Hydrocracking catalyst, preparation method and use method thereof

Abstract

A hydrocracking catalyst comprises an active cracking carrier. The active cracking carrier comprises a post-modified zeolite framework in which aluminum atoms are replaced by zirconium atoms and titanium atoms; wherein: a portion of the zirconium atoms are substituted in the post-modified zeolite by 4 coordination; a part of zirconium atoms are grafted to the post-modified zeolite through 5 coordination; and titanium atoms are substituted in a post-modified zeolite skeleton through 4 coordination.

Description

Cross-reference to related applications

[0001] This application claims the benefit of U.S. Application Serial No. 18 / 480,934, filed on October 4, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0002] This invention relates to zeolites, and more particularly, to zeolites used as components of hydrocracking catalysts. Background Technology

[0003] Catalysts containing hydrotreating / hydrocracking catalysts (such as pretreatment catalysts) typically comprise amorphous-based catalysts, such as amorphous alumina or silica-alumina oxide or titanium dioxide supports containing an active metal (Ni / Mo, Ni / W, or Co / Mo metal) as the active phase, or amorphous catalysts, zeolite catalysts, or composite mixtures thereof, modified with Ni, W, Mo, and Co metals as promoters. A commonly used zeolite is USY. The hydrocracking catalyst comprises a hydrotreating active metal component and an acidic support component. In some embodiments, the hydrocracking catalyst comprises any one of amorphous alumina catalysts, amorphous silica-alumina oxide catalysts, titanium dioxide catalysts, natural or synthetic zeolite-based catalysts, post-modified zeolites, or combinations thereof. The hydrocracking catalyst may have an active phase material, which in some embodiments comprises any one or a combination of Ni, W, Mo, Co, or combinations thereof. In other embodiments, typically in a sulfur-free environment for hydrogenation and / or reforming, the catalyst may comprise one or more noble metals, such as Ru, Rh, Pd, Ag, Os, Ir, Pt, or Au. In some embodiments targeting hydrodenitrogenation, acidic alumina or silica-alumina-based catalysts supported on Ni-Mo or Ni-W active metals or combinations thereof are used. In embodiments targeting the removal of all nitrogen and improvement of hydrocarbon conversion, silica-alumina oxides, zeolites, or combinations thereof are used as catalysts, with the active metal comprising Ni-Mo, Ni-W, or combinations thereof.

[0004] Hydrotreating catalysts (hydroprocessing and hydrocracking) can be manufactured using a variety of methods. The chosen method typically represents a balance between manufacturing costs and the degree to which desired chemical and physical properties are achieved. Although there are relationships between catalyst formulation, preparation procedures, and catalyst properties, the details of these relationships are not always well understood due to the complexity of catalyst systems. The chemical composition of the catalyst plays a critical role in its performance; physical and mechanical properties also play a major role. The preparation of hydrocracking catalysts involves several steps: precipitation, filtration (decantation, centrifugation), washing, drying, shaping, calcination, and impregnation. Additional steps are often required, such as kneading / mixing, grinding, and sieving. The following describes the essential steps in the manufacture of hydrocracking catalysts.

[0005] Precipitation involves the mixing of material solutions or suspensions, resulting in the formation of a precipitate, which can be crystalline or amorphous. Kneading / mixing wet solid materials typically results in the formation of a dough-like material, which is then shaped and dried. The kneaded / mixed product is then heat-treated to achieve closer contact and better homogeneity between the components through thermal diffusion and solid-state reaction. The metal component is subsequently added by impregnation or incipient wetting.

[0006] The characteristics of the support determine the mechanical properties of the catalyst, such as wear resistance, hardness, and compressive strength. High surface area and appropriate pore size distribution are typically required. The pore size distribution and other physical properties of catalyst supports prepared by precipitation are also affected by the precipitation and aging conditions of the precipitate, as well as subsequent drying, shaping, and calcination.

[0007] The final shape and size of the catalyst particles are determined during the manufacturing process. Catalysts and catalyst supports are shaped into a variety of possible forms, such as spherical or cylindrical extrusions, or trilobal or tetralobal shapes. Spherical catalyst supports can be obtained through the "oil-drop method," where precipitation occurs when a liquid is poured into a second immiscible liquid. Other spheroidization processes include the rolling process. Generally, due to cost and process considerations such as pressure drop, most catalysts are currently non-spherical in shape. Spherical catalysts are less commonly used in modern hydrocracking. Non-spherical shapes are obtained by mixing feedstocks to form an extrudable dough-like material, which is then extruded through a die with perforations. The noodle-like extrusion is dried, calcined, and then broken into short segments. Typical aspect ratios of the catalyst matrix vary, for example, between 2 and 4.

[0008] Typical steps in the manufacture of hydrocracking catalysts include: mixing and kneading binder components and zeolite components; extruding the kneaded composite mixture to form composite particles; calcining the composite particles; impregnating the calcined composite particles with an active metal component; and calcining the impregnated composite particles to form the final catalyst product.

[0009] Examples of catalyst and catalyst support shapes include cylindrical, trilobal, twisted trilobal, and tetralobal. Catalysts with multi-lobed cross-sections have a higher surface area to volume ratio than simple cylindrical extrusions. When used in fixed beds, these shaped catalyst particles help reduce diffusion resistance, form a more open bed, and reduce pressure drop.

[0010] Heat treatment is typically performed before and / or after impregnation of the shaped catalyst. For catalyst support materials prepared by precipitation or blending of all components, drying may be the only requirement before shaping, followed by calcination of the shaped product. Heat treatment of the catalyst or support removes water and other volatile substances. Drying and calcination conditions are crucial for determining the physical and catalytic properties of the catalyst support material. Surface area, pore size distribution, stability, abrasion resistance, compressive strength, and catalytic activity are all affected by drying and calcination conditions.

[0011] In conventional catalyst preparation, several methods can be used to add the active metal to the catalyst support material: (a) impregnation, (b) incipient wetness, and (c) evaporative wetness. In one method, the calcined catalyst support material is impregnated in an excess solution containing the active metal or a metal compound. The solution fills the pores and is also adsorbed onto the surface of the support, and then the excess solution is removed. In another method, incipient wetness is used, where a certain volume of solution is applied to the activated support by tumbling or spraying. The concentration of the metal compound in the solution is adjusted to achieve the target metal content, and its volume is equal to or slightly less than the pore volume of the support. The catalyst support material loaded with the metal is then dried and calcined. Metal oxides are formed during this process; the calcination step is also called oxidation. In another method (evaporative wetness), the catalyst support material is saturated with water or an acid solution and then impregnated 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 bagged and transported to its final destination. Summary of the Invention

[0012] When zeolites are used as active cracking supports for hydrocracking catalysts, they can be post-modified by introducing titanium and zirconium atoms. Generally, these titanium and zirconium atoms are linked to the zeolite framework in a 4-coordinate configuration. However, these post-modified zeolites may have different acidity levels and may cause over- or under-cracking of hydrocarbon feedstocks, thereby altering product selectivity. Therefore, there is a need for titanium and zirconium-containing zeolites with different acidity levels. Embodiments of the present invention meet this need by providing post-modified zeolites (and methods for their preparation and use) wherein zirconium is linked to the zeolite framework in 4- and 5-coordinate configurations, and titanium is linked to the zeolite framework in a 4-coordinate configuration. This coordination structure is believed to provide different acidities, which may lead to increased yields of middle fractions in some applications. Further embodiments provide methods for preparing and using the zeolite.

[0013] According to some embodiments of the present invention, a hydrocracking catalyst is provided, comprising an active cracking support. The active cracking support comprises a post-modified zeolite framework in which aluminum atoms are replaced by zirconium and titanium atoms; wherein: a portion of the zirconium atoms are substituted in the post-modified zeolite via 4-coordination; a portion of the zirconium atoms are grafted onto the post-modified zeolite via 5-coordination; and titanium atoms are substituted in the post-modified zeolite framework via 4-coordination.

[0014] According to some embodiments of the present invention, a method for preparing an active cracking support is provided, comprising providing an acidified zeolite suspension containing a zeolite framework; introducing a titanium compound into the acidified zeolite suspension to isomorphically substitute titanium onto the zeolite framework through 4-coordination, thereby obtaining a titanium-substituted zeolite framework; and then introducing a zirconium compound into the titanium-substituted zeolite framework to graft a portion of zirconium atoms onto the zeolite framework through 5-coordination and isomorphically substitute a portion of zirconium atoms onto the zeolite framework through 4-coordination, thereby obtaining the active cracking support.

[0015] According to some embodiments of the present invention, a method for hydrocracking a hydrocarbon feedstock is provided, comprising contacting the hydrocarbon feedstock with hydrogen and a hydrocracking catalyst under hydrocracking conditions; wherein the hydrocracking catalyst comprises an active cracking support; the active cracking support comprises a post-modified zeolite framework in which aluminum atoms are replaced by zirconium and titanium atoms. A portion of the zirconium atoms are grafted onto the post-modified zeolite framework via 5-coordinate bonding. A portion of the zirconium atoms are connected to the post-modified zeolite framework in a 4-coordinate configuration. Titanium atoms are connected to the post-modified zeolite framework in a 4-coordinate configuration. Attached Figure Description

[0016] The following detailed description of specific embodiments of the invention can be best understood when read in conjunction with the following accompanying drawings, wherein like structures are indicated by like reference numerals, and in the drawings: Figure 1 This is a flowchart illustrating a method for preparing post-modified zeolites according to some embodiments of the present invention, the post-modified zeolites comprising 4-coordinated and 5-coordinated zirconium and 4-coordinated titanium.

[0017] Figure 2 The ultraviolet-visible spectra of USY zeolite and modified USY zeolite according to some embodiments of the present invention are depicted graphically.

[0018] Figure 3 Modeled XAFS spectra of USY zeolites containing 4- or 5-coordinated zirconium according to some embodiments of the present invention are depicted graphically.

[0019] Figure 4 The XAFS spectra of post-modified zeolites according to some embodiments of the present invention are shown graphically.

[0020] Reference will now be made to the various aspects in more detail, some of which are shown in the accompanying drawings. Detailed Implementation

[0021] Embodiments of the present invention provide post-modified zeolites, wherein the zirconium is linked to the zeolite framework in 4- and 5-coordinated configurations, and the titanium is linked to the zeolite framework in a 4-coordinated configuration. This coordination structure is believed to impart different acidities to the embedded zircon atoms. Further embodiments of the present invention relate to the preparation and use of such zeolites.

[0022] definition "℃" refers to degrees Celsius.

[0023] A catalyst is any substance that increases the rate of a particular chemical reaction, such as, but not limited to, cracking.

[0024] "Cracking" refers to a chemical reaction in which a molecule with carbon-carbon bonds is broken down into more than one molecule by the breaking of one or more carbon-carbon bonds, or a cyclic moiety with carbon-carbon bonds is converted into an acyclic moiety by the breaking of one or more carbon-carbon bonds. As used herein, the term "catalytic cracking" refers to cracking carried out in the presence of a catalyst. Some catalysts may exhibit multiple forms of catalytic activity, and naming a catalyst after one specific function does not imply that the catalyst cannot be catalytically active for other functions.

[0025] “m 2 " / g" refers to square meters per gram.

[0026] “min” refers to minutes.

[0027] "mL / g" refers to milliliters per gram.

[0028] “mm” refers to millimeters.

[0029] “wt.%” refers to weight percentage.

[0030] Some aspects of this invention relate to the preparation of hydrocracking catalysts having an active cracking support comprising zeolite. Embodiments of this invention relate to the manufacture of hydrocracking catalysts for the hydrocracking of hydrocarbon oils (e.g., vacuum gas oil (VGO) and deasphalted oil (DAO)). Hydrocracking of said hydrocarbon oils with the hydrocracking catalyst of this invention yields middle fractions (e.g., kerosene and gas oil) or similar compounds. The hydrocracking catalyst promotes the diffusion of hydrocarbon oils (e.g., VGO and DAO) into mesopores to obtain middle fractions or similar hydrocarbons.

[0031] The hydrocracking catalyst described in this invention is applicable to the hydrocracking of heavy hydrocarbon oils obtained from crude oil, synthetic crude oil, asphalt, oil sands, shell oil, bio-oil, biomass, plastic-derived oil, or coal slurry. The aforementioned heavy hydrocarbon oils may include one or more of the following: naphtha, vacuum gas oil (VGO), deasphalted oil (DAO) obtained through solvent deasphalting, demetallized oil, light or heavy coking gas oil obtained through coking, circulating oil obtained through fluidized catalytic cracking (FCC), or gas oil obtained through viscosity-reducing cracking.

[0032] Hydrocracking catalyst The hydrocracking catalyst of the present invention may comprise an active cracking support. In embodiments, the active cracking support may be loaded with a hydrogenation component, such as a hydrogenated metal. Further embodiments of the hydrocracking catalyst of the present invention may include a binder.

[0033] The active cracking support may comprise a post-modified zeolite framework. The post-modified zeolite framework may comprise titanium atoms and zirconium atoms, and optionally hafnium atoms. Titanium atoms and a portion of the zirconium atoms may isomorphically replace aluminum atoms in the zeolite framework via 4-coordination. A portion of the zirconium atoms may also be grafted onto the zeolite framework via 5-coordination. Hafnium atoms may isomorphically replace aluminum atoms in the zeolite framework.

[0034] The zeolite framework of the active cracking support can undergo framework substitution (post-modification), whereby some aluminum atoms constituting the zeolite framework are replaced by titanium atoms, some by zirconium atoms, and optionally, some by hafnium atoms. Thus, titanium and zirconium atoms (and optionally hafnium atoms) form part of the framework to obtain the post-modified zeolite framework.

[0035] A portion of zirconium atoms can be grafted onto the zeolite framework via 5-coordination (i.e., a coordination number of 5). The coordination number of an atom refers to the number of atoms bonded to it. In the zeolite framework, the coordination number can be determined using ultraviolet-visible (UV-Vis) spectroscopy, near-infrared (NIR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and X-ray crystallography methods (such as X-ray absorption fine structure (XAFS)). At least 25 wt.%, at least 50 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, at least 99 wt.%, or even at least 99.99 wt.%, of zirconium atoms can be 5-coordinated with the zeolite framework.

[0036] A portion of the zircon atoms can be linked to the zeolite framework in a 4-coordinated manner (i.e., a coordination number of 4). In embodiments, the 4-coordinated zircon atoms can isomorphously replace aluminum atoms in the zeolite framework. This substitution can be verified, for example, by ultraviolet-visible (UV-Vis) spectroscopy; near-infrared (NIR) spectroscopy; Fourier transform infrared (FTIR) spectroscopy; and X-ray crystallography methods (such as X-ray absorption fine structure (XAFS)). At least 25 wt.%, at least 40 wt.%, at least 50 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, at least 99 wt.%, or even at least 99.99 wt.% of zircon atoms can be linked to the post-modified zeolite framework in a 4-coordinated manner.

[0037] Based on the total weight of the post-modified zeolite framework, the post-modified zeolite framework may contain 0.1 wt.% to 5 wt.% zirconium atoms. In embodiments, based on the total weight of the post-modified zeolite framework, the post-modified zeolite framework may contain 0.2 wt.% to 5 wt.%, 0.5 wt.% to 5 wt.%, 1 wt.% to 5 wt.%, 2.5 wt.% to 5 wt.%, 0.1 wt.% to 2.5 wt.%, 0.1 wt.% to 1 wt.%, 0.2 wt.% to 4 wt.%, or 0.3 wt.% to 3 wt.%, or any subset thereof, of zirconium atoms.

[0038] Titanium atoms are linked to the zeolite framework in a 4-coordinate configuration (i.e., a coordination number of 4). In embodiments, titanium atoms are isomorphously substituted for aluminum atoms in the zeolite framework. This substitution can be verified, for example, by ultraviolet-visible (UV-Vis) spectroscopy; near-infrared (NIR) spectroscopy; Fourier transform infrared (FTIR) spectroscopy; and X-ray crystallography methods (such as X-ray absorption fine structure (XAFS)). At least 80 wt.%, at least 90 wt.%, at least 95 wt.%, at least 99 wt.%, or even at least 99.99 wt.% of the titanium atoms can be linked to the post-modified zeolite framework in a 4-coordinate configuration.

[0039] Based on the total weight of the post-modified zeolite framework, the post-modified zeolite framework may contain 0.1 wt.% to 5 wt.% titanium atoms. In embodiments, based on the total weight of the post-modified zeolite framework, the post-modified zeolite framework may contain 0.2 wt.% to 5 wt.%, 0.5 wt.% to 5 wt.%, 1 wt.% to 5 wt.%, 2.5 wt.% to 5 wt.%, 0.1 wt.% to 2.5 wt.%, 0.1 wt.% to 1 wt.%, 0.2 wt.% to 4 wt.%, or 0.3 wt.% to 3 wt.%, or any subset thereof, of titanium atoms.

[0040] When hafnium is present, hafnium atoms can be linked to the zeolite framework in a 4-coordinate manner (i.e., a coordination number of 4). In embodiments, the 4-coordinated hafnium atoms can isomorphically replace aluminum atoms in the zeolite framework. This substitution can be verified, for example, by ultraviolet-visible (UV-Vis) spectroscopy; near-infrared (NIR) spectroscopy; Fourier transform infrared (FTIR) spectroscopy; and X-ray crystallography methods (such as X-ray absorption fine structure (XAFS)). At least 25 wt.%, at least 40 wt.%, at least 50 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, at least 99 wt.%, or even at least 99.99 wt.% of hafnium atoms can be linked to the post-modified zeolite framework in a 4-coordinate manner.

[0041] The titanium and zirconium atom content of the skeletal-substituted zeolite can be measured, for example, using X-ray fluorescence spectrometry, high-frequency inductively coupled plasma atomic emission spectrometry, and atomic absorption spectrometry.

[0042] The post-modified zeolite framework can comprise any zeolite framework suitable for hydrocracking catalysts. In embodiments, the post-modified zeolite framework can be BEA or FAU, such as Y zeolite. In specific embodiments, the zeolite framework can be USY.

[0043] Unmodified zeolites can give a predetermined range of certain properties of the post-modified zeolite framework. These properties may include, for example, lattice constant, specific surface area, and the molar ratio of silicon dioxide (SiO2) to alumina (Al2O3) (silicon-to-alumina ratio). The properties of the post-modified zeolite framework are described below. Furthermore, these properties, their numerical ranges, as well as verification, testing equipment, and other features are discussed in U.S. Patent No. 9,221,036, which is incorporated herein by reference in its entirety for all purposes.

[0044] The lattice constant (or lattice parameter) of the post-modified zeolite framework can be in the range of 2.430 to 2.450 nanometers (nm) or 2.435 nm to 2.445 nm. The specific surface area of ​​the post-modified zeolite framework can be 600 m² / g (m³). 2 / g) to 900 m 2 Within the range of / g, such as in 650 m 2 / g to 800 m 2 The specific surface area value is within the range of / g. The specific surface area value is determined by using the Brunol-Emmett-Taylor (BET) technique with nitrogen adsorption.

[0045] The silica-alumina molar ratio (SAR) of the post-modified zeolite framework can be at least 3, such as at least 5, at least 12, at least 20, at least 40, 1 to 200, 5 to 150, 5 to 100, 12 to 100, 20 to 100, 40 to 100, 60 to 100, 20 to 80, 20 to 60, or any subset thereof. The SAR is the molar ratio of silica (SiO2) to alumina (III) (Al2O3). Without theoretical limitations, the stability of Y zeolite can generally be increased by removing some aluminum or sodium ions from the Y zeolite to obtain ultrastable Y zeolite. Ultrastable Y zeolite exhibits higher stability than conventional Y zeolite. The term "ultrastable Y zeolite" is referred to herein as "USY".

[0046] Crystallinity can be considered. Crystallinity is typically determined by X-ray diffraction. A specific diffraction peak can be selected and its intensity normalized. Zeolites can be analyzed and the diffraction intensity normalized relative to a standard. If the acid treatment is too harsh, the structural integrity of the zeolite framework will decrease (resulting in more amorphous material), and therefore the crystallinity will decrease. Therefore, if relative crystallinity is maintained after acid / heteroatom introduction treatment, it confirms that not only the zeolite structure is preserved, but also a certain level of crystallinity is maintained.

[0047] The post-modified zeolite framework may have pores with a diameter of 600 Å or smaller. The volume of these pores may range from 0.40 mL / g to 0.75 mL / g, or from 0.45 mL / g to 0.70 mL / g. The pore volume is determined by the pore distribution obtained from nitrogen desorption data calculated using the BJH (Barrett, Joyner, and Halenda) method.

[0048] The post-modified zeolite framework can be mixed with a binder (typically an inorganic oxide) and formed into the desired shape (typically in the form of an extrusion), which is then typically dried and calcined to provide an active cracking support for the hydrocracking catalyst. The binder material may contain an inorganic oxide component. The inorganic oxide may comprise porous inorganic oxides. In embodiments, the porous inorganic oxide may comprise alumina, silica, titanium dioxide, aluminum silica, titanium silica, zirconium silica, boron silica, aluminum phosphorus, aluminum silica, boron silica, aluminum phosphorus, silicon silica, titanium silica, and zirconium silica.

[0049] Based on the total weight of the post-modified zeolite framework, the post-modified zeolite framework may contain at least 80 wt.%, such as at least 90 wt.%, at least 95 wt.%, at least 99 wt.%, at least 99.9 wt.%, or even at least 99.999 wt.%, of silicon, aluminum, titanium, zirconium, and oxygen atoms.

[0050] The hydrocracking catalyst may contain a hydrogenation metal. The hydrogenation metal may be introduced into the hydrocracking catalyst through a blending or impregnation process.

[0051] In the blending process, the active cracking support, the binder, and the hydrogenated metal can be mixed and then extruded. In the impregnation process, the active cracking support, the binder, or both of them can be impregnated with the hydrogenated metal as the active phase metal, then dried and calcined to provide the hydrocracking catalyst. In a typical impregnation process, the active cracking support and the binder are mixed and extruded to form an extrudate, which can then be impregnated with the hydrogenated metal.

[0052] The hydrogenated metal can comprise any metal that imparts hydrogenation functionality. In addition to hydrogenation, the hydrogenated metal may also possess hydrodesulfurization and hydrodenitrogenation functions. The hydrogenated metal can be an active phase metal. The hydrogenated metal can be in metallic form, oxide form, sulfide form, or a combination thereof. In a specific embodiment, at least a portion of the hydrogenated metal can be in sulfide form.

[0053] The hydrogenated metal may comprise a metal component from Group 8 of the IUPAC long periodic table (cobalt, nickel, palladium, platinum) or a metal component from Group 6 of the IUPAC long periodic table (molybdenum or tungsten), or both. In embodiments, the hydrogenated metal may comprise one or more non-noble metals selected from the group consisting of cobalt, nickel, molybdenum, or tungsten. Specific examples of the metal component include a combination of Group 6 molybdenum or tungsten and Group 8 cobalt or nickel. Other specific examples include noble metal components from the platinum group, such as platinum, rhodium, or palladium. With respect to molybdenum, tungsten, cobalt, or nickel, the content, as an oxide, may range from 0.1% by mass to 30% by mass based on the mass of the catalyst. With respect to the platinum group (platinum, rhodium, or palladium), the content, as a metal, may, for example, range from 0.01% by mass to 2% by mass based on the mass of the catalyst.

[0054] Based on the total weight of the hydrocracking catalyst, the hydrocracking catalyst may contain 0.1 wt.% to 40 wt.% of a hydrogenation component, such as the hydrogenation metal. In embodiments, based on the total weight of the hydrocracking catalyst, the hydrocracking catalyst may contain 0.1 wt.% to 30 wt.%, 0.1 wt.% to 20 wt.%, 0.1 wt.% to 10 wt.%, 0.1 wt.% to 5 wt.%, 0.1 wt.% to 1 wt.%, 1 wt.% to 40 wt.%, 5 wt.% to 40 wt.%, 10 wt.% to 40 wt.%, 20 wt.% to 40 wt.%, 30 wt.% to 40 wt.%, 1 wt.% to 30 wt.%, 5 wt.% to 20 wt.%, or any subset thereof of a hydrogenation component, such as the hydrogenation metal.

[0055] Preparation method of hydrocracking catalyst The preparation method of the hydrocracking catalyst described in this article is illustrated graphically as follows: Figure 1 As shown and described below, particular attention will be paid to the modification process in which the titanium and zirconium are substituted into the zeolite framework.

[0056] Steps 102 to 118 describe the synthesis process of calcined USY zeolite (referred to herein as USY(c)). Steps 120 to 128 describe the preparation process of the post-modified zeolite framework (introducing titanium and zirconium heteroatoms). Steps 130 to 144 describe the process of converting the post-modified zeolite framework into the hydrocracking catalyst. It should be understood that in some embodiments, the zeolite used in any of steps 102 to 118 is commercially available, and therefore the end user can begin from any of steps 102 to 118. Additionally, when the starting zeolite is of the BEA framework type, the user can skip the synthesis of the USY zeolite.

[0057] First, a starting zeolite is provided. The starting zeolite can be sodium-type or ammonia-type. The starting zeolite can comprise any zeolite framework suitable for hydrocracking catalysts. In embodiments, the zeolite framework can be BEA or FAU, such as Y zeolite. In specific embodiments, the zeolite framework can be USY.

[0058] In the embodiments, the starting FAU zeolite shown may have an effective SiO2 / Al2O3 molar ratio (SAR) in the range of about 3 to 6; an effective cell size (UD) of about 2.430 nanometers (nm) to 2.450 nm; and an effective cell size (m²) of about 600 m² / g. 2 / g) to 900 m 2 / g、600 m 2 / g to 800 m 2 / g、650 m 2 / g to 900 m 2 / g or 650 m 2 / g to 800 m 2 Effective specific surface area (SA) within the range of / g.

[0059] In step 102, a suspension of the sodium-type starting zeolite, such as Y-type zeolite (Na-Y), can be prepared by combining it with the sodium-type starting zeolite. The liquid-to-solid ratio of the Na-Y suspension can be in the range of approximately 5-20, 5-15, 8-15, 5-12, or 8-12 liters (L) of water per kilogram (kg) of zeolite, and the temperature can be, for example, in the range of approximately 15°C to 95°C, 15°C to 80°C, 20°C to 95°C, 20°C to 90°C, 20°C to 80°C, 40°C to 95°C, 40°C to 90°C, or 40°C to 80°C. The sodium-type starting zeolite can have, for example, an effective Na₂O content of approximately 13% by mass.

[0060] In step 104, a first ion-exchange zeolite (NH4-Y) is prepared by ion-exchanging sodium ions with ammonium ions in the sodium-type zeolite suspension from step 102. In the first ion-exchange zeolite, approximately 50% to 70% of the Na contained in the sodium-type zeolite is replaced by NH4.

[0061] Step 104 may include adding to the sodium-type zeolite suspension: an effective concentration of an ammonium source, for example, an ammonium to aluminum molar ratio in the range of about 2-8; an effective temperature in the range of about 15°C to 95°C, 15°C to 80°C, 20°C to 95°C, 20°C to 90°C, 20°C to 80°C, 40°C to 95°C, 40°C to 90°C, or 40°C to 80°C; and a sustained effective residence time, for example, in the range of about 10 min to 600 min, 10 min to 180 min, 30 min to 600 min, or 30 min to 180 min. The ammonium source may be one or more of NH4OH, (NH4)2SO4, and (NH4)2CO3, or another suitable ammonium source.

[0062] The solid obtained from ion exchange step 104 can be filtered, washed with water at an effective temperature, for example, about 20°C to 95°C, 20°C to 90°C, 20°C to 80°C, 40°C to 95°C, 40°C to 90°C, 40°C to 80°C or any subset thereof, and dried at an effective temperature, for example, about 80°C to 180°C or 100°C to 180°C, for an effective residence time, for example, about 30 minutes to 1800 minutes, 60 minutes to 1800 minutes, 30 minutes to 600 minutes or 60 minutes to 600 minutes, to obtain the first ion-exchanged zeolite.

[0063] Optionally, after washing the solid obtained in step 104 of the ion exchange, one or more additional washing cycles may be performed at the effective temperature, concentration, and residence time as described in step 104, each washing cycle comprising washing with an ammonium source followed by washing with water. The solid material after the one or more additional washings is dried at the effective temperature and residence time as described in step 104 to obtain the first ion-exchanged zeolite. In some cases, the one or more additional cycles of the first ion exchange step are not performed.

[0064] In heat treatment step 106, hydrogen-type zeolite can be synthesized from the first ion-exchange zeolite by heating it in a saturated steam atmosphere. In an embodiment, the heat treatment in step 106 may include calcining the first ion-exchange zeolite at an effective temperature for an effective time to prepare H-type zeolite, for example, an effective temperature range of approximately 500°C to 800°C, 500°C to 700°C, 600°C to 800°C, 600°C to 700°C, or any subset thereof (typically in the presence of steam, i.e., in saturated water vapor, or in the presence of air or oxygen), and a time range of approximately 10 min to 600 min, 10 min to 180 min, 30 min to 600 min, 30 min to 180 min, or any subset thereof. In an embodiment, if a large amount of Na is still present in the H-type zeolite, the ion exchange can be repeated one or more times.

[0065] In the embodiment where the starting zeolite is a Y-type zeolite, the H-type zeolite is the hydrogen form of the Y-type zeolite (HY-type zeolite). The HY-type zeolite can be converted to USY zeolite by additional ammonium ion exchange and steam treatment as discussed in steps 108 to 112 below. In steps 108 to 112, the HY-type zeolite is treated to synthesize a second ion-exchanged NH4-Y-type zeolite, which has 80% to 97% of the Na contained in the Na-type zeolite exchanged with NH4, also referred to as NH4. 80-97 -Y-type zeolite. As described in step 108, a suspension containing an effective concentration of HY-type zeolite can be prepared, for example, with a liquid-to-solid ratio of about 5 L / kg to 20 L / kg, 5 L / kg to 15 L / kg, 8 L / kg to 15 L / kg, 5 L / kg to 12 L / kg, 8 L / kg to 12 L / kg or any subset thereof (water / zeolite), and at an effective temperature, for example, about 15°C to 95°C, 15°C to 80°C, 20°C to 95°C, 20°C to 90°C, 20°C to 80°C, 40°C to 95°C, 40°C to 90°C, 40°C to 80°C or any subset thereof.

[0066] In ion exchange step 110, a second ammonium-exchanged zeolite (second NH4- zeolite) is prepared by ion-exchanging the HY-type zeolite suspension from step 108 with ammonium ions, thereby synthesizing the second ion-exchanged zeolite. One embodiment of the ion exchange in step 110 includes adding and stirring an effective concentration of ammonium, for example, an ammonium to aluminum molar ratio in the range of about 2 to 8; an effective temperature range of about 20°C to 95°C, 20°C to 90°C, 20°C to 80°C, 40°C to 95°C, 40°C to 90°C, 40°C to 80°C, or any subset thereof; and an effective residence time, for example, about 10 min to 600 min, 10 min to 180 min, 30 min to 600 min, 30 min to 180 min, or any subset thereof. The ammonium source may be one or more of NH4OH, (NH4)2SO4, (NH4)2CO3, or another suitable ammonium source.

[0067] The solid obtained from ion exchange step 110 can be filtered, washed with water at an effective temperature, for example, about 0°C to 95°C, 20°C to 90°C, 20°C to 80°C, 40°C to 95°C, 40°C to 90°C, 40°C to 80°C or any subset thereof, and dried at an effective temperature, for example, about 80°C to 180°C or 100°C to 180°C, for an effective residence time, for example, about 30 min to 1800 min, 60 min to 1800 min, 30 min to 600 min, 60 min to 600 min or any subset thereof, to obtain the second ion-exchanged NH4-zeolite.

[0068] Optionally, after washing the solid obtained in step 110 of the ion exchange step, one or more additional washing cycles may be performed at the effective temperature, concentration, and residence time as described in step 110, each washing cycle including washing with an ammonium source followed by washing with water. The solid after one or more additional washings is dried at the effective temperature and residence time as described in step 110 to obtain the second ion-exchanged NH4-zeolite. In some cases, one or more additional cycles of the second ion exchange step are not performed.

[0069] In heat treatment step 112, an ultrastable zeolite, such as USY zeolite referred to herein as USY(a), can be synthesized by calcining the NH4-zeolite. The heat treatment in step 112 may include calcining the second ion-exchange NH4-zeolite at an effective temperature, for example, in the range of about 500°C to 800°C, 500°C to 700°C, 600°C to 800°C, or 600°C to 700°C (typically in the presence of steam, i.e., in saturated steam, or in the presence of air or oxygen), for a time range of about 10 min to 600 min, 10 min to 180 min, 30 min to 600 min, or 30 min to 180 min, to recover USY(a). In an embodiment, the heat treatment 112 of the NH4-zeolite can be performed by steam treatment.

[0070] The USY(a) from step 112 can be an ultrastable zeolite whose SAR is approximately equivalent to that of the starting zeolite. Steps 102 through 112 are not expected to significantly change the SAR value because these steps do not require acid treatment to remove aluminum atoms from the zeolite framework. For example, the USY(a) thus obtained in step 112 (such as USY) can have an SAR of about 3 to 6.

[0071] In steps 114 to 118, the USY(a) zeolite is treated to synthesize SAR-enhanced calcined USY zeolite, which serves as the starting material for subsequent framework post-modification. In step 114, an aqueous suspension containing an effective concentration of USY(a) can be prepared, for example, with a liquid-to-solid ratio in the range of about 5-20, 5-15, 8-15, 5-12, or 8-12 L / kg (water / zeolite), and at an effective temperature, for example, in the range of about 15°C to 95°C, 15°C to 80°C, 20°C to 95°C, 20°C to 90°C, 20°C to 80°C, 40°C to 95°C, 40°C to 90°C, or 40°C to 80°C.

[0072] In acid treatment step 116, an effective amount of inorganic or organic acid is dispersed in the suspension to maintain the pH of the suspension within a strongly acidic range, in order to synthesize a second ultrastable zeolite with enhanced SAR (such as a second USY zeolite), referred to herein as USY(b). The USY(b) zeolite can be obtained by removing extra-framework aluminum (aluminum atoms that do not constitute part of the zeolite framework) from the USY(a). This is performed by acid treatment.

[0073] The inorganic acid used can typically be sulfuric acid, nitric acid, hydrochloric acid, etc. In the examples, the selected inorganic acid is sulfuric acid or hydrochloric acid. Additionally, carboxylic acids can be suitably used as organic acids. The amount of the added inorganic or organic acid can be suitable for controlling the pH of the suspension within a strongly acidic range, for example, in the range of about 0.7-2.5, 0.7-2.0, 1.0-2.5, or 1.0-2.0. This amount can, for example, be increased by 0.5-4.0 times, 0.5-3.5 times, 0.7-4.0 times, or 0.7-3.5 times the molar amount of Al₂O₃ in USY(a). The acidic suspension can be maintained at an effective temperature, such as 15°C to 95°C, 15°C to 80°C, 20°C to 95°C, 20°C to 90°C, 20°C to 80°C, 40°C to 95°C, 40°C to 90°C, or 40°C to 80°C, and for an effective residence time, such as in the range of about 10 min to 600 min, 10 min to 180 min, 30 min to 600 min, or 30 min to 180 min. The acid treatment in step 116 can improve the SAR of the zeolite, for example, from the range of about 3-6 to at least 12, such as to 12 to 100, 20 to 100, 30 to 100, 40 to 100, 30 to 80, or 40 to 80.

[0074] The solid obtained from acid treatment step 116 can be filtered, washed with water at an effective temperature in the range of, for example, about 15°C to 95°C, 15°C to 80°C, 20°C to 95°C, 20°C to 90°C, 20°C to 80°C, 40°C to 95°C, 40°C to 90°C, or 40°C to 80°C, and dried at an effective temperature in the range of, for example, about 80°C to 180°C or 100°C to 180°C, for an effective residence time in the range of, for example, about 30 min to 1800 min, 60 min to 1800 min, 30 min to 600 min, or 60 min to 600 min, to recover USY(b).

[0075] Optionally, after washing the solid obtained in acid treatment step 116, it may be subjected to one or more additional cycles at the effective temperature, concentration, and residence time as described in step 116, each cycle comprising treatment with an inorganic or organic acid followed by washing with water. The solid subjected to one or more additional acid treatments may be dried at the effective temperature and residence time as described in step 116 to recover USY(b). In one embodiment, one or more additional cycles of the first acid treatment step are not performed.

[0076] In heat treatment step 118, the USY(b) zeolite can be heat-treated to prepare a third ultrastable zeolite, USY(c). In an embodiment, the heat treatment described in step 118 may include calcining the second USY zeolite (USY(b)) at an effective temperature, for example, in the range of about 500°C to 700°C, 550°C to 700°C, 500°C to 650°C, or 550°C to 650°C (typically in the presence of air or oxygen, or in the presence of steam), and for a time range of about 10 min to 600 min, 10 min to 180 min, 30 min to 600 min, or 30 min to 180 min, to recover USY(c). If the calcination temperature is below about 500°C, the skeletal substitution of zirconium atoms and / or titanium atoms and / or hafnium atoms tends to decrease; at calcination temperatures above about 700°C, the specific surface area of ​​ultrastable zeolites (such as USY) decreases, thereby also reducing the skeletal substitution of zirconium atoms and / or titanium atoms and / or hafnium atoms.

[0077] In steps 120 to 128, heteroatoms may be introduced to prepare the post-modified zeolite framework, wherein a portion of the aluminum atoms within the zeolite framework are replaced by zirconium and / or titanium and / or hafnium atoms, whereby the zirconium atoms replacing the heteroatoms are linked to the zeolite framework in 4-coordinate and 5-coordinate configurations, while the titanium atoms are linked to the zeolite framework in 4-coordinate configurations. The zeolite framework used in step 120 may be the USY zeolite produced in step 118, separately supplied USY zeolite, or BEA zeolite. In embodiments, the post-modified zeolite framework material may be prepared by calcining a zeolite having the properties described herein at approximately 500°C to 700°C. A suspension containing the calcined zeolite may be formed, the liquid-to-solid ratio of which is approximately 5-15 L / kg. Inorganic or organic acids may be added to make the pH of the suspension approximately <2.0. Then, a solution containing a titanium compound is mixed. Subsequently, a solution containing a zirconium compound is added to the acidified zeolite suspension containing the titanium compound. For example, the solution can be neutralized with ammonia to make the pH of the mixed solution approximately 7-7.5.

[0078] Suitable zirconium compounds include one or more of zirconium sulfate, zirconium nitrate, zirconium chloride, etc. In the examples, zirconium sulfate and / or zirconium nitrate are selected. The amount of zirconium compound added is typically from about 0.1 wt.% to 5.0 wt.%, calculated based on its oxide (i.e., zirconium oxide) and measured relative to the mass of the post-modified zeolite framework, such as about 0.1 wt.% to 4.0 wt.%, about 0.1 wt.% to 3.0 wt.%, about 0.2 wt.% to 5.0 wt.%, about 0.2 wt.% to 4.0 wt.%, about 0.2 wt.% to 3.0 wt.%, about 0.3 wt.% to 5.0 wt.%, about 0.3 wt.% to 4.0 wt.%, or about 0.3 wt.% to 3.0 wt.%. Adding less than about 0.1 wt.% of zirconium compound may not improve the solid acid properties of the zeolite. Adding more than 5 wt.% of zirconium compound may cause pore blockage in the zeolite. An aqueous solution of zirconium compound prepared by dissolving a zirconium compound in water can be used as a zirconium compound.

[0079] Suitable titanium compounds include one or more of titanium sulfate, titanium acetate, titanium chloride, titanium nitrate, and titanium lactate. In some embodiments, titanium sulfate and / or titanium acetate are selected. The amount of titanium compound added is typically from about 0.1 wt.% to 5.0 wt.%, calculated based on its oxide (i.e., titanium oxide) and measured relative to the mass of the post-modified zeolite framework component, such as about 0.1 wt.% to 4.0 wt.%, about 0.1 wt.% to 3.0 wt.%, about 0.2 wt.% to 5.0 wt.%, about 0.2 wt.% to 4.0 wt.%, about 0.2 wt.% to 3.0 wt.%, about 0.3 wt.% to 5.0 wt.%, about 0.3 wt.% to 4.0 wt.%, or about 0.3 wt.% to 3.0 wt.%. It is believed that adding less than about 0.1 wt.% of titanium compound may not improve the solid acid properties of the zeolite. It is believed that adding more than 5 wt.% of titanium compounds may cause zeolite pore blockage. Aqueous solutions of titanium compounds prepared by dissolving them in water can be used as titanium compounds.

[0080] If present, suitable hafnium compounds include hafnium chloride, hafnium nitrate, hafnium fluoride, hafnium bromide, hafnium oxalate, etc. The amount of the hafnium compound added, relative to USY-30 122, is 0.1% to 5% by mass (or 0.2% to 4% by mass) based on hafnium oxide. Adding less than 0.1% by mass of the hafnium compound may not improve the solid acidity of the zeolite. Adding more than 4% by mass of the hafnium compound may increase the cost of the catalyst.

[0081] The pH of the suspension can be controlled at approximately <2.0 to prevent precipitation during mixing of aqueous solutions of zirconium compounds and / or hafnium compounds and / or titanium compounds with a suspension of ultrastable zeolite (such as USY).

[0082] In some embodiments, the mixing of aqueous solutions of the respective zirconium and titanium compounds with a suspension of ultrastable zeolite (such as USY) is performed by gradually adding the titanium solution to the suspension, followed by the addition of the zirconium solution. The time interval between adding the aqueous titanium and zirconium metal solutions to the suspension can be at least 0.1 hours, at least 0.25 hours, at least 0.5 hours, at least 1 hour, at least 2.5 hours, at least 5 hours, 0.1 hours to 5 hours, such as 0.5 hours to 5 hours, 1 hour to 5 hours, or any subset thereof. After all solutions have been added, the suspension can be mixed by stirring. In embodiments, stirring can be performed at room temperature (approximately 25°C to 35°C) for approximately 3 to 5 hours. Furthermore, after the above mixing is completed, the mixed solution can be neutralized by adding an alkaline compound (such as ammonia) to control its pH at approximately 7.0 to 7.5, thereby obtaining the post-modified zeolite framework described in this invention.

[0083] It is believed that this sequential addition step causes zirconium atoms to connect to the zeolite framework in both 4- and 5-coordinate configurations, and titanium atoms to connect to the zeolite framework in a 4-coordinate configuration. Without theoretical constraints, it is believed that if titanium and zirconium atoms are introduced simultaneously, both will connect to the zeolite framework in a 4-coordinate configuration. However, it is believed that if titanium atoms are introduced first, they will preferentially occupy the 4-coordinate positions. Then, since most of the 4-coordinate positions are already occupied, subsequent zirconium atoms will be forced to occupy a higher proportion of the 5-coordinate positions.

[0084] If necessary, the resulting skeleton-substituted zeolite can be filtered, washed with water, and dried at about 80°C to 180°C; the mixture can be quasi-equilibrated with steam, for example, at a temperature of about 600°C to 800°C for about 10 to 20 hours.

[0085] In step 120, the calcined USY(c) zeolite from step 118 can be prepared by dispersing it in water at an effective temperature (e.g., in the range of about 15°C to 95°C, 15°C to 80°C, 20°C to 95°C, 20°C to 90°C, 20°C to 80°C, 40°C to 95°C, 40°C to 90°C, or 40°C to 80°C) to form a USY(c) suspension with an effective concentration (e.g., in the range of about 5-15, 5-12, 8-15, or 8-12 L / kg (water / zeolite)).

[0086] In acid treatment step 122, an effective amount of inorganic or organic acid may be dispersed in a suspension to maintain the pH of the suspension in a strongly acidic range in order to prepare zeolite for metal introduction in steps 124 to 128.

[0087] The inorganic acid used may include sulfuric acid, nitric acid, hydrochloric acid, etc. In the embodiments, the inorganic acid may be sulfuric acid, hydrochloric acid, or both. Furthermore, carboxylic acids may be suitable as organic acids. The amount of the inorganic acid and / or organic acid added may be an amount suitable for controlling the pH of the suspension within a strongly acidic range (e.g., less than 2.0, 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 may be maintained at an effective temperature, for example, within the range of about 15°C to 95°C, 15°C to 80°C, 20°C to 95°C, 20°C to 90°C, 20°C to 80°C, 40°C to 95°C, 40°C to 90°C, or 40°C to 80°C, and for an effective residence time, for example, within the range of about 10 min to 600 min, 10 min to 180 min, 30 min to 600 min, or 30 min to 180 min.

[0088] In metal modification steps 124 and 126, metal introduction is performed. Acid-modified USY(c) zeolite (e.g., USY zeolite) suspensions can be metal-treated to introduce metals into the ultrastable zeolite.

[0089] In an embodiment, this can be done by adding a solution containing a transition metal compound to the acidity-modified USY(c). In an embodiment, the transition metal compound may include zirconium and titanium compounds, and optionally a hafnium compound. Each metal modification is performed in a single step. Titanium may be added in step 124. Zirconium may be added in step 126. All solutions are maintained at effective temperatures, such as 15°C to 80°C, 15°C to 60°C, 15°C to 35°C, 15°C to 30°C, 20°C to 60°C, or 20°C to 30°C, and at effective residence times, such as in the range of about 10 min to 600 min, 10 min to 180 min, 30 min to 600 min, or 30 min to 180 min. The suspension from step 126 can be neutralized with, for example, ammonia water to a pH in the range of about 7.0 to 7.5.

[0090] The solids obtained from the metal insertion steps 124 and 126 can be filtered, washed with water at an effective temperature (e.g., in the range of about 15°C to 95°C, 15°C to 80°C, 20°C to 95°C, 20°C to 90°C, 20°C to 80°C, 40°C to 95°C, 40°C to 90°C, or 40°C to 80°C), dried at an effective temperature (e.g., in the range of about 80°C to 180°C or 100°C to 180°C), and kept at an effective residence time (e.g., in the range of about 30 min to 1800 min, 60 min to 1800 min, 30 min to 600 min, or 60 min to 600 min), and the skeleton-modified zeolite (e.g., USY(A)) can be recovered in step 128.

[0091] The heteroatom-containing post-modified zeolites described herein comprise zirconium and titanium, wherein the zirconium atoms grafted onto the framework are 4-coordinated and 5-coordinated. The effective concentrations of zirconium and titanium, calculated based on their oxides (i.e., ZrO2 and TiO2) and measured relative to the mass of the post-framework modified USY zeolite, include approximately 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.%. In some embodiments, the amount of individual zirconium and titanium supplied may be less than 0.1, 0.2, or 0.3 wt.%, but the total amount when combined is at least 0.1, 0.2, or 0.3 wt.%. Those skilled in the art will understand that when the skeleton-substituted zeolite in the catalyst contains the aforementioned zirconium and titanium atoms, there is no particular limitation on the mass ratio of zirconium atoms to titanium atoms (in oxides), and any ratio of zirconium or titanium that is effective for the intended use of the catalyst particles (e.g., for hydrocracking of heavy hydrocarbon oils) can be used.

[0092] The presence of zirconium and titanium atoms (where zirconium atoms replace aluminum atoms in the zeolite framework with 4- and 5-coordinate structures and are bonded to the framework) constitutes a component of the novel modified zeolite. The modification can be verified by extended X-ray absorption fine structure spectroscopy, X-ray fluorescence, high-frequency inductively coupled plasma atomic emission spectroscopy, atomic absorption spectroscopy, ultraviolet-visible-near-infrared spectrophotometry (UV-Vis-NIR), Fourier transform infrared spectroscopy (FT-IR), and / or nuclear magnetic resonance spectroscopy (NMR).

[0093] Subsequent steps (steps 130 and 132) in the process of preparing catalyst particles with an active metal component on a composite support comprising the post-modified zeolite and a binder include forming an inorganic oxide as a binder or granulator, subsequently mixing it with the post-modified zeolite and extruding it (steps 134 and 136). In step 130, a solution is prepared that will precipitate one or more inorganic oxides used as a binder or granulator, hereinafter referred to as the inorganic oxide component. For example, a gel of alumina or another inorganic oxide known in the art can be used to prepare a suitable binder. In some embodiments, the solid inorganic oxide can be used directly as the binder material.

[0094] Alternatively, commercially available inorganic oxide components known to those skilled in the art can be provided and prepared for mixing with the post-modified zeolite, for example by kneading.

[0095] Inorganic oxides, such as porous inorganic oxides used in other catalyst compositions in hydrocracking or related technologies, can be used as binders. Suitable inorganic oxides may include alumina, silica, titanium dioxide, aluminum silicate oxide, titanium silicate oxide, zirconium silicate oxide, boron silicate oxide, aluminum phosphorus oxide, aluminum silicate boron silicate oxide, aluminum phosphorus boron silicate oxide, aluminum silicate titanium silicate oxide, and aluminum silicate zirconium silicate oxide.

[0096] The post-modified zeolite and inorganic binder can be combined using known methods for forming catalysts to form a composite support material, for example, by mixing and kneading the components (step 134), and then forming the composite support particles into the desired shape by co-extrusion or other methods (step 136). The composite support particles can be calcined (step 138), and the active metal component can be impregnated in the calcined composite support particles (step 140). The catalyst particles can then be calcined again (step 142), and the final product, i.e., catalyst particles with the active metal component on the composite support, can be recovered. In embodiments, in addition to the active metal component impregnated in the catalyst particles, the post-modified zeolite material in the final particles can also be used as an active catalytic material.

[0097] The composite support material can be formed from the post-modified zeolite material (e.g., from step 128 herein), one or more inorganic oxide components (e.g., from step 132 herein), and optionally one or more other zeolite materials. The specific surface area of ​​the composite support material is typically around 150 m². 2 / g to 500 m 2 / g, 150 m 2 / g to 450 m 2 / g、200m 2 / g to 500 m2 / g、200 m 2 / g to 450 m 2 / g、300 m 2 / g to 450 m 2 The pore volume is within the range of approximately 0.4 mL / g to 0.8 mL / g, 0.4 mL / g to 0.75 mL / g, 0.4 mL / g to 0.65 mL / g, 0.45 mL / g to 0.8 mL / g, 0.45 mL / g to 0.75 mL / g, 0.45 mL / g to 0.65 mL / g, or any subset thereof. The content of the post-modified USY zeolite component, inorganic oxide component, and active metal component is appropriately determined according to the target. For example, the post-modified zeolite content of the hydrocracking catalyst formed from the composite support material can be in the range of about 0.1 wt.% to 99 wt.%, 0.1 wt.% to 90 wt.%, 0.1 wt.% to 80 wt.%, 0.1 wt.% to 70 wt.%, 2 wt.% to 99 wt.%, 2 wt.% to 90 wt.%, 2 wt.% to 80 wt.%, 2 wt.% to 70 wt.%, 2 wt.% to 100 wt.%, 20 wt.% to 90 wt.%, 20 wt.% to 80 wt.%, 20 wt.% to 70 wt.%, or any subset thereof. The remaining content of the hydrocracking catalyst can be inorganic oxides and active metal components, and optionally one or more other zeolite materials in some embodiments.

[0098] In the mixing / kneading step 134, the post-modified zeolite, for example, recovered from step 128 or otherwise provided, is mixed together with an inorganic binder, for example, recovered from step 132 or otherwise provided. The mixing is carried out at an effective ratio as described above and at a suitable temperature, the suitable temperature range being, for example, about 15°C to 80°C, 15°C to 60°C, 15°C to 35°C, 15°C to 30°C, 20°C to 60°C, or any subset thereof. The mixture can be kneaded / mixed with an effective amount of water, for example, a liquid-to-solid ratio ranging from about 30-80 L / kg, for a sustained effective kneading / mixing time, for example, in the range of about 10 min to 180 min. Thus, the wet solid material is kneaded / mixed to form a dough-like material, which is subsequently shaped and dried. The kneaded / mixed product can be heat-treated to achieve closer contact between the components and better homogeneity through thermal diffusion and solid-state reaction.

[0099] The kneaded / mixed material thus obtained is extruded through a die having an effective cross-sectional shape and size at a suitable temperature (forming step 136), said suitable temperature range being, for example, about 15°C to 80°C, 15°C to 60°C, 15°C to 35°C, 15°C to 30°C, 20°C to 60°C, or any subset thereof. Effective cross-sectional shapes include, for example, cylindrical, trefoil, twisted trefoil, or tetralobed shapes. Effective cross-sectional dimensions include, for example, diameters or effective diameters in the range of about 0.8 mm to 3.2 mm or 0.8 mm to 2.5 mm. The resulting extrudate is dried at an effective temperature (e.g., in the range of about 80°C to 180°C or 100°C to 180°C) for a sustained effective residence time, for example, in the range of about 30 min to 1800 min, 60 min to 1800 min, 30 min to 600 min, or 60 min to 600 min, to recover the dried composite extrudate. Optionally, a separate drying step can be avoided, thereby transferring the composite extrudate to the heat treatment step 138 for calcination.

[0100] In heat treatment step 138, the composite extrudate (optionally dried) is heat-treated to prepare calcined composite particles. In an embodiment, the heat treatment in step 138 includes calcining the composite extrudate (optionally dried) at an effective temperature (typically in the presence of air or oxygen, or in the presence of steam), such effective temperature being, for example, in the range of about 400°C to 800°C, 400°C to 700°C, 400°C to 650°C, 500°C to 800°C, 500°C to 700°C, 500°C to 650°C, 550°C to 800°C, 550°C to 700°C, 550°C to 650°C, 600°C to 800°C, or 600°C to 700°C, for a duration in the range of about 10 min to 600 min, 10 min to 180 min, 30 min to 600 min, or 30 min to 180 min, to recover the calcined composite particles.

[0101] The final product of hydrocracking catalyst particles, i.e., the calcined support, is impregnated with an active metal component, such as a hydrogenation metal. The active metal component may include one or more metals or metal compounds (oxides or sulfides) known in the field of hydrocracking, including those metals selected from Groups 6, 7, 8, 9, and 10 of the IUPAC periodic table. In some embodiments, the active metal component includes those components effective as hydrocracking catalysts, such as one or more of Mo, W, Co, or Ni (oxides or sulfides). In some embodiments, the active metal component includes those metal components 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 these noble metals. The metal component may be contained in the catalyst at an effective concentration. For example, the total active metal content in the hydrocracking catalyst may be present in amounts known in the relevant art, for example, from about 0.01 wt.% to 40 wt.% as metal, oxide, or sulfide. For non-precious metals, including Mo, W, Co, Ni, or combinations thereof, the effective total active metal content, based on the mass of the catalyst and expressed as oxides or sulfides, can be from about 0.1 wt.% to 40 wt.%, or 3 wt.% to 40 wt.%. For precious metals, typically in a sulfur-free environment for hydrogenation and / or reforming, the effective total active metal content, expressed as metals, can be from about 0.01 to 2 wt.%.

[0102] exist Figure 1 In step 140 of the embodiment, the active metal component is impregnated. Several methods can be used to add the active metal component to the carrier, including but not limited to impregnation, equal-volume impregnation, and evaporation. In the most common method, the calcined carrier material is impregnated in an excess of an aqueous solution containing an active metal or metal compound. The solution fills the pores and is also adsorbed onto the carrier surface, and then the excess solution is removed. In another method, impregnation is performed using equal-volume impregnation, where a certain volume of solution is applied to the activated carrier by tumbling or spraying, the concentration of the metal compound in the solution being adjusted to achieve the target metal content. In another method, namely evaporative impregnation, the carrier is saturated with water or an acid solution and impregnated in an aqueous solution containing a metal compound. The compound then diffuses through the aqueous phase into the pores of the carrier. The metal-loaded carrier is then dried and calcined to form a metal oxide.

[0103] In an embodiment, the active metal component impregnation step 140 includes impregnating calcined composite carrier particles formed from post-modified zeolite and a binder in an aqueous solution containing the active metal component. The amount and concentration of the aqueous solution containing the active metal component depend on the desired amount of active metal component to be loaded onto the composite carrier particles. In some embodiments of the above method, the volume of the active metal solution is equal to or slightly smaller than the pore volume of the carrier. The solution can be maintained at an effective temperature, such as approximately 40°C to 100°C, 40°C to 99°C, 60°C to 100°C, 60°C to 99°C, 60°C to 97°C, 70°C to 99°C, 70°C to 97°C, 80°C to 99°C, 80°C to 97°C, or 90°C to 99°C, and maintain an effective residence time, such as approximately 40 min to 1200 min, 40 min to 600 min, 40 min to 360 min, 60 min to 1200 min, 60 min to 600 min, 60 min to 360 min, 120 min to 1200 min, 120 min to 600 min, 120 min to 360 min, 180 min to 1200 min, 180 min to 600 min, 180 min to 360 min, or 240 min to 360 min.

[0104] The resulting solid can be filtered and dried at an effective temperature (e.g., in the range of about 80°C to 180°C or 100°C to 180°C) for a sustained effective residence time, such as in the range of about 30 min to 1800 min, 60 min to 1800 min, 30 min to 600 min, or 60 min to 600 min, to recover the composite carrier particles formed from the post-modified zeolite and binder, on which the active metal is loaded. Optionally, a separate drying step can be avoided, thereby allowing the composite material loaded with the active metal to be fed into heat treatment step 142 for calcination.

[0105] In heat treatment step 142, the loaded composite material is heat-treated to prepare calcined composite particles with an active metal loaded on the composite material. In some embodiments, the heat treatment in step 142 includes calcination at an effective temperature (e.g., within the ranges of about 400°C to 800°C, 500°C to 800°C, 500°C to 700°C, 500°C to 650°C, 550°C to 800°C, 550°C to 700°C, 550°C to 650°C, 600°C to 800°C, or 600°C to 700°C) for a duration within the ranges of about 10 min to 600 min, 10 min to 180 min, 30 min to 600 min, or 30 min to 180 min, to recover the calcined composite particles with the active metal loaded on the composite material. In some embodiments, calcination is performed in air.

[0106] In step 144, the final catalyst product is recovered. In embodiments where the catalyst is a hydrocracking catalyst, the surface area of ​​the composite support material loaded with the active metal is typically about 150 m². 2 / g to 500 m 2 / g, 150 m 2 / g to 450m 2 / g、200 m 2 / g to 500 m 2 / g、200 m 2 / g to 450 m 2 / g or 300 m 2 / g to 450 m 2 The pore volume is in the range of approximately 0.4 mL / g to 0.8 mL / g, 0.4 mL / g to 0.75 mL / g, 0.4 mL / g to 0.65 mL / g, 0.45 mL / g to 0.8 mL / g, 0.45 mL / g to 0.75 mL / g, or 0.45 mL / g to 0.65 mL / g.

[0107] Hydrocracking process A method for hydrocracking a hydrocarbon feedstock may include contacting the hydrocarbon feedstock with hydrogen and a hydrocracking catalyst under hydrocracking conditions.

[0108] The hydrocarbon feedstock may include heavy hydrocarbon oils, such as vacuum gas oil (VGO), deasphalted oil (DAO), demetallized oil, light coking gas oil, heavy coking gas oil, circulating oil, or gas oil, or one or more of these. The hydrocarbon feedstock may also include middle distillate oil, naphtha, and one or more bridged dual aromatic molecules.

[0109] The hydrocarbon feedstock can be contacted with the hydrocracking catalyst at a hydrogen partial pressure of 5,000 kPa (50 bar) to 25,000 kPa (250 bar). In embodiments, the hydrogen partial pressure can be 5,000 kPa to 10,000 kPa, 5,000 kPa to 15,000 kPa, 5,000 kPa to 20,000 kPa, 5,000 kPa to 25,000 kPa, 10,000 kPa to 15,000 kPa, 10,000 kPa to 20,000 kPa, 10,000 kPa to 25,000 kPa, 15,000 kPa to 20,000 kPa, 15,000 kPa to 25,000 kPa, or 20,000 kPa to 25,000 kPa.

[0110] The hydrogen feed rate when the hydrocarbon feed comes into contact with the hydrocracking catalyst can be from 500 standard liters of hydrogen (StLt / L) to 2500 StLt / L per liter of oil. For example, the hydrogen feed rate can be 500 StLt / L to 1000 StLt / L, 500 StLt / L to 1500 StLt / L, 500 StLt / L to 2000 StLt / L, 500 StLt / L to 2500 StLt / L, 1000 StLt / L to 1500 StLt / L, 1000 StLt / L to 2000 StLt / L, 1000 StLt / L to 2500 StLt / L, 1500 StLt / L to 2000 StLt / L, 1500 StLt / L to 2500 StLt / L, or 2000 StLt / L to 2500 StLt / L.

[0111] In this embodiment, the hydrogen feed rate can be approximately a multiple of the hydrogen consumption rate. For example, the hydrogen feed rate can be 2, 3, or even 4 times the hydrogen consumption rate.

[0112] The temperature at which the hydrocarbon feed contacts the hydrocracking catalyst can be from 100°C to 550°C. In embodiments, the temperature at which the hydrocarbon feed contacts the hydrocracking catalyst can be from 100°C to 200°C, 100°C to 300°C, 100°C to 400°C, 100°C to 500°C, 100°C to 550°C, 200°C to 300°C, 200°C to 400°C, 200°C to 500°C, 200°C to 550°C, 300°C to 400°C, 300°C to 500°C, 300°C to 550°C, 400°C to 500°C, 400°C to 550°C, 450°C to 500°C, or 500°C to 550°C.

[0113] The hydrocarbon feed can be in contact with the hydrocracking catalyst and hydrogen in a fixed-bed reactor, a fluidized-bed reactor, a moving-bed reactor, or a slurry-bed reactor.

[0114] aspect According to a first aspect, a hydrocracking catalyst may comprise an active cracking support; said active cracking support comprises a post-modified zeolite framework in which aluminum atoms are replaced by zirconium and titanium atoms; wherein: a portion of the zirconium atoms are substituted in the post-modified zeolite by 4-coordination; a portion of the zirconium atoms are grafted onto the post-modified zeolite by 5-coordination; and titanium atoms are substituted in the post-modified zeolite framework by 4-coordination.

[0115] According to the second aspect, in conjunction with the first aspect, the post-modified zeolite can have an ultrastable Y (USY) framework structure.

[0116] According to the third aspect, in conjunction with the first or second aspect, the specific surface area of ​​the post-modified zeolite can be 600 m². 2 / g to 900 m 2 / g.

[0117] According to the fourth aspect, in conjunction with any one of the first to third aspects, the lattice constant of the post-modified zeolite can be from 2.430 nm to 2.450 nm.

[0118] According to the fifth aspect, in conjunction with any one of the first to fourth aspects, the molar ratio of SiO2 to Al2O3 in the post-modified zeolite can be from 5 to 100.

[0119] According to the sixth aspect, in conjunction with any one of the first to fifth aspects, the hydrocracking catalyst may further comprise a hydrogenation component.

[0120] According to the seventh aspect, in conjunction with any one of the first to sixth aspects, the hydrocracking catalyst may contain 0.1 wt.% to 40 wt.% of hydrogenation components.

[0121] According to the eighth aspect, in conjunction with any one of the first to seventh aspects, the hydrogenated component may contain at least one metal from Group 6 or Group 8 of IUPAC.

[0122] According to the ninth aspect, in conjunction with any one of the first to eighth aspects, the hydrogenation component may comprise one or more metals selected from the group consisting of cobalt, nickel, palladium, platinum, molybdenum or tungsten.

[0123] According to aspect ten, in conjunction with any one of aspects one through nine, the zeolite can have an ultrastable γ (USY) framework structure; and a specific surface area of ​​600 m². 2 / g to 900 m 2 / g; lattice constant of 2.430 nm to 2.450 nm; and molar ratio of SiO2 to Al2O3 of 5 to 100.

[0124] According to the eleventh aspect, in conjunction with any one of the first to tenth aspects, the zeolite may have a Y-framework structure or a BEA-framework structure.

[0125] According to the twelfth aspect, a method for producing an active hydrocracking support may include: providing an acidified zeolite suspension containing a zeolite framework; introducing a titanium compound into the acidified zeolite suspension to isomorphously substitute titanium onto the zeolite framework via 4-coordination, thereby producing a titanium-substituted zeolite framework; and then introducing a zirconium compound into the titanium-substituted zeolite framework to graft a portion of zirconium atoms onto the zeolite framework via 5-coordination and isomorphically substitute a portion of zirconium atoms onto the zeolite framework via 4-coordination, thereby producing an active hydrocracking support.

[0126] According to aspect thirteen, in conjunction with aspect twelf, the time interval between the introduction of the titanium compound and the introduction of the zirconium compound can be from 0.1 hours to 5 hours.

[0127] According to aspect fourteen, in conjunction with any one of aspects twelfth to thirteenth, the liquid-to-solid ratio of the acidified suspension may be 5 to 15 L / kg.

[0128] According to aspect fifteen, in conjunction with any one of aspects twelfth to fourteenth, the acid may be an inorganic acid or an organic acid.

[0129] According to aspect sixteen, in conjunction with any one of aspects twelfth to fifteenth, the pH of the acidified suspension may be less than 2.

[0130] According to the seventeenth aspect, in conjunction with any one of the twelfth to sixteenth aspects, the zeolite can be dried and subsequently heat-treated at 500°C to 700°C.

[0131] According to aspect eighteen, in conjunction with any one of aspects twelve to seventeen, the time interval between the introduction of the titanium compound and the introduction of the zirconium compound may be 0.1 hours to 5 hours; the liquid-to-solid ratio of the acidified suspension may be 5 to 15 L / kg; the pH of the acidified suspension may be less than 2.0; and the zeolite may be heat-treated at 500°C to 700°C.

[0132] According to the nineteenth aspect, a method for hydrocracking a hydrocarbon feedstock may include contacting the hydrocarbon feedstock with hydrogen and a hydrocracking catalyst under hydrocracking conditions; wherein the hydrocracking catalyst comprises an active cracking support; the active cracking support comprises a post-modified zeolite framework in which aluminum atoms are replaced by zirconium and titanium atoms; wherein a portion of the zirconium atoms are grafted onto the post-modified zeolite framework in a 5-coordinate manner; a portion of the zirconium atoms are connected to the post-modified zeolite framework in a 4-coordinate manner; and titanium atoms are connected to the post-modified zeolite framework in a 4-coordinate manner.

[0133] According to aspect 20, in conjunction with aspect 19, the hydrocarbon feedstock may include heavy hydrocarbon oil.

[0134] Example Various aspects of the present invention will be further illustrated by the following embodiments. These embodiments are illustrative in nature and should not be construed as limiting the scope of the invention.

[0135] Material TiO2 powder: The TiO2 powder is MC-90 (anatase) manufactured by Ishihara Sangyo Kaisha, Ltd.

[0136] Unmodified USY-30 was prepared as follows: 50.0 kg of SiO2 / Al2O3 with a molar ratio of 5.2, a cell size (UD) of 2.466 nm, and a specific surface area (SA) of 720 m² was used. 2 NaY zeolite (hereinafter referred to as "NaY") with a Na₂O content of 13.0% by mass was suspended in 500 L of water at 60°C. Then, 14.0 kg of ammonium sulfate was added. 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 formed by dissolving 14.0 kg of ammonium sulfate in 500 L of water at 60°C, followed by washing with 500 L of water at 60°C, and then dried at 130°C for 20 h to obtain approximately 45 kg of Y zeolite (NH₄⁺). 65 NaY), in which 65% of the sodium (Na) in NaY underwent ion exchange with ammonium ions. 40 kg of NH4 65 Y was calcined at 670 °C for 1 h in a saturated steam atmosphere to form hydrogen y zeolite (HY). HY was suspended in 400 L of water at 60 °C. Then, 49.0 kg of ammonium sulfate was added. The resulting mixture was stirred at 90 °C for 1 h and washed with 200 L of water at 60 °C. The mixture was then dried at 130 °C for 20 h to obtain approximately 37 kg of y zeolite (NH4). 95NaY), in which 95% of the Na contained in the initial NaY underwent ion exchange with NH4. 33.0 kg of NH4 95 Y was calcined at 650 °C for 1 h in a saturated steam atmosphere to obtain approximately 15 kg of USY(a), with a SiO2 / Al2O3 molar ratio of 5.2 and a Na2O content of 0.60% by mass. Next, 26.0 kg of this USY(a) was suspended in 260 L of water at 60 °C. After gradually adding 61.0 kg of 25% by mass sulfuric acid to the suspension, the suspension was stirred at 70 °C for 1 h. The suspension was filtered. The resulting solid was washed with 26 L of deionized water at 60 °C and dried at 130 °C for 20 h to obtain USY(b). USY(b) was calcined at 600 °C for 1 h to obtain approximately 17 kg of USY(c), with a silicon-to-aluminum ratio of 30.

[0137] Zirconium-modified USY-30 was prepared as follows. 1 kg of USY-30 (prepared as described in this section) was suspended in 10 L of water at 25°C, and the pH of the solution was adjusted to 1.6 by adding 25% by mass sulfuric acid. 18% by mass zirconium sulfate (86 g) was added to the suspension, and the mixture was stirred at room temperature for 5 h. Then, the pH was adjusted to 7.2 with 15% by mass ammonia, and the suspension was stirred at room temperature for 1 h, followed by filtration. The filtrate was washed with 10 L of water and dried at 130°C for 20 h to obtain approximately 1 kg of zirconium-modified USY-30.

[0138] Titanium-modified USY-30 (in which titanium is 4-coordinated to the framework) was prepared as follows. 1 kg of USY-30 (prepared as described in this section) was suspended in 10 L of water at 25°C, and the pH of the solution was adjusted to 1.6 by adding 25% by mass sulfuric acid. 33% by mass titanium oxysulfate (60 g) was added to the suspension, and the mixture was stirred at room temperature for 5 h. Then, the pH was adjusted to 7.2 with 15% by mass ammonia, and the suspension was stirred at room temperature for 1 h, followed by filtration. The filtrate was washed with 10 L of water and dried at 130°C for 20 h to obtain approximately 1 kg of titanium-modified USY-30.

[0139] Titanium-zirconium modified USY-30 (in which zirconium is linked to the framework in both 4- and 5-coordinate forms and titanium is linked to the framework in a 4-coordinate form) was prepared as follows. 1 kg of USY-30 (prepared as described in this section) was suspended in 10 L of water at 25°C, and the pH of the solution was adjusted to 1.6 by adding 25% by mass sulfuric acid. First, 33% by mass titanium oxysulfate (60 g) was added and mixed for 1 h. Then, 18% by mass zirconium sulfate (86 g) was added to the suspension and mixed at room temperature for 5 h. The pH was then adjusted to 7.2 with 15% by mass ammonia, and the suspension was stirred at room temperature for 1 h, followed by filtration. The filtrate was washed with 10 L of water and dried at 130°C for 20 h to obtain approximately 1 kg of TiZr-USY.

[0140] Example 1: Ultraviolet-Vis Spectroscopy Figure 2 The UV-Vis spectra of unmodified USY-30 zeolite 202, zirconium-modified USY 204, titanium-modified USY 206, and titanium-zirconium-modified USY 208, in which titanium and zirconium are linked to the framework in 4-coordinate and 5-coordinate configurations, were depicted.

[0141] Depend on Figure 2 It is evident that titanium-modified USY 206 and zirconium-modified USY 204 exhibit peak values ​​in the 200 nm to 300 nm range. According to the literature, the peak values ​​at 200–210 nm are attributed to tetracoordinated zirconium atoms, and those at 220–230 nm are attributed to tetracoordinated titanium atoms. Unmodified USY-30 202 does not exhibit peak values ​​in this range, while titanium- and zirconium-modified USY-30 208 do. Therefore, [the following is a continuation of the previous sentence, but the context is unclear]. Figure 2 It is evident that at least a portion of the titanium and zirconium atoms added to the USY zeolite enter the USY zeolite lattice of the titanium-zirconium modified USY-30 208 in a tetracoordinate manner.

[0142] Example 2: XAFS Modeling XAFS spectra of USY zeolite with zirconium 4-coordinated to the zeolite framework and USY zeolite with zirconium 5-coordinated to the zeolite framework were modeled, and the results are as follows: Figure 3 As shown.

[0143] like Figure 3 As shown, the spectrum of USY zeolite 304 with 4-coordinated zirconium is significantly different from that of USY zeolite 302 with 5-coordinated zirconium. Specifically, the characteristic signal indicating the presence of 5-coordinated USY zeolite is at approximately 5 EE. Fermi Peak value at eV.

[0144] Example 3: XAFS Test Then, XAFS tests were performed on the titanium-zirconium modified USY-30. Figure 4 It can be seen that the spectrum of titanium-zirconium modified USY-30 is similar to... Figure 3 The spectrum shown in the 5-coordinate model is similar. This confirms the presence of zirconium atoms with 5 coordination.

[0145] It should be noted that any two quantitative values ​​assigned to a property can constitute a range of that property, and the present invention considers all combinations of ranges formed by all stated quantitative values ​​of a given property.

[0146] It should be noted that the term "characterized in" is used as a transitional phrase in one or more of the following claims. In defining this technology, it should be noted that this term is introduced in the claims as an open-ended transitional phrase used to introduce a description of a series of features of the structure, and should be interpreted in a similar manner to the more commonly used open-ended prepositional term "comprising".

[0147] Having described the subject matter of the invention in detail and referenced specific aspects, it should be noted that the various details of these aspects should not be considered essential components of these aspects. Rather, the appended claims should be considered the sole expression of the breadth of the invention and the respective scope of the various aspects described herein. Furthermore, it will be apparent that various modifications and variations can be made without departing from the scope of the appended claims.

Claims

1. A hydrocracking catalyst comprising an active cracking support; The active cracking support comprises a post-modified zeolite framework in which aluminum atoms are replaced by zirconium and titanium atoms; characterized in that: A portion of the zircon atoms are substituted in the post-modified zeolite framework via 4-coordinate substitution; A portion of the zircon atoms are grafted onto the post-modified zeolite framework via 5-coordination; and The titanium atoms are substituted in the post-modified zeolite framework via 4-coordinate substitution.

2. The hydrocracking catalyst according to claim 1, characterized in that, The post-modified zeolite framework has an ultrastable Y (USY) framework structure.

3. The hydrocracking catalyst according to any one of claims 1 or 2, characterized in that, The specific surface area of ​​the post-modified zeolite framework is 600 m². 2 / g to 900 m 2 / g.

4. The hydrocracking catalyst according to any one of claims 1 to 3, characterized in that, The lattice constant of the post-modified zeolite framework is 2.430 nm to 2.450 nm.

5. The hydrocracking catalyst according to any one of claims 1 to 4, characterized in that, The molar ratio of SiO2 to Al2O3 in the post-modified zeolite framework is 5 to 100.

6. The hydrocracking catalyst according to any one of claims 1 to 5, characterized in that, The hydrocracking catalyst further comprises a hydrogenation component.

7. The hydrocracking catalyst according to claim 6, characterized in that, The hydrocracking catalyst comprises 0.1 wt.% to 40 wt.% of the hydrogenation component.

8. The hydrocracking catalyst according to any one of claims 6 or 7, characterized in that, The hydrogenated component contains at least one metal from Group 6 or Group 8 of the IUPAC.

9. The hydrocracking catalyst according to any one of claims 6 to 8, characterized in that, The hydrogenated component comprises one or more metals selected from the group consisting of cobalt, nickel, palladium, platinum, molybdenum, or tungsten.

10. A method for preparing an active hydrocracking support, comprising: Provides an acidified zeolite suspension containing a zeolite framework; Titanium compounds are introduced into the acidified zeolite suspension to isomorphously replace titanium onto the zeolite framework through 4-coordination, thereby obtaining a titanium-substituted zeolite framework. as well as Then, a zirconium compound is introduced into the titanium-substituted zeolite framework to graft a portion of the zircon atoms onto the zeolite framework via 5-coordination, and The hydrocracking active cracking support is prepared by isomorphically substituting a portion of the zircon atoms onto the zeolite framework through 4-coordination.

11. The method according to claim 10, characterized in that, The zeolite framework has a Y-framework structure or a BEA-framework structure.

12. The method according to any one of claims 10 or 11, characterized in that: The time interval between the introduction of the titanium compound and the introduction of the zirconium compound is 0.1 hours to 5 hours; The liquid-to-solid mass ratio of the acidified suspension is 5 to 15; The acidified zeolite suspension is acidified with inorganic or organic acids. The pH of the acidified zeolite suspension is less than 2.0; and The zeolite framework is heat-treated at 500°C to 700°C.

13. A method for hydrocracking hydrocarbon feedstock, characterized in that, The method includes contacting the hydrocarbon feedstock with hydrogen and a hydrocracking catalyst under hydrocracking conditions; wherein the hydrocracking catalyst comprises an active cracking support; The active cracking support comprises a post-modified zeolite framework in which aluminum atoms are replaced by zirconium and titanium atoms. in A portion of the zircon atoms are grafted onto the post-modified zeolite framework via 5-coordination; A portion of the zircon atoms are linked to the post-modified zeolite framework in a 4-coordinate configuration; and The titanium atoms are connected to the post-modified zeolite framework in a 4-coordinate configuration.

14. The method according to claim 13, characterized in that, The hydrocarbon feedstock includes heavy hydrocarbon oil.

15. The method according to any one of claims 13 or 14, characterized in that, The hydrocracking catalyst further comprises a hydrogenation component, which contains at least one metal from Group 6 or Group 8 of the IUPAC.

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