Catalysts with modified active phase dispersions and methods for preparing catalysts with modified active phase dispersions - Patents.com

Abstract

Catalyst particles containing one or more active metal components and methods for producing such catalyst particles are provided. The particles are composites of a granulating or binder material, such as an inorganic oxide, and an ultrastable Y (hereinafter "USY") zeolite in which some of the aluminum atoms in the framework are replaced with zirconium and / or titanium and / or hafnium atoms. One or more active phase components are incorporated into the composite mixture of the inorganic oxide binder and the post-framework modified USY zeolite prior to forming the catalyst particles.

Description

[Technical field]

[0001] The present disclosure relates to a method for producing a catalyst containing USY zeolite. [Background technology]

[0002] Catalysts including hydrotreating / hydrocracking catalysts, e.g., pretreatment catalysts, typically include amorphous-based catalysts containing active metals, Ni / Mo, Ni / W, or Co / Mo metals as active phases, e.g., amorphous alumina or silica-alumina or titania substrates, or amorphous catalysts promoted with Ni, W, Mo, and Co metals, zeolite catalysts, or composite mixtures thereof. A typically used zeolite is USY. Hydrocracking cracking catalysts include a hydrogenation active 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-based catalysts, post-modified zeolites, or combinations thereof. Hydrocracking catalysts may have active phase materials including any one of Ni, W, Mo, Co, or combinations thereof, in certain embodiments. In other embodiments, typically in sulfur-free environments for hydrogenation and / or reforming, the catalyst may contain one or more precious metals, such as Ru, Rh, Pd, Ag, Os, Ir, Pt, or Au. In certain embodiments aimed at hydrodenitrogenation, acidic alumina or silica alumina-based catalysts loaded with Ni-Mo, or Ni-W active metals, or combinations thereof, are used. In embodiments aimed at removing total nitrogen and improving the conversion of hydrocarbons, silica alumina, zeolites, or combinations thereof with active metals including Ni-Mo, Ni-W, or combinations thereof are used as catalysts.

[0003] Commonly owned U.S. Patents 9,221,036, 10,081,009, and 10,293,332 (the '036, '009, and '332 patents, or the '036 patent family), which are incorporated by reference in their entireties, teach, among other things, hydrocracking catalysts in which the USY framework is partially 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. Methods for making these catalysts and their uses are all described in the '036, '009, and '332 patents.

[0004] Hydroprocessing (hydrotreating and hydrocracking) catalysts can be prepared in a variety of ways. The method chosen usually represents a balance between the production costs and the degree to which the desired chemical and physical properties are achieved. There is a relationship between the catalyst formulation, preparation procedure, and catalytic properties, but the details of that relationship are not always fully understood due to the complex nature of the catalytic systems. The chemical composition of the catalyst plays an important role in its performance, and the physical and mechanical properties also play a major role. The preparation of hydrocracking catalysts involves several steps: precipitation, filtration (decantation, centrifugation), washing, drying, forming, calcination, and impregnation. Other steps, such as kneading / mulling, grinding, and sieving, are typically also required. Below, steps that are an integral part of the process for preparing hydrocracking catalysts are described.

[0005] Precipitation involves the mixing of a solution or suspension of materials resulting in the formation of a precipitate that may be crystalline or amorphous. Kneading of wet solid materials usually results in the formation of a dough, which is then formed and dried. The kneaded product is subjected to a heat treatment to provide better homogeneity and intimate contact between the components by thermal diffusion and solid-state reactions. Metal components are then added by impregnation or incipient wetting methods.

[0006] The characteristics of the support determine the mechanical properties of the catalyst, such as attrition resistance, hardness, and crush strength. A large surface area and a suitable pore size distribution are generally required. The pore size distribution and other physical properties of catalyst supports prepared by precipitation are also influenced by the precipitation and aging conditions of the precipitate, as well as the subsequent drying, forming, and calcination.

[0007] The final shape and size of the catalyst particles are determined by the manufacturing process. The catalyst and catalyst support are formed into several possible shapes, e.g. spheres, cylindrical extrudates, or moulded forms, e.g. trilobes or tetralobes. Spherical catalyst support catalysts can be obtained by "oil dripping", where precipitation occurs by pouring a liquid into a second immiscible liquid. Other spherical processes include marmurising. Generally, due to cost and process considerations, e.g. pressure drop, most catalysts are now formed in shapes other than spheres. In modern hydrocracking, spherical catalysts are used less and less. Non-spherical shapes are obtained by mixing the raw materials to form an extrudable dough, which is then extruded through a perforated die. The spaghetti-like extrudates are dried, calcined and divided into short pieces. The length to diameter ratio of the catalyst base typically varies, e.g., from 2 to 4.

[0008] FIG. 1 illustrates the steps of a typical hydrocracking catalyst manufacturing process: mixing and kneading the binder component and the zeolite component; extruding the kneaded composite mixture to form composite particles; calcining the composite particles; impregnating the calcined composite particles with active metal components; and calcining the impregnated composite particles to form the final catalyst product.

[0009] Examples of catalyst and catalyst support shapes are shown in Figure 2. The simplest shape is cylindrical, but other shapes, such as trilobal, twisted trilobal, or tetralobal, are also in commercial use. Catalysts with multilobal cross sections have a higher surface-to-volume ratio than simple cylindrical extrudates. When used in fixed beds, these shaped catalyst particles help reduce diffusion resistance, create a more open bed, and reduce pressure drop.

[0010] Heat treatment is applied before and / or after impregnation of the formed catalyst. Catalyst support materials prepared by precipitation or co-blending of all components may only require drying before formation, followed by calcination of the formed product. Heat treatment of the catalyst or support removes water and other volatiles. Drying and calcination conditions are very important in determining the physical and catalytic properties of the catalyst support material. Surface area, pore size distribution, stability, attrition resistance, crush strength, and catalytic activity are affected by the drying and calcination conditions.

[0011] In conventional catalyst preparation, several methods may be used to add active metals to the catalyst support material: (a) dipping, (b) incipient wetness, and (c) evaporation. In one method, the calcined catalyst support material is immersed in an excess of solution containing the active metal or metal compound. The solution fills the pores and also adsorbs onto the support surface, and the excess solution is removed. In another method, impregnation is performed using incipient wetness by tumbling or spraying the activator carrier with a volume of solution equal to or slightly smaller than the pore volume of the carrier, with the metal compound concentration adjusted to achieve the target metal level. The metal-loaded catalyst support material is then dried and calcined. Metal oxides form in the process, and the calcination step is also called oxidation. In another method, evaporation impregnation, the catalyst support material is saturated with water or an acid solution and immersed in an aqueous solution containing the metal compound. The compound then diffuses through the aqueous phase into the pores of the catalyst support material. The calcined catalyst is then bagged and shipped to its final destination. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] U.S. Patent No. 9,221,036 [Patent Document 2] U.S. Patent No. 10,081,009 [Patent Document 3] U.S. Patent No. 10,293,332 [Patent Document 4] U.S. Patent No. 10,787,618 [Patent Document 5] U.S. Patent Publication No. 2021 / 0246382A1 [Patent Document 6] U.S. Patent Publication No. 2021 / 0246383A1 [Patent Document 7] U.S. Patent Publication No. 2021 / 0246384A1 [Patent Document 8] U.S. Patent Publication No. 2021 / 0246389A1 [Patent Document 9] U.S. Patent Publication No. 2021 / 0246386A1 [Patent Document 10] U.S. Patent Publication No. 2021 / 0246381A1 [Patent Document 11] U.S. Patent Publication No. 2021 / 0246387A1 [Patent Document 12] U.S. Patent Publication No. 2021 / 0246385A1 [Patent Document 13] U.S. Patent Publication No. 2021 / 0246388A1 [Patent Document 14] U.S. Patent Publication No. 20210077985A1 [Patent Document 15] U.S. Patent Application Serial No. 17 / 577,747 [Patent Document 16] U.S. Patent Application Serial No. 17 / 577,691 Summary of the Invention [Problem to be solved by the invention]

[0013] In the '036 family of patents, the active metal component is added after the post-framework modified USY zeolite and binder are mixed, milled, and extruded. While the catalyst particles produced by the methods taught in the '036 family of patents are suitable for their intended purposes, the industry is constantly seeking improved catalyst particles and methods for their manufacture. [Means for solving the problem]

[0014] Catalyst particles containing one or more active metal components and methods for producing such catalyst particles are provided. The particles are composites of a granulating or binder material, such as an inorganic oxide, and an ultrastable Y (hereinafter "USY") zeolite in which some of the aluminum atoms in the framework are replaced with zirconium and / or titanium and / or hafnium atoms. One or more active phase components are incorporated into the composite mixture of the inorganic oxide binder and the post-framework modified USY zeolite prior to forming the catalyst particles.

[0015] The method for producing catalyst particles includes the steps of providing a post-skeleton-modified ultrastable Y-type (USY) zeolite in which a portion of the aluminum atoms constituting the zeolite framework are replaced with zirconium atoms and / or titanium atoms and / or hafnium atoms; providing an inorganic oxide as a binder; mixing and kneading the post-skeleton-modified USY zeolite with the inorganic oxide binder to form a composite of the post-skeleton-modified USY zeolite and the inorganic oxide binder, the composite being characterized by an outer surface and an inner pore wall surface; impregnating the outer surface and / or the inner pore surface of the composite with one or more active metal components to form a metal-supported composite of the post-skeleton-modified USY zeolite and the inorganic oxide binder; forming catalyst particles from the metal-supported composite of the post-skeleton-modified zeolite and the inorganic oxide binder into extrudates; heat-treating the extrudates; and recovering the calcined catalyst particles.

[0016] In certain embodiments of the above method, the one or more active metal components impregnated into the composite are a second portion of the total active metal component content of the one or more active metal components. The post-framework-modified USY zeolite is characterized by an exterior surface and pores defining an interior surface, and the method further comprises impregnating the exterior surface and / or the interior pore surface of the post-framework-modified USY zeolite with a first portion of the total active metal component content of the one or more active metal components to form a metal-loaded post-framework-modified USY zeolite. Thus, the mixing and kneading step is a step of mixing and kneading the metal-loaded post-framework-modified USY zeolite and an inorganic oxide binder material to form a composite of the metal-loaded post-framework-modified USY zeolite and the inorganic oxide binder material, the composite being a composite impregnated with a second portion of the total active metal component content of the one or more active metal components, and the step of forming the catalyst particles into extrudates is performed from the metal-loaded composite of the metal-loaded post-framework-modified USY zeolite and the inorganic oxide binder.

[0017] In certain embodiments of the above method, the one or more active metal components impregnated into the composite are a second portion of the total active metal component content of the one or more active metal components. The inorganic oxide binder material is characterized by an exterior surface and pores defining an interior surface, and the method further comprises impregnating the exterior surface and / or the interior pore surfaces of the inorganic oxide binder material with a first portion of the total active metal component content of the one or more active metal components to form a metal-loaded inorganic oxide binder. Thus, the mixing and kneading step is a step of mixing and kneading the metal-loaded inorganic oxide binder with the post-skeleton-modified USY zeolite to form a composite of the metal-loaded inorganic oxide binder and the post-skeleton-modified USY zeolite, the composite being a composite impregnated with the second portion of the total active metal component content of the one or more active metal components, and the step of forming catalyst particles into extrudates is performed from the metal-loaded composite of the metal-loaded inorganic oxide binder and the post-skeleton-modified USY zeolite.

[0018] The calcined catalyst particles provided herein comprise a composite of a post-framework modified ultrastable Y (USY) zeolite, in which a portion of the aluminum atoms constituting the zeolite framework have been replaced with zirconium and / or titanium and / or hafnium atoms, and an inorganic oxide binder material. The composite is characterized by pores defining an exterior surface and an interior surface, the exterior surface and / or the interior pore surfaces being metal-loaded with one or more active metal components as a metal-loaded composite. The metal-loaded composite is formed into an extrudate and heat treated as a calcined catalyst particle.

[0019] In certain embodiments of the above methods and compositions, the post-framework-modified USY zeolite is provided in a wet, dry, or calcined state. In certain embodiments of the above methods and compositions, the post-framework-modified USY zeolite contains 0.1-5 wt. % zirconium and / or titanium and / or hafnium, calculated on an oxide basis. In certain embodiments of the above methods and compositions, the inorganic oxide material is selected from the group consisting of alumina, silica, titania, silica-alumina, alumina-titania, alumina-zirconia, alumina-boria, phosphorus-alumina, silica-alumina-boria, phosphorus-alumina-boria, phosphorus-alumina-silica, silica-alumina-titania, and silica-alumina-zirconia. In certain embodiments of the above methods and compositions, the metal-loaded post-framework-modified USY zeolite comprises about 0.1-99 wt. % of the active metal-containing composite catalyst particles, with the remaining mass comprising inorganic oxide components. In certain embodiments of the above methods and compositions, the catalyst particles are formed of a post-framework-modified USY zeolite, an inorganic oxide component, and an additional zeolite component. In certain embodiments of the above methods and compositions, the metal-loaded post-framework-modified USY zeolite comprises about 0.1-99% by weight of the catalyst particles, a first remaining weight comprises the inorganic oxide component, and a second remaining weight comprises the additional zeolite component. In certain embodiments of the above methods and compositions, the active metal component is selected from the group of metals consisting of platinum, palladium, and rhenium, and the active metal component is present in an amount of 0.01-2% by weight of the active metal component relative to the weight of the catalyst particles. In certain embodiments of the above methods and compositions, the active metal component is selected from the group of metals consisting of Mo, W, Co, Ni, and combinations thereof, and the active metal component is present in an amount of 0.1-40% by weight of the active metal component relative to the weight of the catalyst particles.

[0020] Further aspects, embodiments, and advantages of these exemplary aspects and embodiments are discussed in detail below. It is to be further understood that all of the preceding information and the following detailed description are merely illustrative examples of the various aspects and embodiments, and are intended to provide an overview or framework for understanding the nature and features of the claimed aspects and embodiments, and serve to explain the principles and operation of the described and claimed aspects and embodiments.

[0021] The present invention will now be described in more detail with reference to the accompanying drawings, in which identical or similar elements are referenced with the same numerals in certain instances, and in which: [Brief description of the drawings]

[0022] [Figure 1] FIG. 1 is a simplified process flow diagram for producing catalyst particles according to known methods. [Diagram 2] FIG. 2 is a diagram showing the shape of a catalyst. [Diagram 3] FIG. 1 is a process flow diagram showing steps for producing catalyst particles according to known methods. [Figure 4] FIG. 2 is a process flow diagram illustrating steps for producing catalyst particles according to embodiments herein in which a composite of framework-substituted USY zeolite material and binder is impregnated with active metals. [Diagram 5] FIG. 1 is a process flow diagram illustrating steps for producing catalyst particles according to embodiments herein in which extrudates of a framework-substituted USY zeolite material and binder composite and a metal-support composite are impregnated with active metals. [Figure 6] FIG. 2 is a process flow diagram illustrating possible steps for producing catalyst particles according to various embodiments herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] The present disclosure provides a method for producing catalyst particles containing one or more active metal components. The particles are composites of (a) a granulating or binder material, such as an inorganic oxide, and (b) an ultrastable Y (hereinafter "USY") zeolite in which some of the aluminum atoms in the framework are replaced with zirconium atoms and / or titanium atoms and / or hafnium atoms. In the method of the present invention, one or more active phase components are incorporated into a composite mixture of the inorganic oxide binder and the post-framework modified USY zeolite prior to forming the catalyst particles. In an embodiment of the method of the present invention, one or more active phase components are incorporated prior to extruding the resulting composite mixture in which the active phase components are incorporated and prior to forming the catalyst particles. This is in contrast to known methods in which the active metal components are added to the calcined and formed particles.

[0024] In certain embodiments, the catalyst particles formed according to the invention herein are suitable for hydrocracking heavy hydrocarbon oils obtained from crude oil, synthetic crude oil, bitumen, oil sands, Shell oil, or coal liquids, preferably either a) vacuum gas oil (VGO), b) deasphalted oil (DAO) or demetallized oil obtained from a solvent deasphalting process, c) light coker gas oil or heavy coker gas oil obtained from a coker process, d) cycle oil obtained from a fluid catalytic cracking (FCC) process, or e) gas oil obtained from a visbreaking process.

[0025] In certain embodiments, the catalyst particles formed in accordance with the invention herein are suitable for naphtha reforming, as disclosed in U.S. Pat. No. 10,787,618, which is incorporated herein by reference in its entirety.

[0026] In certain embodiments, the catalyst particles formed in accordance with the invention herein are suitable for hydrogenation of middle distillates and conditioning for steam cracking of said middle distillates, as disclosed in U.S. Patent Publication Nos. 2021 / 0246382A1, 2021 / 0246383A1, 2021 / 0246384A1, and 2021 / 0246389A1, which are incorporated by reference in their entireties; or are suitable for hydrogenation of middle distillates and conditioning for steam cracking and / or fluid catalytic cracking of said middle distillates, as disclosed in U.S. Patent Publication No. 2021 / 0246386A1, which is incorporated by reference in its entirety. In certain embodiments, the catalyst particles formed in accordance with the invention herein are suitable for hydrogenating light cycle oils and conditioning said light cycle oils for steam cracking, as disclosed in U.S. Patent Publication No. 2021 / 0246381 A1, the entirety of which is incorporated herein by reference; or are suitable for hydrogenating light cycle oils and conditioning said light cycle oils for steam cracking and / or fluid catalytic cracking, as disclosed in U.S. Patent Publication No. 2021 / 0246387 A1, the entirety of which is incorporated herein by reference. In certain embodiments, the catalyst particles formed in accordance with the invention herein are suitable for hydrogenating a light coker gas oil and conditioning said light coker gas oil for steam cracking, as disclosed in U.S. Patent Publication No. 2021 / 0246385 A1, which is incorporated by reference in its entirety; or are suitable for hydrogenating a light coker gas oil and conditioning said light coker gas oil for steam cracking and / or fluid catalytic cracking, as disclosed in U.S. Patent Publication No. 2021 / 0246388 A1, which is incorporated by reference in its entirety.

[0027] For convenience in illustrating the process of the present invention, Figure 3 illustrates process steps for producing a post-framework modified USY zeolite and for producing catalyst particles having active metal components on a composite support comprising a post-framework modified USY zeolite and a binder, certain of which are similar to those disclosed in the '036 patent family.

[0028] The catalyst particles produced according to the method of FIG. 3 are calcined composite support particles of the framework-modified USY zeolite and binder described herein, to which an active metal component is added and then calcined.

[0029] Steps 1-9 herein provide a description of a method for the synthesis of calcined USY zeolite (herein designated USY(c)), which is then post-skeleton modified in steps 10-13. In embodiments of the present invention herein, the USY to be post-skeleton modified can be obtained from another source, i.e., one or more of steps 1-9 can be avoided. Steps 14-15 relate to the preparation of an inorganic oxide binder, and steps 16-21 relate to the formation of composite catalyst support particles (steps 16-18) and the formation of final particles having effective amounts of active metal components (steps 19-21).

[0030] In step 1, the Y-type zeolite (Na-Y) is prepared by forming a suspension of Na-Y at an effective concentration, for example, in the range of about 5-20, 5-15, 8-15, 5-12, or 8-12 liters (L) of water per kilogram (kg) of zeolite, 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.

[0031] The starting material for step 1 may have an effective SiO2 / Al2O3 molar ratio (SAR), for example, in the range of about 3 to 6; an effective unit cell size (UD), for example, about 2.466 nanometers (nm); an effective specific surface area (SA), for example, about 600 to 900, 600 to 800, 650 to 900, or 650 to 800 square meters per gram (m 2 / g) and an available Na2O content, for example, of about 13 wt. %.

[0032] In the ion exchange step 2, the Na-Y suspension from step 1 is subjected to ion exchange with sodium ions and ammonium ions of Na-Y to synthesize a first ion-exchanged Y-type zeolite (first NH4-Y). In the first NH4-Y, in a specific embodiment, about 50 to 70% of the Na contained in the Y-type zeolite is replaced with NH4, which is equivalent to NH4. 50-70 Also called Y.

[0033] One embodiment of the ion exchange of step 2 includes adding to the Na-Y suspension an ammonium source at an effective concentration, e.g., a molar ratio of ammonium to Al in the range of about 2-8; at an effective temperature in the range of about 20-95, 20-90, 20-80, 40-95, 40-90, or 40-80° C.; and for an effective residence time in the range of about 10-600, 10-180, 30-600, or 30-180 minutes, for example. The ammonium source can be one or more of NH4OH, (NH4)2SO4, (NH4)2CO3, or another suitable ammonium source.

[0034] The solid obtained from 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 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 obtain the first ion exchange NH4-Y, NH4 50-70 You can get Y.

[0035] Optionally, after washing the solids obtained from ion exchange step 2, they can be washed with an ammonium source in one or more additional cycles at an effective temperature, concentration, and residence time, such as the effective temperature, concentration, and residence time of step 2, and then washed with water. The washed solid material one or more additional times can be dried at an effective temperature and residence time, such as the effective temperature and residence time of step 2, to obtain the first ion-exchanged NH4-Y, NH4 50-70 To obtain Y. In certain instances, one or more additional cycles of the first ion exchange step are not performed.

[0036] In the heat treatment step 3, the first ion-exchanged NH4-Y(NH4 50-70 Hydrogen Y (HY) zeolite is synthesized from the first ion-exchanged NH4-Y. In certain embodiments, the heat treatment in step 3 comprises 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 may be repeated one or more times as in step 2. The HY zeolite is converted to USY after additional ammonium ion exchange and steam treatment as discussed in steps 4-6 below.

[0037] In steps 4 to 6, the HY zeolite is treated to synthesize a second ion-exchanged NH4-Y zeolite in which 80 to 97% of the Na contained in the Na-Y is exchanged with NH4. 80-97For example, as shown, in step 4, a suspension containing an effective concentration of HY zeolite in a range of, for example, about 5-20, 5-15, 8-15, 5-12, or 8-12 L / kg water / zeolite by mass is prepared at an effective temperature in a range of, for example, about 15-95, 15-80, 20-95, 20-90, 20-80, 40-95, 40-90, or 40-80° C.

[0038] In the ion exchange step 5, the NH4-Y suspension from step 4 is subjected to ion exchange with 80 to 97% or 90 to 97% of the sodium ions of Na-Y and ammonium ions to synthesize a second ion-exchanged Y-type zeolite, and the second ammonium-exchanged Y-type zeolite (second NH4-Y), NH4 80-97 Y is prepared. One embodiment of the ion exchange of step 5 includes 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, 20-90, 20-80, 40-95, 40-90, or 40-80° C.; and 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.

[0039] The solid obtained from the ion exchange step 5 may be 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 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 obtain the second ion exchange NH4-Y, NH4 80-97 You can get Y.

[0040] Optionally, after washing the solids obtained from ion exchange step 5, they can be washed with an ammonium source in one or more additional cycles at an effective temperature, concentration, and residence time, such as the effective temperature, concentration, and residence time of step 5, and then washed with water. The washed solids in one or more additional cycles can be dried at an effective temperature and residence time, such as the effective temperature and residence time of step 5, to form the second ion-exchanged NH4-Y, NH4 80-97 To obtain Y. In certain instances, one or more additional cycles of the second ion exchange step are not performed.

[0041] In the heat treatment step 6, NH4 80-97 The heat treatment step 6 comprises calcining the second ion-exchanged NH4-Y at an effective temperature in the range of, for example, about 500-800, 500-700, 600-800, or 600-700° C. (typically in the presence of water vapor, i.e., saturated water vapor, 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 to recover USY(a). In certain embodiments, NH4 80-97 The heat treatment of Y is by steam treatment.

[0042] USY(a) from step 6 is a USY zeolite with a SAR approximately equal to that of the starting Na-Y. Steps 1-6 generally should not significantly change the SAR value since they do not involve an acid treatment aimed at expelling aluminum atoms from the zeolite framework. For example, the USY(a) thus obtained in step 6 may have a SAR of about 3-6.

[0043] In steps 7-9, the USY(a) zeolite is treated to synthesize a calcined USY zeolite with improved SAR, which is the starting material for subsequent post-framework modification. In step 7, an aqueous suspension containing an effective concentration of USY(a) in the range of, for example, about 5-20, 5-15, 8-15, 5-12, or 8-12 L / kg (water / zeolite) solid / liquid mass ratio is prepared at an effective temperature in the range of, for example, about 15-95, 15-80, 20-95, 20-90, 20-80, 40-95, 40-90, or 40-80° C.

[0044] In an acid treatment step 8, an effective amount of inorganic or organic acid is dispersed in the suspension such that the pH of the suspension is maintained in the strongly acidic range to synthesize a second ultrastable Y zeolite with improved SAR, referred to herein as USY(b). To obtain USY(b) zeolite, extra-framework aluminum (aluminum atoms that do not form part of the zeolite framework) is removed from USY(a). This is accomplished by acid treatment.

[0045] The inorganic acid used may generally be sulfuric acid, nitric acid, hydrochloric acid, etc. In a particular embodiment, the inorganic acid selected is sulfuric acid or hydrochloric acid. Furthermore, as the organic acid, a carboxylic acid may be suitably used. The amount of the inorganic acid or organic acid added is an amount suitable for controlling the pH of the suspension to a strong acid range, for example, about 0.7 to 2.5, 0.7 to 2.0, 1.0 to 2.5, or 1.0 to 2.0. The amount may be, for example, a molar increase of 0.5 to 4.0 times, 0.5 to 3.5 times, 0.7 to 4.0 times, or 0.7 to 3.5 to 0.5 times based on the amount of Al2O3 in USY(a). The acidic suspension is maintained at an effective temperature, for example, 15-95, 15-80, 20-95, 20-90, 20-80, 40-95, 40-90, or 40-80°, and for an effective residence time, for example, in the range of about 10-600, 10-180, 30-600, or 30-180 minutes. The acid treatment in step 8 increases the SAR of the Y zeolite, for example, from a range of about 3-6 to a range of about 30-100, 40-100, 30-80, or 40-80.

[0046] The solids obtained from the acid treatment step 8 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 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 USY(b).

[0047] Optionally, after the solids obtained from the acid treatment step 8 are washed, they can be treated with an inorganic or organic acid for one or more additional cycles at an effective temperature, concentration, and residence time, such as the effective temperature, concentration, and residence time of step 8, and then washed with water. The acid treated solids for one or more additional times are dried at an effective temperature and residence time, such as the effective temperature and residence time of step 8, to recover USY(b). In certain instances, one or more additional cycles of the first acid treatment step are not performed.

[0048] In a thermal treatment step 9, the USY(b) zeolite is subjected to a thermal treatment to prepare a third ultrastable Y zeolite, USY(c). In certain embodiments, the thermal 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 water vapor), for a time in the range of about 10-600, 10-180, 30-600, or 30-180 minutes to recover USY(c). Calcination temperatures below about 500° C. tend to reduce the amount of framework substitution of zirconium and / or titanium and / or hafnium atoms, while calcination temperatures above about 700° C. may reduce the specific surface area of ​​the ultrastable Y zeolite, thus reducing the amount of framework substitution of zirconium and / or titanium and / or hafnium atoms.

[0049] In steps 10-13, framework substitution is performed to produce a post-framework modified USY zeolite in which a portion of the aluminum atoms in the USY zeolite framework are replaced with zirconium and / or titanium and / or hafnium atoms. In certain embodiments, the post-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 and having a liquid / solid mass ratio of about 5-15 is formed. An inorganic or organic acid is added such that the pH of the suspension is 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, such that the pH of the mixed solution is about 7-7.5.

[0050] The suitable zirconium compounds 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 compounds 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 their oxide basis (i.e., zirconium oxide) and measured relative to the weight of the post-framework modified USY zeolite component. Addition of zirconium compounds in an amount less than about 0.1 wt. % cannot improve the solid acid characteristics of the zeolite. Addition of zirconium compounds in an amount greater than 5 wt. % tends to cause clogging of the zeolite pores. An aqueous solution of zirconium compounds prepared by dissolving a zirconium compound in water can be used as the zirconium compound.

[0051] 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 compounds 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% by weight, calculated on their oxide basis (i.e., titanium oxide) and measured relative to the weight of the post-framework modified USY zeolite component. Addition of titanium compounds in an amount less than about 0.1% by weight cannot improve the solid acid characteristics of the zeolite. Addition of titanium compounds in an amount greater than 5% by weight tends to cause clogging of the zeolite pores. An aqueous solution of titanium compounds prepared by dissolving a titanium compound in water can be used as the titanium compound.

[0052] The suitable hafnium compounds 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 compounds 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 their oxide basis (i.e., hafnium oxide) and measured relative to the weight of the post-framework modified USY zeolite component. Addition of hafnium compounds in an amount less than about 0.1 wt. % fails to improve the solid acid characteristics of the zeolite. Addition of hafnium compounds in an amount greater than 5 wt. % tends to cause clogging of the zeolite pores. An aqueous solution of a hafnium compound prepared by dissolving a hafnium compound in water can be used as the hafnium compound.

[0053] The pH of the suspension is controlled to less than about 2.0 to prevent the formation of precipitates during mixing of the aqueous solution of zirconium and / or hafnium and / or titanium compounds with the suspension of the ultrastable Y zeolite.

[0054] In certain embodiments, the aqueous solution of zirconium compounds and / or hafnium compounds and / or titanium compounds is mixed with the suspension of ultrastable Y-type zeolite by gradually adding the aqueous solution to the suspension. After the addition of the aqueous solution to the suspension is completed, the solution can be mixed by stirring at room temperature (about 25-35° C.) for about 3-5 hours. Furthermore, after the above mixing is completed, the mixed solution is neutralized by adding an alkaline compound, such as aqueous ammonia and / or the like, and the pH is controlled to about 7.0-7.5, thereby obtaining the post-framework modified USY zeolite described herein.

[0055] 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 above suspension, a part of the aluminum atoms forming the framework of the ultrastable Y-type zeolite is replaced by zirconium atoms to form a framework-modified USY zeolite (Zr-USY); when only a titanium compound (or an aqueous solution thereof) is used, a part of the aluminum atoms forming the framework of the ultrastable Y-type zeolite is replaced by titanium atoms to form a framework-modified USY zeolite (Ti-USY); when only a hafnium compound (or an aqueous solution thereof) is used, a part of the aluminum atoms forming the framework of the ultrastable Y-type zeolite is replaced by hafnium atoms to form a framework-modified USY zeolite (Hf-USY); when a zirconium compound and a titanium compound (or an aqueous solution thereof) are used, a part of the aluminum atoms forming the framework of the ultrastable Y-type zeolite is replaced by zirconium atoms and titanium atoms to form a framework-modified USY zeolite in the catalyst. When zirconium and hafnium compounds (or aqueous solutions thereof) are used, post-skeletal-modified USY zeolites (Zr-Hf-USY) are formed in the catalyst, in which a portion of the aluminum atoms forming the framework of the ultrastable Y zeolite are replaced by zirconium and hafnium atoms; when hafnium and titanium compounds (or aqueous solutions thereof) are used, post-skeletal-modified USY zeolites (Hf-Ti-USY) are formed in the catalyst, in which a portion of the aluminum atoms forming the framework of the ultrastable Y zeolite are replaced by hafnium and titanium atoms; when zirconium, titanium, and hafnium compounds (or aqueous solutions thereof) are used, post-skeletal-modified USY zeolites (Zr-Ti-Hf-USY) are formed in the catalyst, in which a portion of the aluminum atoms forming the framework of the ultrastable Y zeolite are replaced by zirconium, titanium, and hafnium atoms.

[0056] The resulting framework-substituted zeolite may be optionally filtered, washed with water, and dried at about 80-180° C.; the mixture may be quasi-equilibrated with steam, for example at a temperature of about 600-800° C. for about 10-20 hours.

[0057] 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, in the 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., to form a suspension of USY(c) at an effective concentration, for example, in the range of about a liquid / solid mass ratio of 5:1-15:1, 5:1-12:1, 8:1-15:1, or 8:1-12:1.

[0058] In the acid treatment step 11, an effective amount of an inorganic or organic acid is dispersed in the suspension such that the pH of the suspension is maintained in the strongly acidic range to prepare the zeolite for metal insertion into the framework step 12. In certain embodiments, this can be stepwise, similar to the '036 patent family. In additional embodiments, the acid treatment to prepare the zeolite for metal insertion into the framework can be performed in conjunction with metal insertion, for example, as disclosed in commonly owned U.S. Patent Publication No. 20210077985A1, which is incorporated by reference in its entirety.

[0059] The inorganic acid used can generally be sulfuric acid, nitric acid, hydrochloric acid, etc. In a particular embodiment, the inorganic acid selected is sulfuric acid or hydrochloric acid. Furthermore, as the organic acid, a carboxylic acid can be suitably used. The amount of inorganic acid or organic acid added is an amount suitable for controlling the pH of the suspension in a strongly acidic range, for example, 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 acidic suspension is maintained at an effective temperature, for example, in the range of 15 to 80, 15 to 60, 15 to 35, 15 to 30, or 20 to 60°C, and maintained 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.

[0060] In metal insertion step 12, framework replacement is performed. The acid modified USY(c) zeolite suspension is subjected to a metal treatment to replace some of the aluminum atoms forming the framework of the ultrastable Y zeolite. In certain embodiments, this is performed by adding a solution containing a transition metal compound to the acidity 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, for example 15-80, 15-60, 15-35, 15-30, 20-60, 15-35, or 15-30° C., for an effective residence time, for example in the range of about 10-600, 10-180, 30-600, or 30-180 minutes. The suspension from step 12 can be neutralized, for example with aqueous ammonia, to a pH in the range of about 7.0-7.5.

[0061] The solids obtained from 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 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 the post-framework modified USY zeolite (USYA) in step 13.

[0062] The ultrastable Y zeolite is used as a raw material to prepare a post-framework modified USY zeolite, referred to above as USY(c). As described above, one or more of steps 1-9 can be used to prepare or otherwise obtain the USY introduced in step 10. The USY introduced in step 10 generally has the properties of known USY zeolites, which can be synthesized or modified (as with one or more of steps 1-9, or alternative methods) or procured such that a USY zeolite having a SAR in the range of about 30-100, 40-100, 30-80, or 40-80 is provided for effective metal insertion.

[0063] Known USY-type zeolites generally have unit cell dimensions (UD) in the range of about 2.425-2.450 or 2.430-2.450 nm; generally about 600-900, 600-800, 650-900, or 650-800 nm. 2 / g; and a pore volume 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 an SAR in the range of about 5-100, 10-100, 20-100, 5-80, 10-80, 20-80, 25-100, or 25-80; as discussed herein, this SAR can be selected or modified to provide a USY that is effective for metal insertion.

[0064] For example, a suitable zeolite is the FAU framework (zeolite Y) whose micropores formed by 12-membered rings are 7.4×7.4 Å when viewed along the

[0111] direction. UD is also called the crystal lattice parameter and can be measured with reference to ASTM method D3942, Standard Test Method for Determination of Unit Cell Dimensions of Faujasite-Type Zeolites. Specific surface area is determined by the BET (Brunauer-Emmett-Teller) method using nitrogen adsorption. The ultrastable Y-type zeolite may be prepared by any method known in the art. This ultrastable Y-type zeolite is subjected to post-framework modification as described herein to form the post-framework modified USY zeolite used to prepare the composite catalyst particles.

[0065] The post-framework modified USY zeolite has one or more of zirconium, titanium, and hafnium incorporated into its framework. Effective concentrations of Zr, Ti, and / or Hf include 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 their oxide basis (i.e., ZrO2, TiO2, and / or HfO2) and measured relative to the weight of the post-framework modified USY zeolite. In certain embodiments, the amount of each material providing Zr, Ti, and / or Hf can be less than 0.1, 0.2, or 0.3 wt. %, but taken together, the total is at least 0.1, 0.2, or 0.3 wt. %. When the framework-substituted zeolite in the catalyst contains the above-mentioned zirconium atoms and titanium atoms and / or hafnium atoms, the mass ratio of zirconium atoms to titanium atoms and / or hafnium atoms (in terms of oxides) is not particularly limited, and it will be understood by those skilled in the art that any ratio of zirconium, titanium or hafnium effective for the intended use of the catalyst particles, for example, the hydrocracking of heavy hydrocarbon oils, can be used.

[0066] In certain embodiments, the post-framework modified USY zeolite is Framework-substituted zeolites in which a portion of the aluminum atoms forming the zeolite framework are replaced by only zirconium atoms, called "zirconium-substituted zeolites" or "Zr-USY"; Framework-substituted zeolites in which a portion of the aluminum atoms forming the zeolite framework are replaced by only titanium atoms, called "titanium-substituted zeolites" or "Ti-USY"; Framework-substituted zeolites in which a portion of the aluminum atoms forming the zeolite framework are replaced by only hafnium atoms, called "hafnium-substituted zeolites" or "Hf-USY"; framework-substituted zeolites, in which a portion of the aluminum atoms forming the zeolite framework are replaced only by zirconium and titanium atoms, called "zirconium-titanium substituted zeolites" or "Zr-Ti-USY"; A portion of the aluminum atoms forming the zeolite framework are replaced by only hafnium and titanium atoms, referred to as "hafnium-titanium replaced zeolites" or "Hf-Ti-USY" framework replaced zeolites; Framework-substituted zeolites, called "zirconium-hafnium substituted zeolites" or "Zr-Hf-USY", in which a portion of the aluminum atoms forming the zeolite framework are replaced with only zirconium and hafnium atoms; and A portion of the aluminum atoms forming the zeolite framework are replaced with only zirconium, titanium, and hafnium atoms, and the framework-substituted zeolite is called "zirconium-titanium-hafnium-substituted zeolite" or "Zr-Ti-Hf-USY."

[0067] The presence of zirconium and / or titanium and / or hafnium atoms replacing aluminum atoms in the post-framework modified USY zeolite serves as framework building blocks of the USY zeolite. The substitution can be confirmed, for example, by X-ray fluorescence, 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).

[0068] The next steps in the method for producing catalyst particles having active metal components on a composite carrier containing post-skeletal modified USY zeolite and a binder, steps 14 and 15, include forming an inorganic oxide as a binder or granulating agent, which is then combined with the post-skeletal modified USY zeolite and extruded (steps 16 and 17). In step 14, a solution is prepared to precipitate one or more inorganic oxides (hereinafter inorganic oxide components) used as binders or granulating agents. For example, a suitable binder can be prepared from a gel of alumina or another inorganic oxide known in the art. In certain embodiments, solid inorganic oxides can be used directly as binder materials.

[0069] Alternatively, as known to those skilled in the art, commercially available inorganic oxide components can be provided and prepared for mixing with the post-framework modified USY zeolite, for example by kneading.

[0070] The inorganic oxide may be a porous inorganic oxide used in hydrocracking catalyst compositions or other catalyst compositions in the related art, examples of which include alumina, silica, titania, silica-alumina, alumina-titania, alumina-zirconia, alumina-boria, phosphorus-alumina, silica-alumina-boria, phosphorus-alumina-boria, phosphorus-alumina-silica, silica-alumina-titania, and silica-alumina-zirconia.

[0071] The post-framework modified USY zeolite and inorganic binder are combined to form a catalyst support material using known processes for forming catalysts, for example, by mixing and kneading the components (step 16), which are then formed into the desired shape by co-extrusion or otherwise forming composite support particles (step 17). The composite support particles are calcined (step 18), and the calcined composite support particles are impregnated with the active metal components (step 19). The catalyst particles thus formed are then calcined again (step 20) to recover the final product, catalyst particles having the active metal components on the composite support. In certain embodiments, the post-framework modified USY zeolite material in the final particles functions as an active catalyst material in addition to the impregnated active metal components of the catalyst particles.

[0072] The composite support material is formed of a post-framework modified USY zeolite material, e.g., from step 13 herein, one or more inorganic oxide components (e.g., from step 15 herein), and optionally one or more other zeolite materials. The composite support material generally has a thickness of about 150-500, 150-450, 200-500, 200-450, or 300-450 m. 2The catalyst particles formed of the composite support material have a surface area in the range of about 0.4-0.8, 0.4-0.75, 0.4-0.65, 0.45-0.8, 0.45-0.75, or 0.45-0.65 ml / g, and a pore volume in the range of about 0.4-0.8, 0.4-0.75, 0.4-0.65 ml / g. The contents of the post-skeleton-modified USY zeolite component, the inorganic oxide component, and the active metal component are appropriately determined depending on the purpose. For example, the post-skeleton-modified USY zeolite content of the catalyst particles formed of the composite support material can be in the range of about 0.1-99, 0.1-90, 0.1-80, 0.1-70, 2-99, 2-90, 2-80, 2-70, 20-100, 20-90, 20-80, or 20-70 mass%, with the remaining content being the inorganic oxide and the active metal component, and optionally one or more other zeolite materials in certain embodiments.

[0073] In the mixing / kneading step 16, the post-framework modified USY zeolite, e.g. recovered from step 13 or otherwise prepared, and the inorganic binder, e.g. recovered from step 15 or otherwise prepared, are mixed together. The mixing is carried out in an effective ratio as described above and at a suitable temperature, e.g. in the range of about 15-80, 15-60, 15-35, 15-30, or 20-60°C. The mixture is kneaded with an effective amount of water, e.g. in the range of about 30-80 liquid / solid weight ratio, for an effective kneading time, e.g. in the range of about 10-180 minutes. Thus, the kneading of the wet solid materials results in the formation of a dough, which is subsequently formed and dried. The kneaded product can be subjected to a heat treatment to achieve better contact between the components and better homogeneity by heat diffusion and solid-state reactions.

[0074] The thus obtained kneaded material is extruded (forming step 17) through a die having an effective cross-sectional shape and size at a suitable temperature, for example, in the range of about 15-80, 15-60, 15-35, 15-30, or 20-60°C. Effective cross-sectional shapes include, for example, cylindrical, trilobal, twisted trilobal, or tetralobal. Effective cross-sectional dimensions include, for example, diameters or effective diameters in the range of about 0.8-3 or 0.8-2.5 millimeters. The obtained extrudates are dried at an effective temperature, for example, in the range of about 80-180 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 a dried composite extrudate. Optionally, a separate drying step can be avoided, whereby the composite extrudates are sent to a heat treatment step 18 for calcination.

[0075] In a heat treatment step 18, the composite extrudates (optionally dried) are subjected to a heat treatment to prepare calcined composite particles. In certain embodiments, the heat treatment in step 18 comprises calcining the composite extrudates (optionally dried) at an effective temperature in the range of, for example, 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. (typically in the presence of air or oxygen, or in the presence of water vapor) for a time in the range of about 10-600, 10-180, 30-600, or 30-180 minutes to recover the calcined composite particles.

[0076] The final product, the calcined composite catalyst particles, is impregnated with active metal components, such as hydrogenation metals. The active metal components may include one or more metals or metal compounds (oxides or sulfides) known in the art 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 metal components include those effective as hydrocracking catalysts, such as one or more of Mo, W, Co, or Ni (oxides or sulfides). In certain embodiments, the active metal components include those effective as hydrogenation and / or reforming catalysts (typically in a sulfur-free environment), such as one or more noble metals, such as Pt, Pd, Rh, Re, Ir, or combinations of such noble metals. The metal components may be contained in the catalyst at effective concentrations. For example, the total active metal content in the hydrocracking catalyst may be present in an amount of about 0.01 to 40% by weight, for example calculated as metal, oxide, or sulfide, as known in the relevant art. For non-noble metals including Mo, W, Co, Ni, or combinations thereof, the effective total active metal content can be about 0.1-40 wt. % or 3-40 wt. % calculated as oxide or sulfide based on the weight of the catalyst. For noble metals, typically in a sulfur-free environment for hydrogenation and / or reforming, the effective total active metal content can be about 0.01-2 wt. % calculated as metal.

[0077] In the embodiment of FIG. 3, the active metal component is impregnated in step 19. Several methods can be used to add the active metal component to the support, including but not limited to immersion, incipient wetness, and evaporation. In the most commonly used method, the calcined support is immersed in an excess of an aqueous solution containing the active metal or metal compound. The solution fills the pores and also adsorbs onto the support surface, and the excess solution is removed. In another method, impregnation is performed using incipient wetness by tumbling or spraying the activated carrier with a volume of solution having a metal compound concentration adjusted to achieve the target metal level. In another method, evaporation impregnation, the support is saturated with water or an acid solution and immersed in an aqueous solution containing the metal compound. The compound then diffuses through the aqueous phase into the pores of the support. The metal-loaded support is then dried and calcined to form the metal oxide.

[0078] In certain embodiments, the active metal component impregnation step 19 comprises immersing the calcined composite support particles formed of the post-framework modified USY zeolite and binder with an aqueous solution containing the active metal component. The amount and concentration of the aqueous solution containing the active metal component depends on the desired amount of active metal component to be loaded on the composite support particles. In certain embodiments of the above method, the volume of the active metal 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.

[0079] The resulting solids can be filtered and dried at an effective temperature, for example, in the range of about 80-180 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 the composite support particles formed of the post-framework modified USY zeolite and binder, carrying the active metal on the composite material. Optionally, a separate drying step can be avoided, whereby the composite material with the active metal is sent to a heat treatment step 20 for calcination.

[0080] In a heat treatment step 20, the supported composite material is subjected to a heat treatment to prepare calcined composite particles having an active metal on the composite material. In certain embodiments, the heat treatment in step 20 includes calcining at an effective temperature in the range of, for example, about 400-800, 500-800, 500-700, 500-650, 550-800, 550-700, 550-650, 600-800, or 600-700° C. for a time in the range of about 10-600, 10-180, 30-600, or 30-180 minutes to recover the calcined composite particles having an active metal on the composite material. In certain embodiments, the calcination is performed in the presence of air.

[0081] In step 21, the final catalyst product is recovered. In embodiments where the catalyst is a hydrocracking catalyst, a hydrogenation catalyst, or a reforming catalyst, the active metal loaded composite support material is typically about 150-500, 150-450, 200-500, 200-450, or 300-450 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.

[0082] 4-6, there are shown embodiments for producing catalyst particles having active metals in which all or a portion of the metal loading occurs prior to forming the composite catalyst particles, thereby providing flexibility to catalyst manufacturers as will become apparent herein.

[0083] As used herein, "active metal component" is distinct from the metals replacing aluminum atoms in the USY zeolite framework, and specifically refers to one or more metals or metal compounds (oxides or sulfides) impregnated in the framework modified zeolite, in the binder, in the extrudates of the framework modified zeolite and binder, in the calcined extrudates of the framework modified zeolite and binder, and combinations thereof.

[0084] Without wishing to be bound by theory, it is understood that controlling metal loading by using wet USYA minimizes clogging of the pores. If the zeolite has pores saturated with water, less metal can diffuse into the pores from the metal solution over a given period of time compared to adding a metal solution to the same zeolite in a dry state.

[0085] In the embodiments described herein, the ratio of the post-framework-modified USY zeolite component to the inorganic oxide binder component is appropriately determined according to the purpose of the catalyst. For example, the post-framework-modified USY zeolite content of the catalyst particles formed with the composite support material can be in the range of about 0.1-99, 0.1-90, 0.1-80, 0.1-70, 2-99, 2-90, 2-80, 2-70, 20-100, 20-90, 20-80, or 20-70 mass %, with the remaining content being the inorganic oxide binder, and optionally one or more other zeolite materials in certain embodiments.

[0086] In one embodiment, a method for producing catalyst particles is provided, in which the catalyst particles are formed from a composite of a granulating or binder material, such as an inorganic oxide, and a framework-substituted USY zeolite material (USYA) in which some of the aluminum atoms in the framework are substituted with zirconium and / or titanium and / or hafnium atoms, and are impregnated with an active metal prior to forming the catalyst particles. In another description of this embodiment, the catalyst particles of this embodiment are referred to as calcined extrudates of the composite support material of binder and USYA carrying the active metal.

[0087] FIG. 4 illustrates the steps of a method for producing the binder and USYA composite catalyst according to this embodiment, in which a mixture of USYA and inorganic oxide is impregnated with active metal components prior to forming the catalyst particles.

[0088] In one embodiment of this preparation method, the framework modified zeolite and inorganic oxide as binder are prepared and / or provided, mixed and kneaded in a desired ratio to form a complex homogeneous mixture of materials. The active metal component is added onto the surface of the zeolite and binder, including the pore wall surface. The mixture containing the active metal component is then extruded and calcined to form active metal-containing catalyst particles. This eliminates steps 19 and 20 from the method of FIG. 3.

[0089] A framework-substituted USY zeolite material, USYA, is provided in step 43 as a wet, dry (uncalcined), or calcined zeolite material. The underlying framework-substituted USY zeolite material and binder material can be provided from any suitable source, including those described herein above in connection with FIG. 3 or another source. Steps corresponding to steps in FIG. 3 that are considered optional in certain embodiments herein are shown in dashed lines in FIG. 4 and can be performed as described with respect to FIG. 3. The composite material formed of the zeolite and inorganic oxide material is characterized by an exterior surface and an interior pore wall surface. In the embodiment of FIG. 4, active metal is applied to the exterior surface and interior pore wall surface of the composite material in step 66.

[0090] The post-framework-modified USY zeolite has one or more of zirconium, titanium, and / or hafnium incorporated into its framework in an effective concentration of 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 their oxide basis (i.e., ZrO2, TiO2, and / or HfO2) and measured relative to the weight of the post-framework-modified USY zeolite; in certain embodiments, the amount of each of the materials providing Zr, Ti, and / or Hf can be less than 0.1, 0.2, or 0.3 wt. %, but taken together, the total 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, whereby the solid material from step 12 of the framework-substitution process is filtered / washed and provided in a wet state, whereby the drying step typically employed is not performed (but is performed to a lesser extent) and water remains entrained in the solid. In certain embodiments, the framework-substituted USY zeolite component is provided in a "dry" state, whereby the solid material from step 12 of the framework-substitution process is filtered and dried, but provided in an uncalcined state, whereby the heat treatment step typically employed to calcinate the material is not performed. In certain embodiments, the framework-substituted USY zeolite component is provided in a "dry" state, whereby the solid material from step 12 of the framework-substitution process is filtered, dried, and calcined. Thus, in the embodiment of FIG. 4, the USYA in step 43 is provided as a wet, dried (uncalcined), or calcined zeolite material.

[0091] The USYA zeolite material from step 43 in the wet, dry (uncalcined) or calcined state is combined (shown as mixing / kneading step 46) with a binder support component (e.g., from step 15), which can be performed as described above with respect to step 16 of FIG. 3. The binder material can be prepared, for example, as shown and described herein with respect to steps 14 and 15 of FIG. 3, or a commercially available inorganic oxide component can be provided, as known to those skilled in the art. As the inorganic oxide, a porous inorganic oxide used in hydrocracking catalyst compositions or other catalyst compositions in the related art can be used. Examples include alumina, silica, titania, silica-alumina, alumina-titania, alumina-zirconia, alumina-boria, phosphorus-alumina, silica-alumina-boria, phosphorus-alumina-boria, phosphorus-alumina-silica, silica-alumina-titania, and silica-alumina-zirconia.

[0092] After forming the composite homogeneous mixture of the post-framework modified USY zeolite and binder material in step 46, and prior to forming into catalyst particles, an effective amount of active metal component is added to the surfaces, including the pore wall surfaces, of the zeolite and binder material in step 66. Although this is shown as a separate step, impregnation of the active metal into the post-framework modified USY zeolite and binder mixture can be performed during the mixing and kneading of the components or as a separate step thereafter. In certain embodiments, all or a portion of the water that would typically be used during the mixing and kneading of the components is replaced with an aqueous metal solution as a source of active metal component. In certain embodiments, the effective amount encompasses the total active metal content of the final catalyst particles, since the active metal component of the final catalyst particles is provided only in the composite homogeneous mixture of the post-framework modified USY zeolite and binder.

[0093] The active metal component may include one or more metals or metal compounds (oxides or sulfides) known in the art 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 metal component is one or more of Mo, W, Co, or Ni (oxides or sulfides). In certain embodiments, the active metal component includes those that are effective as hydrogenation and / or reforming catalysts, typically in sulfur-free environments, such as one or more of the noble metals Pt, Pd, Rh, Re, Ir, or combinations of such noble metals.

[0094] The metal components may be contained in the composite homogeneous mixture of the post-framework modified USY zeolite and binder material in a concentration effective to provide an effective total active metal content in the final catalyst particle. A catalyst produced according to the embodiment of FIG. 4 used for hydrocracking, for example hydrocracking of heavy hydrocarbon oils, may contain about 0.01-40 wt. % of the active metal components calculated as metal, oxide, or sulfide, based on the total weight of the composite catalyst material, similar to the ranges used in conventional hydrocracking catalysts. For non-precious metals including Mo, W, Co, Ni, or combinations thereof, the effective total active metal content may be about 0.1-40 wt. % or 3-40 wt. % calculated as oxide or sulfide, based on the weight of the catalyst. For precious metals, typically in a sulfur-free environment for hydrogenation and / or reforming, the effective total active metal content may be about 0.01-2 wt. % calculated as metal.

[0095] The active metal components can be added to the support (composite homogeneous mixture of post-framework modified USY zeolite and binder material) using several methods, including but not limited to immersion, incipient wetness, and evaporation, or any other suitable method. In certain embodiments, an effective amount of the wet or dry composite homogeneous mixture is immersed in an excess of a solution containing the active metal or metal compound. The solution fills the pores and also adsorbs onto the support surface, and the excess solution is removed to recover the metal-loaded composite homogeneous mixture of the support material. In another method, impregnation is performed using incipient wetness by tumbling or spraying an effective amount of the support material (composite homogeneous mixture of post-framework modified USY zeolite and binder material) with a volume of solution having a metal compound concentration adjusted to achieve the target metal level. The metal-loaded composite homogeneous mixture of the support material is recovered. In another method, evaporation impregnation, an effective amount of the support material (composite homogeneous mixture of post-framework modified USY zeolite and binder material) is saturated with water or an acid solution and immersed in an aqueous solution containing the metal compound. The compound then diffuses through the aqueous phase into the pores of the support. A metal-loaded composite homogeneous mixture of the support material is recovered.

[0096] The amount and concentration of the aqueous solution containing the active metal component added to the composite homogeneous mixture of post-framework modified USY zeolite and binder material depends on the desired amount of active metal component to be loaded on the composite support particles. In certain embodiments of the above method, the volume of the active metal solution added 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.

[0097] In certain embodiments, metal loading can be achieved by loading an appropriate concentration of metal solution into the available pore volume of a composite homogeneous mixture of post-framework modified USY zeolite and binder material. In further embodiments, lesser amounts are used to control metal loading. For example, the effective volume of loaded metal solution can range from, 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 support material.

[0098] The resulting blended material is then formed into composite catalyst particles (shown as forming step 47) in step 66 (either as a separate step from step 16 or together with the blending of step 16). The composite catalyst particles are calcined (shown as heat treating step 48) and the final product is recovered (shown as step 51). Steps 46, 47, 48, and 51 shown and described with respect to Figure 4 can be performed as described above with respect to steps 16, 17, 18, and 21, respectively, of Figure 3. As mentioned above, in certain embodiments, steps 19 and 20 from the method of Figure 3 are thereby eliminated and the final composite catalyst particles are metal-loaded composites of USYA and binder support components that are co-extruded and formed into catalyst particles.

[0099] The final catalyst product, calcined catalyst particles, is recovered in step 51. The final composite catalyst particles, which are calcined extrudates of the active metal loaded binder and USYA composite support material, generally have surface area and pore volume levels in the range of catalysts formed by conventional processes, for example as described with respect to step 21 of FIG.

[0100] Therefore, the overall process for producing metal supported catalyst particles having a composite support of framework substituted USY zeolite material and inorganic oxide is simplified since steps 19 and 20 from the process of FIG. 3 are eliminated.

[0101] In another embodiment, a method for producing catalyst particles is provided, wherein the catalyst particles are formed from a composite of a granulating or binder material, such as an inorganic oxide, and a framework-substituted USY zeolite material (USYA) in which some of the aluminum atoms in the framework are substituted with zirconium and / or titanium and / or hafnium atoms, the mixture is impregnated with an active metal prior to forming the catalyst particles, and the formed catalyst particles are further impregnated with additional active metal. In another description of this embodiment, the catalyst particles of this embodiment are referred to as calcined metal-loaded extrudates of the composite support material of binder and USYA loaded with active metal.

[0102] FIG. 5 illustrates the steps of a method for producing the binder and USYA composite catalyst according to this embodiment, where the active metal is impregnated prior to catalyst formation and the formed extrudates are impregnated with additional active metal.

[0103] In one embodiment of this preparation method, the framework modified zeolite and inorganic oxide as binder are prepared and / or provided, mixed and kneaded in a desired ratio to form a composite homogenous mixture of materials. A portion of the active metal component is added onto the zeolite and binder surfaces, including the pore wall surfaces. The metal-loaded composite mixture is extruded and calcined to form active metal-containing catalyst particles having a first portion of the total active metal content. After the catalyst particles are formed with the binder, another portion (and in certain embodiments the remaining portion) of the total active metal component is added to the extrudate, and the metal-loaded composite catalyst particles, with the metal separately loaded on the binder and framework modified zeolite component, are calcined to form the final product.

[0104] The framework-substituted USY zeolite material, USYA, is provided in step 43 as a wet, dry (uncalcined), or calcined zeolite material, as described herein with respect to Figure 4. The underlying framework-substituted USY zeolite material and binder material can be provided from any suitable source, including those described herein above with respect to Figure 3 or from another source. Steps corresponding to steps in Figure 3 that are considered optional in certain embodiments herein are shown in dashed lines in Figure 5 and can be performed as described with respect to Figure 3. The composite material formed of the zeolite and inorganic oxide material is characterized by an exterior surface and an interior pore wall surface. In addition, the formed extrudate is characterized by an exterior surface and an interior pore wall surface. In the embodiment of Figure 5, an active metal is applied to the exterior and interior pore wall surfaces of the composite material in step 66, and an additional metal is applied to the exterior and interior pore wall surfaces of the formed extrudate in step 49.

[0105] Similar to the embodiment of Figure 4, the USYA zeolite material from step 43 in a wet, dry (uncalcined), or calcined state is combined (shown as mixing / kneading step 46) with a binder support component (e.g., from step 15), which may be performed as described above with respect to step 16 of Figure 3. After forming a composite homogenous mixture of the post-framework modified USY zeolite and binder material in step 46, and prior to formation into catalyst particles, an effective amount of an active metal component is added to the surfaces, including the pore wall surfaces, of the zeolite and binder material in step 66. In the embodiment of Figure 5, only a portion of the active metal content is supported in this step. The amount of active metal component in step 66 is a first portion of the total active metal component content contained in the final composite catalyst particles, and a second portion of the total active metal component content is impregnated into the extrudates in step 49, described below.

[0106] The first portion added to the composite support component can be, for example, about 1-99, 1-90, 1-70, 1-60, 1-99, 5-90, 5-70, 5-60, 20-99, 20-90, 20-70, 20-60, 40-99, 40-90, 40-70, or 40-60 mass % of the total active metal component content contained in the final composite catalyst particle, with the remainder of the total active metal being made up of the second portion of the active metal component content impregnated into the extrudate as formed composite support component.

[0107] The composite catalyst particles having a first portion of the active metal components in the composite support component after being subjected to the heat treatment in step 48 are subjected to an impregnation step 49 in which a second portion of the total active metal component content is impregnated into the composite extruded particles as the support. The second portion is an amount effective to make up the difference to achieve the required total active metal component content. In a particular embodiment, an effective amount of the composite extruded particles is immersed in an excess of a solution containing the active metal or metal compound. The solution fills the pores and also adsorbs onto the support surface, and the excess solution is removed to recover the metal-supported composite. The metal-supported composite catalyst particles from step 49 are calcined (shown as heat treatment step 50) to recover the final product calcined catalyst particles (shown as step 51).

[0108] Several methods can be used to add the additional active metal component to the metal-loaded composite extruded particles as calcined metal-loaded supports from step 48, including but not limited to immersion, incipient wetness, and evaporation. Impregnation of the composite extruded particles once metal-loaded can follow procedures used in conventional processes, such as those described in connection with step 19 of Figure 3. The difference is that in the processes herein, this step requires only a second portion of the total active metal component content to provide the 2x metal-loaded composite extruded particles, rather than the entire active metal content as in conventional processes.

[0109] The procedure for heat treatment, step 50, can follow that used in conventional processes, for example, as described in connection with step 20 of Figure 3. In step 51, the final catalyst product is recovered. The final composite catalyst particles, which are calcined metal-loaded extrudates of the active metal loaded binder and USYA composite support material, will generally have surface area and pore volume levels in the range of catalysts formed in conventional processes, for example, as described in connection with step 21 of Figure 3.

[0110] In an additional embodiment, and generally with reference to Figure 6, a method for producing catalyst particles is provided, in which the catalyst particles are formed from a composite of a granulating or binder material, such as an inorganic oxide, and a framework-substituted USY zeolite material (USYA) in which a portion of the aluminum atoms in the framework are substituted with zirconium and / or titanium and / or hafnium atoms. An active metal is impregnated into the composite of the binder and USYA (step 66 described herein); and (a) an inorganic oxide binder (step 55) (metal impregnation step 49 is not present), as described herein and in co-pending U.S. patent application Ser. No. 17 / 577,747, entitled “Catalysts With Modified Active Phase Dispersion And Method To Prepare Catalysts With Modified Active Phase Dispersion,” filed Jan. 18, 2022, which is hereby incorporated by reference in its entirety; (b) USYA zeolite (step 54) to form USYA(m) (the metal impregnation step 49 is absent), as described herein and in co-pending U.S. patent application Ser. No. 17 / 577,691, entitled “Catalysts With Modified Active Phase Dispersion And Method To Prepare Catalysts With Modified Active Phase Dispersion,” filed Jan. 18, 2022, which is hereby incorporated by reference in its entirety; or (c) Impregnated with both (a) and (b) above.

[0111] Alternatively, the active metal is impregnated into the composite of the binder and USYA (step 66 described herein); and (a) (a1) an inorganic oxide binder (step 55) (metal impregnation step 49 is not present), as described herein and in co-pending U.S. patent application Ser. No. 17 / 577,747, entitled “Catalysts With Modified Active Phase Dispersion And Method To Prepare Catalysts With Modified Active Phase Dispersion,” filed Jan. 18, 2022, which is incorporated herein by reference in its entirety; (a2) USYA zeolite (step 54) to form USYA(m) (the metal impregnation step 49 is absent), as described herein and in co-pending U.S. patent application Ser. No. 17 / 577,691, entitled “Catalysts With Modified Active Phase Dispersion And Method To Prepare Catalysts With Modified Active Phase Dispersion,” filed Jan. 18, 2022, which is incorporated by reference in its entirety; or (a3) Both (a1) and (a2) above; One of the following: (b) impregnating extruded intermediate catalyst particles (step 49) formed from one of (a1), (a2), or (a3) ​​above.

[0112] Figure 6 shows the steps of a method for producing the composite catalyst having an active metal impregnated in one or more stages. The sequence of the individual steps can follow the sequence described herein with respect to Figures 3-5, with certain steps further described in co-pending U.S. Patent Application Serial No. 17 / 577,691, entitled "Catalysts With Modified Active Phase Dispersion And Method To Prepare Catalysts With Modified Active Phase Dispersion," filed January 18, 2022, and / or U.S. Patent Application Serial No. 17 / 577,747, entitled "Catalysts With Modified Active Phase Dispersion And Method To Prepare Catalysts With Modified Active Phase Dispersion," filed January 18, 2022, both of which are incorporated herein by reference in their entirety.

[0113] In any of the above embodiments, for example, in the step of mixing the post-framework-modified USY zeolite or the metal-loaded post-framework-modified USY zeolite with the inorganic oxide, one or more additional zeolitic components (i.e., zeolitic materials other than the post-framework-modified USY zeolite or the metal-loaded post-framework-modified USY zeolite) can be incorporated, including, but not limited to, mordenite, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM35, beta type, Y, and USY (this USY zeolite component is not the same as the post-framework-modified USY zeolite described herein). For example, these include (FAU) frameworks comprising USY, which have a micropore size associated with 12-membered rings of 7.4×7.4 Å when viewed along the

[0111] direction; (MFI) frameworks comprising ZSM-5, which have micropore sizes associated with 10-membered rings of 5.5×5.1 Å and 5.6×5.3 Å when viewed along the

[0100] and

[0010] directions, respectively; (MEL) frameworks comprising ZSM-11, which have a micropore size associated with 10-membered rings of 5.4×5.3 Å when viewed along the

[0100] direction; (MTW) ​​frameworks comprising ZSM-12, which have a micropore size associated with 12-membered rings of 5.6×6.0 Å when viewed along the

[0010] direction; (TON) frameworks comprising ZSM-12, which have a micropore size associated with 10-membered rings of 4.6×5.7 Å when viewed along the

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

[0001] and

[0010] directions; (FER) frameworks comprising ZSM-35, having micropore diameters associated with 10-membered and 8-membered rings of 4.2×5.4 Å and 3.5×4.8 Å when viewed along the

[0001] and

[0001] directions, respectively; (MOR) frameworks comprising mordenite zeolite, having micropore diameters associated with 12-membered and 8-membered rings of 6.5×7.0 Å and 2.6×5.7 Å when viewed along the

[0001] and

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

[0100] and

[0001] directions, respectively.

[0114] Provided herein is a process for hydrocracking a hydrocarbon oil, comprising hydrocracking the hydrocarbon oil with the hydrocracking catalyst described above.

[0115] In a particular embodiment, the method for hydrocracking a hydrocarbon oil includes filling a hydrocracking catalyst into a reaction vessel of a hydrocracker, which is a flow reactor, and hydrocracking a hydrocarbon oil having a boiling point in the range of, for example, about 370 to 816, 370 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 4 to 30, 7 to 15 MPa, and a pressure of about 0.1 to 10, 0.2 to 1.5 h. -1 and about 500-2500, 1000-2000 normal cubic meters of hydrogen (Nm 3 / m 3 ) with a hydrogen / oil ratio in the range of

[0116] In a particular embodiment, the method for hydrocracking a hydrocarbon oil includes filling a hydrocracking catalyst into a reaction vessel of a hydrocracker, which is a flow reactor, 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 a pressure of about 0.2 to 1.5 h. -1 and LHSV in the range of about 1000~2000Nm 3 / m 3 to obtain kerosene-gas oil.

[0117] In the method for hydrocracking hydrocarbon oil according to the present invention, the above-mentioned fluidized reactor can be a fluidized reactor selected from a stirred bath reactor, a bubbling bed reactor, a baffled slurry bath reactor, a fixed bed reactor, a rotating tube reactor, and a slurry bed reactor.

[0118] In the method for hydrocracking a hydrocarbon oil according to the present invention, the hydrocarbon oil preferably contains (1) crude oil, (2) synthetic crude oil, (3) bitumen, (4) oil sand, (5) Shell oil, or (6) heavy hydrocarbon oil obtained from coal liquid oil.

[0119] In a method for hydrocracking a hydrocarbon oil according to a certain embodiment of the present invention, said hydrocarbon oil comprises a heavy hydrocarbon oil obtained from crude oil, synthetic crude oil, bitumen, oil sands, shell oil, or coal liquid oil, and said heavy hydrocarbon oil is preferably any of a) vacuum gas oil (VGO), b) deasphalted oil (DAO) or demetallized oil obtained from a solvent deasphalting process, c) light coker gas oil or heavy coker gas oil obtained from a coker process, d) cycle oil obtained from a fluid catalytic cracking (FCC) process, or e) gas oil obtained from a visbreaking process.

[0120] The hydrocracking catalyst for hydrocarbon oils produced according to the present invention is characterized in that, in the hydrocracking catalyst for hydrocarbon oils containing an ultrastable Y-type zeolite, the ultrastable Y-type zeolite is a framework-substituted zeolite in which a portion of the aluminum atoms constituting the framework are substituted with zirconium atoms and / or titanium atoms and / or hafnium atoms. A hydrogenation-active metal component is imparted, and all or part of the metal loading is carried out before forming the composite catalyst particles as described herein.

[0121] Therefore, the hydrocracking catalyst of the present invention allows heavy hydrocarbons such as VGO, DAO, etc. to diffuse more easily into its mesopores than conventional hydrocracking catalysts containing a zeolite carrier carrying titanium or zirconium fine particles, improving the cracking activity of hydrocarbon oils and enabling a high yield of middle distillates to be obtained. By using the hydrocracking catalyst of the present invention, clogging of mesopores is minimized and the ability of heavy hydrocarbons to diffuse into the mesopores for catalytic reaction is improved.

[0122] Furthermore, the hydrocracking catalyst of the present invention has a slightly lower cracking activity for hydrocarbon oils than that of a conventional hydrocracking catalyst containing a hydrogenation metal component supported on a carrier containing a framework-substituted zeolite in which part of the aluminum atoms constituting the framework of Y-type zeolite are substituted with titanium atoms, but excessive cracking reactions of kerosene and gas oil are suppressed, and therefore middle distillates can be obtained in high yields. Also, the hydrocracking catalyst for hydrocarbon oils of the present invention has an increased number of active sites, and therefore is endowed with high hydrocracking activity. EXAMPLES

[0123] (Comparative Example) The comparative example provides a method for producing a reference catalyst particle by calcining a composite support particle of a post-framework modified USY zeolite and binder as described herein, adding an active metal component to the particle, and then calcining the particle, similar to that disclosed in the '036 patent family.

[0124] First, the SAR is 5.2, the UD is 2.466nm, and the SA is 720m. 2 50.0 kg of Na-Y zeolite having a molecular weight of 1.0 kg / g and a Na2O content of 13.0% by mass was suspended in water at a temperature of 60°C (liquid / solid mass ratio of 12.5 L of water per 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. Next, the solid was washed with an ammonium sulfate solution in which 14.0 kg of ammonium sulfate was dissolved in 500 L of water at a temperature of 60°C, washed with 500 L of water at a temperature of 60°C, and dried at 130°C for 20 hours, whereby 65% ​​of the sodium (Na) contained in Na-Y was converted to ammonium ions (NH 41 ) ion-exchanged with Y zeolite (NH4 65 Y) About 45 kg was obtained. NH4 65 The Na2O content in Y was 4.5 mass%. Next, NH4 65 40 kg of Y was calcined in a saturated steam atmosphere at 670°C for 1 hour to form hydrogen-Y zeolite (HY).

[0125] 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, whereby 95% of the Na contained in the initial Na-Y was ion-exchanged with NH4 to obtain Y zeolite (NH4 95 Y) about 37 kg was obtained. 95 Approximately 33 kg of Y was calcined at 650°C for 1 hour in a saturated steam atmosphere to obtain approximately 15 kg of ultrastable Y zeolite (hereinafter also referred to as "USY(a)") with a SiO2 / Al2O3 molar ratio of 5.2 and a Na2O content of 0.6 mass%.

[0126] 40 kg of USY(a) was suspended in 400 L of water at 60°C. 25% by weight sulfuric acid, 2.35 times the amount of zeolite, was gradually added to the suspension and stirred for 1 hour to dissolve the extra-framework aluminum, thus preparing a second USY zeolite (USY(b)). The suspension was then filtered, and the resulting material was washed with 20 L of purified water at 60°C, and dried at 130°C for 20 hours to obtain a solid material, USY(b). USY(b) was calcined at 600°C for 1 hour, thereby preparing an ultrastable Y-type zeolite (USY(c)).

[0127] 1 kg of USY(c) is suspended in 10 L of water at 25° C. The pH of the suspension is adjusted to 1.6 by gradually adding 25% by weight of sulfuric acid. Then, 86 g of a solution containing 18% by weight of zirconium sulfate and 45 g of a solution containing 33% by weight of titanium sulfate are added thereto. The resulting mixture is stirred at room temperature for 3 hours. Then, the pH is adjusted to 7.2 with 15% by weight of aqueous ammonia. After stirring the mixture at room temperature for 1 hour, the mixture is filtered. The obtained solid is washed with 10 L of water and dried at 130° C. for 20 hours, thereby obtaining about 1 kg of titanium-zirconium substituted zeolite (Ti-Zr-USY).

[0128] To prepare the alumina binder, 40 kg of an aqueous solution of sodium aluminate at 6.8% by weight based on Al2O3 was mixed with 40 kg of an aqueous solution of aluminum sulfate at 2.4% by weight based on Al2O3. The mixture was further stirred at 60°C for 1 hour, and then the product was washed with 150 L of 0.3% by weight aqueous ammonia solution to remove Na2SO4. Water was then added to the product from which Na2SO4 had been removed to adjust the Al2O3 concentration to 10% by weight. The pH was adjusted to 10.5 with 15% by weight aqueous ammonia. The mixture was stirred at 95°C for 10 hours, dehydrated, washed, and kneaded in a kneader, thereby producing an alumina mixture.

[0129] The alumina kneaded product thus prepared was mixed with Ti-Zr-USY zeolite in a dry weight ratio of 3:7. The mixture was formed into a cylindrical shape with a diameter of 1.8 mm and calcined at 550°C for 3 hours, thereby preparing calcined composite particles.

[0130] Next, the hydrogenation active metal component was added to the calcined composite particles. An aqueous solution containing the hydrogenation active metal component was prepared by adding 700 mL of water to 200 g of molybdenum trioxide (an example of a hydrogenation active metal component) and 91 g of nickel carbonate (an example of a hydrogenation active metal component). The aqueous solution was mixed with 500 g of the calcined composite particles (a composite of Ti-Zr-USY zeolite and alumina) and dried at 250°C for 1 hour. The collected mixture was calcined at 550°C for 3 hours to prepare and collect calcined composite particles having an active phase material, thereby obtaining about 0.5 kg of the reference catalyst.

[0131] Example 1 According to the method of the comparative example, a mixture of titanium-zirconium substituted zeolite, Ti-Zr-USY (dry state) and alumina was obtained. The Ti-Zr-USY zeolite and alumina were mixed in a dry weight ratio of 3:7, and the mixture was kneaded. An aqueous solution containing hydrogenation active metal components was prepared by adding 580 mL of water to 240 g of molybdenum trioxide (an example of hydrogenation active metal components) and 110 g of nickel carbonate (an example of hydrogenation active metal components). The aqueous solution of active metal components was mixed with 1200 g of alumina and Ti-Zr-USY zeolite kneaded mixture. The mixture thus formed was formed into a cylindrical shape with a diameter of 1.8 mm and calcined at 550° C. for 3 hours, and about 1.3 kg of catalyst particles were recovered, which were calcined extrudates of a composite support material of binder and USYA carrying active metals.

[0132] Example 2 According to the method of the comparative example, a mixture of titanium-zirconium substituted zeolite, Ti-Zr-USY (dry state) and alumina was obtained. The Ti-Zr-USY zeolite and alumina were mixed in a dry mass ratio of 1:1, and the mixture was kneaded. An aqueous solution containing hydrogenation active metal components was prepared by adding 300 mL of water to 100 g of molybdenum trioxide (an example of a hydrogenation active metal component) and 45 g of nickel carbonate (an example of a hydrogenation active metal component). Half of the aqueous solution of active metal components was mixed with 500 g of a mixture of alumina and Ti-Zr-USY zeolite, thereby obtaining about 0.5 kg of a composite support material carrying active metals. The mixture was formed into a columnar shape with a diameter of 1.8 mm and calcined at 550° C. for 3 hours, and about 0.5 kg of intermediate catalyst particles was recovered.

[0133] The remaining portion of the aqueous solution containing the hydrogenation active metal components was then mixed with 0.5 g of the calcined intermediate catalyst particles (metal-supported composite of Ti-Zr-USY zeolite and alumina) and dried at 250° C. for 1 hour. The recovered mixture was calcined at 550° C. for 1 hour to recover about 0.5 kg of catalyst particles, which were calcined metal-supported extrudates, and the extrudates were formed from a metal-supported composite of Ti-Zr-USY zeolite and alumina.

[0134] Although the method and system of the present invention have been described above, modifications are apparent to those skilled in the art, and the scope of protection of the present invention is defined by the following claims.

Claims

1. 1. A method for producing catalyst particles, comprising: providing a post-framework-modified ultrastable Y (USY) zeolite characterized by an outer surface and pores defining an inner surface, wherein a portion of the aluminum atoms constituting the zeolite framework are replaced with zirconium atoms and / or titanium atoms and / or hafnium atoms; impregnating the outer surface and / or the inner pore surfaces of the post-framework-modified USY zeolite with a first portion of the total active metal component content of one or more active metal components to form a metal-loaded post-framework-modified USY zeolite; providing an inorganic oxide as a binder; mixing and kneading the metal-loaded framework-modified USY zeolite with an inorganic oxide binder to form a composite of the metal-loaded framework-modified USY zeolite and the inorganic oxide binder, the composite being characterized by an outer surface and an inner pore wall surface; impregnating the exterior surface and / or the interior pore surfaces of the composite with a second portion of the total active metal component content of one or more active metal components to form a metal-loaded composite of the framework-modified USY zeolite and the inorganic oxide binder; forming catalyst particles from the metal-loaded composite of the framework-modified USY zeolite and inorganic oxide binder into extrudates; heat treating the extrudate; and recovering the calcined catalyst particles; A method comprising:

2. 2. The method of claim 1, wherein the pores of the post-framework-modified USY zeolite define a volume, and the step of impregnating with one or more active metal components uses metals in a liquid solution, the volume of the liquid solution being less than or equal to the pore volume of the post-framework-modified USY zeolite.

3. 1. A method for producing catalyst particles, comprising: a step of preparing a post-framework-modified ultrastable Y (USY) zeolite in which a portion of the aluminum atoms constituting the zeolite framework are substituted with zirconium atoms and / or titanium atoms and / or hafnium atoms; providing an inorganic oxide as a binder, the inorganic oxide being characterized by an outer surface and pores defining an inner surface; impregnating the outer surface and / or the inner pore surfaces of the inorganic oxide with a first portion of the total active metal component content of one or more active metal components to form a metal-loaded inorganic oxide; mixing and kneading the post-framework-modified USY zeolite with an inorganic oxide binder to form a composite of the post-framework-modified USY zeolite and the inorganic oxide binder, the composite being characterized by an outer surface and an inner pore wall surface; impregnating the exterior surface and / or the interior pore surfaces of the composite with a second portion of the total active metal component content of one or more active metal components to form a metal-loaded composite of the post-framework-modified USY zeolite and the metal-loaded inorganic oxide binder; forming catalyst particles into extrudates from a metal-supported composite of the post-framework modified USY zeolite and a metal-supported inorganic oxide binder; heat treating the extrudate; and recovering the calcined catalyst particles; A method comprising:

4. A post-skeleton-modified ultrastable Y-type (USY) zeolite characterized by outer surfaces and pores defining inner surfaces, in which a portion of the aluminum atoms constituting the zeolite framework are substituted with zirconium atoms and / or titanium atoms and / or hafnium atoms, and the outer surfaces and / or inner surfaces of the pores are metal-loaded with a first portion of the total active metal component content of one or more active metal components; Inorganic oxide binder material and A calcined catalyst particle comprising a composite of the composite is characterized by an exterior surface and pores defining interior surfaces, the exterior surface and / or the interior surfaces of the pores being metal-loaded as a metal-loaded composite with a second portion of the total active metal component content of the one or more active metal components; Calcined catalyst particles, wherein the metal-support composite is formed into an extrudate and heat treated to form calcined catalyst particles.

5. A post-framework-modified ultrastable Y (USY) zeolite in which a portion of the aluminum atoms constituting the zeolite framework are substituted with zirconium atoms and / or titanium atoms and / or hafnium atoms; an inorganic oxide binder material characterized by an exterior surface and pores defining an interior surface, wherein the exterior surface and / or the interior pore surfaces are metal-loaded with a first portion of the total active metal component content of one or more active metal components; A calcined catalyst particle comprising a composite of the composite is characterized by an exterior surface and pores defining interior surfaces, the exterior surface and / or the interior surfaces of the pores being metal-loaded as a metal-loaded composite with a second portion of the total active metal component content of the one or more active metal components; Calcined catalyst particles, wherein the metal-support composite is formed into an extrudate and heat treated to form calcined catalyst particles.

6. 4. The method of claim 1, 2, or 3, further comprising the steps of impregnating the outer surfaces and / or inner pore surfaces of the intermediate calcined catalyst particles with an additional portion of the total active metal component content of one or more active metal components, heat treating the metal-loaded intermediate calcined catalyst particles, and recovering the final calcined catalyst particles.

7. 4. The method for producing catalyst particles according to claim 1, 2 or 3, wherein the post-framework modified USY zeolite is provided in a wet, dry or calcined state.

8. 6. A method for producing catalyst particles according to claim 1, 2 or 3, or calcined catalyst particles according to claim 4 or 5, wherein the post-framework modified USY zeolite is substituted with 0.1 to 5% by mass of zirconium and / or titanium and / or hafnium, calculated on the oxide basis.

9. A method according to claim 1, 2, or 3, or a calcined catalyst particle according to claim 4 or 5, wherein the post-framework modified USY zeolite is substituted with 0.1 to 5 mass % zirconium atoms and 0.1 to 5 mass % titanium ions, calculated on an oxide basis.

10. 6. The method of producing catalyst particles according to claim 1, 2 or 3, or the calcined catalyst particles according to claim 4 or 5, wherein the inorganic oxide material is selected from the group consisting of alumina, silica, titania, silica-alumina, alumina-titania, alumina-zirconia, alumina-boria, phosphorus-alumina, silica-alumina-boria, phosphorus-alumina-boria, phosphorus-alumina-silica, silica-alumina-titania, and silica-alumina-zirconia.

11. 6. The method for producing catalyst particles according to claim 1, 2, or 3, or the calcined catalyst particles according to claim 4 or 5, wherein the metal-loaded framework-modified USY zeolite accounts for about 0.1 to 99% by weight of the active metal-containing composite catalyst particles, with the remaining weight comprising inorganic oxide components.

12. 6. The method of producing catalyst particles according to claim 1, 2, or 3, or the calcined catalyst particles according to claim 4 or 5, wherein the catalyst particles are formed of a post-framework modified USY zeolite, an inorganic oxide component, and an additional zeolite component.

13. A method for producing catalyst particles as described in claim 1, 2, or 3, or calcined catalyst particles as described in claim 4 or 5, wherein the catalyst particles are formed of a post-skeleton-modified USY zeolite, an inorganic oxide component, and an additional zeolite component, the post-skeleton-modified USY zeolite comprising about 0.1 to 99% by mass of the catalyst particles, a first remaining mass comprising the inorganic oxide component, and a second remaining mass comprising the additional zeolite component.

14. The framework-modified USY zeolite has the following characteristics: (a) a crystal lattice constant of 2.430 to 2.450 nm; (b) a crystal lattice constant of 600 to 900 nm; 2 / g specific surface area, and (c) SiO of 12–100 2 Al 2 O 3 6. The method of claim 1, 2, or 3, or the calcined catalyst particle of claim 4 or 5, having a molar ratio to

15. The calcined catalyst particles have a particle size of 200 to 450 m 2 / g; a volume of pores having a diameter of 600 Å or less of 0.40 to 0.75 ml / g; and the one or more active metal components are 0.01 to 40 wt. % based on the total weight of the calcined catalyst particle.

16. 6. The method of claim 1, 2, or 3, or the calcined catalyst particle of claim 4 or 5, wherein the active metal component is selected from the group of metals consisting of platinum, palladium, and rhenium, and the active metal component is present in an amount of 0.01 to 2% by weight, calculated as the weight of the active metal component, based on the weight of the catalyst particle.

17. 6. The method of claim 1, 2, or 3, or the calcined catalyst particle of claim 4 or 5, wherein the active metal component is selected from the group of metals consisting of Mo, W, Co, Ni, and combinations thereof, and the active metal component is present in an amount of 0.1 to 40% by weight, calculated as the weight of the active metal component, based on the weight of the catalyst particle.

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