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CN-117756146-B - Hierarchical pore aluminum oxide material and preparation method and application thereof

CN117756146BCN 117756146 BCN117756146 BCN 117756146BCN-117756146-B

Abstract

The invention discloses a multistage pore aluminum oxide material and a preparation method and application thereof, wherein the aluminum oxide material is of a spherical core-shell structure, mesoporous aluminum oxide is taken as an inner core, macroporous aluminum oxide is taken as an outer shell, the pore size distribution of the aluminum oxide material has the characteristic of multistage pore distribution, wherein the pore volume of pores with the diameters of 6-15nm accounts for 20% -50% of the total pore volume, and the pore volume of pores with the diameters of more than 20nm accounts for not less than 40% of the total pore volume. The preparation method of the hierarchical pore alumina material comprises the following steps of (1) roasting pseudo-boehmite to obtain alumina particles, (2) uniformly mixing and dispersing a surfactant, a hydrocarbon compound and alumina particles to obtain a1 st material flow, (3) uniformly mixing an alumina sol, an emulsifying agent, a curing agent and an auxiliary agent to obtain a2 nd material flow, and (4) mixing the1 st material flow and the2 nd material flow, and then further performing molding, aging, extraction, washing, drying and roasting to obtain the alumina composite material. The alumina material is suitable for preparing heavy oil hydrogenation catalysts with stepped pore channels and acid distribution as carriers, and is further used for heavy oil hydrogenation treatment processes.

Inventors

  • ZHU HUIHONG
  • SHI YIMING
  • JIN HAO
  • LV ZHENHUI
  • YANG TAO

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
20260505
Application Date
20220917

Claims (20)

  1. 1. A multi-stage pore alumina material is of a spherical core-shell structure, takes mesoporous alumina as an inner core and macroporous alumina as an outer shell, and has the characteristics that the pore size distribution of the alumina material has multi-stage pore distribution, wherein the content of the mesoporous alumina in the inner core is 20-60 wt%, the content of the macroporous alumina in the outer shell is 40-80 wt%, the pore size of pores of 6-15nm of the mesoporous alumina in the inner core accounts for 40-70% of the total pore size, the pore size of pores of more than 20nm accounts for less than 20%, the pore size of pores of more than 20nm of the outer shell accounts for more than 50%, and the pore size distribution of the alumina material has the characteristics that the pore size of pores of 6-15nm accounts for 30-60% of the total pore size, and the pore size of pores of more than 20nm accounts for not less than 30%.
  2. 2. The hierarchical porous alumina material according to claim 1, wherein the specific surface area of the alumina material is 100-280 m 2 /g.
  3. 3. The hierarchical porous alumina material according to claim 1, wherein the specific surface area of the alumina material is 120-250 m 2 /g.
  4. 4. The hierarchical porous alumina material according to claim 1, wherein the pore volume of the alumina material is 0.50-0.80 mL/g.
  5. 5. The hierarchical porous alumina material according to claim 1, wherein the pore volume of the alumina material is 0.55-0.75 mL/g.
  6. 6. The hierarchical porous alumina material according to claim 1, wherein the particle diameter of the alumina material is 0.8 to 2.0mm.
  7. 7. The hierarchical porous alumina material according to claim 1, wherein the particle diameter of the alumina material is 1.0 to 2.0mm.
  8. 8. The porous alumina material of claim 1, wherein the alumina material has a wear index of no greater than 0.05%.
  9. 9. The porous alumina material of claim 1, wherein the alumina material has a wear index of no greater than 0.03%.
  10. 10. The porous alumina material of claim 1, wherein the alumina material has a lateral pressure strength greater than 15N/mm.
  11. 11. The porous alumina material of claim 1, wherein the alumina material has a lateral pressure strength greater than 20N/mm.
  12. 12. A preparation method of a hierarchical pore alumina material comprises the following steps: (1) Roasting pseudo-boehmite, and grinding after roasting to obtain alumina particles; (2) Mixing a surfactant, a hydrocarbon compound and the alumina particles obtained in the step (1), and uniformly dispersing to obtain a1 st material flow; (3) Mixing aluminum sol, an emulsifying agent, a curing agent and an auxiliary agent uniformly to obtain a2 nd material flow, wherein the auxiliary agent is one or more selected from methacryloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride and polyacrylamide; (4) Mixing the 1 st material flow obtained in the step (2) and the 2 nd material flow obtained in the step (3), uniformly mixing to obtain an oil-in-water emulsion, and then forming, ageing, extracting, washing, drying and roasting to obtain the aluminum oxide material.
  13. 13. The method for preparing a hierarchical porous alumina material according to claim 12, wherein the firing temperature in the step (1) is 450 ℃ to 750 ℃ and the firing time is 1 to 6 hours.
  14. 14. The method for preparing a hierarchical porous alumina material according to claim 12, wherein the roasting temperature in the step (1) is 500-700 ℃ and the roasting time is 2-5 hours.
  15. 15. The method for preparing a hierarchical porous alumina material according to claim 12, wherein the alumina particles after roasting in the step (1) have the characteristics of a specific surface area of 250-350 m 2 /g, a pore volume of 0.50-1.0 mL/g and a pore diameter of 8-12 nm.
  16. 16. The method for preparing a hierarchical porous alumina material according to claim 12, wherein the particle size of the alumina particles obtained after the completion of the grinding in the step (1) is 2 to 10. Mu.m.
  17. 17. The method for preparing a hierarchical porous alumina material according to claim 12, wherein the alumina particles obtained after the completion of the grinding in the step (1) have a particle size of 3 to 8. Mu.m.
  18. 18. The method for preparing a hierarchical porous alumina material according to claim 12, wherein the surfactant in the step (2) has a hydrophilic-lipophilic balance of 16 to 18 and is at least one of Tween 20, peregal O-25 and peregal O-30.
  19. 19. The method for preparing a hierarchical porous alumina material according to claim 12, wherein the surfactant in the step (2) is added in an amount of 5.0% -15.0% by mass of the alumina particles in the step (1).
  20. 20. The method for preparing a hierarchical porous alumina material according to claim 12, wherein the surfactant in the step (2) is added in an amount of 5.0% -13.0% by mass of the alumina particles in the step (1).

Description

Hierarchical pore aluminum oxide material and preparation method and application thereof Technical Field The invention belongs to the technical field of inorganic materials, relates to alumina and preparation and application thereof, and in particular relates to hierarchical pore alumina and preparation and application thereof. Background At present, the crude oil processing amount in China is about 6.7 hundred million tons/year, wherein the residual oil which is difficult to process and utilize accounts for more than 30-40%, the external dependence of petroleum in China exceeds 70%, and how to efficiently convert and utilize the part of heavy residual oil resources is the key for solving the problem. The hydrogenation of residuum is a key technology for high-efficiency conversion of residuum, and can not only remove impurities, but also produce light fraction products with high added value. Depending on the type of residuum hydrogenation reactor, residuum hydrogenation can be classified into fixed bed, ebullated bed, and suspended bed types. Wherein, the fixed bed residual oil hydrogenation technology is mature, the investment and operation cost is low, the operation is safe and simple, and the common application is obtained. The boiling bed residual oil hydrogenation technology has the capability of processing high-sulfur, high-carbon residue and high-metal heavy crude oil, and has the advantages of uniform temperature in a reactor, long running period, flexible device operation and the like, and is rapidly developed after 2000 years. These two technologies are currently the dominant technologies for the residuum hydrogenation industry application. The residuum contains a large amount of impurities such as metal, sulfur, nitrogen and the like, and the impurities are mostly rich in heavy components such as colloid, asphaltene and the like, so that the difficulty of the residuum hydrogenation technology is how to realize high-efficiency conversion of asphaltene and improve the impurity removal reaction effect. In general, the residual oil hydrogenation adopts a catalyst grading mode to carry out asphaltene conversion and impurity removal reaction, thereby improving the product quality and meeting the subsequent process requirements. However, the catalyst grading process is complex, multiple catalysts are needed to be mutually blended, and how to realize the catalyst grading concept on one catalyst is always a research direction. CN201410540168.1 discloses a residuum hydrotreating catalyst grading method and residuum hydrotreating method. The residual oil hydrotreating catalyst grading method comprises the steps of sequentially filling a hydrogenation protecting catalyst, a hydrodemetallization catalyst, a hydrodesulphurization catalyst and a hydrodecarbon residue catalyst in a residual oil hydrotreating device along a material flow direction, wherein the total acid amount of each catalyst along the material flow direction is gradually increased, the proportion of Lewis acid to total acid is gradually reduced, and the proportion of Bronsted acid to total acid is gradually increased. In the patent, the catalyst macro-grading is used for realizing the directional impurity removal of the residual oil, and the use is more complicated. CN201010509320.1 discloses a heavy feed oil ebullated bed hydroprocessing method. In the patent, a boiling bed hydrotreating reactor is used, heavy raw oil and hydrogen enter the reactor from the bottom, the reaction is carried out under the hydrotreating condition of the heavy raw oil, the reacted materials are discharged from the top of the reactor, and a mixed catalyst of at least two catalysts is used in the boiling bed hydrotreating reactor. The patent realizes the distribution of macroscopically different pore structures and activities by adopting two catalysts, and the back mixing characteristic of the ebullated bed reactor can not fully exert the advantages of the two catalysts. Disclosure of Invention Aiming at the defects in the prior art, the invention provides a multistage pore aluminum oxide material, a preparation method and application thereof, wherein the multistage pore aluminum oxide material is of a spherical core-shell structure, mesoporous aluminum oxide is taken as a core, macroporous aluminum oxide is taken as a shell, a macroscopic and microscopic step pore channel structure is realized on a single aluminum oxide material, and the multistage pore aluminum oxide material is particularly suitable for being used as a carrier to prepare a heavy oil hydrogenation catalyst with step pore channels and acid distribution, and is further used for a heavy oil hydrogenation treatment process of gradual reaction. In order to achieve the aim, the first aspect of the invention provides a multistage pore alumina material which is of a spherical core-shell structure, takes mesoporous alumina as an inner core and macroporous alumina as an outer shell, wherein the content of t