CN-116601271-B - Solid particle bed, fixed bed and oil hydrogenation method

CN116601271BCN 116601271 BCN116601271 BCN 116601271BCN-116601271-B

Abstract

A solid particle 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 particle bed but does not extend to the lower surface, and the void fraction of the island region is 110 to 300% of the void fraction of the sea region, and a fixed bed comprising the solid particle bed. A process for hydrogenating an oil product comprising the step of flowing the oil product through the solid particulate bed or fixed bed under hydrogenation conditions.

Inventors

YANG CHENGMIN
LIU LI
LI YANG
DUAN WEIYU
GUO RONG
ZHOU YONG
YAO YUNHAI
ZHENG BUMEI
SUN JIN

Assignees

中国石油化工股份有限公司
中石化（大连）石油化工研究院有限公司

Dates

Publication Date: 20260512
Application Date: 20211215
Priority Date: 20201222

Claims (20)

1. A solid particle 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 axial direction is a longitudinal direction or a flow direction of a 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 a void fraction of the island region is 110 to 300% of a void fraction of the sea region, and On any cross-section of the bed of solid particles, if the island regions are present, the sum of the cross-sectional areas of all the island regions is 10-60% of the cross-sectional area of the bed of solid particles, Wherein the island region comprises one or more hydrogenation catalysts as solid particles, referred to as hydrogenation catalyst I, and the sea region comprises one or more hydrogenation catalysts as solid particles, referred to as hydrogenation catalyst II.
2. The bed of solid particles of claim 1, wherein the bed of solid particles is an axial bed of solid particles and/or the void fraction of the island region is 140-200% of the void fraction of the sea region.
3. The bed of solid particles according to claim 1, wherein the sea area extends from the upper surface to the lower surface along an axial direction of the bed of solid particles, And/or the number of the groups of groups, The distribution of the at least one island region in the sea region is selected from: i) The at least one island region is distributed in a discrete manner in the sea region; ii) the at least one island region is arranged in a ring shape surrounding a portion of the sea region; iii) i) and ii) a combination of the two modes of distribution.
4. A solid particle bed according to claim 3, wherein the length of extension of any one of the island regions in the axial direction of the solid particle bed is set to Li, the length of extension of the sea region in the axial direction of the solid particle bed, that is, the axial length of the solid particle bed is set to L0, li/L0<1, and/or the length of extension of all the island regions in the axial direction of the solid particle bed is substantially the same, and/or, in all the island regions, the largest of the lengths of extension in the axial direction of the solid particle bed is set to Lmax, lmax/L0<1, and/or, at least a part of the island regions are extended in at least one shape selected from a columnar shape and a tapered shape in the axial direction of the solid particle bed.
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 of the island regions extend in the axial direction of the solid particle bed into at least one shape selected from a cylinder, a prism, a pyramid, and a cone.
6. The bed of solid particles according to claim 1, wherein the number of island regions is provided as n, n is an integer of 1 to 2000, and/or each of the island regions is identical to or different from each other in any cross section of the bed of solid particles, each of the cross sections is independently in any pattern, and/or the proportion of the total island regions is 0.3 to 57% and the proportion of the sea region is 43 to 99.7% based on the total volume of the bed of solid particles.
7. The bed of solid particles according to claim 6, wherein n is an integer of 3 to 50, and/or each of the island regions is identical to or different from each other in any cross section of the bed of solid particles, each cross section being independently at least one pattern selected from the group consisting of rectangular, circular, elliptical, triangular, parallelogram, annular and irregular shapes, and/or the proportion of all the island regions being 3 to 25% and the proportion of the sea region being 75 to 97% based on the total volume of the bed of solid particles.
8. The bed of solid particles according to claim 1, wherein each of the island regions is the same or different from each other, each independently has a void fraction of 0.20-0.90, and/or the sea region has a void fraction of 0.15-0.65.
9. The bed of solid particles according to claim 8, wherein each of the island regions is the same or different from each other, each independently has a void fraction of 0.37-0.60, and/or the void fraction of the sea region is 0.16-0.55.
10. The bed of solid particles according to claim 1, wherein the linear distance of the edges of two adjacent island regions is greater than 20mm in any cross-section of the bed of solid particles, and/or wherein the shortest distance of any point on the cross-section of the sea region to the edge of the cross-section of the island region adjacent thereto is not more than 500mm in any cross-section of the bed of solid particles, if present, and/or wherein each of the island regions is identical or different from each other, each independently having a cross-sectional area of not more than 300000mm 2 , and/or wherein the bed of solid particles has a cross-sectional area of not more than 3000000mm 2 , and/or wherein the sum of the cross-sectional areas of all the island regions is 15-45% of the cross-sectional area of the bed of solid particles in any cross-section of the bed of solid particles, if present.
11. The bed of solid particles according to claim 10, wherein the linear distance of the edges of two adjacent island regions is greater than 100mm in any cross-section of the bed of solid particles, and/or wherein the shortest distance of any point on the cross-section of the sea region to the edge of the cross-section of the island region adjacent thereto is not more than 100mm in any cross-section of the bed of solid particles, if present, and/or wherein each of the island regions is identical or different from each other in any cross-section of the bed of solid particles, each independently has a cross-sectional area of not more than 100000mm 2 , and/or wherein the bed of solid particles has a cross-sectional area of not more than 2000000mm 2 , and/or wherein the sum of the cross-sectional areas of all the island regions is 18-30% of the cross-sectional area of the bed of solid particles in any cross-section of the bed of solid particles, if present.
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 hydrogenation catalyst I has a particle size of 2.0-55.0mm, the hydrogenation catalyst II has a particle size of 0.5-4.0mm, 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 a supported catalyst and an unsupported catalyst, 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 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 is 10 to 90% of 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, and/or each of the hydrogenation catalysts I is the same or different from each other, each independently has the same or different void fraction, and each of the hydrogenation catalysts II is the same or different from each other, each independently has the same or different void fraction, provided that the void fraction of any one of the hydrogenation catalysts I is 110 to 300% of the void fraction of any one of the hydrogenation catalysts II.
13. The bed of solid particles according to claim 12, wherein the particle size of the hydrogenation catalyst I is 3.0-30.0mm, and/or the particle size of the hydrogenation catalyst II is 0.8-3.0mm, and/or 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 is 17-40% of 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, and/or each of the hydrogenation catalysts I is the same or different from each other, each independently has the same or different void fraction, and each of the hydrogenation catalysts II is the same or different from each other, provided that the void fraction of any one of the hydrogenation catalysts I is 140% -200% of the void fraction of any one of the hydrogenation catalysts II.
14. The solid particle bed according to claim 12, wherein in the hydrogenation catalyst I, the hydrogenation active metal is present in an amount of 5-30% by mass as metal oxide based on the total weight of the hydrogenation catalyst, and/or the support is selected from at least one of activated carbon, inorganic refractory oxide and molecular sieve, 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 hydrogenation active metal is present in an amount of 8 to 20% by mass in terms of metal oxide based on the total weight of the hydrogenation catalyst, and/or the inorganic refractory oxide is at least one selected from the group consisting of alumina, silica, magnesia, zirconia and titania, and/or the hydrogenation active metal is at least one selected from the group consisting of Fe and Ni.
16. The bed of solid particles according to claim 12, wherein in the hydrogenation catalyst II the hydrogenation active component is present in an amount of 15-40% by mass based on the total weight of the supported catalyst and/or the hydrogenation active component is present in an amount of 30-80% by mass based on the total weight of the unsupported catalyst and/or the support is selected from at least one of the oxides of the elements of groups II, III, IV and IVB of the periodic table of the elements and/or the binder is selected from at least one of the oxides of the elements of groups II, III, IV and IVB of the periodic table of the elements and/or the hydrogenation active component is selected from at least one of the metals of groups VIB and VIII of the periodic table of the elements and/or the group VIB metal is present in an amount of 15-30% by mass based on the total weight of the supported catalyst and/or the group VIB metal is present in an amount of 15-30% by mass based on the total weight of the metal oxide and/or the group VIB metal is present in an amount of 2-10% by mass based on the total weight of the supported catalyst.
17. The bed of solid particles according to claim 16, wherein in the hydrogenation catalyst II the hydrogenation active component is in a mass content of 20-35% by weight of metal oxide based on the total weight of the supported catalyst and/or the hydrogenation active component is in a mass content of 40-65% by weight of metal oxide based on the total weight of the unsupported catalyst 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 the group VIB metal is in a mass content of 18-27% by weight of metal oxide based on the total weight of the supported catalyst and/or the group VIII metal is in a mass content of 3-7% by weight of metal oxide based on the total weight of the unsupported catalyst and/or the group VIB metal is in a mass content of 3-27% by weight of metal oxide based on the total weight of the unsupported catalyst.
18. A fixed bed comprising a plurality of solid particle beds, wherein at least one of said solid particle beds is a solid particle bed according to claim 1, referred to as solid particle bed a.
19. The fixed bed of claim 18, wherein the height of the bed of solid particles a is 3-60% of the height of the fixed bed.
20. The fixed bed of claim 19, wherein the height of the bed of solid particles a is 4-50% of the height of the fixed bed.

Description

Solid particle bed, fixed bed and oil hydrogenation method Technical Field The invention relates to the technical field of oil product hydrogenation, in particular to a solid particle bed, a fixed bed containing the solid particle bed and application of the beds in oil product hydrogenation. Background Due to the influence of impurities, various oil products can be used after hydrogenation is needed to improve the quality. For example, ethylene pyrolysis gasoline, coker naphtha, catalytic gasoline, fischer-Tropsch synthetic oil, coker diesel, catalytic diesel, high dry point straight-run diesel, wax oil, residual oil, coal tar, coal hydrogenation generated oil and the like mostly contain sulfur, nitrogen, oxygen, alkene, aromatic and other impurities, and hydrofining is usually required to remove the impurities in the oil before the oil can be used. In the hydrofining process, the phenomenon of pressure drop increase caused by factors such as coking or mechanical impurities and the like often occurs in the process of processing inferior oil products. The pressure drop is closely related to the void fraction of the catalyst bed. At present, oil hydrogenation is to slow down the increase of pressure drop, and particles with larger void ratio are filled in the inlet section of a reactor, and particularly, a protecting agent with various shapes is filled in the reverse inlet section in the fixed bed residual oil hydrogenation process so as to prolong the running period of the fixed bed residual oil hydrogenation process. Chinese patent CN101928592a discloses a grading combination of hydrogenation catalysts, wherein the reactors are filled with hydrodemetallization and hydrodesulphurisation catalysts from top to bottom, respectively, the raw material flow is kept from top to bottom along the flow direction, the catalyst activity is gradually increased, the pore size is gradually decreased, the particle size is gradually decreased, and the porosity is gradually decreased. Chinese patent CN1104558a discloses a process and catalyst system for hydrotreating a hydrocarbon feedstock wherein the feedstock is passed through a fixed bed catalyst system of hydrotreating catalyst containing a physical mixture of high void fraction catalyst particles and low void fraction catalyst particles, the particles being mixed in different amounts within different layers of the catalyst bed to form a layered structure within the fixed bed catalyst system, the mixing ratio of the high void fraction and low void fraction particles being different in the different layers. Disclosure of Invention Through diligent researches, the inventor of the invention discovers that the top coking of a hydrofining reactor is easy to occur in the catalytic gasoline hydrogenation, the coke powder deposition and the carbon deposition coking at the top of the reactor are easy to occur in the coking diesel hydrogenation, the top coking of the reactor is easy to occur in the coal tar hydrogenation, and the direct consequence of the top coking is that the pressure drop of the catalyst bed at the inlet section of the reactor is increased. As a result, the catalyst has a small adsorption and deposition capacity for the deposits, and the bed pressure drop increases too fast, resulting in a shortened operating cycle. Through further researches, the inventor of the invention discovers that by adopting a special catalyst grading method, the dispersion and deposition of easy sediments in oil products are realized, the adsorption and deposition capacity of the catalyst to the easy sediments is increased, the rising of the pressure drop of a bed layer can be effectively delayed, and the running period is prolonged. The present invention has been completed based on this finding. In particular, the present invention relates to the following aspects. 1. A catalyst grading method for oil hydrogenation is characterized in that a grading filling section is arranged at the inlet end of a reactor, the space of the grading filling section is divided into a plurality of columnar reaction units parallel to the flow direction, and a hydrogenation catalyst I and a hydrogenation catalyst II are respectively filled in every two adjacent columnar reaction units in a manner that columnar edges are in contact with each other, wherein the hydrogenation catalyst I has a larger void ratio than the hydrogenation catalyst II. 2. The catalyst sizing process according to any of the preceding or subsequent claims, wherein the catalyst bed height of the sizing section is 1% to 95%, preferably 3% to 60%, further preferably 4% to 50% of the total reactor bed height. 3. The catalyst gradation method according to any one of the preceding or subsequent claims, characterized in that the conventional hydrogenation catalyst is packed in the remaining part of the reactor with a void fraction not larger than the void fraction of the hydrogenation catalyst II in the gradation packing section. 4. The cata