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CN-118204102-B - Hydrodesulfurization catalyst and preparation method and application thereof

CN118204102BCN 118204102 BCN118204102 BCN 118204102BCN-118204102-B

Abstract

The invention discloses a hydrodesulfurization catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps of (1) modifying an organic high molecular polymer by acid, and then mixing the modified organic high molecular polymer with pseudo-boehmite powder to obtain a first mixed material; the method comprises the steps of (1) mixing amorphous silica-alumina with an aqueous solution of a heat-treated organic high-molecular polymer, forming the mixture by ball forming to obtain a first precursor, (3) preparing a second precursor, (4) preparing a second mixed material, (5) preparing a third precursor, (6) preparing a carrier, introducing a hydrogenation active metal component, drying and roasting to obtain the hydrodesulfurization catalyst. The prepared catalyst has a non-uniform pore distribution structure, so that the catalyst not only has higher impurity removal capacity, containing capacity and asphaltene conversion capacity, but also can reduce the sediment content in the generated oil, and is particularly suitable for a hydrogenation process for directly producing low-sulfur marine fuel oil by boiling bed heavy oil hydrogenation.

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. A method for preparing a hydrodesulfurization catalyst, comprising the steps of: (1) Modifying the organic high molecular polymer by adopting acid, and further mixing the acid modified organic high molecular polymer obtained after treatment with pseudo-boehmite powder to obtain a first mixed material; (2) Mixing amorphous silica-alumina and an aqueous solution of a heat-treated organic high molecular polymer, and performing ball forming treatment to obtain a first precursor; (3) Putting the first precursor obtained in the step (2) into a ball rolling machine, uniformly adding the first mixed material obtained in the step (1) and the heat-treated organic high polymer aqueous solution in the rolling process, and treating to obtain a second precursor; (4) Mixing an organic high molecular polymer, a weakly basic compound and pseudo-boehmite powder to obtain a second mixed material, wherein the weakly basic compound is one or a mixture of more than two of ammonia water, ammonium carbonate and ammonium bicarbonate; (5) Putting the second precursor obtained in the step (3) into a ball rolling machine, uniformly adding the second mixed material obtained in the step (4) and the heat-treated organic high polymer aqueous solution in the rolling process, and treating to obtain a third precursor; (6) Carrying out heat treatment on the third precursor obtained in the step (5), mixing the material obtained after the heat treatment with a soluble zinc salt solution, and drying and roasting to obtain a carrier; (7) The carrier obtained in the step (6) is introduced with hydrogenation active metal components, and then is dried and roasted to obtain a hydrodesulfurization catalyst, wherein the hydrogenation active metal components are one or more of VIB group metal and/or VIII group metal; wherein the organic high molecular polymer is one or more of starch, cellulose ether and flour; the preparation method of the aqueous solution of the heat-treated organic high-molecular polymer 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 aqueous solution of the heat-treated organic high-molecular polymer after the organic high-molecular polymer is completely dissolved.
  2. 2. The method for preparing the hydrodesulfurization catalyst according to claim 1, wherein the organic high molecular polymer is modified by an acid in the step (1), and the acid-modified organic high molecular polymer is obtained by cooling, optionally washing with water and drying after the modification.
  3. 3. The method for preparing a hydrodesulfurization catalyst according to claim 1, wherein the modification treatment temperature of the organic high molecular polymer with an acid in the step (1) is 30-50 ℃ and the modification treatment time is 2-6 hours.
  4. 4. The method for preparing a hydrodesulfurization catalyst according to claim 1, wherein the acid in the step (1) is an inorganic acid or an organic acid, the organic acid is one or a mixture of two or more of citric acid, acetic acid, lactic acid, malic acid and tartaric acid, and the inorganic acid is one or a mixture of two or more of hydrochloric acid, sulfuric acid and nitric acid.
  5. 5. The method for preparing a hydrodesulfurization catalyst according to claim 1, wherein the acid in the step (1) is an inorganic acid or an organic acid, the organic acid is citric acid, and the inorganic acid is hydrochloric acid.
  6. 6. The method for preparing a hydrodesulfurization catalyst according to claim 1, characterized in that the organic high molecular polymer is starch.
  7. 7. The method for preparing the hydrodesulfurization 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.
  8. 8. The process for preparing a hydrodesulfurization catalyst according to claim 1 or 7, characterized in that the starch is corn starch and/or potato starch and the cellulose ether is methylcellulose.
  9. 9. The method for preparing a hydrodesulfurization catalyst according to claim 1, wherein the pseudo-boehmite powder obtained in the step (1) is calcined at 550-750 ℃ and has a specific surface area of 280-320 m 2 /g and a pore volume of 0.9-1.2 mL/g.
  10. 10. The method for producing a hydrodesulfurization catalyst according to claim 1, characterized in that the pseudo-boehmite powder in step (1) is the same as or different from that in step (4).
  11. 11. The method for preparing a hydrodesulfurization catalyst according to claim 1, wherein the addition amount of the acid-modified organic high molecular polymer in the step (1) is 5 to 35% by weight based on the dry matrix amount of pseudo-boehmite powder.
  12. 12. The method for preparing a hydrodesulfurization catalyst according to claim 1, wherein the addition amount of the acid-modified organic high molecular polymer in the step (1) is 10 to 30% by weight based on the dry matrix amount of pseudo-boehmite powder.
  13. 13. The method for preparing a hydrodesulfurization catalyst according to claim 1, wherein the amorphous silica-alumina in the step (2) has a specific surface area of 250 to 320m 2 /g, a pore volume of 0.7 to 1.0mL/g and a silica content of 10 to 50%.
  14. 14. The method for producing a hydrodesulfurization catalyst according to claim 1, characterized in that the concentration of the aqueous solution of the heat-treated organic high-molecular polymer in the step (2) is 0.5wt% to 8.0wt%.
  15. 15. The method for producing a hydrodesulfurization catalyst according to claim 1, characterized in that the concentration of the aqueous solution of the heat-treated organic high-molecular polymer in the step (2) is 1.0wt% to 5.0wt%.
  16. 16. The method for producing a hydrodesulfurization catalyst according to claim 1, characterized in that the weakly basic compound in the step (4) is aqueous ammonia.
  17. 17. The method for producing a hydrodesulfurization catalyst according to claim 1, characterized in that the concentration of the aqueous solution of the weakly basic compound in the step (4) is 2wt% to 40wt%.
  18. 18. The method for producing a hydrodesulfurization catalyst according to claim 1, characterized in that the concentration of the aqueous solution of the weakly basic compound in the step (4) is 5wt% to 35wt%.
  19. 19. The method for preparing a hydrodesulfurization catalyst according to claim 1, wherein the total addition amount of the organic high molecular polymer and the weakly basic compound in the step (4) is 5 to 25% by weight based on the dry matrix amount of pseudo-boehmite.
  20. 20. The method for preparing a hydrodesulfurization catalyst according to claim 1, wherein the total addition amount of the organic high molecular polymer and the weakly basic compound in the step (4) is 10 to 20% by weight based on the dry matrix amount of pseudo-boehmite.

Description

Hydrodesulfurization catalyst and preparation method and application thereof Technical Field The invention belongs to the technical field of petroleum refining, relates to a hydrogenation catalyst and a preparation method thereof, and in particular relates to a hydrodesulfurization catalyst and a preparation method thereof. Background The sulfur content of the fuel oil used by the global ship cannot be higher than 0.5% from 1 month 1 day 2020. At present, low-sulfur marine fuel oil is mainly produced by adopting a fixed bed residual oil hydrogenation technology, and the produced oil can be directly used as low-sulfur heavy marine fuel oil or blending component, but the technology has higher requirements on the quality of raw oil and higher processing cost. In recent years, the ebullated bed hydrogenation technology has rapidly developed, and can take inferior and low-cost heavy oil as a raw material, and the generated hydrogenated heavy oil can be used as low-sulfur marine fuel oil or blending component, so that the production cost is lower, and the economic benefit is remarkable, but the problem is that the sulfur content of the hydrogenated heavy oil needs to be further reduced so as to increase the blending proportion. In order to enable low-sulfur marine fuel oils or blending components to be produced at low cost by both fixed bed and ebullated bed hydrogenation technologies, there is a need to develop new generation high desulfurization activity hydrogenation catalysts that place higher demands on the hydrodesulfurization activity of the catalyst and the asphaltene conversion capability. CN105772005A discloses a hydrogenation catalyst, a preparation method thereof and a method for hydrodesulfurizing heavy oil. The hydrogenation catalyst comprises a carrier and active metal components, wherein the active metal components are distributed in a double-layer manner along the radial direction of the carrier, the active metal components of a core layer are CoO and MoO 3, and the active metal components of a shell layer are NiO and MoO 3 and/or WO 3. The hydrogenation catalyst provided by the invention has higher hydrogenation demetallization, desulfurization, carbon residue removal and denitrification activities. However, the conversion capability of the catalyst to macromolecules such as asphaltene needs to be further improved. CN104646008a discloses a hydrodesulphurization demetallization catalyst for inferior heavy oil and a preparation method thereof. The catalyst takes alumina as a carrier and Ni-Mo as an active component, and the average pore diameter of the catalyst gradually increases from the center to the outer surface along the radial direction of the catalyst particles. The catalyst is prepared through treating the shaped and roasted carrier particles with acid solution with continuously increased concentration. The catalyst has large surface pore opening, wide pore canal, excellent diffusion performance, high hydrodesulfurization and demetallization activity and high activity stability. However, the active metal of the catalyst is still loaded by adopting a conventional impregnation method, so that the active metal has stronger interaction with the alumina carrier, the utilization rate of the active metal is not high, and the further improvement of the activity of the catalyst is limited. Disclosure of Invention The invention mainly aims to provide a hydrodesulfurization catalyst and a preparation method and application thereof. The prepared catalyst has a non-uniform pore distribution structure, so that the catalyst not only has higher impurity removal capacity, containing capacity and asphaltene conversion capacity, but also can reduce the sediment content in the generated oil, and is particularly suitable for a hydrogenation process for directly producing low-sulfur marine fuel oil by boiling bed heavy oil hydrogenation. The first aspect of the present invention provides a method for preparing a hydrodesulfurization catalyst, comprising the steps of: (1) Modifying the organic high molecular polymer by adopting acid, and further mixing the acid modified organic high molecular polymer obtained after treatment with pseudo-boehmite powder to obtain a first mixed material; (2) Mixing amorphous silica-alumina and an aqueous solution of a heat-treated organic high molecular polymer, and performing ball forming treatment to obtain a first precursor; (3) Putting the first precursor obtained in the step (2) into a ball rolling machine, uniformly adding the first mixed material obtained in the step (1) and the heat-treated organic high polymer aqueous solution in the rolling process, and treating to obtain a second precursor; (4) Mixing an organic high molecular polymer, a weak alkaline compound and pseudo-boehmite powder to obtain a second mixed material; (5) Putting the second precursor obtained in the step (3) into a ball rolling machine, uniformly adding the second mixed material obtained in the step