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CN-120054514-B - Residual oil hydrodecarbonization catalyst and preparation method and application thereof

CN120054514BCN 120054514 BCN120054514 BCN 120054514BCN-120054514-B

Abstract

The invention discloses a residual oil hydrodecarbonization catalyst and a preparation method and application thereof. The residual oil hydrodecarbonization catalyst comprises a modified alumina carrier and a hydrogenation active metal component, wherein the modified alumina carrier comprises alumina and a modification auxiliary agent, the modification auxiliary agent is magnesium, and hexacoordinated Al on the carrier accounts for 75% -95% of total aluminum. The catalyst has good hydrogenation carbon residue removal performance, and is particularly suitable for processing boiling bed hydrogenation tail oil with poor oil quality.

Inventors

  • JIANG SHUJIAO
  • DING SIJIA
  • YUAN SHENGHUA
  • GENG XINGUO
  • YANG GANG

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
20231130

Claims (20)

  1. 1. The residual oil hydrodecarbonization catalyst comprises a modified alumina carrier and a hydrogenation active metal component, wherein the modified alumina carrier comprises alumina and a modification auxiliary agent, the modification auxiliary agent is magnesium, and hexacoordinated Al on the carrier accounts for 80% -95% of total aluminum; The mass content of magnesium is 1-12% based on the mass of the carrier, and the mass content of alumina is 83-99% based on the mass of the carrier; The hydrogenation active metal component is at least one of the VIB metal and the VIII metal, the content of the VIB metal is 10-32% calculated by +6 oxide and the content of the VIII metal is 2-8% calculated by +2 oxide based on the mass of the catalyst; The preparation method of the catalyst comprises the steps of preparing a modified alumina carrier and loading a hydrogenation active metal component, wherein the preparation method of the modified alumina carrier comprises the steps of mixing the alumina carrier with an organic solution of magnesium chloride, performing airtight heating treatment and activating treatment to obtain the modified alumina carrier; in the organic solution of magnesium chloride, the organic solvent is one or more of glycerol, 1, 4-butanediol and 1, 2-butanediol, and the mass content of the magnesium chloride in the organic solution of magnesium chloride is 2-10%.
  2. 2. The catalyst of claim 1 wherein hexacoordinated Al on the support comprises 80% -90% of the total aluminum.
  3. 3. The catalyst according to claim 1, wherein the mass content of magnesium is 2 to 10% based on the mass of the support and/or the mass content of alumina is 85 to 98% based on the mass of the support.
  4. 4. The catalyst according to claim 1, wherein the carrier has a specific surface area of 180-420m 2 /g and a pore volume of 0.5-1.1mL/g.
  5. 5. The catalyst according to claim 4, wherein the carrier has a specific surface area of 220-360m 2 /g and a pore volume of 0.6-1.0mL/g.
  6. 6. The catalyst according to claim 1, wherein the carrier further comprises one or more of silicon, phosphorus and boron as an auxiliary agent, and the auxiliary agent is contained in an amount of 5% or less by mass in terms of elements based on the mass of the carrier.
  7. 7. The catalyst of claim 1 wherein the group VIB metal is selected from at least one of tungsten and molybdenum and the group VIII metal is selected from at least one of nickel and cobalt.
  8. 8. The catalyst according to claim 1, wherein the group VIB metal is present in an amount of 15% to 26% by weight of +6 oxide and the group VIII metal is present in an amount of 3% to 7% by weight of +2 oxide, based on the mass of the catalyst.
  9. 9. The preparation method of the catalyst according to any one of claims 1 to 8, comprising the preparation of a modified alumina carrier and the loading of a hydrogenation active metal component, wherein the preparation method of the modified alumina carrier comprises the steps of mixing the alumina carrier with an organic solution of magnesium chloride, performing airtight heating treatment, and performing activation treatment to obtain the modified alumina carrier; in the organic solution of magnesium chloride, the organic solvent is one or more of glycerol, 1, 4-butanediol and 1, 2-butanediol, and the mass content of the magnesium chloride in the organic solution of magnesium chloride is 2-10%.
  10. 10. The method of claim 9, wherein the alumina support is an alumina-based support for residuum hydroprocessing catalysts.
  11. 11. The method according to claim 10, wherein the alumina carrier is an alumina-based carrier for a residuum hydrodecarbonization catalyst.
  12. 12. The preparation method according to claim 9, wherein the mass content of magnesium chloride in the organic solution of magnesium chloride is 3% -8%.
  13. 13. The method according to claim 9, wherein the mass ratio of the alumina carrier to the organic solution of magnesium chloride is 1:5-1:50.
  14. 14. The method of claim 13, wherein the mass ratio of the alumina carrier to the organic solution of magnesium chloride is 1:10-1:30.
  15. 15. The method according to claim 9, wherein the closed heat treatment is carried out in an inert atmosphere at a pressure of 0.05 to 0.5 MPa and a treatment temperature of 160 to 230 ℃ for a treatment time of 4 to 24 hours.
  16. 16. The method according to claim 15, wherein the closed heat treatment is performed under inert atmosphere at a pressure of 0.1 to 0.4 MPa and a treatment temperature of 180 to 210 ℃ for a treatment time of 6 to 16 hours.
  17. 17. The method according to claim 9, wherein the activation treatment conditions are such that the treatment temperature is 120 to 350 ℃ and the treatment time is 2 to 10 hours, and the treatment atmosphere is an oxygen-containing atmosphere.
  18. 18. The method according to claim 17, wherein the activation treatment conditions are such that the treatment temperature is 160 to 320 ℃ and the treatment time is 2 to 8 hours.
  19. 19. The method according to claim 9, wherein the method for loading the modified alumina carrier with the hydrogenation active metal component adopts an impregnation method.
  20. 20. The method according to claim 19, wherein the drying and firing conditions after the impregnation are such that the drying temperature is 80 to 200 ℃ and the drying time is 2.0 to 10.0 hours, and the firing temperature is 300 to 600 ℃ and the firing time is 2.0 to 8.0 hours.

Description

Residual oil hydrodecarbonization catalyst and preparation method and application thereof Technical Field The invention belongs to the technical field of oil refining, and particularly relates to a residual oil hydrodecarbonization catalyst and a preparation method and application thereof. Background Gamma-alumina is generally used as a carrier for the residuum hydrotreating catalyst, the surface evenness of the carrier is low, the randomness of microscopic surface properties is too strong, the acid distribution is quite wide, the fine regulation and control of the active phase of the catalyst are very difficult, the metal distribution is quite uneven, the surface is rough, the area with more holes, the area with stronger acidity and higher dispersity of active metal is high, the catalytic activity is high but the stability is poor, otherwise, the surface is relatively flat, the area with fewer holes, the area with poorer acidity and lower dispersity of active metal is high, the catalyst stability is high but the activity is poor. In order to improve the usability of the residuum catalyst, various methods for modifying the alumina carrier have been proposed by researchers. CN201310499295.7 discloses a preparation method of alumina carrier of residual oil hydrodemetallization catalyst. The method comprises the steps of kneading a physical pore-expanding agent, pseudo-boehmite dry rubber powder, an extrusion aid and a peptizing agent into a plastic body, extruding strips, drying, then impregnating the dried carrier with the chemical pore-expanding agent by adopting unsaturated spraying, and finally drying and roasting the carrier impregnated with the chemical pore-expanding agent to obtain the residual oil hydrodemetallization catalyst alumina carrier. The alumina prepared by the method has an excellent pore canal structure, but the surface uniformity of the alumina is still not sufficiently improved, so that the dispersion effect of the active metal component is affected. CN201110322448.1 discloses a preparation method of alumina carrier of residuum hydrogenation catalyst. The method comprises the steps of taking activated carbon fibers with developed pore structures as a pore-enlarging agent after impregnating and adsorbing inorganic aluminum salt, kneading with an alumina precursor, forming, drying and roasting to obtain the alumina carrier. The alumina carrier obtained by the method has higher specific surface area, is favorable for removing most of heavy oil and residual oil, is favorable for keeping the activity of the hydrogenation catalyst and prolonging the running period, but has poorer surface uniformity as the alumina carrier, and is easy to cause aggregation of active metal at a certain position in the process of loading the active metal, thereby influencing the efficient utilization of the active metal. CN200410050726.2 discloses a method for preparing alumina carrier. The method comprises the steps of neutralizing acidic aluminum salt and alkaline aluminate, aging a neutralized material, filtering, washing, forming, drying and roasting to obtain the aluminum oxide carrier, wherein the aging is performed at a temperature higher than the neutralization temperature and the neutralization pH value. The alumina carrier prepared by the method has poor surface uniformity, and influences the load of subsequent active metals and the overall activity of the catalyst. Disclosure of Invention Aiming at the defects in the prior art, the invention provides a residual oil hydrodecarbonization catalyst and a preparation method and application thereof. The catalyst has good hydrogenation carbon residue performance, and is particularly suitable for processing boiling bed tail oil with poor oil quality. In gamma-alumina, there are mainly two types of Al, one is stable hexacoordinated framework aluminum, which shows a displacement of-10 to 30ppm in Al nuclear magnetism, and the other is less stable tetracoordinated non-framework aluminum, which shows a displacement of 40 to 80ppm in Al nuclear magnetism. The inventor finds that when the aluminum oxide surface is mainly hexacoordinated aluminum, the aluminum oxide surface can be smooth, the property is uniform, and the activity and the stability of the catalyst are improved. The inventor creatively introduces magnesium element into the surface of the aluminum oxide while removing non-framework aluminum, so that the surface of the aluminum oxide is smooth and has uniform properties, thereby realizing the invention. The invention provides a residual oil hydrodecarbonization catalyst, which comprises a modified alumina carrier and a hydrogenation active metal component, wherein the modified alumina carrier comprises alumina and a modification auxiliary agent, the modification auxiliary agent is magnesium, and hexacoordinated Al on the carrier accounts for 75% -95%, preferably 80% -90% of the total aluminum. Further, the mass content of magnesium in terms of MgO is 1%