but the phosphorus-modified unit cell distorted pseudo-boehmite is directly mixed with pseudo-boehmite C and sesbania powder, and then a peptizing agent is added and kneaded into shape, and then the alumina carrier is obtained after a third drying and a second calcination; in step S40, the alumina carrier is impregnated with solution A containing active metal components and solution B containing active metal components to prepare catalyst Cat-7, and the particle morphology on the catalyst surface is flaky, and the flaky particles cover the catalyst surface to form open channels of 100-300 nm.

[0043] In this application, the properties and catalytic effects of the products obtained in the examples and comparative examples were measured by the following method: Pore ​​structure characterization: First, the pore volume, specific surface area and average pore diameter of the sample were determined using the low-temperature nitrogen adsorption-desorption method (BET).

[0044] Characterization of micro-area composition: The micro-area composition of the sample was analyzed using a scanning electron microscope equipped with an energy dispersive spectrometer (SEM-EDS). In the experiment, 10 flaky particle accumulation micro-areas and granular particle accumulation micro-areas were selected as measurement areas. The content of active metal oxides in the corresponding areas was measured and the average value was taken to calculate the H value.

[0045] Microstructure characterization: Scanning electron microscopy (SEM) was used to characterize the microstructure of the samples.

[0046] Phase characterization: X-ray diffractometer was used to characterize the sample phase.

[0047] Catalytic Effect: Using residual oil as feedstock, the content of metallic impurities nickel and vanadium (Ni+V) in the feedstock was 131 μg / g, and the sulfur content was 0.36 wt%. The reaction conditions were as follows: reaction temperature 380°C, pressure 14.0 MPa, and liquid hourly volume space velocity 0.70 h / min. -1 The volume ratio of hydrogen to oil was 850. The impurity content (metal impurities nickel, vanadium and sulfur) in the generated oil was determined after 3000 hours of reaction, and the impurity removal rate was calculated. The evaluation results are shown in Table 2.

[0048] The properties and catalytic effects of the products obtained in the examples and comparative examples are shown in Table 2 below: Table 2 Properties and catalytic effects of the products obtained in Examples and Comparative Examples

[0049] As can be seen from Table 2, the surface-defective hydrodesulfurization and demetallization catalysts prepared in the examples of the present application have high specific surface area and pore volume. The prepared catalyst has a high content of 20-40 nm pores, and the size of the pores on the catalyst surface is 100-300 nm, which can improve the activity of the catalyst. The relative demetallization rate and relative desulfurization rate after 3000 hours are significantly improved. The effect of removing metal impurities and sulfur impurities is good, and the deposition of impurities such as nickel, vanadium, and sulfur can be prevented. It has high initial activity, high stability over a long period of time, and a long service life.

[0050] The catalysts prepared by Comparative Examples 1 and 2 have insufficient surface defects, relatively small pore volumes, low pore content of 20-40 nm channels, and poor pore control effects. The relative demetallization rate and relative desulfurization rate of the prepared catalysts are relatively low, making it difficult to meet the use requirements of hydrodesulfurization and demetallization catalysts for heavy oil and residual oil with surface defects.

[0051] In Comparative Example 3, solution A containing active metal components was not used for pre-impregnation, but was co-impregnated with solution B containing active metal components. As can be seen from the measurement results in Table 2, although the specific surface area and pore volume of the prepared catalyst are relatively large, and the content of 20-40 nm pores is also significantly higher, the relative desulfurization rate and demetallization rate after 3000 hours are relatively poor compared with those of Examples 1 to 4. In summary, the operating cycle of the catalyst prepared in Comparative Example 3 is not long enough, and the relative desulfurization rate and demetallization effects are not good enough.

[0052] In Comparative Example 4, the second urea solution was replaced by an ammonium carbonate solution. As shown in the measurement results in Table 2, the relative desulfurization rate and demetallization rate after 3000 hours were poorer than those in Examples 1 to 4. The operating cycle of the catalyst prepared in Comparative Example 4 was not long enough, and the relative desulfurization rate and demetallization effects were not good enough.

[0053] In Comparative Example 5, step S50 was omitted, and the catalyst precursor prepared in S40 was used directly as the product. No second urea solution was added, and no third hydrothermal treatment was performed. The results in Table 2 show that the surface particle morphology of the product was granular, with surface pores ranging from 30 to 100 nm. These small pores hindered the diffusion of macromolecular reactants, resulting in poor activity and stability. The relative desulfurization rate and demetallization rate over 3000 hours were both inferior to those of Examples 1 to 4. The catalyst prepared in Comparative Example 5 had an insufficient operating cycle, and the relative desulfurization rate and demetallization performance were also suboptimal.

[0054] This application also provides a surface-defective hydrodesulfurization and demetallization catalyst prepared using any of the above methods for preparing surface-defective hydrodesulfurization and demetallization catalysts. Since the above method is used for preparation, it is believed to have the same beneficial effects as the above catalysts. For the purpose of brevity, a detailed description thereof will not be given here.

[0055] It should be noted that the reaction conditions such as the temperature and time of the first roasting, the first drying, the second roasting, the second drying, the third drying, the third roasting, the fourth roasting, the fourth drying, and the fifth drying in the present application are within the range provided above. When the temperature is low, the time is increased accordingly, and when the temperature is high, the time is shortened accordingly. Table 1 only provides examples of a portion of the data and is not intended to limit the reaction conditions in the present application.

[0056] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the quantity of the technical features being referred to. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the features. Throughout the description of this application, "plurality" means at least two, such as two, three, etc., unless otherwise specifically defined.

[0057] Although the preferred embodiments of the present application have been described, those skilled in the art may make additional changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present application.

[0058] Obviously, those skilled in the art may make various changes and modifications to this application without departing from the spirit and scope of this application. Thus, if these modifications and variations of this application fall within the scope of the claims of this application and their equivalents, this application is intended to include these modifications and variations.

Claims

1. A method for preparing a hydrodesulfurization and demetallization catalyst having surface defects, characterized in that: include: Preparation of phosphorus-modified aluminum oxide compounds; The prepared phosphorus-modified aluminum oxide compound is added with a first urea solution, stirred evenly, and then placed in a closed kettle for a first hydrothermal treatment and a second hydrothermal treatment, and then filtered, washed, and dried for a first time to obtain phosphorus-modified unit cell distorted pseudo-boehmite; The phosphorus-modified unit cell distorted pseudo-boehmite is impregnated with a solution A containing an active metal component in a saturated impregnation manner, and then the material is subjected to a second drying. The material obtained after the second drying, the pseudo-boehmite C, and the sesbania powder are uniformly mixed, a peptizing agent is added, and kneading is performed. The alumina support is then obtained after a third drying and a second calcination. The alumina support is impregnated with the solution B containing the active metal component in a saturated impregnation manner, and then subjected to a fourth drying and a third calcination to obtain a catalyst precursor; The catalyst precursor is added with a second urea solution, and subjected to a third hydrothermal treatment in a closed kettle, and then filtered, washed, dried for a fifth time, and calcined for a fourth time to obtain a hydrodesulfurization and demetallization catalyst with surface defects.

2. The method for preparing a surface-defective hydrodesulfurization and demetallization catalyst according to claim 1, characterized in that: The preparation of phosphorus-modified aluminum oxide compounds specifically includes: Weigh aluminum nitrate and a phosphorus-containing compound, mix them evenly, and grind them to obtain a paste; The paste is first calcined and pulverized to obtain a phosphorus-modified aluminum oxide compound.

3. The method for preparing a surface-defective hydrodesulfurization and demetallization catalyst according to claim 2, characterized in that: The phosphorus-containing compound is one or more of ammonium phosphate, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate.

4. The method for preparing a surface-defective hydrodesulfurization and demetallization catalyst according to claim 3, characterized in that: The mass ratio of aluminum nitrate to phosphorus-containing compound is 60:1-30:

1.

5. The method for preparing a surface-defective hydrodesulfurization and demetallization catalyst according to claim 1, wherein: The first hydrothermal treatment temperature is 90-130° C., and the first hydrothermal treatment time is 1-4 hours; the second hydrothermal treatment temperature is 150-200° C., and the second hydrothermal treatment time is 4-8 hours.

6. The method for preparing a surface-defective hydrodesulfurization and demetallization catalyst according to claim 5, characterized in that: The microscopic morphology of the phosphorus-modified unit cell distorted pseudo-boehmite is curved lamellar, and the curved lamellar particle size is 100-500nm; compared with SB powder, the (020) crystal plane spacing of the phosphorus-modified unit cell distorted pseudo-boehmite is reduced by 0.3%-1.7%.

7. The method for preparing a surface-defective hydrodesulfurization and demetallization catalyst according to claim 1, characterized in that: The active metal component-containing solution A and the active metal component-containing solution B both include Group VIB metals and Group VIII metals.

8. The method for preparing a surface-defective hydrodesulfurization and demetallization catalyst according to claim 7, characterized in that: The active metal component-containing solution A contains 2.5-5.5 g / 100 mL of Group VIB metal in terms of oxide content, and 0.6-1.5 g / 100 mL of Group VIII metal in terms of oxide content.

9. The method for preparing a surface-defective hydrodesulfurization and demetallization catalyst according to claim 8, characterized in that: The active metal component-containing solution B contains 10-20 g / 100 mL of Group VIB metal in terms of oxide content, and 2.5-5 g / 100 mL of Group VIII metal in terms of oxide content.

10. A hydrodesulfurization and demetallization catalyst containing surface defects prepared by the method for preparing a hydrodesulfurization and demetallization catalyst containing surface defects according to any one of claims 1 to 9.

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