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CN-118179546-B - Ebullated bed hydrotreating catalyst and preparation method and application thereof

CN118179546BCN 118179546 BCN118179546 BCN 118179546BCN-118179546-B

Abstract

The invention discloses a fluidized bed hydrotreating catalyst and a preparation method and application thereof, the hydrotreating catalyst comprises a hydrogenation active metal component, a carrier and optionally auxiliary agent phosphorus, wherein the carrier is a carbon-containing alumina composite carrier. The preparation method comprises the following steps of (1) balling and forming a first pseudo-boehmite powder to obtain a first carrier precursor, (2) treating the first carrier precursor, an additive and an aqueous solution of an organic high-molecular polymer B to obtain a second carrier precursor, (3) treating the second carrier precursor, the second pseudo-boehmite powder and an acidic solution to obtain a third carrier precursor, (4) carrying out low-temperature heat treatment on the third carrier precursor to obtain a fourth carrier precursor, (5) mixing the fourth carrier precursor with an auxiliary agent solution, drying and roasting to obtain an auxiliary agent modified carbon-containing alumina composite carrier, and (6) introducing a hydrogenation active metal component onto the composite carrier, drying and roasting to obtain the ebullated bed hydrogenation catalyst.

Inventors

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

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
20221214

Claims (20)

  1. 1. A method for preparing a ebullated bed hydroprocessing catalyst, the method comprising: (1) Performing ball forming treatment on the first pseudo-boehmite powder to obtain a first carrier precursor; (2) The preparation method comprises the steps of putting a first carrier precursor into a ball rolling machine, uniformly adding an additive and an aqueous solution of an organic high molecular polymer B subjected to heat treatment in a rolling process, and obtaining a second carrier precursor after treatment, wherein the additive is a mixture of an organic high molecular polymer A and a nitrogenous weak alkali compound, the organic high molecular polymer A is one or more of starch, cellulose ether and flour, the nitrogenous weak alkali compound is one or more of ammonia water, ammonium carbonate and ammonium bicarbonate, the organic high molecular polymer B is one or more of starch, cellulose ether and flour, and the organic high molecular polymer B is heated and mixed for 10-40 min at 60-100 ℃ until the organic high molecular polymer B is completely dissolved, so that an aqueous solution of the organic high molecular polymer B subjected to heat treatment is obtained; (3) The second carrier precursor is put into a ball rolling machine, second pseudo-boehmite powder and an acidic solution are uniformly added in the rolling process, and a third carrier precursor is obtained after treatment; (4) Carrying out low-temperature heat treatment on the third carrier precursor to obtain a fourth carrier precursor, wherein the low-temperature heat treatment temperature is 100-300 ℃; (5) Mixing the fourth carrier precursor with a soluble ferric salt solution, uniformly mixing, and roasting under an inert atmosphere to obtain an auxiliary agent metal component modified carbon-containing alumina composite carrier; (6) Introducing a hydrogenation active metal component which is one or more of VIB group metal and/or VIII group metal into the composite carrier obtained in the step (5), introducing P when introducing the hydrogenation active metal component, and further drying and roasting to obtain the ebullated bed hydrotreating catalyst.
  2. 2. The method for preparing the ebullated bed hydrotreating catalyst according to claim 1, wherein the first pseudo-boehmite powder has a specific surface area of 300-550 m 2 /g, a pore volume of 0.4-1.0 mL/g, an average pore diameter of 4-12 nm, and a pore volume of <10nm pores accounting for 60% -75% of the total pore volume after roasting at 550-750 ℃.
  3. 3. The method for preparing a ebullated bed hydroprocessing catalyst according to claim 1, wherein the ball forming process in step (1) is one or more of extrusion ball casting, roll forming and spray drying.
  4. 4. The method for producing an ebullated bed hydroprocessing catalyst according to claim 1, wherein the particle size of the first carrier precursor in step (1) is 0.1 to 1.0mm.
  5. 5. The method for preparing a catalyst for ebullated-bed hydrotreatment according to claim 1, wherein the organic high molecular polymer A in the step (2) is starch.
  6. 6. The method for preparing the ebullated bed hydroprocessing catalyst according to claim 1, wherein the starch is one or more of mung bean starch, tapioca starch, sweet potato starch, wheat starch, water chestnut starch, lotus root starch and corn starch, and the cellulose ether is at least one of methylcellulose, hydroxyethyl methylcellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose and phenyl cellulose.
  7. 7. The method for preparing the ebullated-bed hydrotreating catalyst according to claim 1, wherein the starch is corn starch and/or potato starch, and the cellulose ether is methylcellulose.
  8. 8. The method for producing a ebullated-bed hydrotreating catalyst according to claim 1, wherein the nitrogen-containing weak alkali compound in step (2) is aqueous ammonia.
  9. 9. The method for preparing a ebullated bed hydrotreating catalyst according to claim 1, wherein the mass ratio of the organic high molecular polymer A to the nitrogen-containing weak base compound in the step (2) is 1:0.05 to 1:0.5.
  10. 10. The method for preparing a catalyst for ebullated-bed hydrotreatment according to claim 1, wherein the organic high molecular polymer B in the step (1) is starch.
  11. 11. The method for producing a ebullated-bed hydrotreating catalyst according to claim 1, wherein the concentration of the aqueous solution of the organic high molecular polymer B after heat treatment in the step (2) is 0.5wt% to 5wt%.
  12. 12. The method for producing a ebullated-bed hydrotreating catalyst according to claim 1, wherein the concentration of the aqueous solution of the organic high-molecular polymer B after heat treatment in the step (2) is 1wt% to 3wt%.
  13. 13. The method for preparing the ebullated bed hydrotreating catalyst according to claim 1, wherein the second pseudo-boehmite powder in the step (3) is calcined at 550 to 750 ℃ and has the characteristics of a specific surface area of 200 to 320m 2 /g, a pore volume of 0.8 to 1.2mL/g, an average pore diameter of 10 to 30nm, and a pore volume of >10nm pores accounting for 60 to 75% of the total pore volume.
  14. 14. The method for preparing the ebullated bed hydrotreating catalyst according to claim 1, wherein the acidic solution in the step (3) is one or more of acetic acid solution, nitric acid solution and oxalic acid solution, the concentration of the acidic solution is 0.1wt% to 8wt%, and the mass ratio of the addition amount of the acidic solution to the dry base of the second pseudo-boehmite powder is 0.8 to 1.5.
  15. 15. The method for preparing the ebullated bed hydrotreating catalyst according to claim 1, wherein the acidic solution in the step (3) is a nitric acid solution, the concentration of the acidic solution is 0.3wt% to 5wt%, and the mass ratio of the addition amount of the acidic solution to the second pseudo-boehmite powder is 0.8 to 1.5.
  16. 16. The method for preparing the ebullated bed hydrotreating catalyst according to claim 1, wherein the low temperature heat treatment temperature in the step (4) is 150 to 250 ℃, and the low temperature heat treatment time is 1 to 8 hours.
  17. 17. The method for preparing a ebullated bed hydroprocessing catalyst according to claim 16, wherein the low temperature heat treatment time is 3 to 6 hours.
  18. 18. The method for producing an ebullated bed hydroprocessing catalyst according to claim 1, wherein the soluble iron salt in step (5) is one or more of ferric nitrate, ferric chloride and ferric sulfate.
  19. 19. The method for preparing a ebullated bed hydroprocessing catalyst according to claim 1, wherein the drying temperature in step (5) is 60 to 90 ℃.
  20. 20. The method for preparing the ebullated bed hydrotreating catalyst according to claim 1, wherein the step (5) is performed under an inert atmosphere, the inert atmosphere is one or more of nitrogen, helium, neon, argon, krypton and xenon, the calcination temperature is 600-900 ℃, and the calcination time is 1-5 hours.

Description

Ebullated bed hydrotreating catalyst and preparation method and application thereof Technical Field The invention belongs to the technical field of catalytic materials, relates to a hydrogenation catalytic material and a preparation method thereof, and particularly relates to a ebullated bed hydrogenation catalyst and a preparation method thereof. Background Residuum hydrogenation is the most effective method for solving heavy oil deep processing. The existing residual oil hydrogenation technology, the fixed bed hydrogenation technology is relatively most mature and the application is most extensive. But the adaptability to raw materials is poor, so that the limitation of the method is gradually highlighted. The boiling bed residuum hydrotreatment technology has the advantages of strong adaptability to raw oil, basically no pressure drop in the reactor, uniform temperature distribution, good mass transfer and heat transfer, on-line catalyst addition and discharge, high catalyst utilization rate, long operation period, flexible device operation and the like. The catalyst consumption is high during operation of the ebullated bed apparatus, and therefore, higher requirements are placed on the performance and cost of the catalyst. At present, the most widely used carrier in the heavy oil hydrogenation field is alumina, which has the advantages of good mechanical property and low price, but also has the disadvantages of low specific surface area, strong action with active metal and the like. The activated carbon has the advantages of low price, stable property, rich pore structure, large specific surface area, adjustable surface chemical property and the like, and is widely and widely applied to catalytic reaction. In the residual oil hydrogenation process, the activated carbon can selectively adsorb macromolecules such as asphaltene, disperse coke precursors and inhibit reaction coke to a certain extent. Therefore, the composite carrier of the alumina and the activated carbon has wide application prospect. Patent CN201510043976.1 discloses a mesoporous carbon material loaded with alumina and an application method thereof, and the mesoporous carbon material comprises the following steps of dissolving starch and aluminum sulfate in deionized water, ultrasonically mixing, dropwise adding colloidal silicon dioxide at a speed of 1-2 drops/second under the condition of heating and stirring, stirring for 20min under the condition of 110-150 ℃ oil bath, naturally cooling, drying and carbonizing. Stirring the carbonized substance with 20-30wt% sodium hydroxide solution under water bath condition, filtering, washing, and drying to obtain the mesoporous carbon material loaded with alumina. The specific surface of the mesoporous carbon is 400-900 m 2/g, the average pore diameter is 4-8nm, the pore volume is 0.5-1.0cm 3/g, and the loading amount of alumina is 0.05-0.2g/g of the mesoporous carbon material. The patent uses carbon as a main component, and the obtained material has smaller pore diameter and is not suitable for the boiling bed residual oil hydrogenation process. Patent CN104096584B discloses a residuum hydrogenation catalyst and a preparation method thereof. The catalyst takes a mixed body of alumina and active carbon as a carrier, and the active components are Ni 2P、MoO3 and/or WO 3 and/or CoO and/or NiO. A small amount of activated carbon is introduced into the alumina, so that the reaction between Ni 2 P active components and the alumina in the generation process is reduced, the dispersibility of the Ni 2 P active components is improved, the high activity of Ni 2 P and the carrier advantage of an alumina-activated carbon mixed body are fully exerted, and the impurity removal capability of the catalyst is improved. However, due to the introduction of the active carbon in the catalyst carrier, the pore diameter of the carrier becomes smaller, impurities in the raw oil are removed outside the catalyst, the utilization rate of active metals in the catalyst is lower, uneven distribution of the impurity metals on the catalyst can be caused in long-period operation of the catalyst, pore canal blockage is caused, and the catalyst is deactivated. Disclosure of Invention Aiming at a plurality of problems existing in the prior art, the invention mainly aims to provide a boiling bed hydrotreating catalyst and a preparation method and application thereof. The catalyst has uneven pore distribution, and is especially suitable for the hydrogenation field of heavy oil and residual oil. The prepared catalyst not only has higher hydrodemetallization activity and metal-containing impurity capacity, but also has higher hydrodesulphurization activity, and the catalyst is not easy to be blocked by metal-containing impurities, so that the stability of the catalyst in the long-period running process of the device can be ensured. The first aspect of the invention provides a preparation method of an ebullated bed hydrotreating catalyst