Residual oil hydrodesulfurization catalyst as well as preparation method and application thereof

Abstract

The present invention discloses a residual oil hydrodesulfurization catalyst and a preparation method and application thereof, the residual oil hydrodesulfurization catalyst comprises an active metal component, an auxiliary agent metal component and a carrier, the active metal is one or more of VIB group metal and / or VIII group metal, the auxiliary agent metal is iron and / or zirconium, and the carrier is a carrier. Wherein the active metal and the auxiliary metal exist on the carrier in an oxide form, and the carrier is aluminum oxide. The preparation method comprises the following steps: (1) preparing a first material flow; (2) preparing a first catalyst precursor, (3) preparing a second stream; (4) preparing a second catalyst precursor; and (5) carrying out heat treatment on the second catalyst precursor, introducing an active metal component, and further drying and roasting to obtain the hydrodesulfurization catalyst. The hydrodesulfurization catalyst provided by the invention has good metal containing capacity and asphaltene conversion capacity while having high desulfurization performance, and can greatly reduce the content of sediments in generated oil.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of petroleum refining, and relates to a catalyst and a preparation method thereof, in particular to a hydrogenation catalyst and a preparation method thereof. BACKGROUND

[0002] With the continuous exploitation of oil, the proportion of heavy oil increases year by year. How to fully utilize heavy oil is the key to solving the energy problem, especially to improving energy utilization efficiency. The ebullated bed hydrogenation process has wide adaptability to raw materials, and can treat various inferior crude oil, residual oil, oil sand, asphalt oil, shale oil and other raw materials, remove various impurities to realize the lightening and cleaning of inferior heavy oil, convert heavy oil into high value-added light oil, and improve the economic benefit of enterprises. However, to achieve the above-mentioned goals, the continuous improvement of catalyst performance is the key.

[0003] With the increasingly stringent environmental protection regulations, the sulfur content of gasoline and diesel used by automobiles and fuel oil used by ships is required to be more stringent. With the rapid development of new energy vehicles, the demand for gasoline and diesel in the world is slowing down, and the production of low-sulfur heavy ship fuel provides options for some refineries to maintain existing capacity or moderately utilize idle capacity. In order to meet the new needs of refineries, the ebullated bed hydrogenation technology needs to continuously improve the performance of its catalyst, especially the performance of the desulfurization catalyst, to meet the lower requirements of downstream devices for the sulfur content of raw oil.

[0004] CN104646008A discloses a poor quality heavy oil hydrodesulfurization and demetallization catalyst and a preparation method thereof. The catalyst uses alumina as a carrier and Ni-Mo as an active component, and the average pore diameter of the catalyst gradually increases from the center to the outer surface of the catalyst particle in the radial direction. The preparation method of the catalyst is to treat the carrier particle after molding and calcination with an acid solution with continuously increasing concentration. The catalyst provided by the present application has larger surface pore openings, open pores, excellent diffusion performance, high hydrodesulfurization and demetallization activity, and high activity stability. However, the active metal of the catalyst still uses the conventional impregnation method for loading, which makes the active metal have a strong interaction with the alumina carrier, the utilization rate of the active metal is not high, and the further improvement of the catalyst activity is limited.

[0005] CN105772005A discloses a hydrogenation catalyst, a preparation method thereof and a method for heavy oil hydrodesulfurization. The hydrogenation catalyst includes a carrier and an active metal component, and the active metal component is distributed in a double layer along the radial direction of the carrier. The active metal component of the core layer is CoO and MoO3, and the active metal component of the shell layer is NiO and MoO3 and / or WO3. The hydrogenation catalyst provided by the present application has high hydrodemetallization, hydrodesulfurization, hydrodecarbon and hydrodenitrogenation activity. However, the conversion capacity of macromolecules such as asphaltene of the catalyst still needs to be further improved. SUMMARY

[0006] In view of the problems existing in the prior residue hydrodesulfurization catalyst and the preparation method thereof, the present application provides a residue hydrodesulfurization catalyst, a preparation method and application thereof, the provided hydrodesulfurization catalyst not only has a variable pore distribution structure, but also has a non-uniform active metal distribution, has high desulfurization performance, good metal holding capacity and asphaltene conversion capacity, and can greatly reduce the sediment content in the generated oil, and is especially suitable for residue hydrodesulfurization and conversion process in a boiling bed.

[0007] The technical scheme of the present application mainly includes the following aspects:

[0008] The present application provides a preparation method of a residue hydrodesulfurization catalyst, comprising the following steps:

[0009] (1) uniformly mixing an auxiliary metal precursor, an organic acid, an organic high molecular polymer and water, and obtaining a first stream after heating;

[0010] (2) uniformly mixing pseudo-boehmite, the first stream obtained in step (1), a water solution of the organic high molecular polymer after heating treatment, and obtaining a first catalyst precursor after balling and molding,

[0011] (3) uniformly mixing an organic high molecular polymer, an alkaline compound and pseudo-boehmite, and obtaining a second stream;

[0012] (4) uniformly adding the second stream and the water solution of the organic high molecular polymer after heating treatment in the rolling process of the first catalyst precursor under the condition of rolling balling, and obtaining a second catalyst precursor after treatment;

[0013] (5) heat-treating the second catalyst precursor, then introducing an active metal component, and further drying and calcining to obtain a hydrodesulfurization catalyst.

[0014] Further, as a specific embodiment, in the preparation method of the residue hydrodesulfurization catalyst, the auxiliary metal in step (1) can be at least one of iron (Fe) and zirconium (Zr), and further more specifically, the iron precursor can be at least one of ferric nitrate, ferric chloride and ferric sulfate; and the zirconium precursor can be at least one of zirconium nitrate, zirconium chloride and zirconium sulfate.

[0015] Further, as a specific embodiment, in the preparation method of the residue hydrodesulfurization catalyst, the auxiliary metal precursor in step (1) can be added in an amount of 0.5wt% to 4.0wt% of the dry basis content of pseudo-boehmite in step (2), and preferably 1.0wt% to 3.0wt%.

[0016] Further, as a specific embodiment, in the preparation method of the residue hydrodesulfurization catalyst, the organic acid in step (1) can be selected from one or more than two mixtures of citric acid, acetic acid, lactic acid, malic acid, and tartaric acid, and is preferably citric acid.

[0017] Further, as a specific embodiment, in the preparation method of the residue hydrodesulfurization catalyst, the organic high molecular polymer is one or more than two of starch, cellulose ether, and flour, and is preferably starch. Further, the starch is one or more than two of mung bean starch, cassava starch, sweet potato starch, potato starch, wheat starch, water chestnut starch, lotus root starch, and corn starch, and is preferably corn starch and / or potato starch. The cellulose ether can be at least one of methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenyl cellulose, and is preferably methyl cellulose.

[0018] Further, as a specific embodiment, in the preparation method of the residue hydrodesulfurization catalyst, the mass ratio of the organic high molecular polymer to water in step (1) is 0.1 to 0.5, and the mass ratio of the organic high molecular polymer to the organic acid is 1:0.2 to 1:5.

[0019] Further, as a specific embodiment, in the preparation method of the residue hydrodesulfurization catalyst, the heating temperature in step (1) is 30 to 50°C, and the heating time is 2 to 6 hours.

[0020] Further, as a specific embodiment, in the preparation method of the residue hydrodesulfurization catalyst, the pseudo-boehmite in steps (2) and (3) has the following properties after being calcined at 600°C: a specific surface area greater than 280 m 2 / g, preferably 290 to 320 m 2 / g, and a pore volume of 0.9 to 1.2 mL / g, preferably 0.95 to 1.10 mL / g. The pseudo-boehmite can be freely selected from commercially available pseudo-boehmite products meeting the index requirements, and can also be prepared according to the preparation method disclosed in the prior art.

[0021] Further, as a specific embodiment, in the preparation method of the residue oil hydrodesulfurization catalyst, the concentration of the heated organic polymer aqueous solution in step (2) and step (4) is 0.5wt%-8.0wt%, preferably 1.0wt%-5.0wt%. Further, the heated organic polymer aqueous solution is prepared by treating the mixture of the organic polymer and water under heating conditions, and obtaining the heated organic polymer aqueous solution after the organic polymer is completely dissolved, wherein the heating treatment temperature is 60-100°C, and the heating treatment time is 10-40min.

[0022] Further, as a specific embodiment, in the preparation method of the residue oil hydrodesulfurization catalyst, the content of the organic polymer in the first stream in step (2) is 5wt%-25wt% of the dry basis boehmite mass in step (2), preferably 10wt%-20wt%.

[0023] Further, as a specific embodiment, in the preparation method of the residue oil hydrodesulfurization catalyst, the mass ratio of the heated organic polymer aqueous solution in step (2) to the boehmite is 0.1-1.0.

[0024] Further, as a specific embodiment, in the preparation method of the residue oil hydrodesulfurization catalyst, the basic compound in step (3) is an ammonium ion-containing compound, which can be one or a mixture of two or more of ammonia, ammonium carbonate, and ammonium bicarbonate, preferably ammonia. Further, the concentration of the basic compound aqueous solution is 2wt%-40wt%, preferably 5wt%-35wt%.

[0025] Further, as a specific embodiment, in the preparation method of the residue oil hydrodesulfurization catalyst, the total amount (by mass) of the organic polymer and the basic compound added in step (3) is 5wt%-25wt% of the dry basis boehmite mass, preferably 10wt%-20wt%; wherein the mass ratio of the organic polymer to the basic compound is 1:0.05-1:0.5.

[0026] Further, as a specific embodiment, in the preparation method of the residue oil hydrodesulfurization catalyst, in step (3), the organic polymer and the basic compound are mixed first, and then mixed with the boehmite.

[0027] Further, as a specific embodiment, in the preparation method of the residue oil hydrodesulfurization catalyst, the mass ratio of the boehmite in step (2) to the boehmite in step (3) is 1-4:1.

[0028] Further, as a specific embodiment, in the preparation method of the residue oil hydrodesulfurization catalyst, the mass ratio of the heated organic polymer solution to the second stream in step (4) is 0.5-1.2.

[0029] Further, as a specific embodiment, in the preparation method of the residue oil hydrodesulfurization catalyst, the rolling into balls in step (4) can be carried out in a ball rolling machine, and the first catalyst precursor is put into the ball rolling machine, and the second stream and the heated organic polymer solution are added uniformly during the rolling process, and the second catalyst precursor is obtained after the treatment.

[0030] Further, as a specific embodiment, in the preparation method of the residue oil hydrodesulfurization catalyst, the heat treatment temperature in step (5) is 200-300℃, and the heat treatment time is 3-12h.

[0031] Further, as a specific embodiment, in the preparation method of the residue oil hydrodesulfurization catalyst, the process of introducing the active metal component in step (5) is an impregnation treatment of the heat-treated second catalyst precursor with an alkaline active metal precursor solution; the alkaline active metal precursor solution is an aqueous ammonia solution containing an active metal precursor; the active metal is at least one of a Group VIB metal and at least one of a Group VIII metal, and the active metal precursor is a salt containing the active metal, wherein the Group VIB metal can be W and / or Mo, preferably Mo; the Group VIII metal is Ni and / or Co, preferably Ni; the molybdenum precursor can be ammonium heptamolybdate and / or ammonium tetramolybdate; and the nickel precursor can be basic nickel carbonate.

[0032] Further, as a specific embodiment, in the preparation method of the residue oil hydrodesulfurization catalyst, the drying temperature in step (5) is 80-120℃, and the drying time is 4-12h.

[0033] Further, as a specific embodiment, in the preparation method of the residue oil hydrodesulfurization catalyst, the calcination temperature in step (5) is 400-600℃, and the calcination time is 1-5h.

[0034] The second aspect of the present application provides a residue oil hydrodesulfurization catalyst obtained by the above preparation method.

[0035] Further, as a specific embodiment, in the residue oil hydrodesulfurization catalyst, the catalyst comprises active metal components, auxiliary metal components and a carrier, the active metal is one or more of the Group VIB metals and one or more of the Group VIII metals, the auxiliary metal is iron and / or zirconium, wherein the active metal and the auxiliary metal exist in the form of oxides on the carrier, and the carrier is alumina.

[0036] Further, as a specific embodiment, in the residue oil hydrodesulfurization catalyst, the catalyst comprises a core layer and a shell layer, wherein the core layer alumina has mesoporous channels with a pore size of 10-50 nm, and the shell layer alumina has macroporous channels with a pore size greater than 50 nm, and the weight ratio of the core layer alumina to the shell layer alumina is 1-4:1 based on the weight of the catalyst.

[0037] Further, as a specific embodiment, in the residue oil hydrodesulfurization catalyst, the content of the Group VIB metal components is 8wt%-15wt% based on the weight of the catalyst in the form of oxides; the content of the Group VIII metal components is 2wt%-5wt% based on the weight of the catalyst in the form of oxides; and the content of the auxiliary metal components is 0.1wt%-2.5wt% based on the weight of the catalyst in the form of oxides.

[0038] Further, as a specific embodiment, in the residue oil hydrodesulfurization catalyst, the residue oil hydrodesulfurization catalyst has the following properties: a specific surface area of 200-240m 2 / g, a pore volume of 0.55-0.78mL / g, a mesopore volume with a pore size of 10-50nm accounting for 70%-90% of the total pore volume, and a macropore volume with a pore size greater than 50nm accounting for 5%-10% of the total pore volume.

[0039] Further, as a specific embodiment, in the residue oil hydrodesulfurization catalyst, the active metal of the residue oil hydrodesulfurization catalyst is distributed relatively less on the outside and relatively more on the inside, showing uneven distribution.

[0040] The third aspect of the present application provides a use of the residue oil hydrodesulfurization catalyst in a residue oil hydrodesulfurization process.

[0041] Further, in the use, the residue oil is at least one of atmospheric residue oil and vacuum residue oil.

[0042] Further, in the use, the hydrodesulfurization process has the following process conditions: a reaction pressure of 15-20MPa, a temperature of 350-450℃, a liquid hourly space velocity of 0.1-1.5h -1 , and a hydrogen / oil volume ratio of 300-1000.

[0043] The residue oil hydrodesulfurization catalyst and the preparation method thereof provided by the present application have the following advantages compared with the prior art:

[0044] 1. The residue hydrodesulfurization catalyst provided by the application, wherein the carrier is alumina, the proportion of mesopores in the core layer of the carrier is high, and the carrier has high acidity due to the introduction of auxiliary metal; the proportion of macropores in the shell layer of the carrier is high, the pore size of the catalyst gradually increases from inside to outside, the catalyst can effectively remove impurities such as sulfur in residue oil and gradually convert asphaltene, and reduce the content of sediment in the generated oil, and is particularly suitable for residue hydrodesulfurization and conversion process in ebullated bed.

[0045] 2. The preparation method of the residue hydrodesulfurization catalyst provided by the application, wherein the organic polymer is decomposed into small molecules in water after heat treatment, so that the aqueous solution has high cohesiveness, and the interaction force between pseudo-boehmite is enhanced, and the strength and wear resistance of the carrier are improved.

[0046] 3. The preparation method of the residue hydrodesulfurization catalyst provided by the application, wherein the organic polymer is modified by acid, the molecular size is reduced and the cohesiveness is weakened, and the organic polymer is mixed with pseudo-boehmite to increase the proportion of mesopores in the core layer of the carrier. After the organic polymer is reacted with the alkaline compound, the molecular size does not change, but the cohesiveness is poor, and the organic polymer is mixed with pseudo-boehmite, which mainly utilizes the pore expansion function to increase the proportion of macropores in the shell layer of the carrier.

[0047] 4. The preparation method of the residue hydrodesulfurization catalyst provided by the application, wherein the ammonia in the second catalyst precursor interacts with the organic polymer during heat treatment, and is adsorbed by interacting with the strong acidic sites on the shell layer of alumina, and the introduction of the alkaline hydrogenation active metal solution weakens the interaction between the shell layer of alumina, and the active metal is more easily diffused and adsorbed to the core layer of alumina, resulting in uneven dispersion of the active metal, which is less distributed on the shell layer of alumina and more distributed on the core layer of alumina. Although the active metal is less dispersed on the shell layer of alumina, the interaction between the active metal and the shell layer of alumina is weak, and the utilization rate of the active metal is improved.

[0048] 5. The residue hydrodesulfurization catalyst provided by the application, wherein the catalyst has varying pore distribution structure and uneven active metal distribution, the shell layer of the catalyst can effectively remove impurities such as metal, sulfur, nitrogen and the like in residue oil and effectively convert asphaltene, can protect the core layer of the catalyst, and the addition of metal iron or zirconium to the core layer of the carrier can increase the acidity of the core layer of the carrier, so that the core layer of the carrier has higher hydrodesulfurization activity, can further deeply desulfurize residue oil, and can meet the use requirements of ebullated bed residue hydrodesulfurization and conversion process. BRIEF DESCRIPTION OF DRAWINGS

[0049] Figure 1 The electron probe line scanning image of the catalyst section obtained in Example 3 of the application.

[0050] Figure 2MoO3 distribution map of the catalyst cross-section electron probe line scan obtained from Example 3 of the present application. DETAILED DESCRIPTION

[0051] The embodiments of the present application will be further described in conjunction with the following examples. The following examples are intended to illustrate the present application and are not intended to limit the scope of the present application.

[0052] Unless otherwise defined, all terms used in disclosing the application, including technical and scientific terms, have the meaning as commonly understood by one of ordinary skill in the art to which this application belongs. By means of example, the terms "including", "containing" or "comprising" shall be construed as including without numerical limitations to the stated elements or components.

[0053] In the present document, the terms "first", "second" and the like are used to distinguish between two different elements or portions, and are not used to define a particular position or relative relationship. In other words, the terms "first", "second" and the like are interchangeable under some circumstances, and the embodiments of the present application described herein are applicable to any one of the elements or portions regardless of the ordinal numbers of the elements or portions.

[0054] All publications, patent applications, patents and other references mentioned in this specification are herein incorporated by reference. Unless otherwise defined, all technical and scientific terms used in this specification are intended to have the meanings commonly attributed to them by those of ordinary skill in the art. In case of conflict between the definitions in the specification and those in the incorporated references, the definitions in the specification are intended to prevail.

[0055] When the specification states a genus of elements or materials with a word introducing a list of elements and / or materials, e.g., "comprising", it is intended to include individual members of the genus that are listed thereafter and those unknown to the applicant as of the filing date of the application.

[0056] In the context of the present application, all numerical values of parameters (e.g., quantities or conditions) are to be understood as modified in all instances by the term "about" unless otherwise indicated. Absent a further indication, the numerical values of the parameters set forth in the specification and claims are approximations that can vary depending on the desired properties sought to be obtained by the present application.

[0057] In the context of the present application, the term "substantially" means that deviations, which can be accepted or deemed reasonable by a person skilled in the art, are allowed, such as deviations of ±5%, ±2%, ±1%, ±0.5% or ±0.1%.

[0058] Unless specifically indicated otherwise, all percentages, parts, ratios, etc. mentioned in the present specification are based on weight and pressures are to be understood as the gauge pressure.

[0059] In the context of the present application, any two or more embodiments or aspects of the present application can be combined arbitrarily, and the technical solutions thus formed are part of the original disclosure of the present specification and also fall within the scope of protection of the present application.

[0060] The specific surface area and pore volume in the present application are measured by low-temperature liquid nitrogen physical adsorption method, specifically by using a low-temperature nitrogen adsorption instrument of model ASAP2420 of American Micromeritics Company; the specific process is as follows: a small amount of sample is vacuum treated at 300℃ for 3-4h, and finally the product is placed in liquid nitrogen at low temperature (-200℃) for nitrogen adsorption-desorption test. The surface area is obtained according to the BET equation, and the pore size distribution is obtained according to the BJH model.

[0061] In the context of the present application, the attrition index of microsphere carriers with a particle size less than 0.8mm is tested by high-speed air jet method (see ASTM D5757-00), and the attrition index of microsphere carriers with a particle size of 0.8mm or more is measured by a drum method, using a KM-ZV abrasion tester.

[0062] In the context of the present application, the deposit content in the generated oil is determined according to SHT0702-2001 Residual Fuel Oil Total Sediment Determination Method (Aging Method), using a FDR-1431 Residual Fuel Oil Total Sediment Determination Instrument.

[0063] In the context of the present application, various chemical reagents can be obtained by purchasing commercially available products.

[0064] Example 1

[0065] (1) Catalyst preparation

[0066] 28g of corn starch, 28g of citric acid, 19.75g of zirconium nitrate and 100g of water were mixed, uniformly mixed and heated to 30℃, treated for 4h to obtain a first stream; 40g of corn starch was weighed and added to 2000g of water, heated at 90℃ for 15min to obtain a heated organic high polymer aqueous solution; then 400g of pseudo-boehmite powder (dry basis content 70%, specific surface area 300m 2 / g, pore volume 1.01mL / g), the first stream and 220g of the heated organic high polymer aqueous solution were mixed, uniformly mixed and then formed into a sphere to obtain a first precursor; 28.0g of corn starch was first mixed with 30g of ammonia water with a concentration of 10wt%, and then mixed with 400g of pseudo-boehmite powder (dry basis content 70%, specific surface area 300m 2The first stream was mixed with 400 g of the heated organic polymer solution to obtain a second stream; the first precursor was placed in a tumbling machine, and the second stream and 400 g of the heated organic polymer solution were added uniformly during tumbling to obtain a second precursor; 132.1 g of ammonium heptamolybdate and 48.38 g of basic nickel carbonate were dissolved in an ammonia solution having a concentration of 20 wt%, and the solution was filtered and diluted to 450 mL to obtain the Mo-Ni ammonia solution. The second precursor was heat treated at 200°C for 6 h, then mixed with the prepared Mo-Ni ammonia solution, and allowed to stand for 2 h, and then dried at 110°C for 8 h and calcined at 500°C for 4 h to obtain a spherical catalyst having a particle size of 0.5-0.8 mm, a MoO3 content of 15.0 wt%, a NiO content of 3.75 wt%, and a ZrO2 content of 0.81 wt%. The physicochemical properties, yield, and attrition data of the catalyst are shown in Table 1.

[0067] (2) Catalyst evaluation

[0068] The activity of the catalyst was evaluated in a batch autoclave under the following conditions: a reaction temperature of 430°C, a reaction pressure of 15.0 MPa, a volume ratio of oil to catalyst of 13:1, and a reaction time of 60 min. The properties of the feedstock oil used are shown in Table 2, and the evaluation results and the content of the oil deposit are shown in Table 3.

[0069] Example 2

[0070] (1) Catalyst preparation

[0071] A first stream was obtained by mixing 42 g of methyl cellulose, 84 g of acetic acid, 7.07 g of iron nitrate, and 140 g of water, and heating the mixture to 50°C for 2 h; 60 g of methyl cellulose was added to 2000 g of water, and the mixture was heated at 80°C for 20 min to obtain a heated organic polymer solution; and 400 g of pseudo-boehmite powder (dry basis content 70%, specific surface area 300 m 2 A first stream was obtained by mixing 42 g of methyl cellulose, 84 g of acetic acid, 7.07 g of iron nitrate, and 140 g of water, and heating the mixture to 50°C for 2 h; 60 g of methyl cellulose was added to 2000 g of water, and the mixture was heated at 80°C for 20 min to obtain a heated organic polymer solution; and 400 g of pseudo-boehmite powder (dry basis content 70%, specific surface area 300 m 2The first stream was mixed with 300 g pseudo-boehmite powder (dry basis content 70%, specific surface area 300 m2 / g, pore volume 1.01 mL / g) to obtain a second stream; the first precursor was placed in a tumbling machine, and the second stream and 200 g of the heated organic polymer aqueous solution were added uniformly during tumbling to obtain a second precursor; 79.26 g of ammonium heptamolybdate and 29.03 g of basic nickel carbonate were dissolved in an ammonia aqueous solution having a concentration of 20 wt%, and the solution was filtered and diluted to 340 mL to obtain the Mo-Ni ammonia aqueous solution. The second precursor was heat treated at 250 °C for 5 h, then mixed with the prepared Mo-Ni ammonia aqueous solution, and allowed to stand for 2 h, and then dried at 110 °C for 8 h and calcined at 520 °C for 3 h to obtain a spherical catalyst having a particle size of 0.5-0.8 mm, a MoO3 content of 12.0 wt%, a NiO content of 3.0 wt%, and a Fe2O3 content of 0.28 wt%. The physicochemical properties, yield, and attrition data of the catalyst are shown in Table 1.

[0072] (2) Catalyst evaluation

[0073] The activity of the catalyst was evaluated in a batch autoclave under the following conditions: reaction temperature 430 °C, reaction pressure 15.0 MPa, oil-to-agent volume ratio 13:1, and reaction time 60 min. The properties of the raw material oil used are shown in Table 2, and the evaluation results and the content of the oil deposit are shown in Table 3.

[0074] Example 3

[0075] (1) Catalyst preparation

[0076] A first stream was obtained by mixing 42 g of corn starch, 126 g of citric acid, 14.81 g of zirconium nitrate, and 210 g of water, and heating to 40 °C for 3 h; 80 g of corn starch was added to 2000 g of water, and heated at 70 °C for 25 min to obtain a heated organic polymer aqueous solution; then 300 g of pseudo-boehmite powder (dry basis content 70%, specific surface area 300 m 2 A first stream was obtained by mixing 42 g of corn starch, 126 g of citric acid, 14.81 g of zirconium nitrate, and 210 g of water, and heating to 40 °C for 3 h; 80 g of corn starch was added to 2000 g of water, and heated at 70 °C for 25 min to obtain a heated organic polymer aqueous solution; then 300 g of pseudo-boehmite powder (dry basis content 70%, specific surface area 300 m 2The first precursor was put into a rolling ball machine, and the second stream and 100 g of the heated organic polymer aqueous solution were added uniformly during the rolling process to obtain a second precursor. 44.03 g of ammonium heptamolybdate and 16.13 g of basic nickel carbonate were dissolved in an aqueous ammonia solution with a concentration of 20 wt%, and the solution was filtered and made up to 220 mL to obtain the Mo-Ni aqueous ammonia solution. The second precursor was heat treated at 300°C for 4 h, then mixed with the prepared Mo-Ni aqueous ammonia solution, and allowed to stand for 2 h, and then dried at 110°C for 8 h and calcined at 550°C for 3 h to obtain a spherical catalyst with a particle size of 0.5-0.8 mm, a MoO3 content of 10.0 wt%, a NiO content of 2.5 wt%, and a ZrO2 content of 1.31 wt%. Figure 1 and Figure 2 As shown in FIG. 1, the electron probe line scanning of the cross section of the catalyst was performed. Figure 1 As shown in FIG. 2, the MoO3 distribution diagram of the electron probe line scanning of the cross section of the catalyst was obtained. Figure 2 As shown in FIG. 2, the MoO3 distribution diagram of the electron probe line scanning of the cross section of the catalyst was obtained.

[0077] (2) Catalyst evaluation

[0078] The activity of the catalyst was evaluated by using a batch autoclave. The catalyst evaluation conditions were as follows: a reaction temperature of 430°C, a reaction pressure of 15.0 MPa, a volume ratio of oil to catalyst of 13:1, and a reaction time of 60 min. The properties of the raw material oil used are shown in Table 2, and the evaluation results and the content of the oil deposit are shown in Table 3.

[0079] Example 4

[0080] The catalyst was prepared in the same manner as in Example 3, except that the corn starch was replaced with flour and 14.0 g of an aqueous ammonia solution with a concentration of 15 wt% was replaced with 14.0 g of an aqueous ammonium carbonate solution with a concentration of 25 wt%. The catalyst was obtained, and the particle size of the catalyst was 0.5-0.8 mm. The yield and attrition data of the support are shown in Table 1. The MoO3 content of the catalyst was 10.0 wt%, the NiO content was 2.5 wt%, and the ZrO2 content was 1.31 wt%. The physicochemical properties, yield, and attrition data of the catalyst are shown in Table 1.

[0081] The catalyst evaluation was performed in the same manner as in Example 3. The properties of the raw material oil used are shown in Table 2, and the evaluation results are shown in Table 3.

[0082] Example 5

[0083] The long-term activity of the catalyst of Example 3 was evaluated by using a CSTR hydrogenation evaluation device for 1500 h. The catalyst evaluation conditions were as follows: a reaction temperature of 420°C, a reaction pressure of 15.0 MPa, a volume space velocity of 0.3 h -1, hydrogen to oil volume ratio 600:1. The properties of the feedstock oils used are given in Table 2, and the results of the evaluation and the deposit content of the product oil are given in Table 4.

[0084] Comparative Example 1

[0085] (1) Catalyst preparation

[0086] 42 g of corn starch, 126 g of citric acid, 14.81 g of zirconium nitrate and 210 g of water were mixed, heated to 40°C after mixing well, and treated for 3 h to obtain a first stream; 300 g of pseudo-boehmite powder (dry basis content 70%, specific surface area 300 m 2 / g, pore volume 1.01 mL / g), the first stream and 90 g of water were mixed, and after mixing well, a balling molding treatment was performed to obtain a first precursor; 14.0 g of corn starch was first mixed with 14.0 g of ammonia water having a concentration of 15 wt%, and then mixed with 100 g of pseudo-boehmite powder (dry basis content 70%, specific surface area 300 m 2 / g, pore volume 1.01 mL / g) to obtain a second stream; the first precursor was placed in a balling machine, and the second stream and 100 g of water were added uniformly during the rolling process, and after the balling treatment, a second precursor was obtained; 44.03 g of ammonium heptamolybdate and 16.13 g of basic nickel carbonate were dissolved in an ammonia water solution having a concentration of 20 wt%, and after filtration, the solution was made up to 220 mL to obtain the Mo-Ni ammonia solution. The second precursor was heat treated at a temperature of 300°C for 4 h, then mixed with the prepared Mo-Ni ammonia solution, allowed to stand for 2 h, and then dried at 110°C for 8 h and calcined at 550°C for 3 h to obtain a spherical catalyst having a particle size of 0.5-0.8 mm, in which the MoO3 content was 10.0 wt%, the NiO content was 2.5 wt%, and the ZrO2 content was 1.31 wt%. The physicochemical properties, yield and attrition data of the catalyst are given in Table 1.

[0087] (2) Catalyst evaluation

[0088] The activity of the catalyst was evaluated using a batch autoclave, and the catalyst evaluation conditions were: reaction temperature 430°C, reaction pressure 15.0 MPa, oil to catalyst volume ratio 13:1, and reaction time 60 min. The properties of the feedstock oils used are given in Table 2, and the results of the evaluation and the deposit content of the product oil are given in Table 3.

[0089] Comparative Example 2

[0090] (1) Catalyst preparation

[0091] Mix 42 g of corn starch, 126 g of citric acid and 210 g of water, heat to 40°C after mixing evenly, treat for 3 h to obtain a first stream; weigh 80 g of corn starch into 2000 g of water, heat at 70°C for 25 min to obtain a heated organic polymer aqueous solution; then mix 300 g of pseudo-boehmite powder (dry basis content 70%, specific surface area 300 m 2 / g, pore volume 1.01 mL / g), the first stream and 90 g of the heated organic polymer aqueous solution to obtain a first precursor; mix 14.0 g of corn starch with 14.0 g of ammonia water with a concentration of 15 wt%, then mix with 100 g of pseudo-boehmite powder (dry basis content 70%, specific surface area 300 m 2 / g, pore volume 1.01 mL / g) to obtain a second stream; put the first precursor into a ball rolling machine, and uniformly add the second stream and 100 g of the heated organic polymer aqueous solution during rolling, and obtain a second precursor after balling; dissolve 44.03 g of ammonium heptamolybdate and 16.13 g of basic nickel carbonate in an ammonia water solution with a concentration of 20 wt%, filter and make up to 220 mL to obtain a Mo-Ni ammonia solution. Heat treat the second precursor at a temperature of 300°C for 4 h; then mix with the prepared Mo-Ni ammonia solution, stand for 2 h, then dry at 110°C for 8 h and calcine at 550°C for 3 h to obtain a spherical catalyst with a particle size of 0.5-0.8 mm, wherein the MoO3 content is 10.0 wt% and the NiO content is 2.5 wt%. The physicochemical properties, yield and attrition data of the catalyst are shown in Table 1.

[0092] (2) Catalyst evaluation

[0093] The activity of the catalyst was evaluated by using a batch autoclave, and the catalyst evaluation conditions were as follows: reaction temperature 430°C, reaction pressure 15.0 MPa, oil to catalyst volume ratio 13:1, and reaction time 60 min. The properties of the raw material oil used are shown in Table 2, and the evaluation results and the content of the oil deposit are shown in Table 4.

[0094] Comparative Example 3

[0095] (1) Catalyst preparation

[0096] Mix 42 g of corn starch, 126 g of citric acid, 14.81 g of zirconium nitrate and 210 g of water, heat to 40°C after mixing evenly, treat for 3 h to obtain a first stream; weigh 80 g of corn starch into 2000 g of water, heat at 70°C for 25 min to obtain a heated organic polymer aqueous solution; then mix 300 g of pseudo-boehmite powder (dry basis content 70%, specific surface area 300 m 2 / g, pore volume 1.01 mL / g), the first stream and 90 g of the heated organic polymer aqueous solution were mixed, and after uniform mixing, a first precursor was obtained by spheronization; the first precursor was placed in a rolling machine, and 100 g of pseudo-boehmite powder (dry basis content 70%, specific surface area 300 m 2 / g, pore volume 1.01 mL / g) and 100 g of the heated organic polymer aqueous solution, and after spheronization, a second precursor was obtained; 44.03 g of ammonium heptamolybdate and 16.13 g of basic nickel carbonate were dissolved in an ammonia aqueous solution having a concentration of 20 wt%, and after filtration, the solution was made up to 220 mL, and the second precursor was obtained. The second precursor was heat treated at a temperature of 300°C for 4 h, and then mixed with the prepared Mo-Ni ammonia aqueous solution, and after standing for 2 h, the mixture was dried at 110°C for 8 h and calcined at 550°C for 3 h, and a spherical catalyst having a particle size of 0.5-0.8 mm was obtained, wherein the MoO3 content was 10.0 wt%, the NiO content was 2.5 wt%, and the ZrO2 content was 1.31 wt%. The physicochemical properties, yield and attrition data of the catalyst are shown in Table 1.

[0097] (2) Catalyst evaluation

[0098] The catalyst was subjected to long-term activity evaluation using a CSTR hydrogenation evaluation device, and the operation time was 1500 h. The catalyst evaluation conditions were: reaction temperature 420°C, reaction pressure 15.0 MPa, volume space velocity 0.3 h -1 -1, hydrogen / oil volume ratio 600:1. The properties of the raw material oil used are shown in Table 2, and the evaluation results are shown in Table 4.

[0099] Table 1 Physicochemical properties of the catalyst

[0100]

[0101]

[0102] Table 2 Properties of the raw material oil

[0103] Crude properties Values Sulfur, % 4.9 Carbon residue, % 21.5 Nickel + Vanadium / pg-g -1 ]] 230 Asphaltene, % 5.8 Residue yield at >540°C, % 81.0

[0104] Table 3 Autoclave catalyst evaluation results

[0105]

[0106] The evaluation results of Comparative Example 1 were taken as a basis, and were recorded as 100, and the results of the other examples and comparative examples were obtained by comparison with the results of Comparative Example 1.

[0107] Table 4 CSTR catalyst evaluation results

[0108]

[0109] The results in Example 5 are obtained by comparing the results in Comparative Example 3, which is taken as 100.

Claims

1. A method for preparing a residue hydrodesulfurization catalyst, comprising the following steps: (1) mixing an auxiliary metal precursor, an organic acid, an organic polymer and water, and obtaining a first stream after heating; the auxiliary metal is at least one of iron and zirconium; the organic polymer is one or more of starch, cellulose ether, and flour; (2) uniformly mixing pseudo-boehmite, the first stream obtained in step (1), and a water solution of the organic polymer after heat treatment, and obtaining a first catalyst precursor after balling; (3) uniformly mixing an organic polymer, an alkaline compound, and pseudo-boehmite, and obtaining a second stream; (4) uniformly adding the second stream and the water solution of the organic polymer after heat treatment to the first catalyst precursor during rolling, and obtaining a second catalyst precursor after treatment; (5) heat treating the second catalyst precursor, then introducing an active metal component, and further drying and calcining to obtain a hydrodesulfurization catalyst.

2. The process for preparing the residue hydrodesulfurization catalyst according to claim 1, wherein, The auxiliary metal precursor in step (1) is at least one of ferric nitrate, ferric chloride, ferric sulfate, zirconium nitrate, zirconium chloride, and zirconium sulfate.

3. The process for preparing the residue hydrodesulfurization catalyst according to claim 1, wherein, The auxiliary metal precursor in step (1) is added in an amount of 0.5wt%-4.0wt%, preferably 1.0wt%-3.0wt%, of the dry basis content of pseudo-boehmite in step (2), based on the mass of auxiliary metal oxide.

4. The process for preparing the residue hydrodesulfurization catalyst according to claim 1, wherein, The organic acid in step (1) is selected from one or more of citric acid, acetic acid, lactic acid, malic acid, and tartaric acid, and is preferably citric acid.

5. The process for preparing the residue hydrodesulfurization catalyst according to claim 1, wherein, The starch is one or more of mung bean starch, cassava starch, sweet potato starch, potato starch, cereal starch, water chestnut starch, lotus root starch, and corn starch, and is preferably corn starch and / or potato starch; the cellulose ether is at least one of methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenyl cellulose, and is preferably methyl cellulose.

6. The process for preparing the residue hydrodesulfurization catalyst according to claim 1, wherein, The mass ratio of the organic polymer to water in step (1) is 0.1-0.5, and the mass ratio of the organic polymer to the organic acid is 1:0.2-1:

5.

7. The process for preparing the residue hydrodesulfurization catalyst according to claim 1, wherein, The heating temperature in step (1) is 30-50°C.

8. The process for preparing the residue hydrodesulfurization catalyst according to claim 1, wherein, The concentration of the water solution of the organic polymer after heat treatment in steps (2) and (4) is 0.5wt%-8.0wt%, preferably 1.0wt%-5.0wt%, and the water solution of the organic polymer after heat treatment is prepared by the following method: treating a mixed stream of the organic polymer and water under heating conditions, and obtaining the water solution of the organic polymer after heat treatment after the organic polymer is completely dissolved, wherein the heat treatment temperature is 60-100°C, and the heat treatment time is 10-40 min.

9. The process for preparing the residue hydrodesulfurization catalyst according to claim 1, wherein, The content of the organic polymer in the first stream in step (2) is 5wt% to 25wt% of the dry basis mass of the pseudoboehmite in step (2), preferably 10wt% to 20wt%.

10. The process for preparing the residue hydrodesulfurization catalyst according to claim 1, wherein, The mass ratio of the heated organic polymer aqueous solution in step (2) to the pseudoboehmite is 0.1 to 1.

0.

11. The process for preparing the residue hydrodesulfurization catalyst according to claim 1, wherein, The basic compound in step (3) is one of ammonia, ammonium carbonate and ammonium bicarbonate or a mixture of two or more thereof, preferably ammonia, and the concentration of the basic compound aqueous solution is 2wt% to 40wt%, preferably 5wt% to 35wt%.

12. The process for preparing the residue hydrodesulfurization catalyst according to claim 1, wherein, The total amount of the organic polymer and the basic compound added in step (3) is 5wt% to 25wt% of the dry basis mass of the pseudoboehmite, preferably 10wt% to 20wt%; and the mass ratio of the organic polymer to the basic compound is 1:0.05 to 1:0.

5.

13. The process for preparing the residue hydrodesulfurization catalyst according to claim 1, wherein, The ratio of the amount of the pseudoboehmite in step (2) to the amount of the pseudoboehmite in step (3) is 1 to 4:

1.

14. The process for preparing the residue hydrodesulfurization catalyst according to claim 1, wherein, The mass ratio of the heated organic polymer aqueous solution to the second stream in step (4) is 0.5 to 1.

2.

15. The process for preparing the residue hydrodesulfurization catalyst according to claim 1, wherein, The heat treatment temperature in step (5) is 200 to 300℃, and the heat treatment time is 3 to 12h.

16. The process for preparing the residue hydrodesulfurization catalyst according to claim 1, wherein, The process of introducing the active metal component in step (5) is to impregnate the heat-treated second catalyst precursor with a basic active metal precursor solution; the basic active metal precursor solution is an ammonia solution containing an active metal precursor. The active metal is at least one of the Group VIB metals and at least one of the Group VIII metals, and the active metal precursor is a salt containing the active metal.

17. The process for preparing the residue hydrodesulfurization catalyst according to claim 1, wherein, The drying temperature in step (5) is 80 to 120℃, and the drying time is 4 to 12h; the calcination temperature in step (5) is 400 to 600℃, and the calcination time is 1 to 5h.

18. A residue hydrodesulfurization catalyst prepared by the method of any one of claims 1 to 17.

19. The residue hydrodesulfurization catalyst of claim 18, wherein, The catalyst comprises a core layer and a shell layer, wherein the core layer is an alumina having mesoporous channels with a pore size of 10 to 50nm, and the shell layer is an alumina having macroporous channels with a pore size greater than 50nm; and the weight ratio of the core layer alumina to the shell layer alumina is 1 to 4:1, based on the weight of the catalyst.

20. The residue hydrodesulfurization catalyst of claim 18, wherein, The content of the Group VIB metal component is 8wt% to 15wt%, the content of the Group VIII metal component is 2wt% to 5wt%, and the content of the auxiliary metal component is 0.1wt% to 2.5wt%, based on the weight of the catalyst and as oxides.

21. The residue hydrodesulfurization catalyst of claim 18, wherein, The properties of the residue hydrodesulfurization catalyst are as follows: specific surface area 200-240 m 2 / g, pore volume 0.55-0.78 mL / g. The ratio of mesopore volume with pore diameter 10-50 nm to the total pore volume is 70-90%, and the ratio of macropore volume with pore diameter greater than 50 nm to the total pore volume is 5-10%.

22. The use of the residue hydrodesulfurization catalyst of any one of claims 18 to 21 in a residue hydrodesulfurization process.

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