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JP-7856574-B2 - Method for preparing a hydrocracking catalyst

JP7856574B2JP 7856574 B2JP7856574 B2JP 7856574B2JP-7856574-B2

Inventors

  • クーパー，デイビッド・アレン
  • デン・ブレーエン，ヨハン・ペーテル
  • ヒューズ，ジェームズ
  • アウウェハンド，コルネリス
  • リフット，マルセロ・ステファノ

Assignees

  • シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー

Dates

Publication Date
20260511
Application Date
20210315
Priority Date
20200320

Claims (11)

  1. A method for preparing a supported hydrocracking catalyst, wherein the method is a) A step of providing a zeolite Y having at least 10 bulk silica-to-alumina ratios (SAR), b) A step of mixing the zeolite Y provided in step a) with a base, water, and a surfactant to obtain a slurry of the zeolite Y, c) A step of reducing the water content of the slurry obtained in step b), thereby obtaining a solid having the reduced water content, wherein the reduction in water content in step c) is accompanied by the addition of a binder, the binder being amorphous silica-alumina (ASA) present in an amount of 75% to 95% of the weight of the carrier, d) A step of molding the solid having the reduced water content obtained in step c), thereby obtaining a molded catalyst support, e) A step of calcining the molded catalyst support obtained in step d) at a temperature exceeding 300°C in the presence of the surfactant from step b), thereby obtaining a calcined catalyst support, f) The process includes impregnating the catalyst support calcined in step e) with a hydrogenation component to obtain a supported catalyst, A method wherein no heat treatment at a temperature exceeding 500°C is performed between the mixing in step b) and the molding in step d).
  2. The method according to claim 1, wherein the zeolite Y provided in step a) has a bulk silica-to-alumina ratio (SAR) of 20 to 100.
  3. The method according to claim 1 or 2, wherein the surfactant used in step b) comprises an alkylammonium halide.
  4. The method according to any one of claims 1 to 3 , wherein in step b), the zeolite Y is mixed with a C8 to C20 alcohol.
  5. The method according to any one of claims 1 to 4, wherein the zeolite Y in the slurry obtained in step b) has a total mesopore volume in pores having a volume of 2 to 8 nm, determined by Ar adsorption by NLDFT, at least 0.2 ml/ g.
  6. The method according to any one of claims 1 to 5 , wherein the calcination in step e) is carried out in the presence of oxygen.
  7. The method according to any one of claims 1 to 6 , wherein the hydrogenation component comprises a metal selected from the group consisting of Group VIB and Group VIII metals.
  8. The method according to claim 7, wherein the metal is selected from Ni, W, and Mo.
  9. The method according to any one of claims 1 to 8 , wherein no heat treatment at a temperature exceeding 300°C is performed between the mixing in step b) and the molding in step d).
  10. A supported hydrocracking catalyst comprising: a support having a modified zeolite Y having a bulk silica-to-alumina ratio (SAR) of at least 10 and a total mesopore volume in pores having a volume of 2 to 8 nm determined by Ar adsorption by NLDFT, and a binder present in an amount of 75% to 95% of the weight of the support; and a metal supported on the support and selected from the group consisting of group VIB metals and group VIII metals, wherein the binder is amorphous silica-alumina (ASA).
  11. A process for converting hydrocarbon raw materials into lower boiling point substances, the process comprising contacting the raw materials with hydrogen at high temperature and pressure in the presence of a catalyst obtained by the method of any one of claims 1 to 10.

Description

This invention relates to a method for preparing a supported catalyst, preferably a hydrocracking catalyst. Various methods for preparing supported catalysts are known in this field. As an example, CN103769197A discloses a method for preparing a sulfurized hydrocracking catalyst. As a further example, US20130292300A1 discloses mesostructured zeolites, methods for preparing catalyst compositions from such mesostructured zeolites, and the use of such catalyst compositions in a hydrocracking process. According to Examples 7 and 8 of US20130292300A1 (describes small-scale experiments), the zeolite material was mixed with deionized water and CTAB (alkylammonium halide surfactant), followed by the addition of concentrated ammonium hydroxide ( NH4OH ). After stirring at room temperature for 24 hours, the solid was separated by vacuum filtration and washed three times with hot deionized water. The solid was then dried and subsequently calcined in a two-stage calcination, first at 550°C (under nitrogen) and then at 600°C (under air). Next, this calcined material (see Example 8 of US20130292300A1) was combined with a binder material and impregnated with nickel oxide (NiO) and molybdenum trioxide ( MoO3 ) to form several different hydrocracking catalysts. The problem with the catalyst preparation method described in US20130292300A1, where surfactants are present in the zeolite material during combustion in air, is that when scaling up the catalyst preparation process to a commercial scale, considering the presence of surfactants, for example, due to their carbon content, combustion in air may pose an explosive risk. Furthermore, combustion under an inert gas such as nitrogen on a commercial scale requires significant capital investment. Chinese Patent Application Publication No. 103769197 SpecificationU.S. Patent Application Publication No. 2013/0292300 The objective of this invention is to overcome or minimize one or more of the above-mentioned or other problems. A further object of the present invention is to provide an alternative method for preparing supported catalysts, particularly for use as hydrocracking catalysts. One or more of the above or other objectives can be achieved by providing a method for preparing a supported catalyst, preferably a hydrocracking catalyst, which includes at least: a) A step of providing a zeolite Y having at least 10 bulk silica-to-alumina ratios (SAR), b) A step of mixing the zeolite Y provided in step a) with a base, water, and a surfactant to obtain a slurry of zeolite Y, c) A step of reducing the water content of the slurry obtained in step b), thereby obtaining a solid having the reduced water content, wherein the reduction in water content in step c) is accompanied by the addition of a binder. d) A step of molding the solid with reduced water content obtained in step c) to obtain a molded catalyst support, e) A step of calcining the molded catalyst support obtained in step d) at a temperature exceeding 300°C in the presence of the surfactant from step b), thereby obtaining a calcined catalyst support. f) The process includes impregnating the catalyst support calcined in step e) with a hydrogenation component to obtain a supported catalyst, No heat treatment at temperatures exceeding 500°C is performed between the mixing in step b) and the molding in step d). Remarkably, according to the present invention (see, for example, Table 3), the risk of explosion during air calcination is significantly reduced or completely eliminated, thereby improving ease of manufacture (as the use of inert gases such as nitrogen during calcination is eliminated). Furthermore, calcination can be performed in a single step, resulting in process simplification. Another advantage of the present invention is that the supported catalyst prepared by the method according to the present invention provides higher middle distillate (MD) selectivity (150°C to 370°C) when used for the hydrogenation conversion of hydrocarbon feedstocks. This figure shows the m/z = 44 signal indicating CO₂ formation as a function of temperature (°C) and the m/z = 18 signal indicating H₂O formation as a function of temperature (°C) in TGA MS measurements.This figure shows the mass change as a function of temperature (°C) and the first time derivative (δm/δt) of the mass change as a function of temperature (°C) in TGA MS measurements. In step a) of the method according to the present invention, a zeolite Y having at least 10 bulk (molar) silica-to-alumina ratio (SAR) (determined by XRF (X-ray fluorescence)) is provided. Those skilled in the art will readily understand that this zeolite Y (having a faujasite structure) can be broadly varied. It may also be possible to combine zeolite Y with other zeolites (e.g., zeolite beta). However, the amount of zeolite Y used according to the present invention preferably constitutes at least 70% by weight, more preferably at least 75% by weight, even more preferably at least 90% by weight, or