CN-122028984-A - Hydrocracking catalyst, preparation method and use method thereof

Abstract

A hydrocracking catalyst comprising an active cracking support. The active cracking carrier comprises a post-modified zeolite framework with zirconium atoms and titanium atoms substituted for aluminum atoms, wherein a part of the zirconium atoms are substituted in the post-modified zeolite through 4 coordination, a part of the zirconium atoms are grafted on the post-modified zeolite through 5 coordination, and the titanium atoms are substituted in the post-modified zeolite framework through 4 coordination.

Inventors

• Omer Refa Kozeoglu
• Robert Peter Hodgkins
• Guan Haoxing
• NAGANO SHIGEYUKI

Assignees

• 沙特阿拉伯石油公司
• 日挥触媒化成株式会社

Dates

Publication Date

20260512

Application Date

20241003

Priority Date

20231004

Claims (15)

1. 1. A hydrocracking catalyst comprising an active cracking support; The active cracking carrier comprises a post-modified zeolite framework with zirconium atoms and titanium atoms substituted for aluminum atoms, and is characterized in that: A portion of the zirconium atoms are substituted in the post-modified zeolite framework by 4 coordination; a part of the zirconium atoms are grafted to the post-modified zeolite framework through 5 coordination, and The titanium atoms are substituted in the post-modified zeolite framework by 4 coordination.
2. 2. The hydrocracking catalyst of claim 1 wherein the post-modified zeolite framework has a ultrastable Y (USY) framework structure.
3. 3. The hydrocracking catalyst according to any one of claims 1 or 2, characterized in that the specific surface area of the post-modified zeolite framework is 600m 2 /g to 900 m 2 /g.
4. 4. A hydrocracking catalyst according to any one of claims 1 to 3 wherein the lattice constant of the post-modified zeolite framework is from 2.430 nm to 2.450 nm.
5. 5. The hydrocracking catalyst of any one of claims 1 to 4 wherein the molar ratio of SiO 2 to Al 2 O 3 in the post-modified zeolite framework is from 5 to 100.
6. 6. The hydrocracking catalyst of any one of claims 1 to 5, wherein the hydrocracking catalyst further comprises a hydrogenation component.
7. 7. The hydrocracking catalyst of claim 6, wherein the hydrocracking catalyst comprises from 0.1 wt to 40 wt% of the hydrogenation component.
8. 8. The hydrocracking catalyst according to any one of claims 6 or 7 wherein the hydrogenation component comprises at least one metal from IUPAC group 6 or group 8.
9. 9. The hydrocracking catalyst of any one of claims 6 to 8, wherein the hydrogenation component comprises one or more metals selected from the group consisting of cobalt, nickel, palladium, platinum, molybdenum, or tungsten.
10. 10. A method of making a hydrocracking active cracking support comprising: Providing an acidified zeolite suspension comprising a zeolite framework; Introducing a titanium compound into the acidified zeolite suspension to isomorphously substitute titanium onto the zeolite framework by 4-coordination to produce a titanium-substituted zeolite framework, and A zirconium compound is then introduced into the titanium-substituted zeolite framework to graft a portion of the zirconium atoms to the zeolite framework by 5-coordination, and And isomorphously substituting a part of the zirconium atoms to the zeolite framework through 4 coordination, thereby preparing the hydrocracking active cracking carrier.
11. 11. The method of claim 10, wherein the zeolite framework has a Y framework structure or a BEA framework structure.
12. 12. The method according to any one of claims 10 or 11, characterized in that: the time interval between the introduction of the titanium compound and the introduction of the zirconium compound is 0.1 to 5 hours; The acidified suspension has a liquid to solid mass ratio of 5 to 15; acidifying the acidified zeolite suspension with an inorganic or organic acid; The pH of the acidified zeolite suspension is less than 2.0, and The zeolite framework is heat treated at 500 ℃ to 700 ℃.
13. 13. A process for hydrocracking a hydrocarbon feed comprising contacting the hydrocarbon feed with hydrogen and a hydrocracking catalyst under hydrocracking conditions, wherein the hydrocracking catalyst comprises an active cracking support; the active cracking carrier comprises a post-modified zeolite framework with zirconium atoms and titanium atoms substituted for aluminum atoms, wherein A portion of the zirconium atoms are grafted to the post-modified zeolite framework by 5 coordination; A part of the zirconium atoms are connected with the post-modified zeolite framework in a 4-coordination form, and The titanium atoms are attached to the post-modified zeolite framework in a 4-coordinate form.
14. 14. The method of claim 13, wherein the hydrocarbon feed comprises a heavy hydrocarbon oil.
15. 15. The process of any one of claims 13 or 14 wherein the hydrocracking catalyst further comprises a hydrogenation component comprising at least one metal from IUPAC group 6 or group 8.

Description

Hydrocracking catalyst, preparation method and use method thereof Cross Reference to Related Applications The application claims the benefit of U.S. application Ser. No. 18/480,934, filed on 4/10/2023, the entire contents of which are incorporated herein by reference. Technical Field The present invention relates to zeolites, and more particularly to zeolites for use as hydrocracking catalyst components. Background Catalysts comprising hydrotreating/hydrocracking catalysts (e.g., pretreated catalysts) typically comprise an amorphous-based catalyst, such as an amorphous alumina or silica alumina or titania support containing an active metal (Ni/Mo, ni/W or Co/Mo metal) as the active phase, or an amorphous catalyst, zeolite catalyst or composite mixtures thereof, and are promoter modified with Ni, W, mo and Co metals. One commonly used zeolite is USY. The hydrocracking catalyst comprises a hydrogenation active metal component and an acidic support component. In certain embodiments, the hydrocracking catalyst comprises any one of an amorphous alumina catalyst, an amorphous silica alumina catalyst, a titania catalyst, a natural or synthetic zeolite-based catalyst, a post-modified zeolite, or a combination thereof. The hydrocracking catalyst may have an active phase material that, in certain embodiments, comprises any one of Ni, W, mo, co or a combination thereof. In other embodiments, the catalyst may comprise one or more noble metals, such as Ru, rh, pd, ag, os, ir, pt or Au, typically in a sulfur-free environment for hydrogenation and/or reforming. In certain embodiments targeted to hydrodenitrogenation, an acidic alumina or silica alumina based catalyst loaded with a Ni-Mo or Ni-W active metal or combination thereof is used. In embodiments targeted to remove all nitrogen and increase hydrocarbon conversion, a silicon aluminum oxide, zeolite, or a combination thereof is used as a catalyst, and the active metal comprises Ni-Mo, ni-W, or a combination thereof. The hydrogenation process (hydrotreating and hydrocracking) catalysts can be manufactured by a variety of methods. The method chosen generally represents a balance between manufacturing costs and the degree to which desired chemical and physical properties are achieved. Although there is a relationship between catalyst formulation, preparation procedure and catalyst properties, the details of such relationship are not always well understood due to the complexity of the catalyst system. The chemical composition of the catalyst plays a critical role in its performance, as well as the physical and mechanical properties. The preparation of the hydrocracking catalyst involves several steps, precipitation, filtration (decantation, centrifugation), washing, drying, shaping, calcination and impregnation. Additional steps such as kneading/kneading, grinding and sieving are often required. The following is a description of the steps necessary in the production of the hydrocracking catalyst. Precipitation involves the mixing of a solution or suspension of the material, resulting in the formation of a precipitate, which may be crystalline or amorphous. Kneading/kneading wet solid materials typically results in the formation of a dough-like mass that is subsequently shaped and dried. The kneaded/kneaded product is subjected to heat treatment so as to obtain more intimate contact between the components and achieve better uniformity by thermal diffusion and solid state reaction. The metal component is then added by an impregnation method or an isovolumetric impregnation method (INCIPIENT WETTING). The support characteristics determine the mechanical properties of the catalyst, such as attrition resistance, hardness and compressive strength. High surface area and proper pore size distribution are typically required. The pore size distribution and other physical properties of the catalyst support prepared by precipitation are also affected by the precipitation and aging conditions of the precipitate and subsequent drying, shaping and calcination. The final shape and size of the catalyst particles are determined in the manufacturing step. The catalyst and catalyst support shapes are formed in a variety of possible shapes, such as spherical, cylindrical extrudates, or in trilobes or tetralobes, etc. Spherical catalyst supported catalysts can be obtained by the "oil drop method", i.e. precipitation occurs when one liquid is poured into a second immiscible liquid. Other sphericity processes include the rolling ball method. In general, most catalysts currently use non-spherical shapes due to cost and process considerations such as pressure drop. Spherical catalysts are less used in modern hydrocracking. The non-spherical shape is obtained by mixing the raw materials to form an extrudable dough-like material, which is then extruded through a die with perforations. The dough-like extrudate is dried, calcined, and then broken into short pieces. Typical aspect ratios of the cataly