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CN-118204103-B - Heavy oil hydrogenation catalyst and preparation method and application thereof

CN118204103BCN 118204103 BCN118204103 BCN 118204103BCN-118204103-B

Abstract

The invention discloses a heavy oil hydrogenation catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps of (1) preparing a first material; the method comprises the steps of (1) preparing an acid modified organic high molecular polymer, (3) preparing a second material, (4) preparing a third material, and (5) mixing the third material obtained in the step (4) with a soluble zirconium salt solution, uniformly mixing, drying and roasting to obtain a carrier, introducing an active metal component onto the carrier, and drying and roasting to obtain the heavy oil hydrogenation catalyst. The catalyst has a non-uniform pore distribution structure, has higher impurity removal capacity and holding capacity, has higher asphaltene conversion capacity, and is particularly suitable for ebullated bed hydrogenation processes or composite bed hydrogenation processes of a ebullated bed and a fixed bed combination.

Inventors

  • JIN HAO
  • SUN XIAODAN
  • ZHU HUIHONG
  • LV ZHENHUI
  • YANG GUANG

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. The preparation method of the heavy oil hydrogenation catalyst comprises the following steps: (1) Preparing a first material, namely mixing pseudo-boehmite powder, an organic high molecular polymer and a weakly basic compound uniformly to obtain the first material, wherein the weakly basic compound is one or a mixture of more than two of ammonia water, ammonium carbonate and ammonium bicarbonate; (2) Modifying the organic high molecular polymer by acid, and treating to obtain an acid modified organic high molecular polymer; (3) Preparing a second material, namely mixing pseudo-boehmite powder, the acid modified organic high molecular polymer obtained in the step (2) and the organic high molecular polymer aqueous solution subjected to heat treatment, and performing ball forming treatment to obtain the second material; (4) Preparing a third material, namely placing the second material obtained in the step (3) into a ball rolling machine, uniformly adding the first material obtained in the step (1) and the organic high polymer aqueous solution after heat treatment in the rolling process, and obtaining the third material after heat treatment of the obtained material; (5) Mixing the third material obtained in the step (4) with a soluble zirconium salt solution, uniformly mixing, performing primary drying and primary roasting to obtain a carrier, introducing an active metal component onto the carrier, and performing secondary drying and secondary roasting to obtain a heavy oil hydrogenation catalyst, wherein the active metal component is one or more of VIB group metal and/or VIII group metal; The preparation process of the organic high molecular polymer aqueous solution after heat treatment comprises the steps of adding the organic high molecular polymer into water, heating and mixing for 10-40 min at 60-100 ℃, and obtaining the organic high molecular polymer aqueous solution after heat treatment after the organic high molecular polymer is completely dissolved.
  2. 2. The method for producing a heavy oil hydrogenation catalyst according to claim 1, wherein the weakly basic compound in step (1) is aqueous ammonia.
  3. 3. The method for producing a heavy oil hydrogenation catalyst according to claim 1, wherein the mass ratio of the organic high molecular polymer to the weakly basic compound in the step (1) is 1:0.05 to 1:0.5.
  4. 4. The method for producing a heavy oil hydrogenation catalyst according to claim 1, wherein the total addition amount of the organic high molecular polymer and the weakly basic compound in the step (1) is 5 to 25% by weight based on the dry matrix amount of pseudo-boehmite powder.
  5. 5. The method for producing a heavy oil hydrogenation catalyst according to claim 1, wherein the total addition amount of the organic high molecular polymer and the weakly basic compound in the step (1) is 10 to 20% by weight based on the dry matrix amount of pseudo-boehmite powder.
  6. 6. The method for producing a heavy oil hydrogenation catalyst according to claim 1, wherein, in the step (1), when the organic high molecular polymer, the weakly basic compound and the pseudo-boehmite powder are mixed, the organic high molecular polymer and the weakly basic compound are mixed first and then mixed with the pseudo-boehmite powder.
  7. 7. The method for producing a heavy oil hydrogenation catalyst according to claim 1, wherein the organic high molecular polymer is starch.
  8. 8. The method for preparing a heavy oil hydrogenation catalyst according to claim 1 or 7, 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.
  9. 9. The method for preparing a heavy oil hydrogenation catalyst according to claim 1, wherein the starch is corn starch and/or potato starch, and the cellulose ether is methylcellulose.
  10. 10. The method for producing a heavy oil hydrogenation catalyst according to claim 1, wherein the acid in the step (2) is an inorganic acid or an organic acid, wherein the inorganic acid is one or a mixture of two or more of hydrochloric acid, sulfuric acid and nitric acid, and the organic acid is one or a mixture of two or more of citric acid, acetic acid, lactic acid, malic acid and tartaric acid.
  11. 11. The method for producing a heavy oil hydrogenation catalyst according to claim 1, wherein the acid in the step (2) is an inorganic acid or an organic acid, wherein the inorganic acid is hydrochloric acid, and the organic acid is citric acid.
  12. 12. The method for producing a heavy oil hydrogenation catalyst according to claim 1, wherein the modification treatment temperature of the organic high molecular polymer in the step (2) is 30 to 50 ℃ and the modification treatment time is 2 to 6 hours.
  13. 13. The method for preparing a heavy oil hydrogenation catalyst according to claim 1, wherein the concentration of the acid in the step (2) is 5-40 wt%, and the mass ratio of the organic high molecular polymer to the acid is 1:0.1-1:5.
  14. 14. The method for producing a heavy oil hydrogenation catalyst according to claim 1, wherein the amount of the acid-modified organic high molecular polymer added in the step (3) is 5 to 35% by weight based on the dry matrix amount of pseudo-boehmite powder.
  15. 15. The method for producing a heavy oil hydrogenation catalyst according to claim 1, wherein the amount of the acid-modified organic high molecular polymer added in the step (3) is 10 to 30% by weight based on the dry matrix amount of pseudo-boehmite powder.
  16. 16. The method for producing a heavy oil hydrogenation catalyst according to claim 1, wherein the mass concentration of the aqueous solution of the organic high molecular polymer after the heat treatment in the step (3) is 0.5wt% to 8.0wt%.
  17. 17. The method for producing a heavy oil hydrogenation catalyst according to claim 1, wherein the mass concentration of the aqueous solution of the organic high molecular polymer after the heat treatment in the step (3) is 1.0wt% to 5.0wt%.
  18. 18. The method for producing a heavy oil hydrogenation catalyst according to claim 1, wherein the mass ratio of the addition amount of the organic high molecular polymer aqueous solution after the heat treatment in the step (3) to the pseudo boehmite powder is 0.5 to 1.5.
  19. 19. The method for producing a heavy oil hydrogenation catalyst according to claim 1, wherein the mass ratio of the addition amount of the organic high molecular polymer aqueous solution after the heat treatment in the step (4) to the first material is 0.5 to 1.2.
  20. 20. The method for producing a heavy oil hydrogenation catalyst according to claim 1, wherein the heat treatment temperature in step (4) is 100 to 300 ℃ and the heat treatment time is 3 to 12 hours.

Description

Heavy oil hydrogenation catalyst and preparation method and application thereof Technical Field The invention belongs to the field of petroleum refining, relates to a hydrogenation catalyst and a preparation method thereof, and particularly relates to a heavy oil hydrogenation catalyst and a preparation method thereof. Background With the continuous exploitation of petroleum, the imported petroleum in China is continuously heavier and inferior, wherein the proportion of heavy oil is increased year by year. How to realize the full utilization of heavy oil is a key for solving the energy problem and improving the energy utilization efficiency, and is a problem of wide attention of various large refineries. The existing heavy oil treatment technology mainly comprises a heavy oil hydrogenation technology and a delayed coking technology, wherein the hydrogenation technology has higher economic benefit. The heavy oil hydrogenation technology which has been industrialized at present mainly comprises a fixed bed hydrogenation technology and a boiling bed hydrogenation technology. The large continuous petrochemical institute provides a composite bed hydrogenation technology, namely a fluidized bed is combined with a fixed bed, the fluidized bed is used as a pre-protection reactor of the fixed bed, the characteristic that the fluidized bed can be added and discharged on line is utilized, the operation period of the fixed bed can reach more than 30 months, the operation period of a fixed bed device is greatly prolonged, and considerable economic benefits are brought to refineries. With the gradual increase of fuel standards and the gradual stricter environmental protection emission, the hydrogenation technology has higher requirements, and the improvement of the catalyst activity is key to achieving the aim. CN201810893969.4 discloses a method for preparing a boiling bed hydrotreating catalyst. The method comprises the steps of (1) kneading pseudo-boehmite and basic ammonium aluminum carbonate for adsorbing a carbon precursor solution to form a formed product, drying the formed product, (2) spraying and dipping the material obtained in the step (1) by using a solution containing a carbon precursor, drying and roasting the sprayed and dipped material to obtain an alumina carrier, and (3) dipping the alumina carrier obtained in the step (2) by using a dipping liquid containing a hydrogenation active component, and drying and roasting the dipped alumina carrier to obtain the ebullated bed hydrotreating catalyst. The catalyst prepared by the method has higher strength and wear resistance, and is particularly suitable for the heavy oil ebullated bed hydrotreatment process. However, the reaming effect of the carbon-containing precursor is not strong, the metal capacity of the catalyst needs to be improved, the effect of the active metal and the alumina carrier is strong, and the utilization rate is not high. CN103785400a discloses a preparation method of a high-activity residuum hydrodemetallization catalyst. The method comprises the steps of firstly carrying out hydrothermal carbonization treatment on an alumina carrier, drying, loading active components Mo and Ni, then roasting under nitrogen atmosphere, and roasting under air atmosphere to finally obtain the catalyst. The carbonized surface of the alumina carrier produces a layer of carbon deposit, so that the active components have weaker action with the carrier, are more uniformly distributed on the carrier, are easy to completely vulcanize, and obviously improve the demetallization and desulfurization activities of the catalyst. However, the catalyst prepared by the method has weak effect on the carrier, and the metal capacity is required to be improved, which directly affects the long-period stability of the catalyst. Disclosure of Invention The invention provides a heavy oil hydrogenation catalyst and a preparation method and application thereof. The provided catalyst has a non-uniform pore distribution structure, has higher impurity removal capacity and holding capacity, has higher asphaltene conversion capacity, is particularly suitable for a fluidized bed hydrogenation process or a composite bed hydrogenation process of combining a fluidized bed and a fixed bed, can provide high-quality raw materials for downstream devices, and ensures long-period stable operation of the devices. The first aspect of the invention provides a preparation method of a heavy oil hydrogenation catalyst, which comprises the following steps: (1) Preparing a first material, namely mixing pseudo-boehmite powder, an organic high molecular polymer and a weak alkaline compound uniformly to obtain the first material; (2) Modifying the organic high molecular polymer by acid, and treating to obtain an acid modified organic high molecular polymer; (3) Preparing a second material, namely mixing pseudo-boehmite powder, the acid modified organic high molecular polymer obtained in the step (2) and th