Search

CN-118204104-B - Hydrocracking catalyst, preparation method thereof and crude oil hydrocracking process

CN118204104BCN 118204104 BCN118204104 BCN 118204104BCN-118204104-B

Abstract

The invention discloses a hydrocracking catalyst and a preparation method thereof and a crude oil hydrocracking process, wherein the preparation method comprises the following steps of (1) preparing a spherical material A, (2) preparing a first modified organic high molecular polymer and a second modified organic high molecular polymer, (3) placing the material A in a ball rolling machine, uniformly introducing the first modified organic high molecular polymer, the second modified organic high molecular polymer, pseudo-boehmite powder and an organic high molecular polymer aqueous solution after heating treatment while rolling, obtaining a material B after treatment, (5) carrying out low-temperature heat treatment on the material B, then mixing the material B with an iron-containing compound, drying and roasting to obtain a carrier, further introducing a hydrogenation metal component, and then drying and roasting to obtain the hydrocracking catalyst. Also provided is a hydrocracking catalyst comprising a hydrogenating metal component, an adjunct iron oxide, a support, and optionally phosphorus pentoxide. The hydrocracking catalyst provided by the invention has a spherical core-shell structure, has high cracking activity, strong impurity removal capacity and holding capacity, and is suitable for direct hydrocracking reaction taking crude oil as a raw material.

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 of preparing a hydrocracking catalyst, the method comprising the steps of: (1) Under the contact condition, mixing the heated organic high polymer aqueous solution with amorphous silicon aluminum, and then performing molding treatment to obtain a spherical material A; (2) Adding an organic high molecular polymer into an acid solution for first modification treatment, and obtaining a first modified organic high molecular polymer after the first modification treatment; (3) Adding the organic high molecular polymer into a nitrogen-containing weak alkaline compound aqueous solution for second modification treatment to obtain a second modified organic high molecular polymer, wherein the nitrogen-containing weak alkaline compound is at least one selected from ammonia water, ammonium carbonate and ammonium bicarbonate; (4) Under the condition of rolling and balling, placing the material A into a ball rolling machine, uniformly introducing the first modified organic high molecular polymer obtained in the step (2), the second modified organic high molecular polymer obtained in the step (3), pseudo-boehmite powder and the heated organic high molecular polymer aqueous solution while rolling, and obtaining a material B after treatment; (5) Carrying out low-temperature heat treatment on the material B to obtain a material C, wherein the low-temperature heat treatment temperature is 100-300 ℃; (6) Mixing the material C with an iron-containing compound, uniformly mixing, and drying and roasting to obtain a carrier; (7) Introducing a hydrogenation metal component to the carrier obtained in the step (6), and drying and roasting to obtain a hydrocracking catalyst, wherein the hydrogenation metal component is at least one of VIB group metals and at least one of VIII group metals; wherein the organic high molecular polymer is one or more of starch, cellulose ether and flour; The preparation process of the organic high polymer aqueous solution after the heat treatment in the step (1) and the step (4) comprises the steps of mixing the organic high polymer with water under the heat treatment condition until the organic high polymer is dissolved, and then obtaining the organic high polymer aqueous solution after the heat treatment, wherein the heat treatment temperature is 60-100 ℃, and the heat treatment time is 10-40 minutes.
  2. 2. The method for preparing a hydrocracking catalyst according to claim 1, wherein the amorphous silica-alumina in the step (1) has a specific surface area of 250-320 m 2 /g, a pore volume of 0.7-1.0 mL/g and a silica content of 10-50 wt%.
  3. 3. The method for preparing a hydrocracking catalyst according to claim 1, wherein the organic high molecular polymer is starch.
  4. 4. The method for preparing a hydrocracking catalyst according to claim 1, wherein the starch is one or more selected from 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 selected from methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose and phenyl cellulose.
  5. 5. The method for preparing a hydrocracking catalyst according to claim 1, wherein the starch is corn starch and/or potato starch, and the cellulose ether is methylcellulose.
  6. 6. The method for producing a hydrocracking 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 (1) and the step (4) is 0.5% to 8.0%.
  7. 7. The method for producing a hydrocracking 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 (1) and the step (4) is 1.0% to 5.0%.
  8. 8. The method for preparing a hydrocracking catalyst according to claim 1, wherein the organic high molecular polymer is added into an acid solution in the step (2) for the first modification treatment, and after the treatment, the first modified organic high molecular polymer is obtained after cooling, optional water washing and drying, wherein the acid solution is an inorganic acid and/or an organic acid, the inorganic acid is one or a mixture of more than two of hydrochloric acid, sulfuric acid and nitric acid, and the organic acid is one or a mixture of more than two of citric acid, acetic acid, malic acid, lactic acid and tartaric acid.
  9. 9. The method for preparing a hydrocracking catalyst according to claim 8, wherein the inorganic acid is hydrochloric acid and the organic acid is citric acid.
  10. 10. The method for producing a hydrocracking catalyst according to claim 1, wherein the first modification treatment temperature in the step (2) is 30 to 50 ℃ and the first modification treatment time is 2 to 6 hours.
  11. 11. The method for producing a hydrocracking catalyst according to claim 1, wherein the nitrogen-containing weakly basic compound in the step (3) is aqueous ammonia.
  12. 12. The method for preparing a hydrocracking catalyst according to claim 1, wherein the first modified organic high molecular polymer in the step (4) is added in an amount of 10 to 20% by weight based on the dry matrix amount of pseudo-boehmite powder.
  13. 13. The method for preparing a hydrocracking catalyst according to claim 1, wherein the second modified organic high molecular polymer in the step (4) is added in an amount of 5 to 15% by weight based on the dry matrix amount of pseudo-boehmite powder.
  14. 14. The method for producing a hydrocracking catalyst according to claim 1, wherein the ratio of the amount of the aqueous solution of the organic high molecular polymer after the heat treatment in the step (4) to the mass of the pseudo-boehmite powder is 0.8 to 1.5 by mass.
  15. 15. The method for producing a hydrocracking catalyst according to claim 1, wherein the low-temperature heat treatment temperature in step (5) is 150 to 250 ℃ and the low-temperature heat treatment time is 3 to 12 hours.
  16. 16. The method for producing a hydrocracking catalyst according to claim 1, wherein the iron-containing compound in step (6) is a soluble iron salt selected from one or more of iron nitrate, iron chloride, iron acetate and iron sulfate.
  17. 17. The method for preparing a hydrocracking catalyst according to claim 1, wherein the calcination in the step (6) is carried out in the presence of an inert atmosphere of one or more of nitrogen, helium, neon, argon, krypton and xenon, and the calcination temperature is 600-800 ℃.
  18. 18. The method for preparing a hydrocracking catalyst according to claim 1, wherein the group VIII metal is Ni and/or Co and the group VIB metal is W and/or Mo.
  19. 19. The method for producing a hydrocracking catalyst according to claim 1, wherein the drying temperature in the step (7) is 80 to 140 ℃ and the drying time is 4 to 12 hours.
  20. 20. The process for producing a hydrocracking catalyst according to claim 1, wherein the calcination in the step (7) is carried out in the presence of an oxygen-containing atmosphere at a calcination temperature of 400 to 600 ℃ for a calcination time of 1 to 5 hours.

Description

Hydrocracking catalyst, preparation method thereof and crude oil hydrocracking process Technical Field The invention belongs to the technical field of oil refining, relates to a hydrocracking catalyst and a preparation method thereof, and in particular relates to a hydrocracking catalyst for treating crude oil by a hydrocracking process and a preparation method thereof. Background Crude oil is a dark brown viscous oily liquid with green fluorescence and special smell, and is a mixture of various liquid hydrocarbons such as alkane, cycloparaffin, aromatic hydrocarbon, olefin and the like. The main components are carbon and hydrogen which respectively account for 83-87% and 11-14%, and small amounts of sulfur, oxygen, nitrogen and trace amounts of phosphorus, arsenic, potassium, sodium, calcium, magnesium, nickel, iron, vanadium and other elements. The crude oil can be processed to obtain various products such as fuel oil, solvent oil, lubricating grease, paraffin, asphalt, liquefied gas, aromatic hydrocarbon and the like after refining processing, and the products such as fuel, raw materials and chemical products are provided for various departments of national economy. The composition of the crude oil can be divided into paraffin-based crude oil, naphthenic base crude oil and intermediate base crude oil, the sulfur content of the crude oil can be divided into ultra-low sulfur crude oil, sulfur-containing crude oil and high sulfur crude oil, and the specific gravity of the crude oil can be divided into light crude oil, medium crude oil and heavy crude oil. Currently, most of the conventional crude oil in the world has been put into development and is produced to a relatively high degree. However, with the development of world economy, the energy consumption is greatly increased, and the huge gap of the middle energy is mainly made up by heavy crude oil. The importation of crude oil processed in China is gradually heavier and inferior, and the effective processing of heavy crude oil is attracting wide attention of refineries. In recent years, the consumption demands of the automotive fuel gasoline and diesel oil in China are gradually slowed down, the market demands of the automotive fuel oil are further reduced, and meanwhile, the development of national economy brings social consumption upgrading, so that the consumption demands of olefins and aromatic hydrocarbons which can be used as synthetic monomers of various materials are continuously increased. This requires the refinery to change from the fuel oil type to the fuel oil-chemical and full chemical type, with the proportion of chemical products in the refinery product structure increasing gradually. In the face of urgent demands of refinery transformation, the fixed bed hydrogenation device which is commonly adopted at present cannot meet the requirements of enterprises, and risks that the investment cost of device transformation is high or qualified chemical raw materials cannot be produced after transformation are faced. The boiling bed hydrogenation technology has the advantages of strong adaptability to raw oil, good mass transfer and heat transfer, on-line catalyst addition and discharge, high catalyst utilization rate, long running period, flexible device operation and the like, is suitable for hydrogenation of heavy crude oil, and achieves the aim of converting heavy oil into light-weight and productive chemical raw materials. In the crude oil hydrocracking technology, the catalyst is the core of the technology. At present, most of hydrocracking catalysts adopt molecular sieves or amorphous silica-alumina as cores, and the tolerance of the catalysts to impurities is poor. Crude oil contains naphthenic acid, phenols and other oxygen-containing substances, and water produced after hydrogenation can cause the molecular sieve framework to collapse. In addition, basic nitrogen, metal heteroatoms and the like in crude oil can poison the active center of the molecular sieve catalyst, and a single catalyst cannot meet the requirement and needs to be solved through the grading of the catalyst. CN202210024883.4 discloses a crude oil hydrocracking catalyst and a preparation method thereof, the catalyst comprises a carrier and an active metal component, wherein the carrier is a silicon-aluminum material, and the active component is at least one selected from the group consisting of metals of group VIB and group VIII of the periodic table of elements. The preparation method of the catalyst comprises the steps of firstly preparing a silicon-aluminum material, then mixing the obtained silicon-aluminum material, a binder and active metal components, and drying and roasting to obtain the crude oil hydrocracking catalyst. The catalyst has the advantages of strong impurity tolerance, high removal rate, good cracking performance and the like, and meanwhile, the production flow is simple and the energy consumption is low. CN200810246528.1 discloses a method for hydr