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CN-118847134-B - Preparation method of catalyst for hydrodenitrogenation and carbon residue removal of heavy oil

CN118847134BCN 118847134 BCN118847134 BCN 118847134BCN-118847134-B

Abstract

The invention discloses a preparation method of a catalyst for hydrodenitrogenation and carbon residue removal of heavy oil, which comprises the following steps of (1) mixing pseudo-boehmite powder, boron-containing micron spherical active carbon and water into slurry, then carrying out solid-liquid separation, drying solid phase materials, kneading, forming and drying, roasting in an inert atmosphere to obtain an alumina carrier precursor, carrying boron to obtain a boron modified alumina carrier precursor, (2) adding the boron modified alumina carrier precursor and an epoxypropane aqueous solution into a closed autoclave, reacting for 1-4 hours at 60-100 ℃, then heating to 110-180 ℃ for 2-6 hours, drying and roasting to obtain an alumina carrier, and carrying out hydrogenation active components to obtain a catalyst product. The catalyst prepared by the method has vermiform surface particle morphology, pore channels formed by stacking vermiform particles are wide, the catalyst has proper contents of B acid and L acid, and the catalyst is suitable for hydrodenitrogenation and carbon residue removal reactions of inferior heavy oil.

Inventors

  • HUANG XINBO
  • JI HONGHAI
  • WANG SHAOJUN
  • GAO JINGSHAN

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
20230426

Claims (9)

  1. 1. A preparation method of a heavy oil hydrodenitrogenation and carbon residue removal catalyst comprises the following steps of (1) mixing pseudo-boehmite powder, boron-containing micron spherical active carbon and water into slurry, then carrying out solid-liquid separation, drying a solid phase material, kneading, forming and drying, roasting under an inert atmosphere to obtain an alumina carrier precursor, carrying boron and simultaneously decarbonizing to obtain a boron modified alumina carrier precursor, (2) adding the boron modified alumina carrier precursor and an epoxypropane aqueous solution into a closed autoclave, carrying out reaction for 1-4 hours at 60-100 ℃, then heating to 110-180 ℃ for 2-6 hours, carrying out solid-liquid separation, drying and roasting a solid phase material to obtain an alumina carrier, carrying out hydrogenation active component loading to obtain a catalyst product, wherein the boron content in the solution is 2% -4.5% by elemental boron in a mode of impregnating the alumina carrier precursor with a boric acid aqueous solution, the boron content is at least so that the alumina carrier precursor is completely immersed, the impregnating time is 1-4 ℃, the epoxy carrier concentration is 1-4% by weight, the epoxy carrier concentration is 2-10-5% by weight, and the epoxy carrier concentration is 2-10% by weight, and the aqueous solution is roasted at the temperature of the aqueous solution at the step of 1-2, and the step of drying and the aqueous carrier concentration is 2-10% by weight, and the aqueous solution is roasted, and the aqueous solution is subjected to the step of drying and the aqueous carrier is subjected to the drying and the aqueous solution.
  2. 2. The method of claim 1, wherein the preparation method of the boron-containing micron spherical active carbon in the step (1) is characterized in that the micron spherical active carbon is impregnated with boric acid solution, the active carbon is subjected to drying treatment after impregnation, the mass concentration of the boric acid solution is 0.5% -1.5% in terms of element boron, the solution is used for saturating the adsorption of the micron spherical active carbon, the impregnation time is 1-5 hours, the drying treatment is carried out at 120-180 ℃ for 1-4 hours, and the diameter of the micron spherical active carbon is 1-3 microns.
  3. 3. The method of claim 1, wherein the mass ratio of the boron-containing micron spherical active carbon to the pseudo-boehmite in the step (1) is 1:19-1:32, and the deionized water is added in an amount such that the liquid-solid mass ratio in the slurry is 5:1-10:1.
  4. 4. The method according to claim 1, wherein the inert atmosphere in the step (1) is one or more of nitrogen and inert gas, and the roasting condition is that the roasting temperature is 450-700 ℃ and the roasting time is 4-6 hours.
  5. 5. The method according to claim 1, wherein the concentration of the propylene oxide aqueous solution in the step (2) is 4wt% to 8wt%.
  6. 6. The method of claim 1, wherein the mass ratio of the aqueous propylene oxide solution to the boron modified alumina support precursor in step (2) is from 4:1 to 8:1.
  7. 7. The method according to claim 1, wherein the drying temperature in the step (2) is 100-160 ℃, the drying time is 2-8 hours, the baking temperature is 500-750 ℃, and the baking time is 4-6 hours, and the baking is performed in an oxygen-containing atmosphere.
  8. 8. The method of claim 1, wherein the hydrogenation active component is loaded in the step (2) by an impregnation method, the hydrogenation active component impregnation liquid is a solution containing metals of the VIB group and the VIII group, the metals of the VIB group are selected from one or more of W, mo, the metals of the VIII group are selected from one or more of Co and Ni, the content of the metals of the VIB group in the impregnation liquid is 12.5-28.5 g/100mL in terms of metal oxide, the content of the metals of the VIII group is 3.0-6.5 g/100mL in terms of metal oxide, the impregnated material is dried and roasted to obtain the catalyst, wherein the drying temperature is 100-160 ℃, the drying time is 2-8 hours, the roasting temperature is 450-550 ℃, and the roasting time is 4-6 hours.
  9. 9. The use of the catalyst prepared by the method according to any one of claims 1-8 in hydrodenitrogenation and carbon residue removal reactions of heavy oil.

Description

Preparation method of catalyst for hydrodenitrogenation and carbon residue removal of heavy oil Technical Field The invention belongs to the field of catalyst preparation, and in particular relates to a preparation method of a heavy oil hydrodenitrogenation and carbon residue removal catalyst Background With the increasingly sharp contradiction between the worldwide crude oil heaviness and the poor quality and the petrochemical product demand diversification and the light quality, the effect of the residual oil hydrogenation and catalytic cracking combined process is becoming important. The residuum hydrogenation technology mainly provides qualified raw materials for catalytic cracking. As a catalytic cracking feedstock, the properties of residuum hydrogenation products, especially metal, sulfur, nitrogen and carbon residue values, have an important impact on the catalytic cracking process. The residual carbon value of the residual oil hydrogenation product has a large influence on catalytic cracking, the residual carbon value of the heavy oil represents the coking trend of high-boiling components in the processing process, and the residual carbon conversion rate is an important index of the residual oil hydrogenation process. The high yield of coke and slurry oil in the catalytic cracking process of the raw materials with high carbon residue value can greatly influence the operation stability and product distribution of a catalytic cracking device. Reducing the carbon residue value of the oil produced by the residuum hydrogenation device is beneficial to improving the performance of catalytic cracking raw materials, improving the product distribution and improving the economic benefit of the residuum hydrogenation and catalytic cracking combined device. CN103785397A discloses a hydrodecarbonization catalyst and a preparation method thereof, the preparation method of the catalyst comprises the following steps of (1) neutralizing acidic aluminum salt aqueous solution and alkali metal aluminate aqueous solution, then introducing alkaline precipitant or alkaline aluminate aqueous solution to adjust the pH value of slurry to 8.5-9.7, aging at 150-220 ℃ for 0.1-2 hours, (2) filtering, washing and drying the aged material in the step (1), adding 10-40wt% of aluminum ammonium carbonate for molding, and (3) loading active components on the molded material, drying and roasting to obtain the hydrodecarbonization catalyst. The catalyst has high pore channel content of 6-10nm and a certain amount of pore channels of 100nm and above, but the pore channels on the surface of the catalyst are not wide, which is unfavorable for the entry of reactant molecules into the catalyst. CN111821989a discloses a residual oil hydrodenitrogenation catalyst and a preparation method thereof. The catalyst comprises a modified alumina-based carrier, molybdenum and nickel metal components, wherein the modified alumina-based carrier contains tungsten and cobalt metal components, the modified alumina-based carrier comprises main body modified alumina and rod-shaped modified alumina, the main body modified alumina is modified alumina with micron-sized pore channels, and at least part of the rod-shaped modified alumina is distributed on the outer surface of the main body modified alumina and in the micron-sized pore channels with the pore diameter D of 3-7 mu m. The surface of the catalyst prepared by the method is in a rod-shaped structure, but the firmness of the combination of the rod-shaped alumina growing on the surface and the main alumina needs to be further improved. Disclosure of Invention Aiming at the defects in the prior art, the invention provides a preparation method of a catalyst for hydrodenitrogenation and carbon residue removal of heavy oil, the surface particles of the catalyst prepared by the method are vermiform, pore channels formed by stacking vermiform particles are wide, the catalyst has proper contents of B acid and L acid, and the catalyst is suitable for hydrodenitrogenation and carbon residue removal reactions of inferior heavy oil. The preparation method of the catalyst for hydrodenitrogenation and carbon residue removal of heavy oil comprises the following steps: (1) Mixing pseudo-boehmite powder, boron-containing micron spherical active carbon and water into slurry, then carrying out solid-liquid separation, drying a solid material, kneading, forming, drying, roasting in an inert atmosphere to obtain an alumina carrier precursor, carrying out boron loading and simultaneously removing carbon to obtain a boron-modified alumina carrier precursor; (2) Adding boron modified alumina carrier precursor and propylene oxide water solution into a closed autoclave, reacting for 1-4 hours at 60-100 ℃, heating to 110-180 ℃ for 2-6 hours, separating solid from liquid, drying and roasting solid phase materials to obtain alumina carrier, and loading hydrogenation active components to obtain catalyst products. In the method, the p