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CN-120644241-B - Hydrotreating catalyst and preparation method and application thereof

CN120644241BCN 120644241 BCN120644241 BCN 120644241BCN-120644241-B

Abstract

The invention discloses a hydrotreating catalyst and a preparation method and application thereof. The method comprises the steps of supersaturating and immersing an alumina-based carrier in impregnating solution containing dopamine, a protective agent and hydrogenation active metals, adjusting the pH value of the system, enabling the dopamine to self-polymerize on the surface of a pore canal of the alumina-based carrier, and then washing and heat treating the carrier to obtain the hydrogenation catalyst. The hydrogenation catalyst prepared by the method has obviously improved desulfurization and denitrification activities and stability.

Inventors

  • LIU YI
  • YANG ZHANLIN
  • WANG HUIGANG
  • DING SIJIA
  • JIANG HONG

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
20240313

Claims (20)

  1. 1. A method of preparing a hydrotreating catalyst comprising: Supersaturating an alumina-based carrier into impregnating solution containing dopamine, a protective agent and hydrogenation active metal, regulating the pH value of the system to enable dopamine to be self-polymerized on the surface of a pore canal of the alumina-based carrier, washing, and drying under the condition that the decomposition temperature of the generated polydopamine is not exceeded to obtain a hydrotreating catalyst; in the impregnating solution, the addition amount of dopamine accounts for 2-40 wt% based on the mass of the alumina-based carrier; The protective agent is one or more of N-isopropyl acrylamide sodium p-styrene sulfonate, methyl sodium allyl sulfonate, isopentenol, 3-methyl-3-butene-1-ol and allyl alcohol; in the impregnating solution, the addition amount of the protective agent accounts for 0.5-8wt% of the alumina-based carrier; The pH value regulator for regulating the pH value of the system is one or more selected from ethylenediamine, ammonium carbonate, diethanolamine, triethanolamine and Tris buffer.
  2. 2. The preparation method of the alumina-based carrier according to claim 1, wherein the alumina-based carrier has the following properties of pore volume of 0.3-1.5 mL/g and specific surface area of 150-450 m 2 /g.
  3. 3. The preparation method according to claim 1, wherein the addition amount of dopamine in the impregnating solution is 4-24 wt% based on the mass of the alumina-based carrier.
  4. 4. The preparation method of claim 1, wherein the protective agent is one or more of sodium N-isopropyl acrylamide sodium p-styrene sulfonate, sodium methallyl sulfonate and sodium allyl sulfonate.
  5. 5. The preparation method according to claim 1 or 4, wherein the addition amount of the protective agent in the impregnation liquid is 1wt% to 5wt% of the alumina-based carrier.
  6. 6. The method of claim 1, wherein the hydrogenation-active metal comprises a group VIII metal and a group VIB metal.
  7. 7. The method according to claim 6, wherein the group VIII metal is Ni and/or Co and the group VIB metal is Mo.
  8. 8. The preparation method according to claim 1, wherein the addition amount of the hydrogenation active metal in terms of oxide is 12-36 wt% based on the mass of the alumina-based carrier in the impregnation liquid.
  9. 9. The preparation method according to claim 8, wherein the addition amount of the hydrogenation active metal in terms of oxide is 18-32 wt% based on the mass of the alumina-based carrier in the impregnation liquid.
  10. 10. The preparation method of claim 1, wherein the impregnating solution further comprises an auxiliary component, the auxiliary component is one or more selected from phosphorus, titanium, silicon, zinc, copper, zirconium, boron, fluorine, lanthanum, cerium and vanadium, and the addition amount of the auxiliary component in the impregnating solution is 0.5-5 wt% of the alumina-based carrier.
  11. 11. The preparation method of claim 10, wherein the addition amount of the auxiliary agent in the impregnation liquid is 1-3 wt% of the alumina-based carrier.
  12. 12. The preparation method according to claim 1, wherein the volume of the impregnating solution is 1.5-4.5 times the saturated water absorption capacity of the alumina-based carrier.
  13. 13. The method according to claim 12, wherein the volume of the impregnating solution is 1.8 to 4.0 times the saturated water absorption capacity of the alumina-based carrier.
  14. 14. The preparation method according to claim 1, wherein the dipping temperature is 10-80 ℃ and the dipping time is 1-30 h.
  15. 15. The method according to claim 14, wherein the temperature of the impregnation is 30-60 ℃ and the impregnation time is 5-20 hours.
  16. 16. The preparation method of claim 1, wherein the system pH value is adjusted by immersing the carrier in the immersion liquid, and after the shaking lasts for 5-10min, adding the pH value regulator to continue shaking until the system pH value reaches 8-10.
  17. 17. The method of claim 16, wherein the pH of the system is increased by at least 0.5 after the pH adjustor is added compared to before the pH adjustor is not added.
  18. 18. The preparation method according to claim 1, wherein the drying temperature is 30 ℃ to 200 ℃ and the drying time is 0.5h to 20h.
  19. 19. The method according to claim 18, wherein the drying temperature is 50 to 120 ℃ and the drying time is 2 to 10 hours.
  20. 20. The preparation method according to claim 1, wherein the hydrotreating catalyst prepared by the method has a content of group VIII metal of 1wt% to 10wt% in terms of oxide and a content of group VIB metal of 10wt% to 25wt% in terms of oxide based on the mass of the alumina-based carrier.

Description

Hydrotreating catalyst and preparation method and application thereof Technical Field The invention belongs to the technical field of catalysis, and particularly relates to a hydrotreating catalyst, and a preparation method and application thereof. Background Regardless of the context and pace of future energy conversion, fossil fuels, typified by petroleum, continue to be a major source of energy in the next decades. Therefore, hydrotreating catalysts for oil cleaning will still be one of the most important catalysts in the market. Gamma-Al 2O3 has been widely used in the preparation of hydrofining catalysts, hydrocracking catalysts because of its suitable mechanical strength, acidity and pore structure, using it as a carrier or modifying it. With increasing environmental regulations, the development of highly active hydrotreating catalysts becomes necessary, and the requirements for performance and stability thereof become more complex. Increasing the dispersion and loading of active components in the catalyst is one of the effective ways to develop high performance catalysts. The interaction force between the active metal on the surface of the pure Al 2O3 and the carrier is large, and the strong interaction force can lead to strong interaction between the active metal in the finally prepared catalyst and the carrier, which is finally unfavorable for the full vulcanization of the active metal oxide in the catalyst, thereby leading to the unsatisfactory activity of the catalyst. At present, the carrier can be modified by adding an organic auxiliary agent, the acidic functional groups can fully occupy coordination unsaturated centers on the surface of the alumina of the carrier, so that strong interaction between metal and the carrier is effectively prevented, the number of generated active centers of the catalyst is increased, or the same effect can be achieved by coating a carbon layer on the surface of the alumina. CN108067243B discloses a hydrotreating catalyst, its preparation method and application. The method comprises the steps of adopting a nitrogenous organic acid solution or an aromatic carboxylic acid solution to modify an alumina carrier, drying at a low temperature, then dipping an active component solution or an active metal and an auxiliary agent, and carrying out high-temperature heat treatment after dipping to prepare the hydrotreating catalyst. CN107442126B discloses a method for preparing a hydrotreating catalyst. The preparation method of the carbon-containing modified alumina-based carrier comprises the steps of sequentially or simultaneously introducing water-soluble silicone oil, a soluble auxiliary agent and a carbon precursor into the alumina-based carrier, and carrying out heat treatment to obtain the carbon-containing modified alumina-based carrier. CN110935464B discloses a method for preparing a carbon-containing hydrodemetallization catalyst. The method comprises the steps of immersing alumina powder in ammonium bicarbonate aqueous solution for sealing heat treatment, carrying out solid-liquid separation, drying solid materials, immersing the dried materials in carbon-containing precursor solution I, carrying out solid-liquid separation on the immersed materials, drying the solid materials to obtain modified rod-shaped alumina clusters, kneading the modified alumina clusters with pseudo-boehmite for molding, drying the molded products, spraying and immersing the molded products in carbon-containing precursor solution II, drying, carrying out carbonization treatment and microwave treatment in sequence under an inert atmosphere to obtain a carbon-containing alumina carrier, and loading hydrogenation active components on the carbon-containing alumina carrier to obtain the hydrodemetallization catalyst. The disadvantage of the above technology is that the acting force between the active component and the carrier is possibly too weak, so that the active component is easy to flow and aggregate in the reaction process, the active particles are continuously enlarged, the dispersity of the active component in the catalyst is reduced, the activity of the catalyst is continuously reduced, and the service life is greatly shortened. Thus, there is a need for a hydrotreating catalyst that combines "weakening the metal-support forces" and "preventing metal agglomeration" that would greatly aid in improving its activity and stability. Disclosure of Invention In order to overcome the defects in the prior art, the invention provides a hydrotreating catalyst, and a preparation method and application thereof. The hydrogenation catalyst prepared by the method has obviously improved desulfurization and denitrification activities and stability. The first aspect of the present invention provides a method for producing a hydrotreating catalyst, comprising: supersaturating an alumina-based carrier into impregnating solution containing dopamine, a protective agent and hydrogenation active metal, regulati