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CN-118204101-B - Coal tar hydrogenation catalyst, preparation method thereof and coal tar hydrogenation process

CN118204101BCN 118204101 BCN118204101 BCN 118204101BCN-118204101-B

Abstract

The invention discloses a coal tar hydrogenation catalyst and a preparation method thereof as well as a coal tar hydrogenation process, wherein the preparation method comprises the steps of (1) treating an organic high polymer to obtain a material A; the method comprises the steps of (1) mixing a material A, pseudo-boehmite powder and an aqueous solution of a high molecular polymer, forming to obtain a carrier precursor, (3) carrying out heat treatment on the carrier precursor, then mixing the carrier precursor with a soluble nickel salt solution, drying and roasting to obtain a modified carrier, and (4) introducing an active metal component onto the modified carrier, and drying and roasting to obtain the coal tar hydrogenation catalyst. The invention also provides the coal tar hydrogenation catalyst obtained by the preparation method and a coal tar hydrogenation process. The catalyst has high metal impurity capacity, high water resistance, hydrodemetallization activity and stability, and can meet the index requirements of the catalyst in the long-period stable operation process of a hydrogenation device.

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 coal tar hydrogenation catalyst, which comprises the following steps: (1) Mixing the aqueous solution of the weak alkaline compound containing nitrogen with the organic high polymer under the mixing condition, and uniformly mixing to obtain a material A, wherein the weak alkaline compound containing nitrogen is selected from one or more than two of ammonia water, ammonium carbonate and ammonium bicarbonate; (2) Under the contact condition, mixing the material A obtained in the step (1), pseudo-boehmite powder and an aqueous solution of the organic high molecular polymer after heat treatment, uniformly mixing and forming to obtain a carrier precursor, wherein the preparation process of the aqueous solution of the organic high molecular polymer after heat treatment comprises the steps of adding the organic high molecular polymer into water, heating and mixing at 60-100 ℃, and obtaining the aqueous solution of the organic high molecular polymer after heat treatment after the organic high molecular polymer is completely dissolved; (3) Carrying out heat treatment on the carrier precursor obtained in the step (2) at 100-300 ℃, then mixing with a soluble nickel salt solution, uniformly mixing, and drying and roasting to obtain a modified carrier; (4) Introducing an active metal component into the modified carrier obtained in the step (3) and drying and roasting to obtain a coal tar hydrogenation catalyst, wherein the active metal component is one or more of VIB group metal and/or VIII group metal; the organic high molecular polymer is starch and/or cellulose ether.
  2. 2. The method for preparing the coal tar hydrogenation catalyst according to claim 1, wherein the organic high molecular polymer is starch.
  3. 3. The method for preparing the coal tar hydrogenation 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 methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl cellulose, benzyl cellulose, hydroxypropyl methyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose and phenyl cellulose.
  4. 4. The method for preparing the coal tar hydrogenation catalyst according to claim 1, wherein the starch is corn starch and/or potato starch.
  5. 5. The method for preparing a catalyst for hydrogenating coal tar according to claim 1, wherein the weakly basic nitrogen-containing compound in the step (1) is aqueous ammonia.
  6. 6. The method for preparing a coal tar hydrogenation catalyst according to claim 1, wherein the concentration of the aqueous solution of the weak basic nitrogen-containing compound in the step (1) is 2wt% to 40wt%.
  7. 7. The method for preparing a coal tar hydrogenation catalyst according to claim 1, wherein the concentration of the aqueous solution of the weak basic nitrogen-containing compound in the step (1) is 5wt% to 35wt%.
  8. 8. The method for preparing the coal tar hydrogenation catalyst according to claim 1, wherein the mass ratio of the organic high molecular polymer to the nitrogen-containing weakly basic compound in the step (1) is 1:0.05-1:0.5.
  9. 9. The method for preparing the coal tar hydrogenation catalyst according to claim 1, wherein the pseudo-boehmite powder in the step (2) is roasted at 600 ℃ and has the characteristics of 270-320 m 2 /g of specific surface area and 0.9-1.1 mL/g of pore volume.
  10. 10. The method for preparing the coal tar hydrogenation catalyst according to claim 1, wherein the material A in the step (2) is added in an amount of 5-35 wt% of the dry basis weight of pseudo-boehmite powder.
  11. 11. The method for preparing the coal tar hydrogenation catalyst according to claim 1, wherein the material A in the step (2) is added in an amount of 10-30 wt% of the dry basis weight of pseudo-boehmite powder.
  12. 12. The method for preparing a coal tar hydrogenation catalyst according to claim 1, wherein the concentration of the aqueous solution of the organic high molecular polymer in the step (2) is 0.5-8 wt%.
  13. 13. The method for preparing a coal tar hydrogenation catalyst according to claim 1, wherein the concentration of the aqueous solution of the organic high molecular polymer in the step (2) is 1wt% to 5wt%.
  14. 14. The method for preparing a coal tar hydrogenation catalyst according to claim 1, wherein the ratio of the addition amount of the aqueous solution of the organic high molecular polymer after the heat treatment in the step (2) to the total mass of the material A and the pseudo-boehmite powder is 0.5-1.2.
  15. 15. The method for preparing the coal tar hydrogenation catalyst according to claim 1, wherein the carrier precursor obtained in the step (2) is heated at 150-250 ℃ in the step (3), and the heating time is 3-12 hours.
  16. 16. The method for preparing a catalyst for hydrogenating coal tar according to claim 1, wherein the soluble nickel salt in the step (3) is one or more selected from the group consisting of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate.
  17. 17. The method for preparing the coal tar hydrogenation catalyst according to claim 1, wherein the roasting in the step (3) is two-stage roasting, the first stage roasting is carried out under an inert atmosphere, the inert atmosphere is one or more of nitrogen, helium, neon, argon, krypton and xenon, the roasting temperature is 600-800 ℃, the roasting time is 1-5 hours, the second stage roasting is carried out under an air atmosphere, the roasting temperature is 600-800 ℃, and the roasting time is 1-5 hours.
  18. 18. The method for preparing the catalyst for hydrogenating coal tar according to claim 17, wherein the inert atmosphere is nitrogen.
  19. 19. The method for preparing the coal tar hydrogenation catalyst according to claim 1, wherein the group VIB metal is Mo and/or W, and the group VIII metal is Ni and/or Co.
  20. 20. The method for preparing a catalyst for hydrogenating coal tar according to claim 1, wherein the active metal components in the step (4) are Mo and Ni.

Description

Coal tar hydrogenation catalyst, preparation method thereof and coal tar hydrogenation process Technical Field The invention belongs to the technical field of petrochemical industry, relates to a catalytic material and a preparation method thereof, and particularly relates to a coal tar hydrogenation catalyst and a preparation method thereof and a coal tar hydrogenation treatment process. Background The comprehensive utilization of coal is an important component of national energy strategy, and the national coal industry planning has proposed to ' deeply process and clean utilize ' coal, and ' greatly develop coal chemical industry, develop coal-based liquid fuel, advance coal gasification and liquefaction demonstration engineering construction, make up for insufficient oil and gas supply and improve the national energy safety guarantee degree. Develop the comprehensive utilization research of coal tar resources, help to relieve the situation of the increasingly tense petroleum supply and guide the healthy and orderly development of the coal industry. The research and development and industrial application of the coal tar comprehensive utilization technology will drive the development of related industries, and play an important role in the value-added conversion of rich coal resources in China and the economic development of regions. Coal tar is one of liquid products obtained in carbonization and vaporization processes of coal, and has the characteristics of high aromatic hydrocarbon, olefin, oxygen content, high hydrocarbon ratio and the like, and because of imperfect cooling and collecting processes, the coal dust, inorganic salt and other impurities in cooling water are mixed into the coal tar. If fixed bed hydroprocessing is directly employed, fine coal fines particles are deposited on the catalyst surface or between catalyst beds, which can cause pressure drop across the fixed bed, thereby affecting run length and product quality. Therefore, the raw materials need to be pretreated, so that the content of coal dust and impurities is reduced, and qualified raw materials are provided for a fixed bed. CN202110144831.6 discloses a coal tar hydrogenation catalyst and a preparation method thereof. The catalyst comprises a first active material and a second active material, wherein the first active material comprises at least one of VIB group oxides, the second active material comprises at least one of IB, VIIB or VIII group oxides, the molar ratio M1/M2 of metal M1 in the first active material to metal M2 in the second active material is 10-1, the carrier of the catalyst is a molecular sieve subjected to pore expansion treatment, and the active component is doped with C. The preparation method of the catalyst comprises the steps of carrying out low-temperature hydrothermal treatment on a carrier, an active substance precursor and urea to obtain a catalyst precursor A, soaking the catalyst precursor A in a solution containing a carbon source to obtain a catalyst precursor B, and carrying out heat treatment on the catalyst precursor B in an inert atmosphere to obtain the catalyst. The coal tar hydrogenation catalyst provided by the patent has excellent hydrodenitrogenation and hydrodesulfurization capabilities, but has poor water resistance and is not very suitable for coal tar with high oxygen content. CN1206037a discloses a residuum hydrodemetallization catalyst and a preparation method thereof, the catalyst takes VIII and/or VIB metal elements as active components, and is loaded on a large aperture alumina carrier. The pore volume of the carrier is 0.80-1.20 mL/g (mercury intrusion method), the specific surface area is 110-200 m 2/g, the diameter of pores is 15-20 nm, and the stacking density is 0.50-0.60 g/mm. The preparation method of the residual oil hydrodemetallization catalyst comprises the steps of adding carbon black powder as a physical pore-expanding agent and a chemical pore-expanding agent containing phosphorus, silicon or boron compounds which can chemically react with pseudo-boehmite or alumina in the pseudo-boehmite mixing process, kneading the mixture into a plastic body, extruding strips for molding, drying and roasting to obtain a carrier, loading active components on the carrier in a spray impregnation mode, and drying and roasting to obtain the catalyst. However, because the carbon black powder particles of the physical pore-expanding agent used in the preparation process of the carrier are larger and are not concentrated, the distribution of the carrier holes is dispersed and not concentrated, and the mechanical strength is poor. More importantly, the pore canal of the obtained catalyst carrier is not smooth, partial catalyst pore canal can not be fully utilized, and metal is easy to deposit at the narrow part of the pore canal when in use, so that the catalyst deactivation speed can be accelerated. And if the catalyst is directly applied to coal tar hydrogenation reaction, the water r