Hydrocarbon oil hydrocracking catalyst containing titania binder and phosphorus active component, method for producing hydrocracking catalyst, and method for hydrocracking hydrocarbon oil

Abstract

A hydrotreating catalyst is provided in which one or more phosphorus components are supported on a composite support of a titanium-supported binder component and a post-treated, skeletal-modified, ultrastable Y-type (USY) zeolite. The support comprises a titanium-supported binder component and a post-treated, skeletal-modified, ultrastable Y-type (USY) zeolite in which some of the aluminum atoms constituting the zeolite framework have been replaced with zirconium atoms and / or titanium atoms and / or hafnium atoms. Active components, including a phosphorus active component and one or more hydrocracking metal active components, are supported on the support.

Description

[Technical Field]

[0001] Related Applications Not applicable.

[0002] The present invention relates to a hydrocracking catalyst containing USY zeolite, a method for producing the catalyst, and a method for hydrocracking hydrocarbon oils. [Background technology]

[0003] Hydrocracking processes are commercially used in many petroleum refineries. These processes are used to process a variety of feedstocks, such as feedstocks with boiling points ranging from about 370°C to about 520°C in conventional hydrocrackers and feedstocks with boiling points above about 520°C in resid hydrocrackers. Generally, hydrocracking processes break down the heavy, large molecules of the feedstock into smaller, lighter molecules with higher average volatility and greater economic value. Furthermore, hydrocracking processes typically improve the quality of the hydrocarbon feedstock by increasing the hydrogen-to-carbon ratio and removing organic sulfur and nitrogen compounds. The significant economic benefits derived from hydrocracking processes have led to substantial process improvements and the development of more active catalysts.

[0004] Hydrotreating and hydrocracking units typically contain two main zones: a reaction zone and a separation zone. The configuration of the reaction zone is typically determined by key parameters, such as feedstock quality, product specifications, processing objectives, and catalyst. Mild hydrocracking, or single-stage once-through hydrocracking, is performed under more severe operating conditions than hydrotreating processes but milder conditions than conventional full-pressure hydrocracking processes. This hydrocracking process is cost-effective, but typically results in lower product yields and quality. Mild hydrocracking processes produce lower-quality middle distillate products than conventional hydrocracking processes. Depending on the feedstock and product specifications, single- or multiple-catalyst systems can be used. Single-stage hydrocracking is the simplest configuration and is designed to maximize middle distillate yields in single- or dual-catalyst systems. Dual-catalyst systems are used in stacked-bed configurations or in two separate reactors. In a series-flow configuration, the entire hydrotreated / hydrocracked product stream (containing C1-C4 light gases, HS, NH3, and any remaining hydrocarbons) exiting the first reactor is sent to a second reactor. In a two-stage configuration, the feedstock is purified by passing it through a hydrotreating catalyst bed in the first reactor. The effluent is sent to a fractionation column to separate HS, NH3, light gases (C1-C4), naphtha, and diesel products boiling in the range of 36-370°C. Hydrocarbons boiling above about 370°C are then sent to the second reactor. In a two-stage hydrocracking configuration, the feedstock is hydrotreated / hydrocracked in a hydrotreating catalyst bed in the first reactor (typically containing an amorphous catalyst such as an amorphous alumina or silica-alumina substrate containing Co and / or Ni and / or Mo and / or W metals as the active phase). The effluent of the first reactor is then fractionated to separate the light fraction containing H2S, NH3, C1-C4 gases, naphtha, and a diesel fraction boiling at a normal boiling point up to about 370° C. The hydrocarbon fraction boiling above about 370° C. is then sent to a second reactor containing an amorphous and / or zeolitic catalyst having Ni / Mo or Ni / W metals as the active phase.The effluent from the second reactor is sent as a mixed stream with the effluent from the first reactor to a fractionation column for separation of cracked components.

[0005] The use of multiple hydrocracking zones throughout a hydrocracker is known, and for example, U.S. Patent Nos. 3,240,694, 6,113,775, 6,113,775, 6,217,746, 6,312,586, 5,885,440, 5,026,472, 4,713,167, and 4,950,384 show different configurations of hydrocracking processes.

[0006] Catalysts, including hydrotreating / hydrocracking catalysts, such as pretreatment catalysts, typically include amorphous catalysts, such as amorphous alumina, silica-alumina, or titania substrates containing Ni / Mo, Ni / W, or Co / Mo active metals as the active phase; amorphous catalysts promoted with Ni, W, Mo, and Co metals; zeolite catalysts; or composite mixtures thereof. A commonly used zeolite is ultrastable Y (hereinafter "USY") zeolite. Hydrocracking catalysts include a hydrogen-activating metal component and an acidic support component. In certain embodiments, hydrocracking catalysts include any one of amorphous alumina catalysts, amorphous silica-alumina catalysts, titania catalysts, natural or synthetic zeolite catalysts, post-modified zeolites, or combinations thereof. In certain embodiments, hydrocracking catalysts can have an active phase material containing any one of Ni, W, Mo, Co, or a combination thereof. In certain embodiments aimed at hydrodenitrogenation, acidic alumina or silica-alumina catalysts loaded with Ni-Mo, Ni-W active metals, or combinations thereof, are used. In embodiments aimed at complete nitrogen removal and increased hydrocarbon conversion, silica-alumina, zeolites, or combinations thereof loaded with active metals including Ni-Mo, Ni-W, or combinations thereof are used as catalysts.

[0007] U.S. Patent Nos. 9,221,036, 10,081,009, and 10,293,332 (the '036, '009, and '332 patents, or the '036 patent family), owned by the assignee of the present invention and incorporated herein by reference in their entireties, teach, among other things, hydrocracking catalysts in which a portion of the USY framework is substituted with one or more of zirconium, titanium, and hafnium. In these catalysts, the substitution metals (Ti, Zr, and / or Hf) replace a portion of the aluminum in the aluminum / silica framework and essentially become part of the framework. Processes for making and applications of these catalysts are all described in the '036, '009, and '332 patents. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] U.S. Patent No. 3,240,694 [Patent Document 2] U.S. Patent No. 6,113,775 [Patent Document 3] U.S. Patent No. 6,217,746 [Patent Document 4] U.S. Patent No. 6,312,586 [Patent Document 5] U.S. Patent No. 5,885,440 [Patent Document 6] U.S. Patent No. 5,026,472 [Patent Document 7] U.S. Patent No. 4,713,167 [Patent Document 8] U.S. Patent No. 4,950,384 [Patent Document 9] U.S. Patent No. 9,221,036 [Patent Document 10] U.S. Patent No. 10,081,009 [Patent Document 11] U.S. Patent No. 10,293,332 [Patent Document 12] U.S. Patent Application Publication No. 2021 / 0077985 [Patent Document 13] U.S. Patent Application Serial No. 17 / 577,691 [Patent Document 14] U.S. Patent Application Serial No. 17 / 577,747 [Patent Document 15] U.S. Patent Application Serial No. 17 / 577,794 Summary of the Invention [Problem to be solved by the invention]

[0009] With regard to the above background information, the present disclosure aims to provide a technical solution for alternative catalytic materials, including catalysts used in the hydrocracking of hydrocarbon oils. [Means for solving the problem]

[0010] Provided is a hydrocracking catalyst for hydrocarbon oils, the hydrocracking catalyst comprising: a support including a post-treated skeletal-modified ultrastable Y (USY) zeolite component and a binder component, the binder component including titania and one or more additional inorganic oxides in an amount of about 5 to 10 mass % based on the total mass of the binder component; and an active component supported on the support, the active component including a phosphorus active component and one or more hydrocracking metal active components.

[0011] In certain embodiments, the binder component comprises an amorphous alumina-titania binary composite or an amorphous alumina-silica-titania ternary composite, hi certain embodiments, the binder component further comprises about 5-10 wt. % silica and about 80-90 wt. % alumina, each based on the total weight of the binder component.

[0012] In certain embodiments of the hydrocracking catalyst, the phosphorus active component comprises about 0.01 to 5.0 wt. % based on the total weight of the hydrocracking catalyst. In certain embodiments, the hydrocracking catalyst comprises about 1.0 to 3.0 wt. % of the phosphorus active component based on the total weight of the hydrocracking catalyst.

[0013] In certain embodiments, the hydrocracking catalyst comprises, as one or more hydrocracking metal active components, one or more metals or metal compounds (oxides or sulfides) selected from Groups 6, 7, 8, 9, and 10 of the IUPAC Periodic Table of the Elements. In certain embodiments, the hydrocracking catalyst comprises one or more metals or metal compounds (oxides or sulfides) of Mo, W, Co, or Ni.

[0014] In certain embodiments, the hydrocracking catalyst has a specific surface area of ​​200 to 450 m 2 / g, the volume of pores with a diameter of 600 Å or less is 0.40 to 0.75 ml / g, and the amount of phosphorus component is 0.01 to 5.0 mass % with respect to the mass of the catalyst material.

[0015] In certain embodiments, the hydrocracking catalysts described herein are in the form of extrudates, and the extrudates are calcined.

[0016] In certain embodiments, the post-treated skeletal-modified USY zeolite (a USY zeolite whose framework has been subsequently modified) contains one or more of titanium, zirconium, and / or hafnium substituted for aluminum atoms constituting the zeolitic framework of the USY zeolite. In certain embodiments, the post-treated skeletal-modified (a USY zeolite whose framework has been subsequently modified) USY zeolite is substituted with 0.1 to 5 wt. % zirconium atoms and 0.1 to 5 wt. % titanium ions, calculated on an oxide basis. In certain embodiments, the post-treated skeletal-modified USY zeolite contains titanium and zirconium substituted for aluminum atoms constituting the zeolitic framework of the USY zeolite. In certain embodiments, the post-treated skeletal-modified USY zeolite is substituted with 0.1 to 5 wt. % zirconium atoms and 0.1 to 5 wt. % titanium ions, calculated on an oxide basis. In certain embodiments, the post-treated framework-substituted USY zeolite has the following properties: (a) a crystal lattice constant of 2.430 to 2.450 nm; (b) a specific surface area of ​​600 to 900 m 2 / g, and (c) a molar ratio of SiO2 to Al2O3 of 10 to 100.

[0017] A method for producing hydrocracking catalyst particles is provided, comprising the steps of: providing a post-treated, framework-modified, ultrastable Y (USY) zeolite component in which a portion of the aluminum atoms constituting the zeolite framework are replaced with zirconium atoms, titanium atoms, and / or hafnium atoms; providing a titania-containing binder component; mixing and kneading the post-treated, framework-modified USY zeolite component with the titania-containing binder component to form a composite; shaping the composite into an extrudate; heat-treating the extrudate; recovering intermediate calcined catalyst particles (intermediate calcined catalyst particles) characterized by an outer surface and pores defining an inner surface; and supporting an active component comprising a phosphorus component and one or more hydrocracking metal active components.

[0018] In certain embodiments, a method for producing a hydrocracking catalyst includes supporting an active component on the outer surfaces and / or inner pore surfaces of intermediate calcined catalyst particles, heat-treating the active component-supported intermediate calcined catalyst particles, and recovering the final calcined catalyst particles. In certain embodiments, a method for producing a hydrocracking catalyst includes supporting an active component on the outer surfaces and / or inner pore surfaces of a titania-containing binder component, heat-treating the active component-supported intermediate calcined catalyst particles, and recovering the final calcined catalyst particles. In certain embodiments, supporting the active component includes supporting the active component on the outer surfaces and / or inner pore surfaces of a composite of a titania-containing binder component and a post-treated skeletal-modified USY zeolite component, heat-treating the active component-supported intermediate calcined catalyst particles, and recovering the final calcined catalyst particles.

[0019] In certain embodiments, a method for producing a hydrocracking catalyst includes using a titania-containing binder component formed from titania, silica, and an alumina precursor, wherein the titania precursor is selected from the group consisting of Ti(OH), TiO(OH), TiO, Ti(C0), TiSO, or Ti(SO), and combinations comprising two or more of these titania precursors; the alumina precursor is selected from the group consisting of NaAlO, Al(SO), aluminates, alumina, aluminum colloids, boehmite, pseudoboehmite, aluminum hydroxide, aluminum salts, aluminum alkoxides, alumina gels, and combinations comprising two or more of these alumina precursors; and the silica precursor is selected from the group consisting of NaSiO, NaSiO, sodium silicate (water glass), fumed silica, precipitated silica, colloidal silica, silica gel, silicon hydroxide, silicon alkoxides, and combinations comprising two or more of these silica precursors.

[0020] In certain embodiments, the phosphorus component is supported on calcined catalyst particles. In certain embodiments, the phosphorus component and one or more hydrocracking metal active components are supported on intermediate calcined catalyst particles. In certain embodiments, the phosphorus component is supported on a titania-containing binder component. In certain embodiments, the phosphorus component and one or more hydrocracking metal active components are supported on a titania-containing binder component. In certain embodiments, the phosphorus component is supported on a composite of a post-treated skeletal-modified USY zeolite component and a titania-containing binder component. In certain embodiments, the phosphorus component and one or more hydrocracking metal active components are supported on a composite of a post-treated skeletal-modified USY zeolite component and a titania-containing binder component.

[0021] A method for hydrocracking a hydrocarbon oil is provided, comprising the steps of: hydrocracking a hydrocarbon oil using the hydrocracking catalyst described herein. In a specific embodiment, the method includes the steps of: loading the hydrocracking catalyst into a hydrotreating unit that is a flow reactor; and hydrocracking a hydrocarbon oil having a boiling point in the range of about 370 to 833°C in the presence of hydrogen at a reactor temperature in the range of about 300 to 500°C, a hydrogen pressure in the range of about 40 to 300 bar, and a liquid hourly space velocity in the range of about 0.1 to 10 h. -1 and hydrogen / oil ratio is approximately 500 to 2500 Nm 3 / m 3 In a specific embodiment, the method further comprises the steps of: loading a hydrocracking catalyst into a hydrotreating unit that is a flow reactor; and treating a hydrocarbon oil having a boiling point in the range of about 370 to 650°C in the presence of hydrogen at a reactor temperature in the range of about 330 to 450°C, a hydrogen pressure in the range of about 70 to 150 bar, and a liquid hourly space velocity in the range of about 0.2 to 1.5 h. -1 and hydrogen / oil ratio is approximately 1000 to 2500 Nm 3 / m 3wherein the effluent from the flow reactor comprises a middle distillate comprising kerosene and diesel. In certain embodiments, the flow reactor of the above method is selected from the group consisting of a stirred tank, an ebullated bed reactor, a baffled slurry tank, a fixed bed reactor, a rotating tubular reactor, and a slurry bed reactor. In certain embodiments, the hydrocarbon oil comprises (1) crude oil, (2) synthetic crude oil, (3) bitumen, (4) oil sands, (5) shale oil, (6) coal liquid oil, (7) plastic pyrolysis oil, and / or (8) refined oil obtained from biomass-derived oil. In certain embodiments, the hydrocarbon oil comprises a refined oil obtained from crude oil, synthetic crude oil, bitumen, oil sands, shale oil, or coal oil, said refined oil being a) atmospheric gas oil (AGO), b) vacuum gas oil (VGO), c) deasphalted oil (DAO) or demetallized oil obtained from solvent debituminization, d) light coker gas oil or heavy coker gas oil obtained from a coker process, e) cycle oil obtained from a fluid catalytic cracking (FCC) process, f) gas oil obtained from a visbreaking process, g) gas oil obtained from plastic pyrolysis oil, and / or h) biomass-derived gas oil, wherein all of the feedstocks c) through h) have a normal boiling range that matches the boiling range of the atmospheric gas oil or vacuum gas oil. In a specific embodiment, the method includes the steps of: filling a hydrotreating treatment unit that is a flow reactor with a hydrocracking catalyst; and subjecting a hydrocarbon oil having a boiling point of 375°C to 650°C to hydrocracking in the presence of hydrogen at a reactor temperature of 330°C to 450°C, a hydrogen pressure of 7 to 15 MPa, and a liquid hourly space velocity (LHSV) of 0.2 to 1.5 h. -1 , and hydrogen / oil ratio is 1000~2000Nm 3 / m 3 to obtain kerosene-gas oil.

[0022] The various embodiments and implementations disclosed herein can be used in any combination. These and other aspects and features can be understood from the following description of certain specific embodiments, the accompanying drawings, and the claims. [Brief explanation of the drawings]

[0023] [Figure 1] FIG. 1 is a process flow diagram illustrating the steps for producing catalyst particles comprising post-processed skeletal modified USY zeolite, a titania-containing binder component, and phosphorus as the active component. [Figure 2] 1 is a graph showing Arrhenius curves for the catalysts tested in the examples herein. [Figure 3] 1 is a graph showing product yield versus conversion for the catalysts tested in the examples herein. DETAILED DESCRIPTION OF THE INVENTION

[0024] A hydrotreating catalyst is provided in which one or more phosphorus components are supported on a composite support of a titanium-supported binder component and a post-treated, skeletal-modified, ultrastable Y-type zeolite. The support comprises a titanium-supported binder component and a post-treated, skeletal-modified, ultrastable Y-type (USY) zeolite in which some of the aluminum atoms constituting the zeolite framework have been replaced with zirconium atoms and / or titanium atoms and / or hafnium atoms. An active component comprising a phosphorus active component and one or more hydrocracking metal active components is supported on the support.

[0025] In certain embodiments, the present disclosure provides composite catalyst materials and / or catalyst particles comprising one or more phosphorus components supported on a composite of a titanium-supported binder component and a framework-modified USY zeolite in which some of the aluminum atoms in the framework have been replaced with zirconium atoms and / or titanium atoms and / or hafnium atoms. The titanium component of the titanium-supported inorganic oxide is blended before mixing the inorganic oxide with the post-treated framework-modified USY zeolite. The composite mixture of the titanium-binder composite and the post-treated framework-modified USY zeolite is extruded to form intermediate catalyst particles, which are then heat-treated to produce calcined intermediate catalyst particles. In certain embodiments, one or more phosphorus components are blended after the formation of the calcined intermediate catalyst particles. In certain embodiments, the one or more phosphorus components are blended with the composite mixture of the titanium-binder subcomposite and the post-treated framework-modified USY zeolite. In certain embodiments, one or more phosphorus components are combined with the post-treated skeletal-modified USY zeolite prior to forming a composite mixture of the titanium-binder subcomposite and the post-treated skeletal-modified USY zeolite. In certain embodiments, one or more phosphorus components are combined at two or three of the following times: (a) after formation of the calcined catalyst intermediate particles; (b) with the composite mixture of the titanium-binder subcomposite and the post-treated skeletal-modified USY zeolite; and (c) with the post-treated skeletal-modified USY zeolite prior to forming a composite mixture of the titanium-binder subcomposite and the post-treated skeletal-modified USY zeolite. Optionally, catalyst particles having a titanium component combined with a titanium-binder subcomposite and one or more phosphorus components combined with the particles are heat-treated to produce calcined catalyst particles.

[0026] In certain embodiments, the present disclosure provides a method for producing a catalyst material comprising one or more phosphorus components supported on a composite of a titanium-supported binder component and a framework-modified USY zeolite in which a portion of the aluminum atoms in the framework have been replaced with zirconium and / or titanium and / or hafnium atoms. The material is a composite of (a) a binder component as a granulating or binder material containing a titanium component and (b) a post-treated framework-modified USY zeolite component in which a portion of the aluminum atoms in the framework have been replaced with zirconium and / or titanium and / or hafnium atoms, the material being impregnated with one or more phosphorus components. In this method, the titanium component is incorporated into the binder material prior to forming the catalyst particles. In this method embodiment, the titanium component is incorporated before mixing the binder with the post-treated framework-modified USY zeolite, before extruding the resulting composite mixture, and before forming the catalyst particles. One or more phosphorus components are added to the post-treated skeletal-modified USY zeolite component, the composite of the post-treated skeletal-modified USY zeolite and the titanium-containing binder component, and / or particles formed from the composite, and the particles carrying the one or more phosphorus components are calcined.

[0027] In certain embodiments, the catalyst particles formed in accordance with the invention herein are suitable for hydrocracking heavy hydrocarbon oils obtained from crude oil, synthetic crude oil, bitumen, oil sands, shale oil, coal liquids, plastic pyrolysis oil, and / or biomass-derived oil, preferably any of a) atmospheric gas oil (AGO), b) vacuum gas oil (VGO), c) deasphalted oil (DAO) or demetallized oil obtained from solvent debituminization, d) light or heavy coker gas oil obtained from a coker process, e) cycle oil obtained from a fluid catalytic cracking (FCC) process, f) gas oil obtained from a visbreaking process, g) gas oil obtained from plastic pyrolysis oil, or h) biomass-derived gas oil, wherein all of the feedstocks c) through h) have a normal boiling range that matches the boiling range of the atmospheric gas oil or vacuum gas oil.

[0028] FIG. 1 illustrates a process for producing a post-treated skeletal-modified USY zeolite according to an embodiment of the present disclosure, and a process for producing catalyst particles having an active component on a composite support comprising the post-treated skeletal-modified USY zeolite and a binder. In one embodiment of the preparation method, a skeletal-modified USY zeolite is prepared and / or provided. The binder is provided, for example, in the form of a slurry containing a titania component. The post-treated skeletal-modified USY zeolite and the titania-containing binder component are mixed in a desired ratio and kneaded to form a uniform composite mixture of the materials. The mixture containing the post-treated skeletal-modified USY zeolite and the titanium-supported binder component is then extruded and calcined to form intermediate catalyst particles. The active component, including a phosphorus component and one or more other active components, is supported on the intermediate catalyst particles. Alternatively, or in combination therewith, the active component including the phosphorus component and one or more other active components are supported in one or more previous steps, such as during the formation of the titania-containing binder component, after the formation of the titania-containing binder component, and / or during the mixing and kneading step of the framework-modified USY zeolite with the titania-containing binder component.

[0029] Steps 1-9 herein describe the synthesis process of calcined USY zeolite (referred to herein as USY(c)), followed by post-processing framework modification (referred to herein as USYA) in steps 10-13. In embodiments of the invention herein, USYA can be obtained from another source and provided as wet, dry (uncalcined), or calcined zeolite material in step 13. Thus, when USYA is provided for catalyst particle synthesis herein, steps 1-12 are shown as optional in dashed line representation.

[0030] Steps 14 and optionally step 15 relate to the preparation of an inorganic oxide as a binder or granulating agent, and steps 16 to 22 relate to the steps of forming composite catalyst support particles (steps 16 to 19) (optionally omitting the step of supporting the active ingredient (step 17)) and the steps of supporting an effective amount of the active ingredient on the composite catalyst support particles (steps 20 to 21, these steps can be omitted if the active ingredient is supported in the previous step). The active ingredient can be supported in either or both of steps 17 and 20.

[0031] <Step of forming <USYA>> In step 1, for example, in the range of a liquid / solid ratio of about 5 to 20, 5 to 15, 8 to 15, 5 to 12 or 8 to 12 liters (L) of water / zeolite (kg), by forming a suspension having an effective temperature, for example, in the range of about 15 to 95, 15 to 80, 20 to 95, 20 to 90, 20 to 80, 40 to 95, 40 to 90 or 40 to 80 °C and having an effective concentration of Na-Y, Y-type zeolite (Na-Y) is prepared. The starting material for step 1 has an effective SiO2 / Al2O3 molar ratio (SAR), for example, in the range of about 3 to 6; an effective unit cell dimension (UD), for example, about 2.466 nanometers (nm); an effective specific surface area (SA), for example, in the range of about 600 to 900, 600 to 800, 650 to 900 or 650 to 8 2 / g), and contains Na-Y zeolite having an effective Na2O content, for example, about 13% by mass.

[0032] In the ion exchange step 2, ion exchange is performed to exchange the sodium ions of Na-Y in the Na-Y suspension obtained in step 1 with ammonium ions to prepare the first ion-exchanged Y-type zeolite (the first NH4-Y), thereby synthesizing the first ion-exchanged Y-type zeolite. In the first NH4-Y, in certain embodiments, about 50 to 70% of the Na contained in the Y-type zeolite is replaced by NH4, and NH4 50-70One embodiment of the ion exchange of step 2 involves adding to the Na-Y suspension an ammonium source at an effective concentration, e.g., a molar ratio of ammonium to Al ranging from about 2 to 8, at an effective temperature ranging from about 20 to 95°C, 20 to 90°C, 20 to 80°C, 40 to 95°C, 40 to 90°C, or 40 to 80°C, for an effective residence time ranging from about 10 to 600, 10 to 180, 30 to 600, or 30 to 180 minutes. The ammonium source is one or more of NH4OH, (NH4)2SO4, (NH4)2CO3, or another suitable ammonium source.

[0033] The solid obtained in the ion exchange step 2 is filtered, washed with water at an effective temperature, for example, in the range of about 20-95, 20-90, 20-80, 40-95, 40-90, or 40-80°C, and dried at an effective temperature, for example, in the range of about 80-180°C or 100-180°C, for an effective residence time, for example, in the range of about 30-1800 minutes, 60-1800 minutes, 30-600 minutes, or 60-600 minutes, to obtain the first ion-exchanged NH4-Y, NH4 50-70 Optionally, the solid obtained in ion exchange step 2 can be washed and then subjected to one or more additional washing cycles with an ammonium source at an effective temperature, concentration, and residence time similar to those in step 2, followed by washing with water. The one or more additional washed solid materials can be dried at an effective temperature and residence time similar to those in step 2 to obtain the first ion-exchanged NH4-Y, NH4 50-70 Y is obtained. In certain cases, one or more additional cycles of the first ion exchange step are not performed.

[0034] In the heat treatment step 3, the first ion-exchanged NH4-Y(NH4 50-70Hydrogen-type Y (HY) zeolite is synthesized by heating the first ion-exchanged NH4-Y in a saturated steam atmosphere. In certain embodiments, the heat treatment in step 3 involves calcining the first ion-exchanged NH4-Y at a temperature and for a time effective to produce HY zeolite, for example, at a temperature in the range of about 500-800, 500-700, 600-800, or 600-700°C (typically in the presence of steam, i.e., in saturated steam or in the presence of air or oxygen), for a time in the range of about 10-600, 10-180, 30-600, or 30-180 minutes. In certain embodiments, if a significant amount of Na remains in the HY zeolite, the ion exchange can be repeated one or more times, as in step 2. The HY zeolite is converted to USY by additional ammonium ion exchange and steam treatment, as described below in steps 4-6.

[0035] In steps 4-6, the HY zeolite is treated to synthesize a second ion-exchanged NH4-Y zeolite in which 80-97% of the Na contained in the Na-Y zeolite has been exchanged with NH4. 80-97 For example, as shown in the figure, in step 4, a suspension containing an effective concentration of HY zeolite is prepared at an effective temperature, for example, in a range of about 15 to 95°C, 15 to 80°C, 20 to 95°C, 20 to 90°C, 20 to 80°C, 40 to 95°C, 40 to 90°C, or 40 to 80°C, in a solid / liquid mass ratio range of, for example, about 5 to 20, 5 to 15, 8 to 15, 5 to 12, or 8 to 12 L / kg (water / zeolite).

[0036] In the ion exchange step 5, the NH4-Y suspension obtained in step 4 is subjected to ion exchange in which 80 to 97% or 90 to 97% of the sodium ions in the Na-Y are exchanged with ammonium ions to prepare a second ammonium-exchanged Y-type zeolite (second NH4-Y). 80-97Y). One embodiment of the ion exchange of step 5 involves adding and stirring an effective concentration of ammonium, e.g., an ammonium to Al molar ratio in the range of about 2-8, at an effective temperature in the range of about 20-95°C, 20-90°C, 20-80°C, 40-95°C, 40-90°C, or 40-80°C, for an effective residence time in the range of about 10-600, 10-180, 30-600, or 30-180 minutes. The ammonium source can be one or more of NH4OH, (NH4)2SO4, (NH4)2CO3, or another suitable ammonium source.

[0037] The solid obtained in the ion exchange step 5 is filtered, washed with water at an effective temperature, for example, in the range of about 20-95, 20-90, 20-80, 40-95, 40-90, or 40-80°C, and dried at an effective temperature, for example, in the range of about 80-180°C or 100-180°C, for an effective residence time, for example, in the range of about 30-1800 minutes, 60-1800 minutes, 30-600 minutes, or 60-600 minutes, to obtain the second ion exchange NH4-Y, NH4 80-97 Optionally, after washing the solid obtained in ion exchange step 5, it can be washed in one or more additional washing cycles with an ammonium source, such as at an effective temperature, concentration, and residence time similar to those in step 5, followed by washing with water. The washed solid in one or more additional cycles can be dried at an effective temperature and residence time similar to those in step 5, and the second ion-exchanged NH4-Y, NH4 80-97 Y is obtained. In certain cases, one or more additional cycles of the second ion exchange step are not performed.

[0038] In the heat treatment step 6, NH4 80-97Calcining the second ion-exchanged NH4-Y to synthesize a first ultrastable Y zeolite, herein referred to as USY(a). The heat treatment of step 6 involves calcining the second ion-exchanged NH4-Y at an effective temperature, for example, in the range of about 500-800, 500-700, 600-800, or 600-700°C (usually in the presence of steam, i.e., saturated steam, or in the presence of air or oxygen), for a time period ranging from about 10-600, 10-180, 30-600, or 30-180 minutes, to recover USY(a). In certain embodiments, NH4 80-97 The heat treatment of Y is carried out by steam treatment. USY(a) obtained in step 6 is a USY zeolite with an SAR approximately equivalent to that of the starting Na-Y. Steps 1 to 6 generally do not significantly change the SAR value because these steps do not require acid treatment to release aluminum atoms from the zeolite framework. For example, the USY(a) thus obtained in step 6 may have an SAR of approximately 3 to 6.

[0039] In steps 7-9, the USY(a) zeolite is treated to synthesize a calcined USY zeolite with increased SAR. This calcined USY zeolite serves as the starting material for subsequent post-processing framework modification (post-framework modification). In step 7, an aqueous suspension containing an effective concentration of USY(a) is prepared at an effective temperature, for example, in a range of about 15-95°C, 15-80°C, 20-95°C, 20-90°C, 20-80°C, 40-95°C, 40-90°C, or 40-80°C, in a solid / liquid mass ratio range of about 5-20, 5-15, 8-15, 5-12, or 8-12 L / kg (water / zeolite).

[0040] In the acid treatment step 8, an effective amount of an inorganic or organic acid is dispersed in the suspension, and the pH of the suspension is maintained in a strongly acidic range to synthesize a second ultrastable Y zeolite (referred to herein as USY(b)) with an increased SAR. Extraframework aluminum (aluminum atoms that are not part of the zeolite framework) is removed from USY(a) to obtain USY(b) zeolite. The removal is carried out by acid treatment. Examples of inorganic acids that can be used include sulfuric acid, nitric acid, and hydrochloric acid. In certain embodiments, the inorganic acid selected is sulfuric acid or hydrochloric acid. Furthermore, carboxylic acids can be suitably used as the organic acids described above. The amount of inorganic or organic acid added is an amount appropriate for controlling the pH of the suspension in a strongly acidic range, for example, less than about 2.0 or less than 2.5, e.g., in the range of about 0.7 to 2.5, 0.7 to 2.0, 1.0 to 2.5, or 1.0 to 2.0. The amount of Al2O3 added can be, for example, a 0.5-4.0-fold, 0.5-3.5-fold, 0.7-4.0-fold, 0.7-3.5-fold, or 0.5-fold molar increase relative to the amount of Al2O3 in USY(a). The acidic suspension is maintained at an effective temperature, for example, 15-95°C, 15-80°C, 20-95°C, 20-90°C, 20-80°C, 40-95°C, 40-90°C, or 40-80°C, for an effective residence time, for example, in the range of about 10-600°C, 10-180°C, 30-600°C, or 30-180 minutes. The acid treatment in step 8 increases the SAR of the Y zeolite, for example, from about 3-6 to about 30-100°C, 40-100°C, 30-80°C, or 40-80°C.

[0041] The solid obtained in acid-treatment step 8 can be filtered, washed with water at an effective temperature, for example, about 15-95°C, 15-80°C, 20-95°C, 20-90°C, 20-80°C, 40-95°C, 40-90°C, or 40-80°C, and dried at an effective temperature, for example, about 80-180°C or 100-180°C, for an effective residence time, for example, about 30-1800 minutes, 60-1800 minutes, 30-600 minutes, or 60-600 minutes, to recover USY(b). Optionally, after washing, the solid obtained in acid-treatment step 8 can be subjected to one or more additional treatment cycles with an inorganic or organic acid at an effective temperature, concentration, and residence time similar to those in step 8, followed by washing with water. The solid obtained after one or more additional acid treatments is dried at an effective temperature and residence time similar to those in step 8 to recover USY(b). In certain cases, one or more additional cycles of the first acid treatment step are not performed.

[0042] In heat treatment step 9, the USY(b) zeolite is subjected to a heat treatment to prepare a third ultrastable Y zeolite, USY(c). In certain embodiments, the heat treatment in step 9 comprises calcining the second USY zeolite (USY(b)) at an effective temperature, for example, in the range of about 500-700, 550-700, 500-650, or 550-650°C (typically in the presence of air or oxygen, or in the presence of steam), for a time period in the range of about 10-600, 10-180, 30-600, or 30-180 minutes, and recovering USY(c). If the calcination temperature is less than about 500°C, the amount of framework substitution of zirconium atoms and / or titanium atoms and / or hafnium atoms tends to decrease; if the calcination temperature is more than about 700°C, the specific surface area of ​​the ultrastable Y zeolite decreases, which may result in a decrease in the amount of framework substitution of zirconium atoms and / or titanium atoms and / or hafnium atoms.

[0043] In steps 10-13, framework substitution is performed to produce a post-processed framework-modified USY zeolite, in which a portion of the aluminum atoms in the framework of the USY zeolite are replaced with zirconium and / or titanium and / or hafnium atoms. In certain embodiments, the post-processed framework-modified USY zeolite material is produced by calcining a USY zeolite having the properties described herein at about 500-700°C. A suspension containing the calcined USY zeolite is formed. The suspension has a liquid / solid mass ratio of about 5-15. An inorganic or organic acid is added to adjust the pH of the suspension to less than about 2.0. A solution containing a zirconium compound and / or a titanium compound and / or a hafnium compound is then mixed. The solution is neutralized, for example with aqueous ammonia, to adjust the pH of the mixed solution to about 7-7.5.

[0044] Suitable zirconium compounds discussed above include one or more of zirconium sulfate, zirconium nitrate, zirconium chloride, and the like. In certain embodiments, zirconium sulfate and / or zirconium nitrate are selected. The amount of zirconium compound added, calculated on an oxide basis (i.e., zirconium oxide) and measured relative to the weight of the post-treated framework-modified USY zeolite component, is generally about 0.1-5.0, 0.1-4.0, 0.1-3.0, 0.2-5.0, 0.2-4.0, 0.2-3.0, 0.3-5.0, 0.3-4.0, or 0.3-3.0 wt.%. Addition of a zirconium compound in an amount less than about 0.1 wt.% does not improve the solid acidity properties of the zeolite. Addition of a zirconium compound in an amount greater than 5 wt.% tends to cause clogging of the pores of the zeolite. An aqueous solution of a zirconium compound prepared by dissolving a zirconium compound in water can be used as the zirconium compound.

[0045] Suitable titanium compounds include one or more of titanium sulfate, titanium acetate, titanium chloride, titanium nitrate, and titanium lactate. In certain embodiments, titanium sulfate and / or titanium acetate are selected. The amount of titanium compound added, calculated on an oxide basis (i.e., titanium oxide) and measured relative to the weight of the post-treated framework-modified USY zeolite component, is generally about 0.1 to 5.0, 0.1 to 4.0, 0.1 to 3.0, 0.2 to 5.0, 0.2 to 4.0, 0.2 to 3.0, 0.3 to 5.0, 0.3 to 4.0, or 0.3 to 3.0 wt.%. Addition of titanium compounds in amounts less than about 0.1 wt.% does not improve the solid acid properties of the zeolite. Addition of titanium compounds in amounts greater than 5 wt.% tends to cause clogging of the zeolite pores. An aqueous solution of titanium prepared by dissolving a titanium compound in water can be used as the titanium compound.

[0046] Suitable hafnium compounds discussed above include one or more of hafnium chloride, hafnium nitrate, hafnium fluoride, hafnium bromide, hafnium oxalate, and the like. In certain embodiments, hafnium chloride and / or hafnium nitrate are selected. The amount of hafnium compound added is generally about 0.1-5.0, 0.1-4.0, 0.1-3.0, 0.2-5.0, 0.2-4.0, 0.2-3.0, 0.3-5.0, 0.3-4.0, or 0.3-3.0 wt. %, calculated on an oxide basis (i.e., hafnium oxide) and measured relative to the weight of the post-treated framework-modified USY zeolite component. Addition of a hafnium compound in an amount less than about 0.1 wt. % does not improve the solid acid properties of the zeolite. Addition of a hafnium compound in an amount greater than 5 wt. % tends to clog the pores of the zeolite. An aqueous solution of a hafnium compound prepared by dissolving a hafnium compound in water can be used as the hafnium compound.

[0047] The pH of the suspension is adjusted to less than about 2.0 to prevent precipitation when mixing the aqueous solution of zirconium and / or hafnium and / or titanium compounds with the suspension of ultrastable Y zeolite described above. In certain embodiments, the aqueous solution of zirconium and / or hafnium and / or titanium compounds with the suspension of ultrastable Y zeolite is mixed by gradually adding the aqueous solution to the suspension. After the addition of the aqueous solution to the suspension is complete, the solution can be stirred and mixed for about 3 to 5 hours at a suitable temperature, for example, about 20 to 40°C or 25 to 35°C. Furthermore, after the mixing is complete, the mixed solution can be neutralized by adding an alkali compound, such as aqueous ammonia and / or a similar alkali compound, and the pH can be adjusted to about 7.0 to 7.5 to obtain the post-treated framework-modified USY zeolite described herein.

[0048] In this regard, when only a zirconium compound (or an aqueous solution thereof) is used as the compound (or an aqueous solution thereof) and added to the suspension described above, a post-treated skeletal-modified USY zeolite (Zr-USY) is formed in which some of the aluminum atoms forming the framework of the ultrastable Y zeolite are replaced with zirconium atoms; when only a titanium compound (or an aqueous solution thereof) is used, a post-treated skeletal-modified USY zeolite (Ti-USY) is formed in which some of the aluminum atoms forming the framework of the ultrastable Y zeolite are replaced with titanium atoms; when only a hafnium compound (or an aqueous solution thereof) is used, a post-treated skeletal-modified USY zeolite (Hf-USY) is formed in which some of the aluminum atoms forming the framework of the ultrastable Y zeolite are replaced with hafnium atoms; when a zirconium compound and a titanium compound (or an aqueous solution thereof) are used, a catalyst in which some of the aluminum atoms forming the framework of the ultrastable Y zeolite are replaced with zirconium atoms and titanium atoms is formed. When a zirconium compound and a hafnium compound (or an aqueous solution thereof) are used, a post-treated skeletal-modified USY zeolite (Zr-Ti-USY) is formed in the catalyst in which some of the aluminum atoms forming the framework of the ultrastable Y zeolite are replaced with zirconium atoms and hafnium atoms. When a hafnium compound and a titanium compound (or an aqueous solution thereof) are used, a post-treated skeletal-modified USY zeolite (Hf-Ti-USY) is formed in the catalyst in which some of the aluminum atoms forming the framework of the ultrastable Y zeolite are replaced with hafnium atoms and titanium atoms. When a zirconium compound, a titanium compound, and a hafnium compound (or an aqueous solution thereof) are used, a post-treated skeletal-modified USY zeolite (Zr-Ti-Hf-USY) is formed in the catalyst in which some of the aluminum atoms forming the framework of the ultrastable Y zeolite are replaced with zirconium atoms, titanium atoms, and hafnium atoms.

[0049] The resulting framework-substituted zeolite can be optionally filtered, washed with water, and dried at about 80-180°C. The mixture can be maintained in quasi-equilibrium with the steam for 10-20 hours, for example, at a temperature of about 600-800°C. For example, in step 10, the calcined USY(c) zeolite from step 9 is prepared for acid treatment by dispersing it in water at an effective temperature, for example, about 15-95°C, 15-80°C, 20-95°C, 20-90°C, 20-80°C, 40-95°C, 40-90°C, or 40-80°C, in a liquid / solid mass ratio of, for example, about 5:1-15:1, 5:1-12:1, 8:1-15:1, or 8:1-12:1, to form a suspension having an effective concentration of USY(c).

[0050] In the acid treatment step 11, an effective amount of an inorganic or organic acid is dispersed in the suspension to maintain the pH of the suspension in a strongly acidic range and prepare the zeolite for metal intercalation into the framework in step 12. In certain embodiments, this can be performed in a stepwise manner, as in the '036 patent family. In additional embodiments, the acid treatment to prepare the zeolite for metal intercalation into the framework can be performed simultaneously with the metal intercalation, as disclosed, for example, in commonly owned U.S. Patent Application Publication No. 2021 / 0077985 A1, which is incorporated herein by reference in its entirety. Examples of inorganic acids that can be used include sulfuric acid, nitric acid, and hydrochloric acid. In certain embodiments, the inorganic acid selected is sulfuric acid or hydrochloric acid. Furthermore, carboxylic acids can be suitably used as the organic acids described above. The amount of inorganic or organic acid added is an amount appropriate to control the pH of the suspension in a strongly acidic range, e.g., less than about 2.0 or less than 2.5, e.g., in a range of about 0.7-2.5, 0.7-2.0, 1.0-2.5, or 1.0-2.0. The acidic suspension is maintained at an effective temperature, for example, 15 to 80°C, 15 to 60°C, 15 to 35°C, 15 to 30°C, or 20 to 60°C, for an effective residence time, for example, in the range of about 10 to 600, 10 to 180, 30 to 600, or 30 to 180 minutes.

[0051] In step 12, framework substitution is performed. The acid-modified USY(c) zeolite suspension is subjected to a metal treatment to replace a portion of the aluminum atoms forming the framework of the ultrastable Y zeolite. In certain embodiments, framework substitution is performed by adding a solution containing a transition metal compound to the acid-modified USY(c). In certain embodiments, the transition metal compound comprises a zirconium compound and / or a titanium compound and / or a hafnium compound. The solution is maintained at an effective temperature, e.g., 15-80°C, 15-60°C, 15-35°C, 15-30°C, 20-60°C, 15-35°C, or 15-30°C, for an effective residence time, e.g., about 10-600°C, 10-180°C, 30-600°C, or 30-180°C. The suspension obtained in step 12 can be neutralized to a pH range of about 7.0-7.5, e.g., using ammonium hydroxide. The solid obtained in the metal insertion step 12 can be filtered, washed with water at an effective temperature, for example, in the range of about 15-95, 15-80, 20-95, 20-90, 20-80, 40-95, 40-90, or 40-80°C, and dried at an effective temperature, for example, in the range of about 80-180°C or 100-180°C, for an effective residence time, for example, in the range of about 30-1800 minutes, 60-1800 minutes, 30-600 minutes, or 60-600 minutes, to recover the post-treated framework-modified USY zeolite (USYA) in step 13.

[0052] The ultrastable Y-type zeolite is used as a raw material to prepare the post-processed framework-modified USY zeolite, referred to above as USY(c). As noted above, one or more of steps 1-9 can be used to prepare the USY introduced in step 10, or it can be obtained by other methods. The USY introduced in step 10 generally has the properties of known USY zeolites, and can be synthesized, modified (by one or more of steps 1-9 or alternative methods), or procured to provide USY zeolites with SARs in the range of about 30-100, 40-100, 30-80, or 40-80 for efficient metal insertion. Known USY-type zeolites generally have a unit cell dimension (UD) in the range of about 2.425-2.450 or 2.430-2.450 nm; a specific surface area generally in the range of about 600-900, 600-800, 650-900, or 650-800 m².2 / g; or pore volumes of about 0.3-0.75, 0.4-0.75, 0.3-0.6, or 0.4-0.6 ml / g. Known USY-type zeolites also generally have SARs in the ranges of about 5-100, 10-100, 20-100, 5-80, 10-80, 20-80, 25-100, or 25-80. As described herein, this SAR can be selected or modified to provide a USY effective for metal insertion. For example, a suitable zeolite has the FAU framework (zeolite Y), in which micropores are formed by 12-membered rings, and its pore size in the

[0111] direction is 7.4 × 7.4 Å. UD, also known as the crystal lattice parameter, can be measured according to ASTM standard D3942, "Standard Test Method for Determination of the Unit Cell Dimension of a Faujasite-Type Zeolite." The specific surface area is determined by the Brunauer-Emmett-Teller (BET) method using nitrogen adsorption. The ultrastable Y zeolite can be prepared by any method known in the art. The ultrastable Y zeolite is subjected to a post-treatment skeletal modification as described herein to form the post-treated skeletal-modified USY zeolite used to prepare the composite catalyst particles.

[0053] The post-treated framework-modified USY zeolite incorporates one or more of zirconium, titanium, and hafnium into its framework. Effective concentrations of Zr, Ti, and / or Hf, calculated on an oxide basis (i.e., ZrO2, TiO2, and / or HfO2) and measured relative to the weight of the post-treated framework-modified USY zeolite, include about 0.1 to 5.0, 0.1 to 4.0, 0.1 to 3.0, 0.2 to 5.0, 0.2 to 4.0, 0.2 to 3.0, 0.3 to 5.0, 0.3 to 4.0, or 0.3 to 3.0 wt.%. In certain embodiments, the amount of each individual material providing Zr, Ti, and / or Hf may be less than 0.1, 0.2, or 0.3 wt.%, but when combined, the total amount is at least 0.1, 0.2, or 0.3 wt.%. Those skilled in the art will understand that when the framework-substituted zeolite in the catalyst contains zirconium atoms as described above, as well as titanium and / or hafnium atoms, the mass ratio (in terms of oxides) of zirconium atoms to titanium and / or hafnium atoms is not particularly limited, and any ratio of zirconium, titanium, or hafnium that is effective when the catalyst particles are used, for example, in the hydrocracking of heavy hydrocarbon oils, can be used.In certain embodiments, the post-treated framework-modified USY zeolite is a framework-substituted zeolite in which a portion of the aluminum atoms forming the zeolite framework are replaced with only zirconium atoms, referred to as a "zirconium-substituted zeolite" or "Zr-USY"; a portion of the aluminum atoms forming the zeolite framework are replaced with only titanium atoms, referred to as a "titanium-substituted zeolite" or "Ti-USY"; a portion of the aluminum atoms forming the zeolite framework are replaced with only hafnium atoms, referred to as a "hafnium-substituted zeolite" or "Hf-USY"; a portion of the aluminum atoms forming the zeolite framework are replaced with only zirconium and titanium atoms, referred to as a "zirconium-titanium-substituted zeolite" or " framework-substituted zeolites in which some of the aluminum atoms forming the zeolite framework are replaced only with hafnium and titanium atoms, and are called "hafnium-titanium substituted zeolites" or "Hf-Ti-USY" framework-substituted zeolites; framework-substituted zeolites in which some of the aluminum atoms forming the zeolite framework are replaced only with zirconium and hafnium atoms, and are called "zirconium-hafnium substituted zeolites" or "Zr-Hf-USY" framework-substituted zeolites; and framework-substituted zeolites in which some of the aluminum atoms forming the zeolite framework are replaced only with zirconium, titanium, and hafnium atoms, and are called "zirconium-titanium-hafnium substituted zeolites" or "Zr-Ti-Hf-USY" framework-substituted zeolites.

[0054] In post-processed framework-modified USY zeolites, zirconium and / or titanium and / or hafnium atoms that replace aluminum atoms function as framework components of the USY zeolite. The substitution can be confirmed, for example, by X-ray fluorescence analysis, radio frequency plasma emission spectroscopy, atomic absorption spectroscopy, ultraviolet-visible-near infrared spectroscopy (UV-Vis-NIR), Fourier transform infrared spectroscopy (FT-IR), and / or nuclear magnetic resonance spectroscopy (NMR).

[0055] In the discussion herein, the titanium component and one or more phosphorus components of the binder are clearly distinct and separate from the metals that replace aluminum atoms in the framework of the USY zeolite.

[0056] In embodiments herein, a post-treated skeletal-modified USY zeolite is provided in step 13, which zeolite may be formed as described herein or provided from another source. The post-treated skeletal-modified USY zeolite generally has one or more of zirconium, titanium, and / or hafnium incorporated into its framework at an effective concentration of about 0.1 to 5.0, 0.1 to 4.0, 0.1 to 3.0, 0.2 to 5.0, 0.2 to 4.0, 0.2 to 3.0, 0.3 to 5.0, 0.3 to 4.0, or 0.3 to 3.0 wt. %, calculated on an oxide basis (i.e., ZrO, TiO, and / or HfO) and measured relative to the weight of the post-treated skeletal-modified USY zeolite. In certain embodiments, the amount of each material providing Zr, Ti, and / or Hf may be less than 0.1, 0.2, or 0.3 wt. %, but when combined, the total amount is at least 0.1, 0.2, or 0.3 wt. In certain embodiments, the framework-substituted USY zeolite component is provided in a "wet" state. The solid material obtained in the framework substitution step (step 12) is filtered / washed and provided in a wet state. In this case, the usual drying step is not performed (or is performed only slightly), so moisture is retained in the solid. In certain embodiments, the framework-substituted USY zeolite component is provided in a "dry" state. The solid material obtained in the framework substitution step (step 12) is filtered and dried, but not calcined. Therefore, the usual heat treatment step of calcining the material is not performed. In certain embodiments, the framework-substituted USY zeolite component is provided in a "dry" state. The solid material obtained in the framework substitution step (step 12) is filtered, dried, and calcined. Thus, the USYA in step 13 may be provided as wet, dry (uncalcined) or calcined zeolite material.

[0057] <Binder> Step 14 corresponds to providing and / or forming a titania-containing binder component, which is then mixed with the post-treated skeletal-modified USY zeolite and extruded in steps 16 and 17. The binder component includes titania and one or more other inorganic oxides. In embodiments herein, the binder component includes titania and / or one or more other inorganic oxides and is formed as an amorphous composite. In certain embodiments, the binder component includes an amorphous alumina-titania binary composite. In certain embodiments, the binder component includes an amorphous alumina-silica-titania ternary composite. Any of these embodiments can be combined with one or more other components, including one or more of phosphorus, boron, or zirconia. In certain embodiments, the binder component is an inorganic oxide selected from the group consisting of alumina-titania, silica-alumina-titania, alumina-zirconia-titania, alumina-boron-titania, phosphorus-alumina-titania, silica-alumina-boron-titania, phosphorus-alumina-boron-titania, phosphorus-alumina-silica-titania, silica-alumina-zirconia-titania, alumina-zirconia-titania, and phosphorus-alumina-zirconia-titania. In certain embodiments, the binder component is an inorganic oxide selected from the group consisting of alumina, titania, and silica.

[0058] The titania-containing binder component contains about 0.01 to 15, 0.1 to 15, 1 to 15, 2 to 15, 5 to 15, 0.01 to 10, 0.1 to 10, 1 to 10, 2 to 10, 5 to 10, 0.01 to 8, 0.1 to 8, 1 to 8, or 2 to 8 weight percent titania based on the total weight of the binder component. In certain embodiments, the titania-containing binder component comprises about 0.01-15, 0.1-15, 1-15, 2-15, 5-15, 0.01-10, 0.1-10, 1-10, 2-10, 5-10, 0.01-8, 0.1-8, 1-8, or 2-8 weight percent titania, about 0.01-10, 0.1-10, 1-10, 2-10, 5-10, 0.01-8, 0.1-8, 1-8, or 2-8 weight percent silica, and about 80-99.98, 80-99.8, 80-98, 80-96, 80-90, 84-99.98, 84-99.8, 84-98, 84-96, or 84-90 weight percent alumina. In one particular embodiment, the titania-containing binder component comprises about 5-10 wt.% titania, about 5-10 wt.% silica, and about 80-90 wt.% alumina.

[0059] Suitable binders can be formed from a gel of titania and other inorganic oxides, such as alumina and / or silica. Suitable precursors for forming titania in the binder include, but are not limited to, one or more of Ti(OH), TiO(OH), TiO, Ti(C), Ti(C), TiSO, or Ti(SO). Suitable precursors for forming alumina in the binder include, but are not limited to, one or more of NaAlO and Al(SO). In certain embodiments, precursors for forming alumina include those selected from aluminates, alumina, aluminum colloids, boehmite, pseudoboehmite, aluminum hydroxide, aluminum salts, aluminum alkoxides, and alumina gel. Suitable precursors for forming silica in the binder include, but are not limited to, one or more of NaSiO and NaSiO. In certain embodiments, precursors for forming silica include those selected from the group consisting of sodium silicate (water glass), fumed silica, precipitated silica, colloidal silica, silica gel, silicon hydroxide, and silicon alkoxide. Each precursor is provided at an effective concentration, for example, about 1-15, 1-10, or 1-5 wt. % in aqueous solution. In certain embodiments, the precursors are mixed for a suitable time and temperature, for example, for about 15-180, 15-120, 15-90, 15-75, 30-180, 30-120, 30-90, or 30-75 minutes at about 30-90°C, 30-75°C, 30-70°C, 40-90°C, 90-75°C, or 40-70°C. The product is then washed, for example, to remove sodium sulfate, ion-exchanged to adjust the alumina content, adjusted to a pH of, for example, about 10 using an ammonium source, dehydrated, and kneaded.

[0060] In certain embodiments, an intimate mixture of solid titania and one or more other solid inorganic oxides can be used directly as a binder component. For example, a solid mixture of solid titania particles and one or more other inorganic oxides can be formed into a slurry or paste, intimately mixed into a uniform mixture, and used as a binder. For example, titania, one or both of alumina and silica, and optionally one or more of phosphorus, boron, or zirconia are mixed in the above-mentioned effective ratios at an appropriate temperature, for example, in the range of about 15-80°C, 15-60°C, 15-35°C, 15-30°C, or 20-60°C. The mixture is mixed with an effective amount of water, for example, in a liquid / solid mass ratio of about 30-80, for an effective mixing / stirring time, for example, in the range of about 10-180 minutes, or until an effective amount of water is removed. Thus, a dough formed by kneading / stirring wet solid materials is mixed with post-treated framework-modified USY zeolite as described herein.

[0061] The post-treated skeletal-modified USY zeolite and the titania-containing binder component are mixed to form a catalyst support material. The post-treated skeletal-modified USY zeolite (wet, dry (uncalcined), or calcined) is mixed with the titania-containing binder component (wet, dry (uncalcined), or calcined). In certain embodiments, the mixing and forming can follow known processes for forming catalysts. For example, the components can be mixed and kneaded (step 16), followed by coextrusion or other methods to form composite support particles into the desired shape (step 18), and calcining the composite support particles (step 19).

[0062] The composite support material is formed from the post-treated framework-modified USY zeolite material, e.g., obtained from step 13 herein, and a titania-containing binder component (e.g., obtained from step 14 herein), and optionally one or more other zeolite materials. The composite support material generally has a viscosity of about 150-500, 150-450, 200-500, 200-450, or 300-450 m 2The post-treated framework-modified USY zeolite component, titania-containing binder component, and active component have a surface area in the range of about 0.4 to 0.8, 0.4 to 0.75, 0.4 to 0.65, 0.45 to 0.8, 0.45 to 0.75, or 0.45 to 0.65 ml / g, respectively, and a pore volume in the range of about 0.4 to 0.8, 0.4 to 0.75, 0.45 to 0.75, or 0.45 to 0.65 ml / g. The contents of the post-treated framework-modified USY zeolite component, titania-containing binder component, and active component are appropriately determined depending on the purpose. For example, the post-treated skeletal modified USY zeolite content of catalyst particles formed with the composite support material may be in the range of about 0.1 to 99, 0.1 to 90, 0.1 to 80, 0.1 to 70, 0.1 to 50, 0.1 to 40, 2 to 99, 2 to 90, 2 to 80, 2 to 70, 2 to 50, 2 to 40, 20 to 99, 20 to 90, 20 to 80, 20 to 50, or 20 to 40 wt %, with the remaining content being the titania-containing binder component and active component, and, in certain embodiments, optionally one or more other zeolite materials.

[0063] In the mixing / kneading step 16, the post-treated framework-modified USY zeolite and the titania-containing binder component are mixed in the effective ratios described above at a suitable temperature, for example, in the range of about 15-80°C, 15-60°C, 15-35°C, 15-30°C, or 20-60°C. The mixture is kneaded / mixed with an effective amount of water, for example, at a liquid / solid mass ratio in the range of about 30-80°C, for an effective kneading / mixing time, for example, in the range of about 10-180 minutes. Thus, by kneading / mixing the wet solid materials, a dough is formed, which is then shaped and dried. The kneaded / mixed product can be subjected to a heat treatment to achieve more intimate contact and uniformity between the components through thermal diffusion and solid-state reaction. The resulting kneaded / stirred material is extruded through a die having an effective cross-sectional shape and dimensions at a suitable temperature, for example, about 15-80°C, 15-60°C, 15-35°C, 15-30°C, or 20-60°C (forming step 18). Effective cross-sectional shapes include, for example, cylindrical, trilobe, twisted trilobe, or quadrilobe. Effective cross-sectional dimensions include, for example, a diameter or effective diameter in the range of about 0.8-3 millimeters or 0.8-2.5 millimeters. The resulting extrudate is dried at an effective temperature, for example, about 80-180°C or 100-180°C, for an effective residence time, for example, about 30-1800, 60-1800, 30-600, or 60-600 minutes, and the dried composite extrudate is recovered. Optionally, in some cases, the separate drying step can be omitted, whereby the composite extrudate is sent to and calcined in heat treatment step 19. In heat treatment step 19, the composite extrudate (optionally dried) is subjected to a heat treatment to prepare calcined composite particles. In certain embodiments, the heat treating in step 19 comprises calcining the composite extrudate (optionally optionally dried) at an effective temperature (typically in the presence of air or oxygen, or in the presence of steam), for example, in the range of about 400-800, 400-700, 400-650, 500-800, 500-700, 500-650, 550-800, 550-700, 550-650, 600-800, or 600-700°C, for a time period ranging from about 10-600, 10-180, 30-600, or 30-180 minutes, and recovering the calcined composite particles.

[0064] An active component comprising a phosphorus component and one or more other hydrocracking metals and / or promoters is included in the catalyst particles. In certain embodiments, in addition to the active component impregnated in the catalyst particles, the post-treated skeletal-modified USY zeolite material in the final particles functions as the active catalyst material.

[0065] The titania-containing binder component, post-treated skeletal-modified USY zeolite, and calcined composite particles are characterized by outer surfaces and pore-wall surfaces, and the active component is supported on one or more of these surfaces. The resulting particles / extrudates include: (a) the titania-containing binder component and the active component, including the phosphorus component and one or more other hydrocracking metals and / or promoters, supported on the outer surfaces and pore-wall surfaces of the calcined composite particles; (b) the outer surfaces and pore-wall surfaces of a kneaded / stirred composite of the titania-containing binder component and the post-treated skeletal-modified USY zeolite; and / or (c) the outer surfaces and pore-wall surfaces of the titania-containing binder component.

[0066] In certain embodiments, all or a portion of the active component (in terms of amount, type of active component, or both amount and type of active component) is supported on the calcined composite particles (designated step 20), the titania-containing binder component (designated step 15), and / or the kneaded / stirred composite of the titania-containing binder component and the post-treated framework-modified USY zeolite (designated step 17). While steps 20, 15, and 17 are shown in dashed lines in FIG. 1 , it should be understood that one or more of these steps are required to produce the catalyst particles herein. In certain embodiments, only step 20 is performed. In certain embodiments, only step 15 is performed. In certain embodiments, only step 17 is performed. In certain embodiments, only steps 15 and 20 are performed. In certain embodiments, only steps 17 and 20 are performed. In certain embodiments, only steps 15 and 17 are performed. In certain embodiments, each of steps 20, 15, and 17 is performed.

[0067] The final product, a calcined composite catalyst particle, is supported with an active component comprising a phosphorus component and one or more other hydrocracking metals and / or promoters.

[0068] The phosphorus component can be provided by blending it with one or more other active components in an active component solution. For example, phosphoric acid can be used in the active component solution at an effective concentration, e.g., about 1-10, 1-5, or 1-3 wt. % in aqueous solution. Catalysts produced according to embodiments herein can contain about 0.01-5.0, 0.1-5.0, 1-5.0, 0.01-3.0, 0.1-3.0, or 1.0-3.0 wt. % of the phosphorus component, in terms of metal, oxide, or sulfide, based on the total weight of the composite catalyst material.

[0069] In addition to the phosphorus component, the active component can also include any one or more metals or metal compounds (oxides or sulfides) known in the field of hydrocracking, including those selected from Groups 6, 7, 8, 9, and 10 of the IUPAC Periodic Table of the Elements. In certain embodiments, the active component includes a phosphorus component and one or more additional components effective as hydrocracking catalysts (e.g., one or more of Mo, W, Co, or Ni (oxides or sulfides)). In certain embodiments, the active component includes a phosphorus component, Mo and / or W metal or compound as a hydrocracking component, and Co and / or Ni metal or compound as a promoter. In certain embodiments, the catalysts herein include Ni / Mo / P as the active component. In certain embodiments, the catalysts herein include Co / Mo / P as the active component. In certain embodiments, the catalysts herein include Ni / W / P as the active component. In certain embodiments, the catalysts herein include Co / W / P as the active component.

[0070] The active components can be present in the catalyst at any effective concentration. For example, the total active component content (phosphorus and one or more hydrocracking metals and / or promoters) can be present in an amount of about 0.01 to 40, 0.1 to 40, 1 to 40, 2 to 40, 5 to 40, 0.01 to 30, 0.1 to 30, 1 to 30, 2 to 30, 5 to 30, 0.01 to 20, 0.1 to 20, 1 to 20, 2 to 20, or 5 to 20 wt. % of the metal, oxide, or sulfide.

[0071] In one particular embodiment, designated herein as "Embodiment 1a," the active component is supported on calcined composite support particles (Step 20). The catalyst particles thus formed are then calcined again (Step 21) to recover the final product, catalyst particles with the active component on the composite support.

[0072] In the active ingredient loading step 20, the active ingredient is loaded onto the surface of the support (including the pore wall surface). Several methods can be used to load the active ingredient onto the support, including, but not limited to, immersion, incipient wetness, and evaporation. In certain embodiments, the calcined support is immersed in an excess amount of an aqueous solution containing the active ingredient. The solution fills the pores and also adsorbs onto the support surface, and the excess solution is removed. In certain embodiments, impregnation is performed using incipient wetness by tumbling or spraying the support with a volume of solution in which the concentration of the metal compound is adjusted to achieve the target metal level. In certain embodiments, evaporation impregnation is performed by saturating the support with water or an acid solution and immersing it in an aqueous solution containing the active ingredient, after which the compound diffuses through the aqueous phase into the pores of the support. The metal-loaded support is then dried and calcined (step 21), which forms oxides of the active ingredient and aluminum orthophosphate.

[0073] In certain embodiments, the active ingredient loading step 20 comprises immersing the calcined composite support particles formed from the post-treated framework-modified USY zeolite and a binder in an active ingredient-containing aqueous solution. The amount and concentration of the active ingredient-containing aqueous solution depend on the desired amount of active ingredient to be loaded onto the composite support particles. In certain embodiments of the above method, the volume of the active ingredient solution is equal to or slightly less than the pore volume of the support. The solution is maintained at an effective temperature, for example, about 40-100, 40-99, 60-100, 60-99, 60-97, 70-99, 70-97, 80-99, 80-97, or 90-99°C, for an effective residence time, for example, in the range of about 40-1200, 40-600, 40-360, 60-1200, 60-600, 60-360, 120-1200, 120-600, 120-360, 180-1200, 180-600, 180-360, or 240-360 minutes. The resulting solid can be filtered and dried at an effective temperature, for example, in the range of about 80-180°C or 100-180°C, for an effective residence time, for example, in the range of about 30-1800, 60-1800, 30-600, or 60-600 minutes, to recover composite support particles formed from the post-treated framework-modified USY zeolite and the binder, with the active component supported on the composite material. Optionally, in some cases, the separate drying step can be omitted, whereby the composite material containing the active component can be sent to a heat treatment step 21 for calcination.

[0074] In step 21, the supported composite material is subjected to a heat treatment to prepare calcined composite particles having an active component on the composite material. In certain embodiments, the heat treatment in step 21 involves calcining at an effective temperature, for example, in the range of about 400-800, 500-800, 500-700, 500-650, 550-800, 550-700, 550-650, 600-800, or 600-700°C, for a time period ranging from about 10-600, 10-180, 30-600, or 30-180 minutes, and recovering the calcined composite particles having an active component on the composite material. In certain embodiments, the calcination is carried out in the presence of air. In step 22, the final catalyst product is recovered. In embodiments where the catalyst is a hydrocracking catalyst, a hydrogenation catalyst, or a reforming catalyst, the composite support material carrying the active component generally has a thickness of about 150 to 500, 150 to 450, 200 to 500, 200 to 450, or 300 to 450 m 2 / g and a pore volume in the range of about 0.4-1.0, 0.4-0.8, 0.4-0.75, 0.4-0.65, 0.45-1.0, 0.45-0.8, 0.45-0.75, or 0.45-0.65 ml / g.

[0075] In one particular embodiment, designated herein as "Embodiment 1b," the active ingredient is supported on a titania-containing binder component (Step 15). The titania-containing binder component thus formed is subsequently sent to Step 16, where it is mixed with a post-processed framework-modified USY zeolite material.

[0076] The active ingredient loading step 15 involves loading the active ingredient onto the surface (including the pore wall surfaces) of the titania-containing binder component. Several methods can be used to add the active ingredient to the titania-containing binder component, including, but not limited to, co-mulling, immersion, incipient wetness, and evaporation.

[0077] Although step 15 is shown as a separate step, loading of the titanium-containing binder component with the active ingredients may occur during the mixing and kneading / stirring step of the titanium-containing binder component (e.g., in the process described with respect to step 14) or may occur as a separate step thereafter. In certain implementations of embodiment 1b, all or a portion of the water normally used in the mixing and kneading / stirring step of the binder components is replaced with an aqueous solution containing one or more of the active ingredients.

[0078] In certain embodiments of step 15, an effective amount of titania-containing binder component is co-stirred with the active ingredient-containing solution. In certain embodiments of step 15, an effective amount of titania-containing binder component (including titania, and: alumina, silica, or alumina and silica; alone or in combination with one or more of phosphorus, boron, or zirconia) is co-stirred with the active ingredient-containing solution.

[0079] In certain embodiments of step 15, an effective amount of titania-containing binder, e.g., in a kneaded state, is immersed in an excess amount of active ingredient-containing solution. The solution fills the pores and adsorbs onto the outer surface, and the excess solution is removed to recover the loaded binder component. In certain embodiments, the volume of the active ingredient solution is equal to or slightly less than the pore volume of the binder.

[0080] In certain embodiments, step 15 is carried out using incipient wetness by tumbling or spraying an effective amount of titania-containing binder with a volume of solution in which the active ingredient concentration has been adjusted to achieve the target metal level. In certain embodiments, the volume of solution is equal to or slightly less than the pore volume of the binder. The supported binder material is recovered.

[0081] In one particular embodiment, step 15 is carried out by evaporation impregnation, in which an effective amount of titania-containing binder is saturated with water or an acid solution and immersed in an aqueous solution containing the active ingredient. The active ingredient compound then diffuses through the aqueous phase into the pores of the binder. The loaded binder material is recovered.

[0082] In certain embodiments of the above method, the volume of the active ingredient solution is equal to or slightly less than the pore volume of the binder material, and the solution is maintained at an effective temperature, such as about 40-100, 40-99, 60-100, 60-99, 60-97, 70-99, 70-97, 80-99, 80-97, or 90-99°C, for an effective residence time, such as about 40-1200, 40-600, 40-360, 60-1200, 60-600, 60-360, 120-1200, 120-600, 120-360, 180-1200, 180-600, 180-360, or 240-360 minutes.

[0083] In certain embodiments of step 15, loading can be achieved by loading an appropriate concentration of active ingredient solution to the available pore volume of the binder. In further embodiments of step 15, a smaller amount is used to control the loading amount of active ingredient. For example, the effective volume of the loaded metal solution can be in the range of, for example, about 1-100, 1-99, 1-90, 20-100, 20-99, or 20-90 volume percent relative to the total pore volume of the binder.

[0084] In a further embodiment of step 15, a wet binder material is used. The wet binder material contains water in all or a portion of the pore volume, e.g., in the range of about 1-100, 1-99, 1-90, 50-100, 50-99, or 50-90 volume percent of the total pore volume. This volume can be controlled by partially drying the material to vary the degree of wetting. The active ingredient solution, whether provided by immersion, incipient wetness, or evaporation impregnation, is fully or partially blocked from the saturated pores, thereby reducing diffusion of the metal into the pores. Thus, the active ingredient can be primarily located on the exterior surface of the binder component material, with only limited amounts present within the pores.

[0085] In one particular embodiment, designated herein as "Example 1c," the active ingredient is supported on a composite of a titania-containing binder component and a post-treated framework-modified USY zeolite material (Step 17). The composite thus formed is then sent for subsequent formation in Step 18.

[0086] The active ingredient loading step 17 involves loading the active ingredient onto the surface (including the pore wall surfaces) of the composite of the titania-containing binder component and the post-treated framework-modified USY zeolite material. Several methods can be used to add the active ingredient to the composite, including, but not limited to, co-mixing, immersion, incipient wetness, and evaporation.

[0087] Although step 17 is shown as a separate step, loading of the active ingredient(s) onto the composite of the titania-containing binder component and post-treated framework-modified USY zeolite material may occur during the mixing and kneading / stirring step of the titania-containing binder component (e.g., in the process described with respect to step 16) or may occur as a separate step thereafter. In certain implementations of embodiment 1c, all or a portion of the water normally used in the mixing and kneading / stirring step of the composite support components is replaced with an aqueous solution containing one or more of the active ingredients.

[0088] In one particular embodiment of step 17, an effective amount of a composite of a titania-containing binder component and a post-treated framework-modified USY zeolite material is co-stirred with an active ingredient-containing solution.

[0089] In certain embodiments of step 17, an effective amount of the composite (e.g., in a kneaded state) of the titania-containing binder component and the post-treated framework-modified USY zeolite material is immersed in an excess amount of an active ingredient-containing solution. The solution fills the pores and adsorbs onto the outer surface, and the excess solution is removed to recover the supported composite. In certain embodiments, the volume of the active ingredient solution is equal to or slightly less than the pore volume of the composite.

[0090] In certain embodiments, step 17 is performed using incipient wetness by tumbling or spraying an effective amount of the composite with a volume of solution in which the active ingredient concentration has been adjusted to achieve the target metal level. In certain embodiments, the volume of solution is equal to or slightly less than the pore volume of the composite. The loaded composite material is recovered.

[0091] In certain embodiments, step 17 is carried out by evaporation impregnation, in which an effective amount of titania-containing composite is saturated with water or an acid solution and immersed in an aqueous solution containing the active ingredient. The active ingredient compound then diffuses through the aqueous phase into the pores of the composite. The loaded composite material is recovered.

[0092] In certain embodiments of the above method, the volume of the active ingredient solution is equal to or slightly less than the pore volume of the composite material, and the solution is maintained at an effective temperature, e.g., about 40-100, 40-99, 60-100, 60-99, 60-97, 70-99, 70-97, 80-99, 80-97, or 90-99°C, for an effective residence time, e.g., about 40-1200, 40-600, 40-360, 60-1200, 60-600, 60-360, 120-1200, 120-600, 120-360, 180-1200, 180-600, 180-360, or 240-360 minutes.

[0093] In certain embodiments of step 17, loading can be achieved by loading an appropriate concentration of active ingredient solution to the available pore volume of the composite. In further embodiments of step 17, smaller amounts are used to control the amount of active ingredient loaded. For example, the effective volume of the loaded metal solution can be in the range of, for example, about 1-100, 1-99, 1-90, 20-100, 20-99, or 20-90 volume percent of the total pore volume of the composite.

[0094] In a further embodiment of step 17, a wet composite material is used. The wet composite material contains water in all or a portion of the pore volume, e.g., in the range of about 1-100, 1-99, 1-90, 50-100, 50-99, or 50-90 volume percent of the total pore volume. This volume can be controlled by partially drying the material to vary the degree of wetting. The active ingredient solution, whether provided by immersion, incipient wetness, or evaporation impregnation, is fully or partially blocked from the saturated pores, thereby reducing diffusion of the metal into the pores. Thus, the active ingredient can be primarily located on the exterior surface of the composite material, with only limited amounts present within the pores.

[0095] In certain embodiments, one or more of embodiments 1a, 1b, and / or 1c are performed, which is commonly referred to as "hybrid" loading. In certain embodiments of the hybrid loading method, all or a portion of one or more active ingredients are loaded in step 15, and all or a portion of one or more active ingredients different from the active ingredients loaded in step 15 are loaded in step 17 and / or step 20. In certain embodiments of the hybrid loading method, all of one or more active ingredients are loaded in step 15, and all of one or more active ingredients different from the active ingredient loaded in step 15 are loaded in step 17 and / or step 20. In certain embodiments of the hybrid loading method, a first amount of one or more active ingredients is loaded in step 15, and one or more other amounts of one or more active ingredients are loaded in step 17 and / or step 20, and the one or more active ingredients loaded in the different steps can be the same type or different types of active ingredients. In certain embodiments of the hybrid loading method, all or a portion of one or more active ingredients are loaded in step 15 and / or step 17, and all or a portion of one or more active ingredients different from the active ingredients loaded in step 15 and / or step 17 are loaded in step 20. In certain embodiments of the hybrid loading method, all of one or more active ingredients are loaded in step 15 and / or step 17, and all of one or more active ingredients different from the active ingredients loaded in step 15 and / or step 17 are loaded in step 20. In certain embodiments of the hybrid loading method, a first amount of one or more active ingredients is loaded in step 15 and / or step 17, and one or more other amounts of one or more active ingredients are loaded in step 20, and the one or more active ingredients loaded in the different steps can be the same type or different types of active ingredients.Processes involving hybrid supports are disclosed in commonly owned U.S. patent applications Ser. Nos. 17 / 577,691, 17 / 577,747, and 17 / 577,794, filed Jan. 18, 2022, entitled "Catalysts with Modified Active Phase Dispersion and Method to Prepare Catalysts with Modified Active Phase Dispersion," all of which are incorporated by reference herein in their entireties.

[0096] Additional Zeolite In any of the above embodiments, one or more additional zeolitic components (i.e., zeolitic materials other than the post-treated skeletal-modified USY zeolite or the metal-loaded post-treated skeletal-modified USY zeolite) can be incorporated, for example, during the step of mixing the post-treated skeletal-modified USY zeolite or the metal-loaded post-treated skeletal-modified USY zeolite with the inorganic oxide. The additional zeolitic materials can include, but are not limited to, mordenite, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, Beta, Y, and USY (wherein the USY zeolite component is different from the post-treated skeletal-modified USY zeolite described herein). For example, additional zeolitic materials include a (FAU) framework comprising USY, having a micropore size of 7.4×7.4 Å for the 12-membered rings when viewed along the

[0111] direction; a (MFI) framework comprising ZSM-5, having a micropore size of 5.5×5.1 Å and 5.6×5.3 Å for the 10-membered rings when viewed along the

[0100] and

[0010] directions, respectively; a (MEL) framework comprising ZSM-11, having a micropore size of 5.4×5.3 Å for the 10-membered rings when viewed along the

[0100] direction; a (MTW) ​​framework comprising ZSM-12, having a micropore size of 5.6×6.0 Å for the 12-membered rings when viewed along the

[0010] direction; a (TON) framework comprising ZSM-12, having a micropore size of 4.6×5.7 Å for the 10-membered rings when viewed along the

[0001] direction; (MTT) frameworks comprising ZSM-23, having micropore diameters of 4.5×5.2 Å for 10-membered rings when viewed along the

[0001] direction; (FER) frameworks comprising ZSM-35, having micropore diameters of 4.2×5.4 Å and 3.5×4.8 Å for 10-membered rings and 8-membered rings when viewed along the

[0001] and

[0010] directions, respectively; (MOR) frameworks comprising mordenite zeolite, having micropore diameters of 6.5×7.0 Å and 2.6×5.7 Å for 12-membered rings and 8-membered rings when viewed along the

[0001] and

[0001] directions, respectively; and (BEA) frameworks comprising zeolite Beta polymorph A, having micropore diameters of 6.6×6.7 Å and 5.6×5.6 Å for 12-membered rings when viewed along the

[0100] and

[0001] directions, respectively.

[0097] Hydrocracking process The present specification provides a method for hydrocracking a hydrocarbon oil, which includes a step of hydrocracking the hydrocarbon oil using the hydrocracking catalyst described above. In a specific embodiment, the method for hydrocracking a hydrocarbon oil includes, for example, hydrocracking a hydrocarbon oil having a boiling point in the range of about 370 to 833, 370 to 816, 370 to 650, 375 to 833, 375 to 816, or 375 to 650°C in the presence of hydrogen at a reactor temperature in the range of about 300 to 500, 330 to 450°C, a hydrogen partial pressure in the range of about 40 to 300, 40 to 150, 70 to 300, or 70 to 150 bar, and a liquid hourly space velocity ("LHSV", which refers to the volumetric flow rate of the liquid feedstock divided by the volume of the catalyst) of about 0.1 to 10, 0.2 to 1.5 h -1 and hydrogen / oil ratios of approximately 500 to 2500, 1000 to 2000 normal cubic meters of hydrogen / cubic meter of oil (Nm 3 / m 3 ) into a hydrocracking zone comprising one or more reactors operated in the range of 0.1 to 1.5° C. "Hydrocracking zone" means one or more reactors and associated effluent separation equipment, and may include two or more reactors.

[0098] In a specific embodiment, a method for hydrocracking a hydrocarbon oil includes filling a reaction vessel, which is a flow reactor of a hydrocracking apparatus, with a hydrocracking catalyst, and subjecting a hydrocarbon oil having a boiling point, for example, in the range of about 370 to 816°C or 370 to 650°C to hydrocracking in the presence of hydrogen at a reactor temperature of about 300 to 500°C or 330 to 450°C, a hydrogen partial pressure of about 4 to 30 or 7 to 15 MPa, and a liquid hourly space velocity ("LHSV", which refers to the volumetric flow rate of the liquid feedstock divided by the volume of the catalyst) of about 0.1 to 10 or 0.2 to 1.5 h . -1 The hydrogen / oil ratio is about 500-2500, 1000-2000 normal cubic meters of hydrogen / cubic meter of oil (Nm 3 / m 3 ) in the range of

[0099] In a specific embodiment, a method for hydrocracking a hydrocarbon oil includes filling a reaction vessel, which is a flow reactor of a hydrocracking apparatus, with a hydrocracking catalyst, and hydrocracking a hydrocarbon oil having a boiling point in the range of about 370 to 650°C in the presence of hydrogen at a reactor temperature in the range of about 330 to 450°C, a hydrogen partial pressure in the range of about 7 to 15 MPa, and an LHSV of about 0.2 to 1.5 h. -1 and hydrogen / oil ratio is about 1000-2000Nm 3 / m 3 to obtain a middle distillate comprising kerosene and diesel. In certain embodiments, "middle distillate" refers to hydrocarbons having a normal boiling point in the range of about 135-370, 140-370, 145-370, 135-365, 140-365, 145-365, 135-360, 140-360, or 145-360°C. In certain embodiments, "kerosene" refers to hydrocarbons having a normal boiling point in the range of about 135-270, 140-270, 145-270, 135-265, 140-265, 145-265, 135-260, 140-260, or 145-260°C. In certain embodiments, "gas oil" refers to atmospheric gas oil comprising hydrocarbons with normal boiling points in the range of about 250-370, 255-370, 260-370, 250-365, 255-365, 260-365, 250-360, 255-360, or 260-360°C.

[0100] In certain embodiments, the flow reactor used in the above-described process for hydrotreating hydrocarbon oils may be a flow reactor selected from a stirred bath reactor, an ebullated bed reactor, a baffled slurry bath reactor, a fixed bed reactor, a rotating tubular reactor, or a slurry bed reactor.

[0101] In certain embodiments, the hydrocarbon oils hydrotreated by the methods described above include heavy hydrocarbon oils obtained from (1) crude oil, (2) synthetic crude oil, (3) bitumen, (4) oil sands, (5) shale oil, (6) coal liquids, (7) plastic pyrolysis oil, and / or (8) biomass-derived oil.

[0102] In certain embodiments, the hydrocarbon oil in the above-described methods comprises, consists of, or consists essentially of heavy hydrocarbon oil obtained from (1) crude oil, (2) synthetic crude oil, (3) bitumen, (4) oil sands, (5) shale oil, (6) coal liquids, (7) plastic pyrolysis oil, and / or (8) biomass-derived oil.

[0103] In certain embodiments, the hydrocarbon oil in the above-described method comprises a heavy hydrocarbon oil obtained from crude oil, synthetic crude oil, bitumen, oil sands, shale oil, or coal liquids, wherein the heavy hydrocarbon oil comprises, consists of, or consists essentially of one or more of: a) atmospheric gas oil (AGO); b) vacuum gas oil (VGO); c) deasphalted oil (DAO) or demetallized oil obtained from a solvent debituminization process; d) light coker gas oil or heavy coker gas oil obtained from a coker process; e) cycle oil obtained from a fluid catalytic cracking (FCC) process; f) gas oil obtained from a visbreaking process; g) gas oil obtained from plastic pyrolysis oil; or h) biomass-derived gas oil, wherein all of the feedstocks c) through h) comprise a normal boiling range that corresponds to the boiling range of the atmospheric gas oil or vacuum gas oil. [Example]

[0104] Reference Ti-Zr-USY This reference provides a method for producing a post-treated framework-modified USY zeolite described herein, in which aluminum atoms in the framework of the USY zeolite are replaced with titanium and zirconium (Ti-Zr-USY). This method corresponds to the method disclosed in the '036 patent family (Examples 1 and 5).

[0105] First, the SiO2 / Al2O3 molar ratio is 5.2, the unit cell size is 2.466 nm, and the specific surface area is 720 m 250.0 kg of Na-Y zeolite having a saturation of 1 / g and a Na2O content of 13.0% by mass was suspended in water at a temperature of 60°C (liquid / solid mass ratio: 12.5 L of water / 1 kg of zeolite). Then, 14.0 kg of ammonium sulfate was added thereto. The resulting suspension was stirred at 70°C for 1 hour and filtered. The resulting solid was washed with water. The solid was then washed with an ammonium sulfate solution prepared by dissolving 14.0 kg of ammonium sulfate in 500 L of water at a temperature of 60°C, washed with 500 L of water at a temperature of 60°C, dried at 130°C for 20 hours, and purified to obtain Y zeolite (NH4 65 About 45 kg of Na-Y was obtained. This zeolite was found to have 65% of the sodium (Na) contained in Na-Y converted to ammonium ions (NH4 + ) is ion-exchanged with NH4 65 The Na2O content in Y was 4.5 mass%. 65 40 kg of Y was calcined in a saturated steam atmosphere at 670°C for 1 hour to form hydrogen-Y zeolite (HY).

[0106] 40 kg of HY was suspended in 400 L of water at a temperature of 60°C. Then, 49.0 kg of ammonium sulfate was added thereto. The resulting mixture was stirred at 90°C for 1 hour and washed with 200 L of water at a temperature of 60°C. The mixture was then dried at 130°C for 20 hours to obtain Y zeolite (NH4) in which 95% of the Na contained in the original Na-Y had been ion-exchanged with NH4. 95 Y) about 37 kg of synthesized NH4 95 Approximately 33 kg of Y was calcined for 1 hour in a saturated steam atmosphere at 650°C, resulting in a SiO2 / Al2O3 molar ratio of 5.2, a Na2O content of 0.6 mass%, a crystal lattice constant of 2.438 nm, and a specific surface area of ​​635 m 2 Approximately 15 kg of ultrastable Y-type zeolite (hereinafter also referred to as "USY(a)") having a molecular weight of 1.001 g / g and a crystallinity of 98% was obtained.

[0107] Next, 26 kg of this USY(a) was suspended in 260 L of water at a temperature of 60°C. 61.0 kg of 25% by mass sulfuric acid was gradually added to the suspension, and the suspension was stirred at 70°C for 1 hour to dissolve the extraframework aluminum. The suspension was filtered. The resulting solid was washed with 260 L of deionized water at a temperature of 60°C and dried at 130°C for 20 hours to give a SiO2 / Al2O3 molar ratio of 30.2, a crystal lattice constant of 2.436 nm, and a specific surface area of ​​710 m 2 An ultrastable Y-type zeolite (hereinafter also referred to as "USY(b)") having a SiO2 / Al2O3 molar ratio of 30.1, a crystal lattice constant of 2.436 nm, and a specific surface area of ​​712 m2 was obtained. USY(b) was calcined at 600°C for 1 hour. 2 Approximately 17 kg of ultrastable Y-type zeolite (hereinafter also referred to as "USY(c)") having a molecular weight of 1.06 / g and a crystallinity of 105% was obtained.

[0108] 1 kg of USY(c) was suspended in 10 L of water at 25°C. 25% by mass sulfuric acid was gradually added to adjust the pH of the suspension to 1.6. 86 g of a solution containing 18% by mass zirconium sulfate and 60 g of a solution containing 33% by mass titanium sulfate were then added to the suspension. The resulting mixture was stirred at room temperature for 4 hours. The pH was then adjusted to 7.2 with 15% by mass ammonium hydroxide. After stirring the mixture at room temperature for 1 hour, the mixture was filtered. The resulting solid was washed with 10 L of water and dried at 130°C for 20 hours to obtain a solid having a SiO2 / Al2O3 molar ratio of 40, a crystal lattice constant of 2.432 nm, and a specific surface area of ​​720 m 2 Approximately 1 kg of titanium-zirconium substituted zeolite (Ti-Zr-USY) was obtained, having a crystallinity of 95%, a ZrO content (based on the total mass of Ti-Zr-USY) of 0.97% by mass, and a TiO content (based on the total mass of Ti-Zr-USY) of 0.98% by mass.

[0109] Reference hydrocracking catalyst Calcined extrudates formed from a composite of Ti-Zr-USY (SAR40) and alumina were used as reference hydrocracking catalysts. The composition of the reference catalysts is summarized in Table 1.

[0110] To prepare the alumina binder, 40 kg of a 3.3 wt% sodium aluminate aqueous solution (based on Al2O3) and 27 kg of a 2.5 wt% aluminum sulfate aqueous solution (based on Al2O3) were mixed. The mixture was stirred at 60°C for 1 hour, and the product was then washed with 150 L of 0.3 wt% ammonia aqueous solution to remove Na2SO4. The Na2SO4-removed product was then diluted with deionized water to adjust the Al2O3 concentration to 10 wt%, and the pH was adjusted to approximately 10 with 15 wt% aqueous ammonia. The mixture was stirred at 95°C for 10 hours, dehydrated, washed, and kneaded in a kneader to obtain an alumina mixture. The alumina mixture product thus prepared was mixed with Ti-Zr-USY zeolite in a dry mass ratio of alumina to zeolite of 7:3. The mixture was formed into a cylindrical shape with a diameter of 1.8 mm, dried at 110°C for 12 hours, and calcined at 550°C for 3 hours to prepare calcined composite particles.

[0111] The active ingredient was then added to the calcined composite particles. An aqueous solution containing the active ingredient was prepared by adding 500 mL of deionized water to 200 g of molybdenum trioxide and 90 g of nickel carbonate. The suspension was stirred at 90°C for 5 hours, and then 125 g of 100% maleic acid was added to obtain an impregnation solution. The impregnation solution was mixed with 1,000 g of calcined composite particles (a composite of Ti-Zr-USY zeolite and an alumina binder), and the active ingredient was incorporated using a pore-filling method. The mixture was then dried at 200°C for 1 hour. The recovered mixture was calcined at 500°C for 1 hour to prepare calcined composite particles containing the active ingredient. The calcined composite particles were then recovered to obtain approximately 1,200 g of the reference catalyst.

[0112] Hydrocracking catalysts A and B Calcined extrudates formed of Ti-Zr-USY (SAR 40 and 80) composites with an alumina-silica-titania binder were prepared and loaded with phosphorus (Catalysts A and B). The compositions are summarized in Table 1. The reference catalyst and Catalysts A and B contain equivalent proportions of Ti-Zr-USY zeolite. Catalysts A and B contain equal concentrations of P2O5 (2.4 wt%) and zeolite (30 wt%), differing from each other in the silica-to-alumina ratio of the Ti-Zr-USY zeolite (40 for Catalyst A and 80 for Catalyst B). The reference catalyst also differs from Catalysts A and B in the binder: the reference catalyst contains alumina, while Catalysts A and B use an alumina-silica-titania ternary composite binder.

[0113] To prepare the silica-alumina-titania binder for both Catalysts A and B, 38 kg of a 3.0 wt% aqueous sodium aluminate solution (based on AlO) was mixed with 22 kg of a 2.5 wt% aqueous aluminum sulfate solution (based on AlO), 3.2 kg of a 5 wt% aqueous titanium disulfide solution (based on TiO), and 0.67 kg of a 24 wt% aqueous SiO solution. The mixture was stirred at 60°C for 1 hour, and then the product was washed with 150 L of a 0.3 wt% aqueous ammonia solution to remove NaSO. The NaSO-free product was then diluted with deionized water to adjust the AlO concentration to 10 wt%, and the pH was adjusted to approximately 10 with 15 wt% aqueous ammonia. The mixture was stirred at 95°C for 10 hours, dehydrated, washed, and kneaded in a kneader to obtain an alumina mixture. The silica-alumina-titania kneaded product thus prepared was mixed with Ti-Zr-USY zeolite in an alumina to zeolite dry mass ratio of 7:3. In the preparation of Catalyst A, the SAR of the Ti-Zr-USY zeolite was 40. In the preparation of Catalyst B, the SAR of the Ti-Zr-USY zeolite was 80. The mixture was formed into pillars with a diameter of 1.8 mm, dried at 110°C for 12 hours, and calcined at 550°C for 3 hours to prepare calcined composite particles.

[0114] The active ingredient was then added to the calcined composite particles. An aqueous solution containing the active ingredient was prepared by adding 500 mL of deionized water to 200 g of molybdenum trioxide and 90 g of nickel carbonate. The suspension was stirred at 90°C for 5 hours, and then 77 g of 100 wt% citric acid and 50 g of 62 wt% phosphoric acid were added to obtain an impregnation solution. The impregnation solution was mixed with 1,000 g of calcined composite particles (a composite of Ti-Zr-USY zeolite and an alumina-silica-titania binder) to incorporate the active ingredient using a pore-filling method. The mixture was then dried at 200°C for 1 hour. The recovered mixture was calcined at 500°C for 1 hour to prepare calcined composite particles containing the active ingredient. The calcined composite particles were then recovered to obtain approximately 1,200 g of the reference catalyst.

[0115] Test example: Catalytic activity evaluation The catalyst was subjected to hydrocracking tests using straight run vacuum gas oil (SR VGO) derived from Arabian crude oil. The properties and composition are shown in Table 2. A pilot plant system with two reactors was used. The first reactor was loaded with 100 ml of a commercial pretreatment catalyst, followed by the second reactor, loaded with 100 ml of a hydrocracking catalyst (reference catalyst, catalyst A, catalyst B). The tests were carried out under the following conditions: hydrogen partial pressure 13.5 MPa, hydrogen / oil ratio 1,000 StL / 1 L of oil, LHSV 0.50 hr -1 The reaction was carried out at various reaction temperatures of 360°C, 375°C, and 390°C. The products were analyzed by simulated distillation (ASTM D2887) to determine the product yields of naphtha (boiling points ranging from C5 to 145°C), kerosene (boiling points ranging from 145 to 260°C), and diesel (boiling points ranging from 260 to 360°C). Figure 2 shows the Arrhenius curves for the three catalysts tested. As evident from the slopes of the Arrhenius plots, all catalysts have similar activation energies. Catalyst A, containing phosphorus and titania, was the most active catalyst among all the catalysts tested. Figure 3 shows the product yield as a function of conversion. All catalysts tested exhibit similar yields at low conversions (e.g., approximately 5 to 60% by mass). At full conversion, the reference catalyst produced higher middle distillate yields.

[0116] It should be understood that like numerals in the figures represent like elements throughout the several figures, and that not all components and / or steps described and illustrated with reference to the figures are required for all embodiments or configurations. Furthermore, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms unless the context clearly dictates otherwise. It will be further understood that as used herein, the terms "including," "comprising," "having," or "containing," "involving," and variations thereof, specify the presence of stated features, integers, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive "or," not an exclusive "or." For example, if condition A or B is satisfied, then any of the following is true: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), or both A and B are true (or exist).

[0117] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the case of conflict, the present specification (including definitions) will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. Additionally, the materials, methods, and examples are illustrative only and are not intended to be limiting.

[0118] When an amount, concentration, or other value or parameter is specified as either a range, a preferred range, or a list of upper and lower preferred values, that is understood to specifically disclose all ranges formed from any pairing of any upper or preferred value with any lower or preferred value, whether or not a range is otherwise disclosed. When a range of numerical values ​​is described herein, unless otherwise stated, the range is intended to include the endpoints, and to include all integers and fractions within the range.

[0119] It should be noted that the use of ordinal terms such as "first," "second," "third," etc. to modify claim elements in a claim does not, in itself, imply any priority, precedence, or order of one claim element relative to another, nor does it indicate the chronological order in which the actions of a method are performed; rather, these terms are merely labels used to distinguish a claim element having a particular name from another claim element having the same name (but excluding the use of ordinal terms).

[0120] In particular, the above figures and examples are not intended to limit the scope of the present disclosure to a single implementation; other implementations are possible by replacing some or all of the elements described or illustrated. Furthermore, where certain elements of the present disclosure can be implemented partially or completely using known components, only those portions of such known components necessary for understanding the present disclosure will be described, and other portions of such known components will not be described in detail so as to avoid obscuring the present disclosure. An implementation depicting a single component herein is not necessarily limited to other implementations including multiple instances of the same component, unless expressly stated otherwise, and vice versa. Furthermore, the applicant does not intend to assign an unusual or special meaning to any term in the specification or claims unless expressly so defined. Furthermore, the present disclosure encompasses currently and future known equivalents of known components illustratively referred to herein.

[0121] The above description of specific implementations fully reveals the general nature of the present disclosure, and others, applying knowledge of the relevant art, can easily modify and / or adapt specific implementations for various applications without undue experimentation and without departing from the general concept of the present disclosure. Therefore, such adaptations and modifications are intended to be within the meaning and range of equivalents of the disclosed implementations, based on the teaching and guidance provided herein. It is understood that the expressions or terms used herein are for purposes of description and not limitation. Therefore, the terms or terms used herein should be interpreted by those skilled in the art in light of the teaching and guidance provided herein, in combination with the knowledge of those skilled in the relevant art. It is understood that the dimensions described or illustrated are illustrative examples, and that other dimensions can be used without departing from the scope of the present disclosure.

[0122] The subject matter described above is presented by way of example only and should not be construed as limiting. Various modifications and variations can be made to the subject matter described herein without following the exemplary embodiments and applications shown and described and without departing from the true spirit and scope of the invention encompassed by this disclosure. The true spirit and scope of the invention is defined by the following claims and their equivalent structures, functions, or steps.

[0123] [Table 1]

[0124] [Table 2]

Claims

1. A hydrocracking catalyst for hydrocarbon oils, comprising: a support including a framework-modified ultrastable Y (USY) zeolite component and a binder component, the binder component including about 5 to 10% by weight of titania and one or more additional inorganic oxides, based on the total weight of the binder component; A hydrocracking catalyst comprising a phosphorus active component supported on the support and an active component comprising one or more hydrocracking metal active components.

2. 2. The hydrocracking catalyst of claim 1, wherein the binder component comprises an amorphous alumina-titania binary composite or an amorphous alumina-silica-titania ternary composite.

3. 10. The hydrocracking catalyst of claim 1, wherein the binder component further comprises about 5 to 10 wt. % silica and about 80 to 90 wt. % alumina, each based on the total weight of the binder component.

4. 4. The hydrocracking catalyst according to claim 1, comprising about 0.01 to 5.0 wt. % of a phosphorus active component, based on the total weight of the hydrocracking catalyst.

5. 5. The hydrocracking catalyst of claim 4, comprising about 1.0 to 3.0 wt. % of a phosphorus active component, based on the total weight of the hydrocracking catalyst.

6. 6. The hydrocracking catalyst according to claim 1, comprising, as one or more hydrocracking metal active components, one or more metals or metal compounds (oxides or sulfides) selected from Groups 6, 7, 8, 9, and 10 of the IUPAC Periodic Table of the Elements.

7. 7. The hydrocracking catalyst according to claim 1, comprising, as one or more hydrocracking metal active components, one or more metals or metal compounds (oxides or sulfides) of Mo, W, Co, or Ni.

8. Specific surface area is 200 to 450 m ２ / g, the volume of pores with a diameter of 600 Å or less is 0.40 to 0.75 ml / g, and the amount of the phosphorus component is 0.01 to 5.0 mass% based on the mass of the catalyst material.

9. 9. The hydrocracking catalyst of claim 1 in the form of an extrudate, the extrudate being calcined.

10. 10. The hydrocracking catalyst of claim 1, wherein the USY zeolite, the framework of which has subsequently been modified, comprises one or more of titanium, zirconium and / or hafnium substituting for aluminum atoms that make up the zeolitic framework of the USY zeolite.

11. 11. The hydrocracking catalyst according to claim 1, wherein the USY zeolite, the framework of which has been subsequently modified, contains titanium and zirconium substituting for aluminum atoms constituting the zeolitic framework of the USY zeolite.

12. 12. The hydrocracking catalyst according to claim 11, wherein the USY zeolite, the framework of which has been subsequently modified, is substituted with 0.1 to 5% by mass of zirconium atoms and 0.1 to 5% by mass of titanium ions, calculated on the oxide basis.

13. The framework-modified USY zeolite was subsequently found to have the following properties: (a) a crystal lattice constant of 2.430-2.450 nm; (b) a specific surface area of ​​600-900 m ２ / g, and (c) Al ２ O ３ SiO ２ The hydrocracking catalyst according to any one of claims 1 to 12, wherein the molar ratio of

14. 1. A method for producing hydrocracking catalyst particles, comprising: providing a post-framework modified ultrastable Y (USY) zeolite component in which a portion of the aluminum atoms comprising the zeolite framework have been replaced with zirconium and / or titanium and / or hafnium atoms; providing a titania-containing binder component; subsequently mixing and kneading the framework-modified USY zeolite component with a titania-containing binder component to form a composite; forming the composite into an extrusion; heat treating the extruded body; recovering intermediate calcined catalyst particles characterized by an outer surface and pores defining an inner surface; and A method comprising supporting an active component comprising a phosphorus component and one or more hydrocracking metal active components.

15. 15. The method of claim 14, wherein the step of supporting the active component comprises supporting the active component on the outer surface and / or the inner pore surface of the intermediate calcined catalyst particles, and further comprising the steps of heat-treating the intermediate calcined catalyst particles on which the active component is supported, and recovering the final calcined catalyst particles.

16. 15. The method of claim 14, wherein the step of supporting the active component comprises supporting the active component on the outer surface and / or the inner pore surface of the titania-containing binder component, and further comprising the steps of heat-treating the intermediate calcined catalyst particles on which the active component is supported, and recovering final calcined catalyst particles.

17. 15. The method according to claim 14, wherein the step of supporting the active component comprises supporting the active component on the outer surface and / or the inner pore surface of a composite of the titania-containing binder component and the USY zeolite component whose framework has been subsequently modified, and further comprising the steps of heat-treating the intermediate calcined catalyst particles on which the active component is supported, and recovering final calcined catalyst particles.

18. the titania-containing binder component is formed from titania, silica, and alumina precursors; The titania precursor is Ti(OH) ４ , TiO(OH) ２ , TiO ２ , Ti(C ２ O ４ ) ２ , TiSO ４ , or Ti(SO ４ ) ２ and combinations comprising two or more of these titania precursors; The alumina precursor is NaAlO ２ , Al ２ (SO ４ ) ３ , aluminates, alumina, aluminum colloids, boehmite, pseudoboehmite, aluminum hydroxide, aluminum salts, aluminum alkoxides, alumina gels, and combinations comprising two or more of the foregoing alumina precursors; and The silica precursor is Na ２ SiO ３ , Na ４ SiO ４ 19. The method of any one of claims 14 to 18, wherein the silica precursor is selected from the group consisting of sodium silicate (water glass), fumed silica, precipitated silica, colloidal silica, silica gel, silicon hydroxide, silicon alkoxide, and combinations comprising two or more of said silica precursors.

19. 19. The method of any one of claims 14 to 18, wherein the phosphorus component is supported on calcined catalyst particles.

20. 19. The method of any one of claims 14 to 18, wherein the phosphorus component and one or more hydrocracking metal active components are supported on intermediate calcined catalyst particles.

21. 19. The method of any one of claims 14 to 18, wherein the phosphorus component is supported on a titania-containing binder component.

22. 19. The method of any one of claims 14 to 18, wherein the phosphorus component and one or more hydrocracking metal active components are supported on a titania-containing binder component.

23. 19. The method of any one of claims 14 to 18, wherein the phosphorus component is subsequently supported on a composite of the framework-modified USY zeolite component and the titania-containing binder component.

24. 19. The method of any one of claims 14 to 18, wherein the phosphorus component and one or more hydrocracking metal active components are subsequently supported on a composite of the framework-modified USY zeolite component and the titania-containing binder component.

25. A method for hydrocracking a hydrocarbon oil, comprising a step of hydrocracking a hydrocarbon oil using the hydrocracking catalyst according to any one of claims 1 to 13.

26. a step of filling a hydrotreating treatment unit, which is a flow reactor, with a hydrocracking catalyst; and a step of subjecting a hydrocarbon oil having a boiling point in the range of about 370 to 833°C to hydrocracking in the presence of hydrogen at a reactor temperature in the range of about 300 to 500°C, a hydrogen pressure in the range of about 40 to 300 bar, and a liquid hourly space velocity in the range of about 0.1 to 10 h －１ and a hydrogen / oil ratio of about 500 to 2500 Nm ３ / m ３ The method for hydrocracking a hydrocarbon oil according to claim 25, further comprising the step of treating in a range of

27. a step of filling a hydrotreating treatment unit, which is a flow reactor, with a hydrocracking catalyst; and a step of subjecting a hydrocarbon oil having a boiling point in the range of about 370 to 650°C to a hydrocracking reaction in the presence of hydrogen at a reactor temperature in the range of about 330 to 450°C, a hydrogen pressure in the range of about 70 to 150 bar, and a liquid hourly space velocity in the range of about 0.2 to 1.5 h －１ and a hydrogen / oil ratio of about 1000 to 2500 Nm ３ / m ３ 26. The method for hydrocracking hydrocarbon oils according to claim 25, further comprising the step of treating in the range of

28. 28. The method for hydrocracking hydrocarbon oils according to claim 26 or 27, wherein the flow reactor is a flow reactor selected from the group consisting of a stirred tank, an ebullated bed reactor, a baffled slurry tank, a fixed bed reactor, a rotating tubular reactor, and a slurry bed reactor.

29. 29. The method for hydrocracking a hydrocarbon oil according to any one of claims 25 to 28, wherein the hydrocarbon oil comprises (1) crude oil, (2) synthetic crude oil, (3) bitumen, (4) oil sands, (5) shale oil, (6) coal liquid oil, (7) plastic pyrolysis oil, and / or (8) refined oil obtained from biomass-derived oil.

30. 30. The method for hydrocracking a hydrocarbon oil according to any one of claims 25 to 29, wherein the hydrocarbon oil comprises a refined oil obtained from crude oil, synthetic crude oil, bitumen, oil sands, shale oil, or coal oil, and the refined oil comprises a) atmospheric gas oil (AGO), b) vacuum gas oil (VGO), c) deasphalted oil (DAO) or demetallized oil obtained from a solvent debituminization process, d) light coker gas oil or heavy coker gas oil obtained from a coker process, e) cycle oil obtained from a fluid catalytic cracking (FCC) process, f) gas oil obtained from a visbreaking process, g) gas oil obtained from plastic pyrolysis oil, and / or h) biomass-derived gas oil, and all of the feedstocks c) to h) have a normal boiling point range that coincides with the boiling point range of the atmospheric gas oil or vacuum gas oil.

31. a step of filling a hydrotreating treatment unit, which is a flow reactor, with a hydrocracking catalyst; and a step of subjecting a hydrocarbon oil having a boiling point of 375°C to 650°C to hydrocracking in the presence of hydrogen at a reactor temperature of 330°C to 450°C, a hydrogen pressure of 7 to 15 MPa, and a liquid hourly space velocity (LHSV) of 0.2 to 1.5 h －１ , and hydrogen / oil ratio is 1000 to 2000 Nm ３ / m ３ The method for hydrocracking hydrocarbon oil according to any one of claims 25 to 29, further comprising the step of treating with to obtain kerosene-gas oil.

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