Solid particulate bed, fixed bed and oil hydroprocessing method

Abstract

A solid particulate bed and a fixed bed comprising the solid particulate bed, the solid particulate bed comprising a sea region and at least one island region distributed in the sea region, and having an upper surface, a lower surface, an axial direction and a radial direction, wherein the island region extends along the axial direction of the solid particulate bed but does not extend to the lower surface, and the void fraction of the island region is 110-300% of the void fraction of the sea region. An oil product hydrogenation method comprising the step of flowing an oil product through the solid particulate bed or fixed bed under hydrogenation reaction conditions.

Description

Technical Field

[0001] This invention relates to the field of oil hydrotreating technology, and more specifically to solid particle beds, fixed beds comprising the solid particle beds, and the application of these beds in oil hydrotreating. Background Technology

[0002] Due to the influence of impurities, many petroleum products require hydrotreating to improve their quality before use. For example, ethylene cracked gasoline, coking naphtha, catalytic gasoline, Fischer-Tropsch synthetic oil, coking diesel, catalytic diesel, high-drying-point straight-run diesel, wax oil, residual oil, coal tar, and coal hydrotreating products mostly contain impurities such as sulfur, nitrogen, oxygen, alkenes, and aromatics. These impurities typically require hydrorefining to remove before use. During the hydrorefining process, processing inferior petroleum products often results in increased pressure drop due to factors such as coking or mechanical impurities.

[0003] The magnitude of pressure drop is closely related to the porosity of the catalyst bed. Currently, in order to mitigate the increase in pressure drop, oil hydrotreating often employs the method of filling the reactor inlet section with particulate matter with a larger porosity. In particular, in the hydrotreating process of fixed-bed residue oil, various shapes of protective agents are filled in the inlet section of the reactor to extend its operating cycle.

[0004] Chinese patent CN101928592A discloses a graded combination of hydrogenation catalysts; the reactor is filled with hydrogenation demetallization catalysts and hydrogenation desulfurization catalysts from top to bottom; the raw material flow is from top to bottom, maintaining the flow direction, and the catalyst activity gradually increases, the pore size gradually decreases, the particle size gradually decreases, and the porosity gradually decreases.

[0005] Chinese patent CN1104558A discloses a method and catalyst system for hydrogenating hydrocarbon feedstocks. The feedstock is passed through a fixed-bed catalyst system for hydrogenation, which contains a physical mixture of high-porosity catalyst particles and low-porosity catalyst particles. The particles are mixed in different amounts in different layers of the catalyst bed, thereby forming a layered structure in the fixed-bed catalyst system. The mixing ratio of high-porosity and low-porosity particles is different in different layers. Summary of the Invention

[0006] Through painstaking research, the inventors of this invention discovered that catalytic gasoline hydrotreating is prone to coking at the top of the hydrorefining reactor, while coking diesel hydrotreating and coal tar hydrotreating are also prone to coking at the top of the reactor. The direct consequence of this top coking is an increased pressure drop in the catalyst bed at the reactor inlet. As a result, the catalyst has a low adsorption and deposition capacity for easily deposited substances, leading to a rapid increase in bed pressure drop and a shortened operating cycle. Further research by the inventors revealed that by using a special catalyst gradation method to achieve dispersed deposition of easily deposited substances in the oil, thereby increasing the catalyst's adsorption and deposition capacity for these substances, the increase in bed pressure drop can be effectively slowed down, and the operating cycle extended. This invention is based on this discovery.

[0007] Specifically, the present invention relates to the following aspects.

[0008] 1. A method for catalyst gradation for oil hydrotreating, characterized in that a gradation packing section is provided at the inlet end of the reactor, the space of the gradation packing section is divided into several columnar reaction units parallel to the flow direction, and hydrotreating catalyst I and hydrotreating catalyst II are respectively packed in each two adjacent columnar reaction units with their columnar edges in contact with each other, wherein hydrotreating catalyst I has a larger porosity than hydrotreating catalyst II.

[0009] 2. The catalyst gradation method according to any of the foregoing or the following aspects, characterized in that the catalyst bed height of the gradation packing section accounts for 1%-95% of the total reactor bed height, preferably 3%-60%, and more preferably 4%-50%.

[0010] 3. The catalyst gradation method according to any of the foregoing or hereinafter described, characterized in that conventional hydrogenation catalyst is packed in the remaining part of the reactor, and its porosity is not greater than that of hydrogenation catalyst II in the above-described gradation packing section.

[0011] 4. The catalyst gradation method according to any of the foregoing or hereinafter described, characterized in that the porosity of the catalyst bed formed after the hydrogenation catalyst I is loaded is 0.30-0.80, and the porosity of the hydrogenation catalyst I used for gradation is 110%-300% of the porosity of the hydrogenation catalyst II.

[0012] 5. The catalyst gradation method according to any of the foregoing or hereinafter described, characterized in that the hydrogenation catalyst I is a hollow particle and / or a toothed particle.

[0013] 6. The catalyst gradation method according to any of the foregoing or the following, characterized in that, in each of two adjacent columnar reaction units, hydrogenation catalyst I and hydrogenation catalyst II are respectively loaded in such a way that the columnar edges are in contact with each other, specifically, the two catalysts are loaded in an alternating adjacent manner or in an inserted manner.

[0014] 7. The catalyst gradation method according to any of the foregoing or the following aspects, characterized in that the alternating adjacent loading method involves loading the same catalyst into a columnar reaction unit in the material flow direction, and from a radial perspective, each pair of adjacent columnar reaction units is filled with the two different catalysts mentioned above; the cross-section of each columnar reaction unit is of arbitrary shape.

[0015] 8. The catalyst gradation method according to any of the foregoing or the following aspects, characterized in that the insertion method of filling involves loading hydrogenation catalyst I in a columnar manner that is separated from each other in the material flow direction to form the columnar reaction unit, while hydrogenation catalyst II is filled in the remaining positions to form a continuous or discontinuous columnar reaction unit with an irregular cross-sectional shape, wherein the columnar reaction unit formed by hydrogenation catalyst I should be inserted as uniformly as possible into the columnar reaction unit of hydrogenation catalyst II.

[0016] 9. The catalyst gradation method according to any of the foregoing or the following, characterized in that, in the same reactor, the hydrogenation catalyst I and hydrogenation catalyst II used in the gradation packing section are not limited to catalysts with only one type of void fraction, but the void fraction of any hydrogenation catalyst I should be greater than the void fraction of any hydrogenation catalyst II.

[0017] 10. The catalyst gradation method according to any of the foregoing or the following aspects, characterized in that, on the same radial cross section, the shortest distance from any point on the columnar reaction unit cross section of hydrogenation catalyst II to the edge of the columnar reaction unit cross section of the adjacent hydrogenation catalyst I does not exceed 500 mm, preferably not more than 300 mm, more preferably not more than 200 mm, and most preferably not more than 100 mm.

[0018] 11. The catalyst gradation method according to any of the foregoing or hereinafter described, characterized in that the total cross-sectional area of ​​the columnar reaction unit of hydrogenation catalyst I is 10%-60% of the total cross-sectional area of ​​the reactor.

[0019] 12. The catalyst gradation method according to any of the foregoing or hereinafter described, characterized in that the particle size of the hydrogenation catalyst I is 2.0-55.0 mm and the particle size of the hydrogenation catalyst II is 0.5-4.0 mm.

[0020] 13. The catalyst gradation method according to any of the foregoing or hereinafter described, characterized in that the mass content of the hydrogenation active metal in hydrogenation catalyst I, calculated as oxide, is 10%-90% of that in hydrogenation catalyst II used for gradation.

[0021] 14. The catalyst gradation method according to any of the foregoing or hereinafter described, characterized in that the hydrogenation active metal in hydrogenation catalyst I, hydrogenation catalyst II and the conventional hydrogenation catalyst packed in the remainder of the reactor is selected from at least one of Fe, Co, Ni, Cu, Zn, Cr, Mo and W.

[0022] 15. The catalyst gradation method according to any of the foregoing or hereinafter described, characterized in that the hydrogenation catalyst I comprises a support material and a hydrogenation active metal, wherein the hydrogenation active metal, as an oxide, accounts for 5%-30% of the weight of the catalyst, and the support material is selected from at least one of activated carbon, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, and molecular sieve.

[0023] 16. The catalyst gradation method according to any of the foregoing or hereinafter described, characterized in that the hydrogenation catalyst II and the conventional hydrogenation catalyst are catalysts capable of desulfurization, and are selected from at least one of supported catalysts and unsupported catalysts.

[0024] 17. The catalyst gradation method according to any of the foregoing or the following aspects, characterized in that the supported catalyst comprises a support and a hydrogenation active component, and a catalyst modified thereon, wherein the hydrogenation active component, based on the total weight of the catalyst, has a mass content of 15%-40% as a metal oxide.

[0025] 18. The catalyst gradation method according to any of the foregoing or hereinafter described, characterized in that the unsupported catalyst includes at least necessary binders and hydrogenation active components, wherein the mass content of the hydrogenation active components, calculated as metal oxides, is 30%-80% based on the total weight of the catalyst.

[0026] 19. A method for hydrotreating oil, characterized in that hydrotreating catalyst I and hydrotreating catalyst II are packed in a graded manner according to the method described above or below, a conventional hydrotreating catalyst with desulfurization activity is packed in the remaining part of the reactor, sulfidation is performed after packing is completed, and then oil is introduced for hydrotreating.

[0027] 20. The method according to any one of the foregoing or the following aspects, characterized in that the oil is selected from at least one of ethylene cracked gasoline, coking naphtha, catalytic gasoline, Fischer-Tropsch synthetic oil, coking diesel, catalytic diesel, high dry point straight-run diesel, wax oil, residue oil, coal tar, and coal hydrogenation product oil.

[0028] In particular, the present invention relates to the following aspects.

[0029] 1. A solid particle bed (particularly an axial solid particle bed), characterized in that it comprises a sea region and at least one island region distributed in the sea region, and has an upper surface, a lower surface, an axial direction (i.e., the length direction or the direction of material flow from the upper surface to the lower surface in the solid particle bed) and a radial direction (i.e., the cross-sectional direction or the direction perpendicular to the axial direction), wherein the island region (preferably from the upper surface) extends along the axial direction of the solid particle bed but not to the lower surface, and the porosity of the island region is 110-300% (preferably 130-240%, more preferably 140-200%) of the porosity of the sea region.

[0030] 2. A solid particle bed according to any of the foregoing or hereinafter described, wherein the marine region extends from the upper surface along the axial direction of the solid particle bed to the lower surface.

[0031] And / or,

[0032] The distribution pattern of the at least one island region in the sea area is selected from:

[0033] i) The at least one island region is distributed discretely in the sea area;

[0034] ii) The at least one island region is arranged in a ring shape to surround a portion of the sea region;

[0035] iii) A combination of the two distribution methods, i) and ii).

[0036] 3. A solid particle bed according to any of the foregoing or hereinafter described, wherein the extension length of any one of the island regions along the axial direction of the solid particle bed is Li, and the extension length of the sea region along the axial direction of the solid particle bed (i.e., the axial length of the solid particle bed) is L0, then Li / L0 < 1 (preferably Li / L0 ≤ 0.95, more preferably 0.03 ≤ Li / L0 ≤ 0.80, most preferably 0.04 ≤ Li / L0 ≤ 0.50), and / or, all the island regions along the axial direction of the solid particle bed The extension lengths are substantially the same, and / or, in all the island regions, let the maximum extension length along the axial direction of the solid particle bed be Lmax, then Lmax / L0 < 1 (preferably Lmax / L0 = 0.95-0.5, more preferably Lmax / L0 = 0.8-0.5), and / or, at least a portion (preferably all) of the island regions extend along the axial direction of the solid particle bed into at least one shape selected from columnar and conical (preferably selected from at least one shape selected from cylindrical, prismatic, pyramidal and conical).

[0037] 4. A solid particle bed according to any of the foregoing or hereinafter, wherein the number of island regions is n, where n is an integer from 1 to 2000 (preferably an integer from 1 to 200, more preferably an integer from 3 to 50), and / or, on any cross-section of the solid particle bed, each island region is the same or different from the others, and each cross-section is independently an arbitrary shape (e.g., selected from at least one of rectangle, circle, ellipse, triangle, parallelogram, ring, and irregular shape), and / or, based on the total volume of the solid particle bed, the proportion of all island regions is 0.3-57% (preferably 1-40%, more preferably 3-25%), and the proportion of the sea region is 43-99.7% (preferably 60-99%, more preferably 75-97%).

[0038] 5. A solid particle bed according to any of the foregoing or hereinafter, wherein each of the island regions is the same or different from each other and each independently has a porosity of 0.20-0.90 (preferably 0.30-0.80, more preferably 0.33-0.70, more preferably 0.37-0.60), and / or the porosity of the sea region is 0.10-0.80 (preferably 0.15-0.65, more preferably 0.16-0.55).

[0039] 6. A solid particle bed according to any of the foregoing or hereinafter, wherein, on any cross-section of the solid particle bed, the straight-line distance between the edges of two adjacent island regions is greater than 20 mm (preferably greater than 100 mm), and / or, on any cross-section of the solid particle bed, if island regions exist, the shortest distance from any point on the cross-section of the sea area to the edge of the cross-section of the adjacent island region does not exceed 500 mm (preferably not more than 300 mm, more preferably not more than 200 mm, most preferably not more than 100 mm), and / or, on any cross-section of the solid particle bed, each island region may be the same as or different from each other, and each independently has a length not exceeding 300,000 mm. 2 (Preferred size not exceeding 100,000 mm) 2 The cross-sectional area of ​​the solid particle bed is, and / or the solid particle bed has a cross-sectional area not exceeding 3,000,000 mm². 2 (Preferred size not exceeding 2,000,000 mm) 2 The cross-sectional area of ​​the solid particle bed, and / or, on any cross-section of the solid particle bed, if the island regions exist, the sum of the cross-sectional areas of all the island regions is 10-60% (preferably 15-45% or 18-30%) of the cross-sectional area of ​​the solid particle bed.

[0040] 7. A solid particle bed according to any of the foregoing or hereinafter, wherein the island region comprises one or more hydrogenation catalysts (referred to as hydrogenation catalyst I), the sea region comprises one or more hydrogenation catalysts (referred to as hydrogenation catalyst II), and / or, the hydrogenation catalyst I is a hollow and / or toothed particle, the hydrogenation catalyst II is a porous particle, and / or, the particle size of the hydrogenation catalyst I is 2.0-55.0 mm (preferably 3.0-30.0 mm), the particle size of the hydrogenation catalyst II is 0.5-4.0 mm (preferably 0.8-3.0 mm), and / or, the hydrogenation catalyst I comprises a support and a hydrogenation-active metal, the hydrogenation catalyst II is selected from at least one of supported catalysts and unsupported catalysts, and the supported catalyst comprises a support and a hydrogenation-active component, the unsupported catalyst comprises a binder and a hydrogenation-active component, and / or, the The mass content of the hydrogenation active metal in hydrogenation catalyst I, calculated as metal oxide (based on the total weight of hydrogenation catalyst I), is 10-90% (preferably 15-60% or 17-40%) of the mass content of the hydrogenation active component in hydrogenation catalyst II, calculated as metal oxide (based on the total weight of hydrogenation catalyst II), and / or, each of the hydrogenation catalysts I may be the same or different from each other, each independently having the same or different porosity, and each of the hydrogenation catalysts II may be the same or different from each other, each independently having the same or different porosity, provided that the porosity of any one of the hydrogenation catalysts I is greater than the porosity of any one of the hydrogenation catalysts II (preferably, the porosity of any one of the hydrogenation catalysts I is 110-300% of the porosity of any one of the hydrogenation catalysts II, preferably 130-240%, more preferably 140-200%).

[0041] 8. A solid particle bed according to any of the foregoing or hereinafter described, wherein in the hydrogenation catalyst I, the mass content of the hydrogenation active metal, based on the total weight of the hydrogenation catalyst, is 5-30% (preferably 8-20%) as a metal oxide, and / or the support is selected from activated carbon, inorganic refractory oxides (particularly at least one selected from alumina, silica, magnesia, zirconium oxide and titanium oxide) and molecular sieves (particularly at least one selected from alumina and silica), and / or the hydrogenation active metal is selected from at least one selected from Fe, Co, Ni, Cu, Zn, Cr, Mo and W (preferably at least one selected from Fe, Zn, Ni, Co and Cu, more preferably at least one selected from Fe and Ni).

[0042] 9. A solid particle bed according to any of the foregoing or hereinafter described, wherein in the hydrogenation catalyst II, the mass content of the hydrogenation active component, based on the total weight of the supported catalyst, is 15-40% (preferably 20-35%) as a metal oxide, and / or, based on the total weight of the unsupported catalyst, the mass content of the hydrogenation active component, based on the metal oxide, is 30-80% (preferably 40-65%), and / or, the support is an inorganic refractory oxide (preferably at least one selected from oxides of elements in Groups II, III, IV and IVB of the periodic table, more preferably at least one selected from alumina and silicon oxide), and / or, the binder is an inorganic refractory oxide (preferably at least one selected from oxides of elements in Groups II, III, IV and IVB of the periodic table, more preferably... The hydrogenation active component is selected from at least one of Group VIB and Group VIII metals of the periodic table (preferably, the Group VIB metal is Mo and / or W, and the Group VIII metal is Co and / or Ni), and / or, based on the total weight of the supported catalyst, the mass content of the Group VIB metal as metal oxide is 15-30% (preferably 18-27%), the mass content of the Group VIII metal as metal oxide is 2-10% (preferably 3-7%), and / or, based on the total weight of the unsupported catalyst, the mass content of the Group VIB metal as metal oxide is 15-30% (preferably 18-27%), the mass content of the Group VIII metal as metal oxide is 2-10% (preferably 3-7%).

[0043] 10. A fixed bed comprising multiple segments of solid particle bed, wherein at least one segment of the solid particle bed is a solid particle bed according to any of the foregoing or the following aspects (referred to as solid particle bed A).

[0044] 11. A fixed bed according to any of the foregoing or hereinafter, wherein the height of the solid particle bed A is 1-95% (preferably 3-60%, more preferably 4-50%) of the height of the fixed bed.

[0045] 12. The fixed bed according to any of the foregoing or hereinafter further includes a solid particle bed B located upstream of the solid particle bed A and / or a solid particle bed C located downstream of the solid particle bed A, wherein the porosity of the solid particle bed B is not less than the porosity of the island region in the solid particle bed A, and the porosity of the solid particle bed C is not greater than the porosity of the sea region in the solid particle bed A.

[0046] 13. A fixed bed according to any of the foregoing or hereinafter described, wherein the solid particle bed B comprises one or more hydrogenation catalysts B, the solid particle bed C comprises one or more hydrogenation catalysts C, wherein the hydrogenation catalysts B and C are the same or different from each other, each independently selected from at least one of supported catalysts and unsupported catalysts, and the supported catalyst comprises a support and a hydrogenation active component, the unsupported catalyst comprises a binder and a hydrogenation active component (preferably the hydrogenation catalysts B and C are the same or different from each other, each independently selected from the hydrogenation catalyst II).

[0047] 14. A method for hydrotreating an oil product, comprising the step of passing the oil product through a solid particle bed or a fixed bed as described in either the foregoing or the following description under hydrotreating reaction conditions (referred to as a hydrotreating step).

[0048] 15. The method according to any of the foregoing or the following aspects, wherein the oil is selected from at least one of ethylene cracked gasoline, coking naphtha, catalytic gasoline, Fischer-Tropsch synthesis oil, coking diesel, catalytic diesel, high-dry-point straight-run diesel, wax oil, residue oil, coal tar, and coal hydrotreating oil, and / or the hydrotreating reaction conditions include: a reaction temperature of 40-500°C (preferably 40-450°C), a reaction pressure of 0.3-20 MPaG (preferably 0.5-15 MPaG), and a volume hourly space velocity of 1-10 h⁻¹. -1 (Preferred 2-10h) -1 The hydrogen-to-oil ratio is 10:1-2000:1 (preferably 15:1-1000:1).

[0049] 16. The method according to any of the foregoing or the following aspects further includes a step of sulfiding the solid particle bed or the fixed bed prior to the hydrogenation step, and / or sulfiding the hydrogenation catalyst outside the apparatus beforehand, and / or the reaction conditions for the sulfidation treatment include: dry sulfidation or wet sulfidation, the sulfiding agent being at least one selected from hydrogen sulfide, carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide, the sulfidation pressure being 1.2-15 MPaG (1.2-9.4 MPaG), the sulfidation temperature being 280-400°C, and the sulfidation time being 4-22 h.

[0050] Technical effect

[0051] According to the present invention, during the hydrotreating process, impurities in oil containing easily deposited substances preferentially deposit in the final section of the island region with a larger porosity. After a large amount of sediment is deposited, the oil mainly enters the sea region with a smaller porosity through the side of the island region, thereby obtaining a larger sedimentation interface area and sedimentation capacity, slowing down the pressure drop increase process, and maintaining a good hydrodesulfurization effect.

[0052] According to the solid particle bed of the present invention, by combining filling zones with large and small porosities, oil preferentially enters the small porosity filling zone through the end of the large porosity filling zone. As the deposition amount increases, it gradually enters the small porosity filling zone through its side, thereby increasing the adsorption and deposition capacity of easily deposited substances, slowing down the pressure drop rise process, and maintaining a good hydrodesulfurization effect. Attached Figure Description

[0053] Figure 1 This is a schematic diagram of the reactor cross-section after catalyst D1 and catalyst A1 are graded and packed in Example 7;

[0054] Figure 2 This is a schematic diagram of the reactor cross-section after catalyst D2 and catalyst A2 are graded and packed in Example 8;

[0055] Figure 3 This is a schematic diagram of the reactor cross-section after catalyst D3 and catalyst A3 are graded and packed in Example 9.

[0056] Figure 4 The diagram illustrates Li and L0 in a solid particle bed.

[0057] Figure 5 The diagram illustrates the straight-line distance La between the edges of two adjacent island regions on any cross section of a solid particle bed, and the shortest distance Lb from any point on the cross section of the sea region to the edge of the cross section of the adjacent island region. Detailed Implementation

[0058] The specific embodiments of the present invention will be described in detail below. However, it should be noted that the scope of protection of the present invention is not limited to these specific embodiments, but is determined by the claims in the appendix.

[0059] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0060] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0061] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this instruction manual are based on weight, and the pressure is gauge pressure.

[0062] In the context of this specification, the porosity is measured using capacitance imaging.

[0063] In the context of this specification, unless otherwise specified, particle size refers to volume average particle size, which is generally measured by laser method.

[0064] In the context of this specification, any two or more embodiments of the present invention can be arbitrarily combined, and the resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0065] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0066] According to one embodiment of the present invention, a section of solid particle bed, particularly a section of axial solid particle bed, is involved. Here, "section" refers to at least one segment of a particle bed (generally a fixed bed) packed in a reactor, wherein one or more solid particle bed segments constitute the entire fixed bed. Furthermore, "axial" means that the flow direction of material (e.g., reactants) through the solid particle bed is perpendicular to the cross-section of the solid particle bed, or that the solid particle bed is packed along the axial direction of the reactor, such that the axial direction of the solid particle bed is the axial direction of the reactor, and the radial direction of the solid particle bed is the radial direction of the reactor.

[0067] According to one embodiment of the present invention, the solid particle bed is generally located at the inlet end of the reactor, while the remaining part of the reactor is filled with a conventional hydrogenation catalyst with desulfurization activity, depending on the situation. Those skilled in the art should understand that the inlet end of the reactor is the end where the oil enters the reactor; specifically, for a co-current reactor, it refers to the top of the reactor; for an upflow reactor, it refers to the bottom of the reactor; for a mid-feed reactor and a gas-liquid counter-current reactor, it refers to the inlet end in the direction of oil flow, and so on for other reactor types.

[0068] According to one embodiment of the present invention, the solid particle bed comprises a sea region and at least one island region distributed within the sea region. Here, "sea region" generally refers to the region constituting the main body of the solid particle bed as a substantially continuous material phase, but does not exclude the possibility that the sea region is divided into multiple regions by the island regions (e.g., in the case of a lagoon). Furthermore, "island region" generally refers to one or more independent regions existing as discrete material phases within the sea region, these independent regions being separated from each other by a certain distance and not connected or interconnected, and each of the independent regions having a clearly defined boundary with the sea region.

[0069] According to one embodiment of the present invention, the solid particle bed has an upper surface, a lower surface, an axial direction, and a radial direction. Here, the axial direction is the length direction or the flow direction of the material in the solid particle bed from the upper surface to the lower surface, and the radial direction is the cross-sectional direction or the direction perpendicular to the axial direction. Furthermore, the upper surface refers to the surface that the material contacts when it is about to enter the solid particle bed, while the lower surface refers to the surface that the material is about to leave the solid particle bed.

[0070] According to one embodiment of the invention, from the perspective of obtaining a larger depositional surface area and depositional capacity, the island region extends along the axial direction of the solid particle bed but does not extend to the lower surface; preferably, the island region extends from the upper surface along the axial direction of the solid particle bed but does not extend to the lower surface. According to this embodiment, the island region is preferably exposed from the upper surface of the solid particle bed but not from the lower surface, and its end is embedded in the sea area. According to this embodiment, the "island" of the present invention takes the form of a floating island in the "sea" region.

[0071] According to one embodiment of the invention, the sea area extends from the upper surface along the axial direction of the solid particle bed to the lower surface. In other words, the sea area is exposed on both the upper and lower surfaces of the solid particle bed.

[0072] According to one embodiment of the present invention, from the perspective of obtaining a larger depositional surface area and depositional capacity, let the extension length of any island region along the axial direction of the solid particle bed be Li, and let the extension length of the sea region along the axial direction of the solid particle bed (that is, the axial length of the solid particle bed) be L0, then Li / L0 < 1, preferably Li / L0 ≤ 0.95, more preferably 0.03 ≤ Li / L0 ≤ 0.80, and most preferably 0.04 ≤ Li / L0 ≤ 0.50.

[0073] According to one embodiment of the present invention, from the perspective of obtaining a larger deposition surface area and deposition capacity, in all the island regions, let the maximum extension length along the axial direction of the solid particle bed be Lmax, then Lmax / L0 < 1, preferably Lmax / L0 = 0.95-0.5, more preferably Lmax / L0 = 0.8-0.5.

[0074] According to one embodiment of the present invention, from the perspective of ease of filling solid particles, the extension length of all said island regions along the axial direction of the solid particle bed is substantially the same.

[0075] According to one embodiment of the invention, at least a portion (preferably all) of the island region extends along the axial direction of the solid particle bed in at least one shape selected from columnar and conical. There are no particular limitations on the shape; for example, at least one shape selected from cylindrical, prismatic, pyramidal, and conical shapes can be cited.

[0076] According to one embodiment of the present invention, the porosity of the island region is 110-300% of the porosity of the sea region, preferably 130-240%, and more preferably 140-200%. Based on the difference in porosity, a clear boundary is formed between the island region and the sea region. Here, porosity refers to the proportion of the void volume between solid particles (generally catalyst particles) to the total volume of the solid particle bed after the solid particles (generally catalyst particles) are packed into the reactor.

[0077] According to one embodiment of the present invention, there is no particular limitation on the distribution of the island areas in the sea area; it can be any distribution that can be anticipated by those skilled in the art. Preferably, the distribution of the island areas in the sea area can be selected from the following:

[0078] i) The at least one island region is distributed discretely in the sea area;

[0079] ii) The at least one island region is arranged in a ring shape to surround a portion of the sea region;

[0080] iii) A combination of the two distribution methods, i) and ii).

[0081] According to one embodiment of the present invention, if the number of island regions is n, then n is an integer from 1 to 2000, preferably an integer from 1 to 200, and more preferably an integer from 3 to 50.

[0082] According to one embodiment of the present invention, on any cross-section of the solid particle bed, each of the island regions may be the same or different from each other, and each cross-section is independently an arbitrary shape, such as at least one selected from rectangles, circles, ellipses, triangles, parallelograms, rings, and irregular shapes.

[0083] According to one embodiment of the invention, the proportion of the entire island region, based on the total volume of the solid particle bed, is 0.3-57%, preferably 1-40%, and more preferably 3-25%. Furthermore, the proportion of the sea region is 43-99.7%, preferably 60-99%, and more preferably 75-97%.

[0084] According to one embodiment of the invention, each of the island regions may be the same as or different from each other, and each independently has a porosity of 0.20-0.90, preferably 0.30-0.80, more preferably 0.33-0.70, and even more preferably 0.37-0.60.

[0085] According to one embodiment of the present invention, the porosity of the sea area is 0.10-0.80, preferably 0.15-0.65, and more preferably 0.16-0.55.

[0086] According to one embodiment of the present invention, to achieve a better effect in delaying pressure drop, the sea area should be matched with its adjacent island area, such that the island area is sufficient to influence the sea area. Therefore, to reduce the difficulty of the filling process while ensuring a better hydrogenation effect than existing technologies, the straight-line distance between the edges of two adjacent island areas on any cross-section of the solid particle bed is greater than 20 mm, preferably greater than 100 mm. Alternatively, on any cross-section of the solid particle bed, if island areas exist, the shortest distance from any point on the cross-section of the sea area to the edge of the cross-section of the adjacent island area does not exceed 500 mm, preferably not more than 300 mm, more preferably not more than 200 mm, and most preferably not more than 100 mm.

[0087] According to one embodiment of the present invention, on any cross-section of the solid particle bed, each of the island regions may be identical or different from one another, and each independently has a length not exceeding 300,000 mm. 2 The cross-sectional area, preferably not exceeding 100,000 mm². 2 .

[0088] According to one embodiment of the present invention, the solid particle bed has a diameter of no more than 3,000,000 mm. 2 The cross-sectional area, preferably not exceeding 2,000,000 mm². 2 .

[0089] According to one embodiment of the present invention, if island regions exist on any cross-section of the solid particle bed, the sum of the cross-sectional areas of all the island regions is 10-60%, preferably 15-45% or 18-30% of the cross-sectional area of ​​the solid particle bed.

[0090] According to one embodiment of the present invention, the island region comprises one or more hydrogenation catalysts (referred to as hydrogenation catalyst I) as solid particles. Preferably, the island region is filled with the hydrogenation catalyst I. The present invention does not impose any particular limitation on the hydrogenation catalyst I, but preferably, the hydrogenation catalyst I comprises a support and a hydrogenation-active metal.

[0091] According to one embodiment of the present invention, the hydrogenation catalyst I can be prepared using a supported catalyst preparation method well known to those skilled in the art. More specifically, it is obtained by extruding a support material, drying and calcining it, impregnating it with the hydrogenation active metal, and then drying and calcining it again. As a more specific embodiment, the extrusion molding is performed by mixing an adsorbent porous material with a solvent, an extrusion aid, etc., mixing them evenly, and then extruding them on an extruder or other molding machine to form hollow particles in the support, including but not limited to five-hole spheres, six-hole spheres, seven-hole spheres, Raschig rings, cylindrical strips with three internal holes, cylindrical strips with five internal holes, discs with seven internal holes, and discs with nine internal holes; or forming toothed particles, including but not limited to three-toothed spheres, five-toothed spheres, six-toothed spheres, four-toothed strips, and five-toothed strips. The impregnation is preferably an equal-volume impregnation, in which the adsorbent porous material is impregnated and extruded with an equal-volume stable salt solution of the hydrogenated active metal; the two drying processes in the above preparation process are both dried at 70-150℃ for 1-24 hours, and the two calcinations are both calcined at 300-600℃ for 1-10 hours.

[0092] According to one embodiment of the present invention, the sea area comprises one or more hydrotreating catalysts (referred to as hydrotreating catalyst II) as solid particles. Preferably, the sea area is filled with the hydrotreating catalyst II. The present invention does not impose any particular limitation on the hydrotreating catalyst II, which is a desulfurization catalyst well known to those skilled in the art and used in oil hydrotreating; however, it is preferred that the hydrotreating catalyst II is selected from at least one of supported catalysts and unsupported catalysts. Here, the supported catalyst includes a support and a hydrotreating active component, while the unsupported catalyst includes a binder and a hydrotreating active component.

[0093] According to one embodiment of the present invention, the hydrogenation catalyst II is readily obtained by those skilled in the art. As one specific embodiment, the supported catalyst is prepared by extruding an inorganic refractory oxide, drying and calcining it, impregnating it with the hydrogenation active component, and then drying and calcining it again to obtain the hydrogenation catalyst component with desulfurization activity. As a more specific embodiment, the extrusion molding involves mixing an adsorbent porous material with a solvent, extrusion aid, etc., mixing it uniformly, and then extruding it on an extruder. Preferably, the material is a strip with a circular, elliptical, clover-shaped, or tetraclover-shaped cross-section, or spherical particles obtained by ball rolling, oil column forming, etc. The impregnation is preferably an equal-volume impregnation, where a stable salt solution of the hydrogenation active component is impregnated in an equal volume onto the extruded support. Both drying processes in the above preparation process are carried out at 70-150°C for 1-24 hours, and both calcinations are carried out at 300-600°C for 1-10 hours. The unsupported catalyst is a homogeneous catalyst prepared by combining the hydrogenation active component and a binder component using methods including but not limited to co-precipitation.

[0094] According to one embodiment of the present invention, the hydrogenation catalyst I is a hollow and / or toothed particle. For example, hollow particles include, but are not limited to, five-pore spheres, six-pore spheres, seven-pore spheres, Raschig rings, cylindrical strips with three internal pores, cylindrical strips with five internal pores, disc-shaped particles with seven internal pores, and disc-shaped particles with nine internal pores. For example, toothed particles include, but are not limited to, three-toothed spheres, five-toothed spheres, six-toothed spheres, four-toothed strips, and five-toothed strips.

[0095] According to one embodiment of the present invention, from the perspective of mitigating the increase in pressure drop, the particle size of the hydrogenation catalyst I is generally 2.0-55.0 mm, preferably 3.0-30.0 mm. Furthermore, from the perspective of mitigating the increase in pressure drop, the particle size of the hydrogenation catalyst II is generally 0.5-4.0 mm, preferably 0.8-3.0 mm.

[0096] According to one embodiment of the present invention, the hydrogenation catalyst II is a porous particle.

[0097] According to a preferred embodiment of the present invention, the hydrogenation catalyst I and the hydrogenation catalyst II are respectively loaded with their columnar edges in contact with each other. Specifically, the two catalysts are loaded in an alternating adjacent manner or inserted into each other. Preferably, the alternating adjacent loading means that the same catalyst is loaded into a columnar reaction unit in the material flow direction, and each pair of adjacent columnar reaction units in the radial direction is filled with the two different catalysts mentioned above. Here, the cross-section of each columnar reaction unit can be any shape, specifically rectangular, circular, triangular, parallelogram, annular, or similar shapes, or other irregular shapes. In addition, the cross-sections of the columnar reaction units in the same reactor can be the same or different.

[0098] According to one embodiment of the invention, each of the hydrogenation catalysts I may be identical or different from each other, each independently having the same or different porosity, and each of the hydrogenation catalysts II may be identical or different from each other, each independently having the same or different porosity, provided that the porosity of any one of the hydrogenation catalysts I is greater than the porosity of any one of the hydrogenation catalysts II. Preferably, the porosity of any one of the hydrogenation catalysts I is 110-300% of the porosity of any one of the hydrogenation catalysts II, more preferably 130-240%, and even more preferably 140-200%.

[0099] According to one embodiment of the present invention, the mass content of the hydrogenation active metal in the hydrogenation catalyst I, calculated as metal oxide (based on the total weight of the hydrogenation catalyst I), and the mass content of the hydrogenation active component in the hydrogenation catalyst II, calculated as metal oxide (based on the total weight of the hydrogenation catalyst II), are 10-90%, preferably 15-60% or 17-40%.

[0100] According to one embodiment of the present invention, in the hydrogenation catalyst I, the mass content of the hydrogenation active metal, calculated as metal oxide, is 5-30%, preferably 8-20%, based on the total weight of the hydrogenation catalyst.

[0101] According to one embodiment of the present invention, in the hydrogenation catalyst I, the support is selected from at least one of activated carbon, inorganic refractory oxides, and molecular sieves. Here, examples of the inorganic refractory oxides include those conventionally used in the art, particularly at least one selected from alumina, silicon oxide, magnesium oxide, zirconium oxide, and titanium oxide, and more particularly at least one selected from alumina and silicon oxide.

[0102] According to one embodiment of the present invention, in the hydrogenation catalyst I, the hydrogenation active metal is selected from at least one of Fe, Co, Ni, Cu, Zn, Cr, Mo and W, preferably selected from at least one of Fe, Zn, Ni, Co and Cu, and more preferably selected from at least one of Fe and Ni.

[0103] According to one embodiment of the present invention, in the hydrogenation catalyst II, the mass content of the hydrogenation active component, calculated as metal oxide, is 15-40%, preferably 20-35%, based on the total weight of the supported catalyst.

[0104] According to one embodiment of the present invention, in the hydrogenation catalyst II, the mass content of the hydrogenation active component, calculated as metal oxide, is 30-80%, preferably 40-65%, based on the total weight of the unsupported catalyst.

[0105] According to one embodiment of the present invention, in the hydrogenation catalyst II, the support is an inorganic refractory oxide, preferably selected from at least one oxide of elements in Group II, Group III, Group IV and Group IVB of the periodic table, more preferably selected from at least one alumina and silicon oxide.

[0106] According to one embodiment of the present invention, in the hydrogenation catalyst II, the binder is an inorganic refractory oxide, preferably selected from at least one oxide of elements in Group II, Group III, Group IV and Group IVB of the periodic table, more preferably selected from at least one alumina and silicon oxide.

[0107] According to one embodiment of the present invention, in the hydrogenation catalyst II, the hydrogenation active component is selected from at least one metal from Group VIB and Group VIII of the periodic table, preferably, the Group VIB metal is Mo and / or W, and the Group VIII metal is Co and / or Ni.

[0108] According to one embodiment of the present invention, in the hydrogenation catalyst II, the mass content of the Group VIB metal as metal oxide is 15-30%, preferably 18-27%, based on the total weight of the supported catalyst, and the mass content of the Group VIII metal as metal oxide is 2-10%, preferably 3-7%.

[0109] According to one embodiment of the invention, in the hydrogenation catalyst II, the mass content of the Group VIB metal as metal oxide is 15-30%, preferably 18-27%, based on the total weight of the unsupported catalyst, and the mass content of the Group VIII metal as metal oxide is 2-10%, preferably 3-7%.

[0110] According to one embodiment of the present invention, in the hydrogenation catalyst I or the hydrogenation catalyst II, the support or binder may be modified, for example, by modifying elements such as B, P, and F. Here, based on the weight of the modified support or binder, the weight percentage of the modifying element is generally 0.8-8 wt%.

[0111] According to one embodiment of the present invention, there is no particular limitation on the manufacturing method of the solid particle bed (i.e., the filling method of the solid particles). Generally, those skilled in the art can find filling methods to achieve the catalyst gradation scheme of the present invention. Specifically, those skilled in the art can use any of the following specific embodiments to achieve this. The following specific embodiments are only used to illustrate the feasibility of the technical solution of the present invention, but are not limited to the following methods.

[0112] One specific filling method is to pre-fill solid particles into the designed geometric shape outside the reactor according to the pre-designed catalyst gradation scheme before transferring them into the reactor; the specific operation involves pre-forming the solid particles into the designed geometric shape in a mold of a certain geometric shape.

[0113] The second specific filling method is to first divide the inside of the reactor into the designed geometric shape using a mesh before filling. The mesh used does not affect the contact between adjacent solid particles.

[0114] The third specific filling method is to fill directly inside the reactor. When filling the sea area or the island area, a baffle can be used temporarily to fill a solid particle according to the designed geometry.

[0115] According to one embodiment of the present invention, a fixed bed is also provided, which includes multiple solid particle bed segments (or multiple solid particle bed sections), wherein at least one of the solid particle bed segments is the solid particle bed described in the present invention (referred to as solid particle bed A).

[0116] According to one embodiment of the present invention, the height of the solid particle bed A is 1-95% of the height of the fixed bed, preferably 3-60%, and more preferably 4-50%.

[0117] According to one embodiment of the present invention, the fixed bed further includes a solid particle bed B located upstream of the solid particle bed A, wherein the porosity of the solid particle bed B is not less than the porosity of the island region in the solid particle bed A. Here, the solid particle bed B contains one or more hydrogenation catalysts B, or is packed with one or more hydrogenation catalysts B.

[0118] According to one embodiment of the present invention, the fixed bed further includes a solid particle bed C located downstream of the solid particle bed A, wherein the porosity of the solid particle bed C is not greater than the porosity of the marine region in the solid particle bed A. Here, the solid particle bed C comprises one or more hydrogenation catalysts C, or is packed with one or more hydrogenation catalysts C.

[0119] According to one embodiment of the invention, the hydrogenation catalyst B and the hydrogenation catalyst C may be the same as or different from each other, and each is independently selected from at least one of supported catalysts and unsupported catalysts. Here, the supported catalyst includes a support and a hydrogenation active component, and the unsupported catalyst includes a binder and a hydrogenation active component. Preferably, the hydrogenation catalyst B and the hydrogenation catalyst C may be the same as or different from each other, and each is independently selected from the hydrogenation catalyst II.

[0120] According to one embodiment of the present invention, a method for hydrotreating oil is also provided, comprising the step of passing the oil through the solid particle bed or the fixed bed described in the present invention under hydrotreating reaction conditions (referred to as the hydrotreating step).

[0121] Those skilled in the art should understand that the oil hydrotreating method of the present invention is applicable to processing any oil feedstock, especially oils containing easily deposited substances. Here, the feedstocks include, but are not limited to, ethylene cracked gasoline, coking naphtha, catalytic gasoline, Fischer-Tropsch synthesis oil, coking diesel, catalytic diesel, high-dry-point straight-run diesel, wax oil, residual oil, coal tar, and coal hydrotreating product oil. These feedstocks mostly contain impurities such as sulfur, nitrogen, oxygen, alkenes, and aromatics, and usually require hydrorefining to remove these impurities before use. During the hydrorefining of these feedstocks, an increase in reactor pressure drop and a shortened operating cycle often occur. This increase in pressure drop is partly due to the accumulation of impurities, such as the deposition of solids like coke dust inherent in the feedstock, the condensation and dehydrogenation of unsaturated components in the feedstock leading to coking, and the accumulation of metal ions from corrosion of upstream pipelines and containers. These impurities gradually clog the catalyst bed pores, leading to a decrease in porosity, causing an increase in reactor pressure drop and affecting operating life.

[0122] Without being limited by any theoretical constraints, the inventors of this invention believe that easily depositable materials readily penetrate catalyst beds with higher porosity. When these easily depositable materials reach the catalyst sections with lower porosity, they are easily adsorbed and deposited, ultimately depositing primarily on the catalyst with lower porosity. Current techniques for delaying pressure drop mainly involve using a single catalyst with higher porosity packed in the reactor inlet section, where easily depositable materials gradually accumulate, with the depositable area limited to the reactor's cross-sectional area. According to this invention, easily depositable materials primarily pass through the island region with higher porosity (e.g., a columnar reaction unit packed with hydrogenation catalyst I) and initially deposit at the bottom of the island region (here, the bottom refers to the end of the material flow direction). When the deposition increases to a certain extent, causing bottom blockage, the easily depositable materials flow radially from the sides of the island region to the sea region with lower porosity (e.g., a columnar reaction unit packed with hydrogenation catalyst II), thereby increasing the depositable area and slowing the rate of pressure drop increase.

[0123] According to one embodiment of the present invention, the hydrogenation reaction conditions include: a reaction temperature of 40-500°C, preferably 40-450°C; a reaction pressure of 0.3-20 MPaG, preferably 0.5-15 MPaG; and a volume hourly space velocity of 1-10 h⁻¹. -1 Preferred 2-10h -1 The hydrogen-to-oil ratio is 10:1-2000:1, preferably 15:1-1000:1.

[0124] According to one embodiment of the present invention, the oil hydrotreating method further includes a step of sulfiding the solid particle bed or the fixed bed before performing the hydrotreating step. Alternatively, the hydrotreating catalyst may be pre-sulfided outside the apparatus. Here, the reaction conditions for the sulfidation treatment include: dry sulfidation or wet sulfidation, the sulfiding agent being at least one selected from hydrogen sulfide, carbon disulfide, dimethyl disulfide, methyl sulfide, and n-butyl sulfide, the sulfidation pressure being 1.2-15 MPaG (1.2-9.4 MPaG), the sulfidation temperature being 280-400°C, and the sulfidation time being 4-22 h.

[0125] Example

[0126] The present invention will be further described in detail below through embodiments and comparative examples, but the present invention is not limited to the following embodiments.

[0127] In Examples 1-17, hydrogenation catalysts IID1-D17 with high desulfurization activity and relatively small porosity were prepared:

[0128] Example 1

[0129] Preparation of hydrogenation catalyst D1:

[0130] Take 1000g of macroporous aluminum hydroxide, add nitric acid and water to obtain a paste-like mixture with HNO3 content of 1.5% and water content of 60%. Extrude the above mixture on an extruder to obtain clover-shaped strips with a diameter of 1.5 mm and a particle size of 1.5 mm. Dry at 100℃ for 2 hours, and then calcine at 560℃ for 8 hours to obtain a support. Prepare an aqueous solution of ammonium heptamolybdate and nickel nitrate, and impregnate the above support with an equal volume for 30 minutes to obtain a wet strip with a molybdenum oxide content of 24% and a nickel oxide content of 4% (based on dry basis after calcination). Dry at 100℃ for 2 hours, and then calcine at 560℃ for 2 hours to obtain catalyst D1.

[0131] The bed porosity of catalyst D1 was determined to be 0.24.

[0132] Example 2

[0133] Preparation of hydrogenation catalyst D2:

[0134] Take 1000g of macroporous amorphous silica-alumina, add nitric acid and water to obtain a paste-like mixture with HNO3 content of 1.7% and water content of 63%. Extrude the above mixture on an extruder to obtain clover-shaped strips with a diameter of 1.8 mm and a particle size of 2.8 mm. Dry at 80℃ for 18 hours, and then calcine at 540℃ for 4 hours to obtain a support. Take ammonium heptamolybdate and nickel nitrate to prepare an aqueous solution, and impregnate the above support with an equal volume for 30 minutes to obtain a wet strip with a molybdenum oxide content of 27% and a nickel oxide content of 5% (based on the dry basis after calcination). Dry at 100℃ for 2 hours, and then calcine at 540℃ for 4 hours to obtain catalyst D2.

[0135] The bed porosity of catalyst D2 was determined to be 0.36.

[0136] Example 3

[0137] Preparation of hydrogenation catalyst D3:

[0138] Take 1000g of aluminum hydroxide containing 0.9% fluorine, add nitric acid and water to obtain a paste-like mixture with HNO3 content of 1.5% and water content of 60%. Extrude the above mixture on an extruder to obtain clover-shaped columnar strips with a diameter of 1.5 mm and a particle size of 1.7 mm. Dry at 120℃ for 6 hours, and then calcine at 550℃ for 5 hours to obtain a support. Prepare an aqueous solution of ammonium heptamolybdate and cobalt nitrate, and impregnate the above support with an equal volume for 30 minutes to obtain a wet strip with a molybdenum oxide content of 16% and a cobalt oxide content of 3% (based on the dry basis after calcination). Dry at 100℃ for 2 hours, and then calcine at 550℃ for 3 hours to obtain catalyst D3.

[0139] The bed porosity of catalyst D3 was determined to be 0.28.

[0140] Example 4

[0141] Preparation of hydrogenation catalyst D4:

[0142] Take 1000g of macroporous alumina containing 2% silica, add nitric acid and water to obtain a paste-like mixture with 1.3% HNO3 content and 53% water content. Extrude the above mixture on an extruder to obtain cylindrical strips with a diameter of 1 mm and a particle size of 0.6. Dry at 150℃ for 8 hours, and then calcine at 600℃ for 10 hours to obtain a support. Prepare an aqueous solution of ferric nitrate and ammonium metatungstate, and impregnate the above support with an equal volume for 30 minutes to obtain a wet strip with 5% ferric oxide content and 18% tungsten oxide content (based on dry basis after calcination). Dry at 130℃ for 2 hours, and then calcine at 600℃ for 8 hours to obtain catalyst D4.

[0143] The bed porosity of catalyst D4 was determined to be 0.13.

[0144] Example 5

[0145] Preparation of hydrogenation catalyst D5:

[0146] Take 1000g of macroporous aluminum hydride, add nitric acid and water to obtain a paste-like mixture with 2% HNO3 content and 67% water content. Extrude the above mixture on an extruder to obtain clover-shaped strips with a diameter of 2 mm and a particle size of 3 mm. Dry at 100℃ for 4 hours, and then calcine at 520℃ for 3 hours to obtain a support. Prepare an aqueous solution of ammonium heptamolybdate and nickel nitrate water, and impregnate the above support with an equal volume for 30 minutes to obtain a wet strip with a nickel oxide content of 5% and a molybdenum oxide content of 20% (based on the dry basis after calcination). Dry at 100℃ for 2 hours, and then calcine at 520℃ for 3 hours to obtain catalyst D5.

[0147] The bed porosity of catalyst D5 was determined to be 0.41.

[0148] Example 6

[0149] Preparation of hydrogenation catalyst D6:

[0150] The preparation method is the same as that of D1, except that the impregnating metal is replaced with ferric nitrate, resulting in catalyst D6 with an iron oxide content of 28% (based on dry weight after calcination). The bed porosity of catalyst D6 is 0.24.

[0151] Example 7

[0152] Preparation of hydrogenation catalyst D7:

[0153] Take 1000g of aluminum hydroxide containing 0.9% fluorine, add nitric acid and water to obtain a paste-like mixture with HNO3 content of 1.5% and water content of 56%. After molding, obtain spheres with a diameter of 2.0 mm, dry at 120℃ for 6 hours, and then calcine at 580℃ for 10 hours to obtain a support. Take ammonium heptamolybdate and cobalt nitrate to prepare an aqueous solution, and impregnate the above support with an equal volume for 30 minutes to obtain a wet strip with molybdenum oxide content of 16% and cobalt oxide content of 3% (based on dry basis after calcination). Dry at 100℃ for 2 hours, and then calcine at 580℃ for 3 hours to obtain catalyst D7.

[0154] The bed porosity of catalyst D7 was determined to be 0.22.

[0155] Example 8

[0156] Preparation of hydrogenation catalyst D8:

[0157] Take 1000g of aluminum hydroxide containing 0.9% fluorine, add nitric acid and water to obtain a paste-like mixture with HNO3 content of 2.3% and water content of 70%. Extrude the above mixture on an extruder to obtain four-leaf clover-shaped strips with a diameter of 1.5 mm and a particle size of 3.5 mm. Dry at 100℃ for 6 hours, and then calcine at 500℃ for 5 hours to obtain a support. Prepare an aqueous solution of ammonium heptamolybdate and cobalt nitrate, and impregnate the above support with an equal volume for 30 minutes to obtain a wet strip with a molybdenum oxide content of 16% and a cobalt oxide content of 3% (based on the dry basis after calcination). Dry at 100℃ for 2 hours, and then calcine at 500℃ for 3 hours to obtain catalyst D8.

[0158] The bed porosity of catalyst D8 was determined to be 0.46.

[0159] Example 9

[0160] Preparation of hydrogenation catalyst D9:

[0161] Take 1000g of aluminum hydroxide containing 0.9% fluorine, add nitric acid and water to obtain a paste-like mixture with HNO3 content of 1.8% and water content of 60%. Extrude the above mixture on an extruder to obtain clover-shaped columnar strips with a diameter of 1.5 mm and a particle size of 2. Dry at 100℃ for 5 hours, and then calcine at 550℃ for 2 hours to obtain a support. Prepare an aqueous solution of ammonium heptamolybdate and cobalt nitrate, and impregnate the above support with an equal volume for 30 minutes to obtain a wet strip with a molybdenum oxide content of 16% and a cobalt oxide content of 3% (based on the dry basis after calcination). Dry at 100℃ for 2 hours, and then calcine at 530℃ for 3 hours to obtain catalyst D9.

[0162] The bed porosity of catalyst D9 was determined to be 0.31.

[0163] Example 10

[0164] Preparation of hydrogenation catalyst D10:

[0165] Take 1000g of macroporous alumina containing 2% silica, add nitric acid and water to obtain a paste-like mixture with 1.5% HNO3 content and 61% water content. Extrude the above mixture on an extruder to obtain four-leaf clover-shaped strips with a diameter of 1.5 mm and a particle size of 1.6 mm. Dry at 110℃ for 5 hours, and then calcine at 550℃ for 2 hours to obtain a support. Prepare an aqueous solution of ammonium heptamolybdate and cobalt nitrate, and impregnate the above support with an equal volume for 30 minutes to obtain a wet strip with a molybdenum oxide content of 16% and a cobalt oxide content of 3% (based on the dry basis after calcination). Dry at 100℃ for 2 hours, and then calcine at 550℃ for 3 hours to obtain catalyst D10.

[0166] The bed porosity of catalyst D10 was determined to be 0.29.

[0167] Example 11

[0168] Preparation of hydrogenation catalyst D11:

[0169] Take 1000g of macroporous alumina containing 2% silica, add nitric acid and water to obtain a paste-like mixture with 1.8% HNO3 content and 60% water content. Extrude the above mixture on an extruder to obtain four-leaf clover-shaped strips with a diameter of 1.5 mm and a particle size of 2.5 mm. Dry at 120℃ for 3 hours, and then calcine at 550℃ for 2 hours to obtain a support. Prepare an aqueous solution of ammonium heptamolybdate and cobalt nitrate, and impregnate the above support with an equal volume for 30 minutes to obtain a wet strip with a molybdenum oxide content of 16% and a cobalt oxide content of 3% (based on the dry basis after calcination). Dry at 100℃ for 2 hours, and then calcine at 510℃ for 3 hours to obtain catalyst D11.

[0170] The bed porosity of catalyst D11 was determined to be 0.32.

[0171] Example 12

[0172] Preparation of hydrogenation catalyst D12:

[0173] Take 1000g of macroporous alumina containing 2% silica, add nitric acid and water to obtain a paste-like mixture with 1.9% HNO3 content and 70% water content. Extrude the above mixture on an extruder to obtain four-leaf clover-shaped strips with a diameter of 1.5 mm and a particle size of 3.2 mm. Dry at 100℃ for 7 hours, and then calcine at 530℃ for 3 hours to obtain a support. Prepare an aqueous solution of ammonium heptamolybdate and cobalt nitrate, and impregnate the above support with an equal volume for 30 minutes to obtain a wet strip with a molybdenum oxide content of 16% and a cobalt oxide content of 3% (based on the dry basis after calcination). Dry at 100℃ for 7 hours, and then calcine at 530℃ for 3 hours to obtain catalyst D12.

[0174] The bed porosity of catalyst D12 was determined to be 0.40.

[0175] Example 13

[0176] Preparation of hydrogenation catalyst D13:

[0177] Take 1000g of porous alumina containing 5% zirconium oxide, add nitric acid and water to obtain a paste-like mixture with 1.5% HNO3 content and 73% water content. Extrude the above mixture on an extruder to obtain four-leaf clover-shaped strips with a diameter of 1.5 mm and a particle size of 4 mm. Dry at 130℃ for 6 hours, and then calcine at 500℃ for 8 hours to obtain a support. Prepare an aqueous solution of ammonium heptamolybdate and cobalt nitrate, and impregnate the above support with an equal volume for 30 minutes to obtain a wet strip with a molybdenum oxide content of 16% and a cobalt oxide content of 3% (based on the dry basis after calcination). Dry at 100℃ for 2 hours, and then calcine at 480℃ for 3 hours to obtain catalyst D13.

[0178] The bed porosity of catalyst D13 was determined to be 0.40.

[0179] Example 14

[0180] Preparation of hydrogenation catalyst D14:

[0181] Take 1000g of macroporous alumina, add nitric acid and water to obtain a paste-like mixture with HNO3 content of 1.5% and water content of 60%. Extrude the above mixture on an extruder to obtain cylindrical strips with a diameter of 1.5 mm and a particle size of 2.8 mm. Dry at 120℃ for 6 hours, and then calcine at 560℃ for 3 hours to obtain a support. Prepare an aqueous solution of ammonium heptamolybdate and cobalt nitrate, and impregnate the above support with an equal volume for 30 minutes to obtain a wet strip with a molybdenum oxide content of 16% and a cobalt oxide content of 3% (based on the dry basis after calcination). Dry at 100℃ for 2 hours, and then calcine at 560℃ for 3 hours to obtain catalyst D14.

[0182] The bed porosity of catalyst D14 was determined to be 0.27.

[0183] Example 15

[0184] Preparation of hydrogenation catalyst D15:

[0185] Take 1000g of macroporous alumina containing 2% silica, add nitric acid and water to obtain a paste-like mixture with 2.1% HNO3 content and 70% water content. Extrude the above mixture on an extruder to obtain cylindrical strips with a diameter of 3 mm and a particle size of 3.6 mm. Dry at 120℃ for 5 hours, and then calcine at 510℃ for 2 hours to obtain a support. Prepare an aqueous solution of ammonium heptamolybdate and cobalt nitrate, and impregnate the above support with an equal volume for 30 minutes to obtain a wet strip with a molybdenum oxide content of 16% and a cobalt oxide content of 3% (based on the dry basis after calcination). Dry at 100℃ for 2 hours, and then calcine at 510℃ for 3 hours to obtain catalyst D15.

[0186] The bed porosity of catalyst D15 was determined to be 0.44.

[0187] Example 16

[0188] Preparation of hydrogenation catalyst D16:

[0189] Take 1000g of small-pore aluminum hydroxide containing 1.0% fluorine, add nitric acid and water to obtain a paste-like mixture with HNO3 content of 1.5% and water content of 73%. Shape it to obtain four-leaf clover strips with a diameter of 2 mm and a particle size of 4 mm. Dry at 130℃ for 5 hours, and then calcine at 460℃ for 7 hours to obtain a carrier. Prepare an aqueous solution of ammonium heptamolybdate and nickel nitrate water, and impregnate the above carrier with an equal volume for 30 minutes to obtain a wet strip with nickel oxide content of 5% and molybdenum oxide content of 20% (based on dry basis after calcination). Dry at 100℃ for 2 hours, and then calcine at 380℃ for 3 hours to obtain catalyst D16.

[0190] The bed porosity of catalyst D16 was determined to be 0.56.

[0191] Example 17

[0192] Preparation of hydrogenation catalyst D17:

[0193] Take 1000g of macroporous aluminum hydroxide, add nitric acid and water to obtain a paste-like mixture with HNO3 content of 1.5% and water content of 50%. Extrude the above mixture on an extruder to obtain cylindrical strips with a diameter of 1 mm and a particle size of 1 mm. Dry at 150℃ for 2 hours, and then calcine at 600℃ for 6 hours to obtain a support. Prepare an aqueous solution of ammonium heptamolybdate and nickel nitrate water, and impregnate the above support with an equal volume for 30 minutes to obtain a wet strip with nickel oxide content of 5% and molybdenum oxide content of 20% (based on dry basis after calcination). Dry at 100℃ for 2 hours, and then calcine at 550℃ for 3 hours to obtain catalyst D17.

[0194] The bed porosity of catalyst D17 was determined to be 0.19.

[0195] Hydrogenation catalysts IA1-A8 with relatively large porosity were prepared in Examples 18-25:

[0196] Example 18

[0197] Preparation of hydrogenation catalyst A1:

[0198] 1000g of porous aluminum hydroxide was mixed with nitric acid and water to obtain a paste-like mixture with an HNO3 content of 2.8% and a water content of 80%. This mixture was extruded using an extruder to obtain hollow cylindrical strips with a diameter of 6mm, a particle size of 9mm, and a hollow portion diameter of 3mm. The strips were dried at 100℃ for 2 hours and then calcined at 500℃ for 5 hours to obtain a support. Nickel nitrate was prepared into an aqueous solution, and an equal volume of the above support was impregnated for 30 minutes to obtain a wet strip with a nickel oxide content of 5% (based on a dry basis after calcination). This wet strip was dried at 100℃ for 2 hours and then calcined at 500℃ for 2 hours to obtain catalyst A1.

[0199] The bed porosity of catalyst A1 was determined to be 0.56, and the total metal oxide content was 17.9% of that of the corresponding catalyst D1.

[0200] Example 19

[0201] Preparation of hydrogenation catalyst A2:

[0202] 1000g of porous amorphous silica-alumina was taken, and nitric acid and water were added to obtain a mixture with an HNO3 content of 1.5% and a water content of 65%. This mixture was shaped into five-toothed spheres with a diameter of 5mm, dried at 70℃ for 20 hours, and then calcined at 580℃ for 9 hours to obtain a support. Ferric nitrate was prepared into an aqueous solution, and an equal volume of the above support was impregnated for 30 minutes to obtain a wet strip with an iron oxide content of 4% (based on a dry basis after calcination). This strip was dried at 100℃ for 2 hours and then calcined at 580℃ for 8 hours to obtain catalyst A2.

[0203] The bed porosity of catalyst A2 was determined to be 0.46, and the total metal oxide content was 12.5% ​​of that of catalyst D2.

[0204] Example 20

[0205] Preparation of hydrogenation catalyst A3:

[0206] 1000g of porous aluminum hydroxide containing 3% silica was added to nitric acid and water to obtain a paste-like mixture with 2.5% HNO3 and 80% water content. This mixture was pressed on a tablet press to obtain a nine-hole disc with a diameter of 12mm, a height of 6mm, and an inner diameter of 1.5mm. The disc was dried at 130℃ for 6 hours and then calcined at 540℃ for 7 hours to obtain a support. An aqueous solution of ferric nitrate was prepared and impregnated with an equal volume of the above support for 30 minutes to obtain a wet strip with an iron oxide content of 6% (based on a dry basis after calcination). This strip was dried at 100℃ for 2 hours and then calcined at 540℃ for 6 hours to obtain catalyst A3.

[0207] The bed porosity of catalyst A3 was determined to be 0.63, and the total metal oxide content was 31.6% of that of the corresponding catalyst D3.

[0208] Example 21

[0209] Preparation of hydrogenation catalyst A4:

[0210] Take 1000g of small-pore aluminum hydroxide containing 3% B, add nitric acid and water to obtain a paste-like mixture with an HNO3 content of 1.1% and a water content of 53%. Extrude the mixture on an extruder to obtain tridentate strips with a diameter of 1 mm and a particle size of 2 mm. Dry at 150°C for 2 hours, and then calcine at 600°C for 10 hours to obtain a support. Prepare an aqueous solution of cobalt nitrate and impregnate the above support with an equal volume for 30 minutes to obtain a wet strip with a cobalt oxide content of 3% (based on the dry basis after calcination). Dry at 150°C for 2 hours, and then calcine at 600°C for 3 hours to obtain catalyst A4.

[0211] The bed porosity of catalyst A4 was determined to be 0.23, and the total metal oxide content was 13% of that of the corresponding catalyst D4.

[0212] Example 22

[0213] Preparation of hydrogenation catalyst A5:

[0214] 1000g of amorphous silica-alumina with small pores was taken, and nitric acid and water were added to obtain a mixture with an HNO3 content of 1.7% and a water content of 74%. The mixture was pressed on a tablet press to obtain seven-hole discs with a diameter of 8 mm, a particle size of 5 mm, and an inner diameter of 1 mm. The discs were dried at 90°C for 5 hours and then calcined at 560°C for 9 hours to obtain a support. Nickel nitrate was prepared into an aqueous solution, and an equal volume of the above support was impregnated for 30 minutes to obtain a wet strip with a nickel oxide content of 10% (based on the dry basis after calcination). The strips were dried at 90°C for 2 hours and then calcined at 560°C for 8 hours to obtain catalyst A5.

[0215] The bed porosity of catalyst A5 was determined to be 0.59, and the total metal oxide content was 40% of that of the corresponding catalyst D5.

[0216] Example 23

[0217] Preparation of hydrogenation catalyst A6:

[0218] 1000g of porous alumina was mixed with nitric acid and water to obtain a mixture with 2.3% HNO3 and 76% water. This mixture was then extruded using an extruder to obtain cylindrical strips with a diameter of 15mm, a particle size of 20mm, and an inner diameter of 2mm, containing seven holes. These strips were dried at 130℃ for 12 hours and then calcined at 520℃ for 8 hours to obtain a support. An aqueous solution of ferric nitrate was prepared and impregnated with an equal volume of the above support for 30 minutes to obtain a wet strip with an iron oxide content of 20% (based on a dry basis after calcination). This wet strip was dried at 130℃ for 6 hours and then calcined at 520℃ for 6 hours to obtain catalyst A6.

[0219] The bed porosity of catalyst A6 was determined to be 0.65, and the total metal oxide content was 71.4% of that of the corresponding catalyst D1.

[0220] Example 24

[0221] Preparation of hydrogenation catalyst A7:

[0222] 1000g of porous aluminum hydroxide containing 3% titanium oxide was added with nitric acid and water to obtain a paste-like mixture with 2.6% HNO3 and 85% water content. This mixture was extruded using an extruder to produce honeycomb strips with a diameter of 20 mm and a particle size of 46 mm, containing 32 uniformly distributed square grids. The strips were dried at 100°C for 3 hours and then calcined at 450°C for 9 hours to obtain a support. Zinc nitrate was prepared into an aqueous solution, and an equal volume of the above support was impregnated for 30 minutes to obtain a wet strip with a zinc oxide content of 16% (based on a dry basis after calcination). This wet strip was dried at 120°C for 3 hours and then calcined at 380°C for 4 hours to obtain catalyst A7.

[0223] The bed porosity of catalyst A7 was determined to be 0.8, and the total metal oxide content was 84.2% of that of the corresponding catalyst D3.

[0224] Example 25

[0225] Preparation of hydrogenation catalyst A8:

[0226] The preparation method is consistent with that of A6, except that the impregnating metal is changed to nickel nitrate and ammonium heptamolybdate, resulting in catalyst A8 with a molybdenum oxide content of 16% and a nickel oxide content of 4% (based on dry weight after calcination). The bed porosity of catalyst A8 is 0.65, and the total metal oxide content is 71.4% of that of the corresponding catalyst D6.

[0227] Example 26

[0228] Catalyst D1 and catalyst A1 are packed into a cylindrical hydrogenation reactor:

[0229] The reactor is a co-current reactor. The oil to be hydrogenated and hydrogen gas enter from the top of the reactor, and the reactant flows out from the bottom. During loading, catalyst D1 with high desulfurization activity is first uniformly loaded into the bottom of the reactor, and this catalyst bed occupies 70% of the reactor height. Then, catalyst D1 and catalyst A1 are loaded in the upper graded loading section according to the present invention. For the graded loading section, in cross-section, the reactor is divided into several square, approximately square, and approximately triangular spaces by intersecting horizontal and vertical lines, in which catalyst D1 and catalyst A1 are loaded in a crisscross pattern, as shown below. Figure 1 As shown.

[0230] In this embodiment, the porosity of the island region is 233.3% of that of the sea region, Li / L0 = 0.3, the number of island regions is 30, the shortest distance from any point on the cross-section of the sea region to the edge of the cross-section of the adjacent island region is no greater than 120 mm, the particle size of hydrogenation catalyst I is 9 mm, and the particle size of hydrogenation catalyst II is 1.5 mm.

[0231] Example 27

[0232] Catalyst D2 and catalyst A2 are packed into a cylindrical hydrogenation reactor:

[0233] The reactor is an upflow reactor. The oil and hydrogen to be hydrogenated enter from the bottom of the reactor, and the reactants flow out from the top. During loading, catalyst D2 and catalyst A2 are first graded and loaded into the bottom of the reactor according to the scheme of this invention. In cross-section, the reactor is divided into several concentric rings. Catalyst D2 and catalyst A2 are alternately packed in the spaces between every two adjacent rings, as shown below. Figure 2 As shown. The thickness of each concentric ring is 20 mm. The height of the graded catalyst bed is 40% of the total height of the reactor bed. Then, catalyst D2 is uniformly packed on top of the graded catalyst bed.

[0234] In this embodiment, the porosity of the island region is 127.3% of that of the sea region, Li / L0 = 0.4, the number of island regions is 20, the shortest distance from any point on the cross-section of the sea region to the edge of the cross-section of the adjacent island region is no greater than 10 mm, the particle size of hydrogenation catalyst I is 5 mm, and the particle size of hydrogenation catalyst II is 2.8 mm.

[0235] Example 28

[0236] Catalyst D3 and catalyst A3 are packed into a cylindrical hydrogenation reactor:

[0237] The reactor is an upflow reactor. The oil and hydrogen to be hydrogenated enter from the bottom of the reactor, and the reactants flow out from the top. During loading, catalyst D3 and catalyst A3 are first graded and loaded into the bottom of the reactor according to the scheme of this invention. In cross-section, the reactor contains 18 evenly distributed cylinders, each with a diameter of 30 mm. One cylinder is filled with catalyst A3, and the remaining portion is filled with catalyst D3. Figure 3 As shown. The height of the graded catalyst bed in the staged packing section is 60% of the total height of the reactor bed. Then, catalyst D3 is uniformly packed on top of the graded catalyst bed.

[0238] In this embodiment, the porosity of the island region is 225.0% of that of the sea region, Li / L0 = 0.6, the number of island regions is 18, the shortest distance from any point on the cross-section of the sea region to the edge of the cross-section of the adjacent island region is no greater than 60 mm, the particle size of hydrogenation catalyst I is 6 mm, and the particle size of hydrogenation catalyst II is 1.7 mm.

[0239] Example 29

[0240] Catalyst D4 and catalyst A4 are packed into a cylindrical hydrogenation reactor:

[0241] The reactor is an upflow reactor. The oil and hydrogen to be hydrogenated enter from the bottom of the reactor, and the reactants flow out from the top. During loading, catalyst D4 and catalyst A4 are first graded and loaded into the bottom of the reactor according to the scheme of this invention. In cross-section, the reactor contains 55 evenly distributed cylinders, each with a diameter of 30 mm. One cylinder is filled with catalyst A4, and the remaining portion is filled with catalyst D4. Figure 3 Similarly, the height of the graded catalyst bed in the staged packing section is 75% of the total reactor bed height. Then, catalyst D4 is uniformly packed on top of the graded catalyst bed.

[0242] In this embodiment, the porosity of the island region is 176.9% of that of the sea region, Li / L0 = 0.75, the number of island regions is 55, the shortest distance from any point on the cross-section of the sea region to the edge of the cross-section of the adjacent island region is no greater than 60 mm, the particle size of hydrogenation catalyst I is 2 mm, and the particle size of hydrogenation catalyst II is 0.6 mm.

[0243] Example 30

[0244] Catalysts D5 and A5 are packed into a cylindrical hydrogenation reactor:

[0245] The reactor is an upflow reactor. The oil and hydrogen to be hydrogenated enter from the bottom of the reactor, and the reactants flow out from the top. During loading, catalyst D5 and catalyst A5 are first graded and loaded into the bottom of the reactor according to the scheme of this invention. In cross-section, the reactor contains 45 evenly distributed cylinders, each with a diameter of 30 mm. One cylinder is filled with catalyst A5, and the remaining portion is filled with catalyst D5. Figure 3 Similarly, the height of the graded catalyst bed in the staged packing section is 50% of the total height of the reactor bed. Then, catalyst D5 is uniformly packed on top of the graded catalyst bed.

[0246] In this embodiment, the porosity of the island region is 143.9% of that of the sea region, Li / L0 = 0.5, the number of island regions is 45, the shortest distance from any point on the cross-section of the sea region to the edge of the cross-section of the adjacent island region is no greater than 95 mm, the particle size of hydrogenation catalyst I is 5 mm, and the particle size of hydrogenation catalyst II is 3 mm.

[0247] Example 31

[0248] Catalyst D1 and catalyst A6 were loaded into a cylindrical hydrogenation reactor:

[0249] The reactor is an upflow reactor. The oil and hydrogen to be hydrogenated enter from the bottom of the reactor, and the reactants flow out from the top. During loading, catalyst D1 and catalyst A6 are first graded and loaded into the bottom of the reactor according to the scheme of this invention. In cross-section, the reactor contains 145 evenly distributed cylinders, each with a diameter of 50 mm. One cylinder is filled with catalyst A6, and the remaining portion is filled with catalyst D1. Figure 3 Similarly, the height of the graded catalyst bed in the staged packing section is 45% of the total height of the reactor bed. Then, catalyst D1 is uniformly packed on top of the graded catalyst bed.

[0250] In this embodiment, the porosity of the island region is 270.8% of that of the sea region, Li / L0 = 0.45, the number of island regions is 145, the shortest distance from any point on the cross-section of the sea region to the edge of the cross-section of the adjacent island region is no greater than 60 mm, the particle size of hydrogenation catalyst I is 20 mm, and the particle size of hydrogenation catalyst II is 1.5 mm.

[0251] Example 32

[0252] Catalysts D3 and A7 were loaded into a cylindrical hydrogenation reactor:

[0253] The reactor is an upflow reactor. The oil and hydrogen to be hydrogenated enter from the bottom of the reactor, and the reactants flow out from the top. During loading, catalyst D3 and catalyst A7 are first graded and loaded into the bottom of the reactor according to the scheme of this invention. In cross-section, the reactor contains 65 evenly distributed cylinders, each with a diameter of 140 mm. One cylinder is filled with catalyst A7, and the remaining portion is filled with catalyst D3. Figure 3 Similarly, the height of the graded catalyst bed in the staged packing section is 50% of the total height of the reactor bed. Then, catalyst D3 is uniformly packed on top of the graded catalyst bed.

[0254] In this embodiment, the porosity of the island region is 285.7% of that of the sea region, Li / L0 = 0.5, the number of island regions is 65, the shortest distance from any point on the cross-section of the sea region to the edge of the cross-section of the adjacent island region is no greater than 100 mm, the particle size of hydrogenation catalyst I is 46 mm, and the particle size of hydrogenation catalyst II is 1.7 mm.

[0255] Example 33

[0256] Catalysts D7 and A3 were loaded into a cylindrical hydrogenation reactor:

[0257] The reactor is an upflow reactor. The oil and hydrogen to be hydrogenated enter from the bottom of the reactor, and the reactants flow out from the top. During loading, catalyst D7 and catalyst A3 are first graded and loaded into the bottom of the reactor according to the scheme of this invention. In cross-section, the reactor contains 30 evenly distributed cylinders, each with a diameter of 30 mm. One cylinder is filled with catalyst A3, and the remaining portion is filled with catalyst D7. Figure 3 Similarly, the height of the graded catalyst bed in the staged packing section is 60% of the total height of the reactor bed. Then, catalyst D7 is uniformly packed on top of the graded catalyst bed.

[0258] In this embodiment, the porosity of the island region is 280.1% of that of the sea region, Li / L0 = 0.6, the number of island regions is 30, the shortest distance from any point on the cross-section of the sea region to the edge of the cross-section of the adjacent island region is no greater than 85 mm, the particle size of hydrogenation catalyst I is 6 mm, and the particle size of hydrogenation catalyst II is 2 mm.

[0259] Example 34

[0260] Catalysts D8 and A3 were loaded into a cylindrical hydrogenation reactor:

[0261] The reactor is an upflow reactor. The oil and hydrogen to be hydrogenated enter from the bottom of the reactor, and the reactants flow out from the top. During loading, catalyst D8 and catalyst A3 are first graded and loaded into the bottom of the reactor according to the scheme of this invention. In cross-section, the reactor contains five evenly distributed cylinders, each with a diameter of 150 mm. One cylinder is filled with catalyst A3, and the remaining portion is filled with catalyst D8. Figure 3 Similarly, the height of the graded catalyst bed in the staged packing section is 45% of the total height of the reactor bed. Then, catalyst D8 is uniformly packed on top of the graded catalyst bed.

[0262] In this embodiment, the porosity of the island region is 135.6% of that of the sea region, Li / L0 = 0.45, the number of island regions is 5, the shortest distance from any point on the cross-section of the sea region to the edge of the cross-section of the adjacent island region is no greater than 100 mm, the particle size of hydrogenation catalyst I is 6 mm, and the particle size of hydrogenation catalyst II is 3.5 mm.

[0263] Example 35

[0264] Catalysts D9 and A3 were loaded into a cylindrical hydrogenation reactor:

[0265] The reactor is an upflow reactor. The oil and hydrogen to be hydrogenated enter from the bottom of the reactor, and the reactants flow out from the top. During loading, catalyst D9 and catalyst A3 are first graded and loaded into the bottom of the reactor according to the scheme of this invention. In cross-section, the reactor contains 35 evenly distributed cylinders, each with a diameter of 30 mm. One cylinder is filled with catalyst A3, and the remaining portion is filled with catalyst D9. Figure 3 Similarly, the height of the graded catalyst bed in the staged packing section is 15% of the total height of the reactor bed. Then, catalyst D9 is uniformly packed on top of the graded catalyst bed.

[0266] In this embodiment, the porosity of the island region is 200.8% of that of the sea region, Li / L0 = 0.15, the number of island regions is 35, the shortest distance from any point on the cross-section of the sea region to the edge of the cross-section of the adjacent island region is no greater than 70 mm, the particle size of hydrogenation catalyst I is 6 mm, and the particle size of hydrogenation catalyst II is 2 mm.

[0267] Example 36

[0268] Catalysts D10 and A3 were loaded into a cylindrical hydrogenation reactor:

[0269] The reactor is an upflow reactor. The oil and hydrogen to be hydrogenated enter from the bottom of the reactor, and the reactants flow out from the top. During loading, catalyst D10 and catalyst A3 are first graded and loaded into the bottom of the reactor according to the scheme of this invention. In cross-section, the reactor contains 18 evenly distributed cylinders, each with a diameter of 25 mm. One cylinder is filled with catalyst A3, and the remaining portion is filled with catalyst D10. Figure 3 Similarly, the height of the graded catalyst bed in the staged packing section is 60% of the total height of the reactor bed. Then, catalyst D10 is uniformly packed on top of the graded catalyst bed.

[0270] In this embodiment, the porosity of the island region is 215.5% of that of the sea region, Li / L0 = 0.6, the number of island regions is 18, the shortest distance from any point on the cross-section of the sea region to the edge of the cross-section of the adjacent island region is no greater than 520 mm, the particle size of hydrogenation catalyst I is 6 mm, and the particle size of hydrogenation catalyst II is 1.6 mm.

[0271] Example 37

[0272] Catalysts D11 and A3 were loaded into a cylindrical hydrogenation reactor:

[0273] The reactor is an upflow reactor. The oil and hydrogen to be hydrogenated enter from the bottom of the reactor, and the reactants flow out from the top. During loading, catalyst D11 and catalyst A3 are first graded and loaded into the bottom of the reactor according to the scheme of this invention. In cross-section, the reactor contains 18 evenly distributed cylinders, each with a diameter of 30 mm. One cylinder is filled with catalyst A3, and the remaining portion is filled with catalyst D11. Figure 3 Similarly, the height of the graded catalyst bed in the staged packing section is 60% of the total height of the reactor bed. Then, catalyst D11 is uniformly packed on top of the graded catalyst bed.

[0274] In this embodiment, the porosity of the island region is 197% of that of the sea region, Li / L0 = 0.6, the number of island regions is 18, the shortest distance from any point on the cross-section of the sea region to the edge of the cross-section of the adjacent island region is no greater than 310 mm, the particle size of hydrogenation catalyst I is 6 mm, and the particle size of hydrogenation catalyst II is 2.5 mm.

[0275] Example 38

[0276] Catalysts D12 and A3 were packed into a cylindrical hydrogenation reactor:

[0277] The reactor is an upflow reactor. The oil and hydrogen to be hydrogenated enter from the bottom of the reactor, and the reactants flow out from the top. During loading, catalyst D12 and catalyst A3 are first graded and loaded into the bottom of the reactor according to the scheme of this invention. In cross-section, the reactor contains 10 evenly distributed cylinders, each with a diameter of 100 mm. One cylinder is filled with catalyst A3, and the remaining portion is filled with catalyst D12. Figure 3 Similarly, the height of the graded catalyst bed in the staged packing section is 30% of the total height of the reactor bed. Then, catalyst D12 is uniformly packed on top of the graded catalyst bed.

[0278] In this embodiment, the porosity of the island region is 157.4% of that of the sea region, Li / L0 = 0.3, the number of island regions is 10, the shortest distance from any point on the cross-section of the sea region to the edge of the cross-section of the adjacent island region is no greater than 157 mm, the particle size of hydrogenation catalyst I is 6 mm, and the particle size of hydrogenation catalyst II is 3.2 mm.

[0279] Example 39

[0280] Catalysts D13 and A3 are packed into a cylindrical hydrogenation reactor:

[0281] The reactor is an upflow reactor. The oil and hydrogen to be hydrogenated enter from the bottom of the reactor, and the reactants flow out from the top. During loading, catalyst D13 and catalyst A3 are first graded and loaded into the bottom of the reactor according to the scheme of this invention. In cross-section, the reactor contains 15 evenly distributed cylinders, each with a diameter of 50 mm. One cylinder is filled with catalyst A3, and the remaining portion is filled with catalyst D13. Figure 3 Similarly, the height of the graded catalyst bed in the staged packing section is 60% of the total height of the reactor bed. Then, catalyst D13 is uniformly packed on top of the graded catalyst bed.

[0282] In this embodiment, the porosity of the island region is 124.9% of that of the sea region, Li / L0 = 0.6, the number of island regions is 15, the shortest distance from any point on the cross-section of the sea region to the edge of the cross-section of the adjacent island region is no greater than 60 mm, the particle size of hydrogenation catalyst I is 6 mm, and the particle size of hydrogenation catalyst II is 4 mm.

[0283] Example 40

[0284] Catalysts D14 and A3 were loaded into a cylindrical hydrogenation reactor:

[0285] The reactor is an upflow reactor. The oil and hydrogen to be hydrogenated enter from the bottom of the reactor, and the reactants flow out from the top. During loading, catalyst D14 and catalyst A3 are first graded and loaded into the bottom of the reactor according to the scheme of this invention. In cross-section, the reactor contains 75 evenly distributed cylinders, each with a diameter of 40 mm. One cylinder is filled with catalyst A3, and the remaining portion is filled with catalyst D14. Figure 3 Similarly, the height of the graded catalyst bed in the staged packing section is 60% of the total height of the reactor bed. Then, catalyst D14 is uniformly packed on top of the graded catalyst bed.

[0286] In this embodiment, the porosity of the island region is 230% of that of the sea region, Li / L0 = 0.6, the number of island regions is 75, the shortest distance from any point on the cross-section of the sea region to the edge of the cross-section of the adjacent island region is no greater than 400 mm, the particle size of hydrogenation catalyst I is 6 mm, and the particle size of hydrogenation catalyst II is 2.8 mm.

[0287] Example 41

[0288] Catalysts D15 and A3 were loaded into a cylindrical hydrogenation reactor:

[0289] The reactor is an upflow reactor. The oil and hydrogen to be hydrogenated enter from the bottom of the reactor, and the reactants flow out from the top. During loading, catalyst D15 and catalyst A3 are first graded and loaded into the bottom of the reactor according to the scheme of this invention. In cross-section, the reactor contains 30 evenly distributed cylinders, each with a diameter of 30 mm. One cylinder is filled with catalyst A3, and the remaining portion is filled with catalyst D15. Figure 3 Similarly, the height of the graded catalyst bed in the staged packing section is 90% of the total height of the reactor bed. Then, catalyst D15 is uniformly packed on top of the graded catalyst bed.

[0290] In this embodiment, the porosity of the island region is 143.0% of that of the sea region, Li / L0 = 0.9, the number of island regions is 30, the shortest distance from any point on the cross-section of the sea region to the edge of the cross-section of the adjacent island region is no greater than 110 mm, the particle size of hydrogenation catalyst I is 6 mm, and the particle size of hydrogenation catalyst II is 3.6 mm.

[0291] Example 42

[0292] The loading process is the same as in Example 31, except that D1 and A6 are replaced with D6 and A8 respectively, while keeping other conditions unchanged.

[0293] Comparative Example 1

[0294] In the same hydrogenation reactor as in Example 26, only catalyst D1 was loaded, wherein the loading volume of catalyst D1 was equal to the total volume of the two catalysts in Example 26.

[0295] Comparative Example 2

[0296] In the same hydrogenation reactor as in Example 27, only catalyst A2 was loaded, wherein the loading volume of catalyst A2 was equal to the total volume of the two catalysts in Example 27.

[0297] Comparative Example 3

[0298] In the same hydrogenation reactor as in Example 28, the catalyst A3 section was replaced with four stainless steel fouling baskets of the same size. These baskets were made of Johnson mesh, hollow, and unfilled with catalyst, with an open top. The remaining parts of the reactor were filled with catalyst D3, with the same filling volume as in Example 28.

[0299] Comparative Example 4

[0300] In the same hydrogenation reactor as in Example 30, an equal volume of catalyst D16 was used instead of D5 for packing, while keeping other conditions unchanged. In this comparative example, the porosity of the island region is 105.7% of the porosity of the sea region.

[0301] Comparative Example 5

[0302] In the same hydrogenation reactor as in Example 30, an equal volume of catalyst D17 was used instead of D5 for packing, while keeping other conditions unchanged. In this comparative example, the porosity of the island region is 308% of the porosity of the sea region.

[0303] Comparative Example 6

[0304] In the same upflow hydrogenation reactor as in Example 30, the reactor was fully graded and packed throughout its entire height. In cross-section, the reactor contained 45 uniformly distributed cylinders, each 30 mm in diameter, filled with catalyst A5, with the remaining portion filled with catalyst D5. The Li / L0 ratio was 1, while other conditions remained constant. In this comparative example, the porosity of the island region was 143.9% of that of the sea region.

[0305] Comparative Example 7

[0306] In the same upflow reactor as in Example 28, a mixed catalyst consisting of catalyst A3 and catalyst D3 was first loaded into the lower 60% of the reactor height, and then catalyst D3 was loaded into the remaining upper part. The amounts of the two catalysts were the same as in Example 28.

[0307] Comparative Example 8

[0308] In the same upflow reactor as in Example 28, catalyst A3 was first loaded into the lower part of the reactor in the same amount as in Example 28, and then catalyst D3 was loaded into the remaining upper part of the reactor.

[0309] Reaction effect measurement:

[0310] The reaction was carried out in the reactors packed with catalysts as described in Examples 26-42 and Comparative Examples 1-8 according to the following steps:

[0311] (1) Sulfurization: Wet sulfurization was adopted. Raw materials diesel and hydrogen were introduced into the reactor and pressurized to 4.0 MPa. After heating to 160℃, carbon disulfide, a sulfiding agent, was introduced, with the amount being 10% of the total weight of the catalyst. The temperature was then raised to 330℃ and kept constant for 19 hours. The temperature was then lowered to room temperature to await the next experimental step.

[0312] (2) Hydrodesulfurization reaction: reaction temperature 410℃, reaction pressure 12MPa, liquid hourly space velocity 0.4h -1 The hydrogen-to-oil ratio was 1200:1, and the reactor flow pattern is described in the various embodiments. The feedstock was atmospheric residue from a Sinopec refinery, with a sulfur content of 3.1%, a metal (Ni+V) content of 81 ppm, and a residual carbon value of 13%.

[0313] The sulfur content of the generated oil was analyzed. The results are shown in Table 1.

[0314] Table 1 Activity Evaluation

[0315]

Claims

1. A single-stage solid particle bed, characterized in that, The device comprises a sea area and at least one island region distributed within the sea area, and has an upper surface, a lower surface, an axial direction, and a radial direction, wherein the axial direction is a lengthwise direction or the flow direction of material in the solid particle bed from the upper surface to the lower surface, the radial direction is a cross-sectional direction or a direction perpendicular to the axial direction, wherein the island region extends from the upper surface along the axial direction of the solid particle bed but does not extend to the lower surface, and the porosity of the island region is 110-300% of the porosity of the sea area. If island regions exist on any cross-section of the solid particle bed, the sum of the cross-sectional areas of all island regions is 10-60% of the cross-sectional area of ​​the solid particle bed. The island region contains one or more hydrogenation catalysts as solid particles, referred to as hydrogenation catalyst I, and the sea region contains one or more hydrogenation catalysts as solid particles, referred to as hydrogenation catalyst II.

2. The solid particle bed according to claim 1, wherein the solid particle bed is an axial solid particle bed, and / or, the porosity of the island region is 140-200% of the porosity of the sea region.

3. The solid particle bed of claim 1, wherein the marine region extends from the upper surface along the axial direction of the solid particle bed to the lower surface. And / or, The distribution pattern of the at least one island region in the sea area is selected from: i) The at least one island region is distributed discretely in the sea area; ii) The at least one island region is arranged in a ring shape to surround a portion of the sea region; iii) A combination of the two distribution methods, i) and ii).

4. The solid particle bed according to claim 3, wherein the extension length of any one of the island regions along the axial direction of the solid particle bed is Li, and the extension length of the sea region along the axial direction of the solid particle bed, i.e., the axial length of the solid particle bed, is L0, then Li / L0 < 1, and / or, the extension lengths of all the island regions along the axial direction of the solid particle bed are substantially the same, and / or, among all the island regions, the largest extension length along the axial direction of the solid particle bed is Lmax, then Lmax / L0 < 1, and / or, at least a portion of the island regions extend along the axial direction of the solid particle bed into at least one shape selected from columnar and conical.

5. The solid particle bed according to claim 4, wherein 0.04 ≤ Li / L0 ≤ 0.50, and / or, Lmax / L0 = 0.8-0.5, and / or, all said island regions extend along the axial direction of said solid particle bed in at least one shape selected from cylindrical, prismatic, pyramidal and conical.

6. The solid particle bed according to claim 1, wherein the number of island regions is n, where n is an integer from 1 to 2000, and / or, on any cross-section of the solid particle bed, each island region is the same or different from the others, and the cross-section is independently an arbitrary shape, and / or, based on the total volume of the solid particle bed, the proportion of all island regions is 0.3-57%, and the proportion of the sea region is 43-99.7%.

7. The solid particle bed according to claim 6, wherein n is an integer from 3 to 50, and / or, on any cross-section of the solid particle bed, each of the island regions is the same or different from each other, and the cross-section is independently at least one shape selected from rectangles, circles, ellipses, triangles, parallelograms, rings, and irregular shapes, and / or, based on the total volume of the solid particle bed, the proportion of all the island regions is 3-25%, and the proportion of the sea region is 75-97%.

8. The solid particle bed according to claim 1, wherein each of the island regions is the same as or different from each other, and each independently has a porosity of 0.20-0.90, and / or the porosity of the sea region is 0.15-0.

65.

9. The solid particle bed according to claim 8, wherein each of the island regions is the same as or different from each other, and each independently has a porosity of 0.37-0.60, and / or the porosity of the sea region is 0.16-0.

55.

10. The solid particle bed according to claim 1, wherein on any cross-section of the solid particle bed, the straight-line distance between the edges of two adjacent island regions is greater than 20 mm, and / or, on any cross-section of the solid particle bed, if island regions exist, the shortest distance from any point on the cross-section of the sea area to the edge of the cross-section of the adjacent island region does not exceed 500 mm, and / or, on any cross-section of the solid particle bed, each island region is identical or different from each other, and each independently has a length not exceeding 300,000 mm. 2 The cross-sectional area, and / or the solid particle bed having a cross-sectional area not exceeding 3,000,000 mm² 2 The cross-sectional area of ​​the solid particle bed, and / or, on any cross-section of the solid particle bed, if the island regions exist, the sum of the cross-sectional areas of all the island regions is 15-45% of the cross-sectional area of ​​the solid particle bed.

11. The solid particle bed of claim 10, wherein on any cross-section of the solid particle bed, the straight-line distance between the edges of two adjacent island regions is greater than 100 mm, and / or, on any cross-section of the solid particle bed, if island regions exist, the shortest distance from any point on the cross-section of the sea area to the edge of the cross-section of the adjacent island region does not exceed 100 mm, and / or, on any cross-section of the solid particle bed, each island region is identical or different from each other, and each independently has a length not exceeding 100,000 mm. 2 The cross-sectional area, and / or the solid particle bed having a cross-sectional area not exceeding 2,000,000 mm². 2 The cross-sectional area of ​​the solid particle bed, and / or, on any cross-section of the solid particle bed, if the island regions exist, the sum of the cross-sectional areas of all the island regions is 18-30% of the cross-sectional area of ​​the solid particle bed.

12. The solid particle bed according to claim 1, wherein the hydrogenation catalyst I is a hollow and / or toothed particle, the hydrogenation catalyst II is a porous particle, and / or, the particle size of the hydrogenation catalyst I is 2.0-55.0 mm, the particle size of the hydrogenation catalyst II is 0.5-4.0 mm, and / or, the hydrogenation catalyst I comprises a support and a hydrogenation-active metal, the hydrogenation catalyst II is selected from at least one of supported catalysts and unsupported catalysts, and the supported catalyst comprises a support and a hydrogenation-active component, the unsupported catalyst comprises a binder and a hydrogenation-active component, and / or, the hydrogenation catalyst II is used to... The mass content of the hydrogenation active metal in the hydrogenation catalyst I, based on the total weight of catalyst I, is 10-90% of the mass content of the hydrogenation active component in the hydrogenation catalyst II, based on the total weight of catalyst II, and / or, each of the hydrogenation catalysts I is the same or different from each other, and each independently has the same or different porosity, and each of the hydrogenation catalysts II is the same or different from each other, and each independently has the same or different porosity, provided that the porosity of any one of the hydrogenation catalysts I is 110-300% of the porosity of any one of the hydrogenation catalysts II.

13. The solid particle bed according to claim 12, wherein the particle size of the hydrogenation catalyst I is 3.0-30.0 mm, and / or the particle size of the hydrogenation catalyst II is 0.8-3.0 mm, and / or the mass content of the hydrogenation active metal in the hydrogenation catalyst I, based on the total weight of the hydrogenation catalyst I, is 17-40% of the mass content of the hydrogenation active component in the hydrogenation catalyst II, based on the total weight of the hydrogenation catalyst II, based on the metal oxide, and / or each of the hydrogenation catalysts I is the same or different from each other, each independently having the same or different porosity, and each of the hydrogenation catalysts II is the same or different from each other, each independently having the same or different porosity, provided that the porosity of any one of the hydrogenation catalysts I is 140%-200% of the porosity of any one of the hydrogenation catalysts II.

14. The solid particle bed according to claim 12, wherein in the hydrogenation catalyst I, the mass content of the hydrogenation active metal as a metal oxide is 5-30% based on the total weight of the hydrogenation catalyst, and / or the support is selected from at least one of activated carbon, inorganic refractory oxides and molecular sieves, and / or the hydrogenation active metal is selected from at least one of Fe, Co, Ni, Cu, Zn, Cr, Mo and W.

15. The solid particle bed according to claim 14, wherein in the hydrogenation catalyst I, the mass content of the hydrogenation active metal as a metal oxide is 8-20% based on the total weight of the hydrogenation catalyst, and / or the inorganic refractory oxide is at least one selected from alumina, silicon oxide, magnesium oxide, zirconium oxide and titanium oxide, and / or the hydrogenation active metal is at least one selected from Fe and Ni.

16. The solid particle bed according to claim 12, wherein in the hydrogenation catalyst II, the mass content of the hydrogenation active component, based on the total weight of the supported catalyst, is 15-40% by weight of metal oxides, and / or, based on the total weight of the unsupported catalyst, the mass content of the hydrogenation active component, based on metal oxides, is 30-80% by weight, and / or, the support is selected from at least one oxide of elements in Groups II, III, IV, and IVB of the periodic table, and / or, the binder is selected from elements in Groups II, III, IV, and IVB of the periodic table. The active hydrogenation component is selected from at least one oxide of a group VIB element, and / or, the active hydrogenation component is selected from at least one metal of group VIB and group VIII of the periodic table, and / or, based on the total weight of the supported catalyst, the mass content of the group VIB metal as metal oxide is 15-30%, and the mass content of the group VIII metal as metal oxide is 2-10%, and / or, based on the total weight of the unsupported catalyst, the mass content of the group VIB metal as metal oxide is 15-30%, and the mass content of the group VIII metal as metal oxide is 2-10%.

17. The solid particle bed according to claim 16, wherein in the hydrogenation catalyst II, the mass content of the hydrogenation active component, based on the total weight of the supported catalyst, is 20-35% by weight as a metal oxide, and / or, based on the total weight of the unsupported catalyst, the mass content of the hydrogenation active component, based on the metal oxide, is 40-65% by weight, and / or, the support is at least one selected from alumina and silica, and / or, the binder is at least one selected from alumina and silica, and / or, the Group VIB metal is Mo and / or W, and the Group VIII metal is Co and / or Ni, and / or, based on the total weight of the supported catalyst, the mass content of the Group VIB metal, based on the metal oxide, is 18-27% by weight, and the mass content of the Group VIII metal, based on the metal oxide, is 3-7% by weight, and / or, based on the total weight of the unsupported catalyst, the mass content of the Group VIB metal, based on the metal oxide, is 18-27% by weight, and the mass content of the Group VIII metal, based on the metal oxide, is 3-7% by weight.

18. A fixed bed comprising multiple segments of solid particle bed, wherein at least one segment of the solid particle bed is the solid particle bed according to claim 1, referred to as solid particle bed A.

19. The fixed bed according to claim 18, wherein the height of the solid particle bed A is 3-60% of the height of the fixed bed.

20. The fixed bed according to claim 19, wherein the height of the solid particle bed A is 4-50% of the height of the fixed bed.

21. The fixed bed according to claim 18, further comprising a solid particle bed B located upstream of the solid particle bed A and / or a solid particle bed C located downstream of the solid particle bed A, wherein the porosity of the solid particle bed B is not less than the porosity of the island region in the solid particle bed A, and the porosity of the solid particle bed C is not greater than the porosity of the sea region in the solid particle bed A.

22. The fixed bed according to claim 21, wherein the solid particle bed B comprises one or more hydrogenation catalysts B, the solid particle bed C comprises one or more hydrogenation catalysts C, wherein the hydrogenation catalysts B and C are the same as or different from each other, each independently selected from at least one of supported catalysts and unsupported catalysts, and the supported catalyst comprises a support and a hydrogenation active component, and the unsupported catalyst comprises a binder and a hydrogenation active component.

23. The fixed bed according to claim 22, wherein the hydrogenation catalyst B and the hydrogenation catalyst C are the same as or different from each other, and are each independently selected from the hydrogenation catalyst II.

24. A method for hydrotreating an oil product, comprising the step of passing the oil product through a solid particle bed according to claim 1 or a fixed bed according to claim 18 under hydrotreating reaction conditions, referred to as a hydrotreating step.

25. The method according to claim 24, wherein the oil is selected from at least one of ethylene cracked gasoline, coking naphtha, catalytic gasoline, Fischer-Tropsch synthetic oil, coking diesel, catalytic diesel, high-dry-point straight-run diesel, wax oil, residue oil, coal tar, and coal hydrotreating oil, and / or the hydrotreating reaction conditions include: The reaction temperature is 40-500℃, the reaction pressure is 0.3-20 MPaG, and the volume hourly space velocity is 1-10 h⁻¹. -1 The hydrogen-to-oil ratio is 10:1-2000:

1.

26. The method of claim 24, further comprising the step of sulfiding the solid particle bed or the fixed bed prior to the hydrogenation step, and / or, pre-sulfiding the hydrogenation catalyst outside the apparatus, and / or, the reaction conditions for the sulfidation treatment including: Dry vulcanization or wet vulcanization is used, with the vulcanizing agent being at least one selected from hydrogen sulfide, carbon disulfide, dimethyl disulfide, methyl sulfide, and n-butyl sulfide. The vulcanization pressure is 1.2-15 MPaG (1.2-9.4 MPaG), the vulcanization temperature is 280-400℃, and the vulcanization time is 4-22h.

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