In situ crystallized ultra-low zeolite content fluid catalytic cracking catalyst

Abstract

Disclosed herein is a fluid catalytic cracking catalyst comprising an in situ crystallized zeolite material and a matrix material. In at least one embodiment, the deactivated catalyst has a ratio of zeolite surface area to matrix surface area (Z / M) of less than about 1 and a unit cell size of at least about 24.3 Å.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 270,464, filed October 21, 2021, the disclosure of which is incorporated herein by reference in its entirety.

[0002] The present disclosure relates to petroleum refining catalysts and compositions thereof. In particular, the present disclosure relates to fluid catalytic cracking (FCC) catalysts and compositions thereof, methods for their preparation and methods of their use. [Background technology]

[0003] The fluid catalytic cracking (FCC) process aims to catalytically break (crack) large organic molecules into smaller, more useful compounds. Zeolite-containing materials have been used as catalysts in the FCC process for decades. Summary of the Invention [Problem to be solved by the invention]

[0004] In practice, the ultimate efficiency of FCC processes is often limited by the production of waste by-products such as coke. Reducing the production of waste by-products per mass of useful product would provide significant economic advantages in terms of reactor uptime, value of product produced between maintenance intervals, feed conversion, etc. There is a need to develop FCC catalyst components that exhibit lower coke formation per amount of feed cracked than those currently available. [Means for solving the problem]

[0005] The present disclosure provides a fluid catalytic cracking (FCC) catalyst component comprising a zeolite crystallized in-situ on alumina particles, wherein the deactivated (e.g., steamed) FCC catalyst component has a zeolite surface area (ZSA) to matrix surface area (MSA) ratio of less than about 1.

[0006] Various zeolites may be crystallized on the pure alumina particles, including, but not limited to, zeolites having the structures BEA, MSE, -SVR, FAU, MOR, CON, SOF, MFI, IMF, FER, MWW, MTT, TON, EUO, MRE, NAT, CHA, EMT, or mixtures of two or more thereof. In certain embodiments, the zeolite may be selected from zeolite X, Y-zeolite, ZSM-5, beta zeolite, ZSM-11, ZSM-14, ZSM-17, ZSM-18, ZSM-20, ZSM-31, ZSM-34, ZSM-41, ZSM-46, mordenite, chabazite, or mixtures of two or more thereof. In one embodiment, the zeolite is zeolite Y. In certain embodiments, for example when the zeolite is zeolite Y, the fresh catalyst zeolite may have a unit cell size of at least about 24.50 Å and the deactivated (eg, steamed) catalyst may have a unit cell size of at least about 24.3 Å.

[0007] In at least one embodiment, the alumina microspheres may comprise one or more of boehmite-derived alumina, pseudo-boehmite-derived alumina, flash-calcined gibbsite-derived alumina, boehmite, pseudo-boehmite, flash-calcined gibbsite, calcined flash-calcined gibbsite, silica-doped alumina, gamma-alumina (including gamma-alumina A or B), alumina C or D, χ-alumina, δ-alumina, θ-alumina, κ-alumina, α-alumina, rare earth modified versions thereof, alkaline earth metal modified versions thereof, bismuth modified versions thereof, or mixtures of two or more thereof.

[0008] In one embodiment, alumina microspheres may be made by first grinding alumina particles (e.g., dry grinding, such as, but not limited to, chopping, hammering, or ball grinding), slurrying the ground alumina particles, and spray drying the ground and slurried alumina to produce alumina microspheres having an appropriate average particle size. The ground alumina for spray drying may have a particle size in the range of 2-10 μm.

[0009] In certain embodiments, the alumina and / or zeolite may be modified with a non-aluminous component selected from rare earth elements, bismuth, alkaline earth elements, or mixtures of two or more thereof. Suitable rare earth elements may include ytterbium, gadolinium, cerium, lanthanum, or mixtures of two or more thereof. Suitable alkaline earth elements may include barium, strontium, calcium, magnesium, or mixtures of two or more thereof.

[0010] In certain embodiments, the present disclosure provides a method for preparing any of the FCC catalyst components described herein. The method includes in situ crystallizing a zeolite on an alumina microsphere, where the deactivated FCC catalyst component has a ratio of ZSA to MSA of less than about 1 and a unit cell size of at least about 24.3 Å. The zeolite can be any of the zeolites described herein. The alumina can be any of the aluminas described herein.

[0011] In certain embodiments, the crystallization comprises mixing the alumina-containing microspheres with an aluminum source, a silicon source, optionally sodium hydroxide, and water to form an alkaline slurry, in certain embodiments, the crystallization further comprises heating the alkaline slurry to a temperature and for a time sufficient to crystallize a desired amount of zeolite to form zeolite microspheres.

[0012] In certain embodiments, the method includes forming alumina microspheres prior to crystallization, for example, by grinding an alumina particle precursor, slurrying the ground alumina particle precursor, and spray drying the slurried and ground alumina particle precursor to form alumina microspheres of appropriate size as described herein.

[0013] In certain embodiments, the method of preparing any of the FCC catalyst components further comprises modifying the zeolite microspheres (after crystallization) and / or the alumina particles (before crystallization) with a non-alumina component selected from rare earth elements, bismuth, alkaline earth elements, or mixtures of two or more thereof. Suitable rare earth elements may include ytterbium, gadolinium, cerium, lanthanum, or mixtures of two or more thereof. Suitable alkaline earth elements may include barium, strontium, calcium, magnesium, or mixtures of two or more thereof. In one embodiment, the modification may comprise impregnating the zeolite microspheres and / or the alumina particles with a precursor of the selected non-alumina component (e.g., cerium nitrate, cerium acetate, lanthanum nitrate, lanthanum acetate).

[0014] In certain embodiments, the present disclosure provides a method for cracking a hydrocarbon feedstock by contacting the hydrocarbon feedstock with an FCC catalyst component according to any of the embodiments described herein or an FCC catalyst composition according to any of the embodiments described herein. The method of the present disclosure may result in one or more of improved feedstock conversion, improved bottom cracking, improved bottom coke selectivity, or reduced coke production.

[0015] definition As used herein, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Thus, for example, reference to "a microsphere" includes not only a single microsphere but also a mixture of two or more microspheres, and the like.

[0016] As used herein, the term "about" in connection with a measurand refers to normal variation in that measurand that would be expected by one of ordinary skill in the art making the measurement and exercising a level of care commensurate with the purpose of the measurement and the precision of the measurement device. In certain embodiments, the term "about" includes the referenced number ±10%, so that "about 10" would include 9 to 11.

[0017] As used herein, the term "catalyst" or "catalyst composition" or "catalyst material" or "catalyst component" refers to a material that promotes a reaction. As used herein, the term "composition" refers to a blend or mixture of two or more separate and distinct components, such as a first component mixed or blended with a second component, when referring to an FCC catalyst composition or an FCC additive composition. In certain embodiments, the components in the composition are combined and cannot be separated by physical means (e.g., filtration). In other embodiments, the components in the composition are not combined and can be separated by physical means (e.g., filtration).

[0018] As used herein, the term "fluid catalytic cracking" or "FCC" refers to the conversion process in petroleum refineries in which the higher boiling, higher molecular weight hydrocarbon fractions of petroleum crude oil are converted into more valuable gasoline, olefinic gases and other products.

[0019] "Cracking conditions" or "FCC conditions" refers to typical FCC process conditions. A typical FCC process is carried out at a reaction temperature of 450°C to 650°C, with a catalyst regeneration temperature of 600°C to 850°C. Hot regenerated catalyst is added to the hydrocarbon feedstock at the bottom of the riser reactor. Fluidization of the solid catalyst particles may be aided with a lift gas. The catalyst vaporizes and superheats the feedstock to the desired cracking temperature. During the upward passage of the catalyst and feedstock, the feedstock is cracked and coke is deposited on the catalyst. The coked catalyst and cracked products exit the riser and enter a solid-gas separation system, e.g., a series of cyclones, at the top of the reactor vessel. The cracked products are fractionated into a series of products including gas, gasoline, light gas oil, and heavy cycle gas oil. Some of the heavier hydrocarbons may be recycled to the reactor.

[0020] As used herein, the term "feedstock" or "feedstock" refers to the portion of crude oil having a high boiling point and high molecular weight. In the FCC process, the hydrocarbon feedstock is injected into the riser section of the FCC unit where the feedstock is cracked into lighter, more valuable products when it contacts the hot catalyst circulated from the catalyst regenerator to the riser reactor.

[0021] As used herein, microspheres can be obtained by spray drying. As will be understood by those skilled in the art, microspheres are not necessarily perfectly spherical in shape. The various catalyst components described herein can be particles in the form of microspheres.

[0022] As used herein, the terms "matrix" or "non-zeolitic matrix" refer to constituents of an FCC catalyst component that are not zeolites or molecular sieves.

[0023] As used herein, the term "zeolite" refers to a crystalline aluminosilicate having a framework based on an extensive three-dimensional network of silicon, aluminum and oxygen ions, with a substantially uniform pore distribution.

[0024] As used herein, the term "intergrown zeolite" refers to a zeolite formed by an in situ crystallization process.

[0025] As used herein, the term "in situ crystallization" refers to a process in which zeolites are grown or intergrown directly on / in microspheres and intimately associated with a matrix or non-zeolitic material, as described, for example, in U.S. Patents 4,493,902 and 6,656,347. Zeolites are intergrown directly on / in the macropores of precursor microspheres such that the zeolites are intimately associated and uniformly dispersed on the matrix or non-zeolitic material.

[0026] As used herein, the term "preformed microspheres" or "precursor microspheres" refers to microspheres obtained by spray drying and calcining non-zeolitic components.

[0027] As used herein, the term "zeolite-containing microspheres" refers to microspheres obtained by in situ crystallization of a zeolite material on a preformed precursor.

[0028] The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated herein as if it were individually recited herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples or exemplary language (e.g., "etc.") provided herein is intended only to illustrate particular materials and methods and does not pose a limitation on the scope. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosed materials and methods.

[0029] Embodiments of the present disclosure are illustrated by way of example and not by way of limitation in the figures of the accompanying drawings. [Brief description of the drawings]

[0030] [Figure 1] 1 shows performance data measured in a circulating riser unit for scaled-up catalyst samples according to embodiments and a reference material. [Diagram 2] 1 shows SEM images of a catalyst according to an embodiment and a reference material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0031] The present disclosure relates, in certain embodiments, to a fluid catalytic cracking (FCC) catalyst component comprising in situ crystallized zeolite on alumina-containing microspheres, the FCC catalyst component having a ratio of zeolite surface area (ZSA) to matrix surface area (MSA), which may also be described herein as Z / M ratio, of less than about 1.8. In certain embodiments, the Z / M ratio of the FCC catalyst component may be less than about 1.7, less than about 1.6, less than about 1.5, less than about 1.3, or less than about 1. In certain embodiments, the Z / M ratio may range from any of about 0.7, about 0.9, or about 1.1 to any of about 1.5, about 1.6, about 1.7, or about 1.8, or any subrange or single Z / M value therein. In one embodiment, the Z / M ratio of the FCC catalyst component ranges from about 0.9 to about 1.8. Although not intended to be limiting, it is believed that the amount of feed converted to useful products per amount of coke produced is a function of the Z / M ratio. Specifically, it is believed that larger molecules (e.g., those that make up the feedstock) are cracked into somewhat smaller products by interaction with the matrix material (e.g., gamma alumina), and these intermediate products are converted to final products (e.g., light cycle oil, heavy cycle oil, gasoline, etc.) by interaction with the zeolitic material. Increasing the available matrix surface area (i.e., decreasing Z / M) allows more feedstock to be cracked while producing the same amount of coke, or reduces the amount of coke produced while cracking a given amount of feedstock. Additionally, larger unit cell size is believed to promote low coke feedstock cracking.

[0032] In certain embodiments, the steam deactivation Z / M ratio (sZ / M ratio) of the FCC catalyst component after it is subjected to steaming conditions (e.g., 100% steaming at 800° C., e.g., for about 1 to 24 hours) is less than about 1.0. In certain embodiments, the sZ / M ratio can be less than about 0.9, less than about 0.8, or less than about 0.7. In certain embodiments, the sZ / M ratio can range from about 0.2, about 0.25, or about 0.3 to about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, or about 1.0, or any subrange or single sZ / M value therein. In one embodiment, the sZ / M ratio of the FCC catalyst component is in the range of about 0.2 to about 0.7. In one embodiment, the sZ / M ratio of the FCC catalyst component is in the range of about 0.25 to about 0.6. In one embodiment, the sZ / M ratio of the FCC catalyst component ranges from about 0.3 to about 0.5.

[0033] To arrive at the Z / M ratio (or sZ / M ratio), the total surface area (TSA) of the FCC catalyst component is determined according to the BET method, and the matrix surface area (MSA) of the FCC catalyst component is determined according to the t-plot method. The difference between the TSA and the MSA is the zeolitic surface area (ZSA) of the FCC catalyst component.

[0034] In certain embodiments, the BET TSA of the FCC catalyst component is about 50 m 2 / g, approx. 75m 2 / g, about 100m 2 / g or about 125m 2 / g ~ approx. 150m 2 / g, approx. 175m 2 / g, approx. 200m 2 / g, approx. 250m 2 / g, approx. 275m 2 / g, approx. 300m 2 / g, approx. 350m 2 / g, approx. 400m 2 / g, approx. 450m 2 / g or about 500m 2 In one embodiment, the BET TSA of the FCC catalyst component is about 100 m / g or any subrange or single BET TSA value therein. 2 / g~about 300m 2In one embodiment, the BET TSA of the FCC catalyst component is in the range of about 125 m 2 / g ~ approx. 270m 2 In one embodiment, the BET TSA of the FCC catalyst component is in the range of about 185 m 2 / g ~ approx. 250m 2 / g range.

[0035] In certain embodiments, the t-plot MSA of the FCC catalyst component is about 25 m 2 / g, approx. 50m 2 / g, approx. 75m 2 / g or about 90m 2 / g ~ approx. 110m 2 / g, approx. 125m 2 / g, approx. 130m 2 / g, approx. 140m 2 / g, approx. 150m 2 / g, approx. 160m 2 / g, approx. 170m 2 / g, approx. 175m 2 / g, approx. 180m 2 / g or about 190m 2 In one embodiment, the t-plot MSA of the FCC catalyst component is about 25 m / g or any subrange or single t-plot MSA value therein. 2 / g~approx. 175m 2 In one embodiment, the t-plot MSA of the FCC catalyst component is in the range of about 50 m 2 / g~about 150m 2 In one embodiment, the t-plot MSA of the FCC catalyst component is in the range of about 65 m 2 / g ~ approx. 130m 2 / g range.

[0036] In certain embodiments, the ZSA of the FCC catalyst component is about 25 m 2 / g, approx. 50m 2 / g, approx. 75m 2 / g or about 90m 2 / g ~ approx. 110m 2 / g, approx. 125m 2 / g, approx. 130m 2 / g, approx. 140m 2 / g, approx. 150m 2 / g, approx. 160m 2 / g, approx. 170m 2 / g, approx. 175m 2 / g, approx. 180m 2 / g or about 190m 2 In one embodiment, the ZSA of the FCC catalyst component is about 25 m / g or any subrange or single ZSA value therein. 2 / g~approx. 175m 2 In one embodiment, the ZSA of the FCC catalyst component is in the range of about 50 m 2 / g~about 150m 2 In one embodiment, the ZSA of the FCC catalyst component is in the range of about 110 m 2 / g ~ approx. 145m 2 / g range.

[0037] The FCC catalyst component according to the embodiments described herein may include various zeolites, including but not limited to zeolites selected from zeolites having the structures BEA, MSE, -SVR, FAU, MOR, CON, SOF, MFI, IMF, FER, MWW, MTT, TON, EUO, MRE, NAT, CHA, EMT, or mixtures of two or more thereof. In certain embodiments, the zeolite is selected from zeolite X, Y-zeolite, ZSM-5, beta zeolite, ZSM-11, ZSM-14, ZSM-17, ZSM-18, ZSM-20, ZSM-31, ZSM-34, ZSM-41, ZSM-46, mordenite, chabazite, or mixtures of two or more thereof. In one embodiment, the zeolite is zeolite Y.

[0038] In some embodiments, the zeolite has a unit cell parameter of about 24.10 Å to about 24.80 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.30 Å to about 24.75 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.50 Å to about 24.70 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.50 Å to about 24.80 Å. Although not intended to be limiting, it is believed that a larger effective unit cell size results in more liquefied petroleum gas (LPG). LPG is also of greater interest in the FCC market.

[0039] In some embodiments, the zeolite has a unit cell parameter of about 24.30 Å to about 24.75 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.30 Å to about 24.74 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.30 Å to about 24.73 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.30 Å to about 24.72 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.30 Å to about 24.71 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.50 Å to about 24.75 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.50 Å to about 24.74 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.50 Å to about 24.73 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.50 Å to about 24.72 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.50 Å to about 24.71 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.60 Å to about 24.75 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.60 Å to about 24.74 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.60 Å to about 24.73 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.60 Å to about 24.72 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.60 Å to about 24.71 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.65 Å to about 24.75 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.65 Å to about 24.74 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.65 Å to about 24.73 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.65 Å to about 24.72 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.65 Å to about 24.71 Å.In some embodiments, the zeolite has a unit cell parameter of about 24.45 Å to about 24.75 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.45 Å to about 24.74 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.45 Å to about 24.73 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.45 Å to about 24.72 Å. In some embodiments, the zeolite has a unit cell parameter of about 24.45 Å to about 24.71 Å. In some embodiments, the zeolite has a molecular weight of about 24.10 Å, 24.11 Å, 24.12 Å, 24.13 Å, 24.14 Å, 24.15 Å, 24.16 Å, 24.17 Å, 24.18 Å, 24.19 Å, 24.20 Å, 24.21 Å, 24.22 Å, 24.23 Å, 24.24 Å, 24.25 Å, 24.26 Å, 24.27 Å, 24.28 Å, 24.29 Å, 24.30 Å, 24.31 Å, 24.32 Å, 24.33 Å, 24.34 Å, 24.35 Å, 24.36 4.26Å, 24.27Å, 24.28Å, 24.29Å, 24.30Å, 24.31Å, 24.32Å, 24.33Å, 24.34Å, 24.3 5Å, 24.36Å, 24.37Å, 24.38Å, 24.39Å, 24.40Å, 24.41Å, 24.42Å, 24.43Å, 24.44Å, 2 4.45Å, 24.46Å, 24.47Å, 24.48Å, 24.49Å, 24.50Å, 24.51Å, 24.52Å, 24.53Å, 24.5 4Å, 24.55Å, 24.56Å, 24.57Å, 24.58Å, 24.59Å, 24.60Å, 24.61Å, 24.62Å, 24.63Å, 2 The unit cell parameters are 4.64 Å, 24.65 Å, 24.66 Å, 24.67 Å, ​​24.68 Å, 24.69 Å, 24.70 Å, 24.71 Å, 24.72 Å, 24.73 Å, 24.74 Å, 24.75 Å, 24.76 Å, 24.77 Å, 24.78 Å, 24.79 Å or 24.80 Å.

[0040] The above unit cell sizes may be particularly suitable for zeolites having a FAU zeolite structure, such as zeolite Y. As will be understood by those skilled in the art, some of the zeolite structures described herein above may have unit cell sizes different from those described herein.

[0041] The alumina-containing microspheres in the FCC catalyst components contemplated herein may include one or more of boehmite-derived alumina, pseudo-boehmite-derived alumina, flash-calcined gibbsite-derived alumina, boehmite, pseudo-boehmite, flash-calcined gibbsite, calcined flash-calcined gibbsite, silica-doped alumina, gamma-alumina (including gamma-alumina A or B), alumina C or D, χ-alumina, δ-alumina, θ-alumina, κ-alumina, α-alumina, rare earth modified variants thereof, alkaline earth metal modified variants thereof, bismuth modified variants thereof, or mixtures of two or more thereof. In certain embodiments, the alumina particles include one or more of boehmite-derived alumina, pseudo-boehmite-derived alumina, flash-calcined gibbsite-derived alumina, flash-calcined gibbsite, calcined flash-calcined gibbsite, gamma-alumina, rare earth modified variants thereof, alkaline earth metal modified variants thereof, or mixtures of two or more thereof. In one embodiment, the alumina particles include lanthanum doped gamma alumina derived from calcination of boehmite and / or pseudo-boehmite and modified with a lanthanum precursor. In one embodiment, the alumina particles include calcined flash calcined gibbsite, which may include chialumina, aluminas similar to gamma-alumina, or combinations thereof. In one embodiment, the alumina particles include gamma-alumina and peptized boehmite.

[0042] As used herein, "flash calcined gibbsite" refers to gibbsite that has been passed through a hot column, for example at a temperature of about 500°C to about 800°C, to form a mixture of steam and substantially anhydrous alumina. The substantially anhydrous alumina is called flash calcined gibbsite. The term "calcined flash calcined gibbsite" refers to flash calcined gibbsite that has been subjected to further calcination, for example at about 700°C to about 900°C, or about 750°C to about 850°C, or about 800°C.

[0043] In certain embodiments, one or more of the above pure alumina particles form the entire non-zeolite matrix of the FCC catalyst component. In one embodiment, the FCC catalyst component is free or substantially free of clay (i.e., has less than about 15 wt%, less than about 12 wt%, less than about 10 wt%, less than about 8 wt%, less than about 5 wt%, less than about 3 wt%, less than about 1 wt%, or 0 wt% clay based on the total weight of the FCC catalyst component). Without being limited, it is believed that the alumina matrix (i.e., the non-zeolite matrix containing one or more of the above pure alumina particles) is superior to the clay matrix in coke minimization.

[0044] There are several reasons why clay matrices are inferior to alumina-based matrices in minimizing coke.

[0045] One reason, but not intended to be limiting, may be that spinel has a relatively high level of strong Lewis acid sites and can bind strongly with the hydrocarbon fragments. The hydrocarbons that do not desorb and reach the regenerator are coke. The pure alumina matrix, in certain embodiments, may have a strong Lewis acid site density of less than about 70 μmol / g, less than about 65 μmol / g, less than about 60 μmol / g, less than about 55 μmol / g, less than about 50 μmol / g, less than about 45 μmol / g, less than about 40 μmol / g, or any subrange or single Lewis acid density value therein.

[0046] The pure alumina microspheres may have an average particle size of about 40 μm to about 150 μm, about 60 μm to about 120 μm, or about 70 μm to about 90 μm. In one embodiment, the pure alumina particles undergo one or more of milling (e.g., dry milling such as, but not limited to, chop milling, hammer milling, or ball milling to a D90 of 5-10 μm alumina particles), slurrying, and / or spray drying to reach an average particle size of about 40 μm to about 150 μm, about 60 μm to about 120 μm, or about 70 μm to about 90 μm.

[0047] In some embodiments, alumina is present in the FCC catalyst component in an amount ranging from about 50 weight percent, about 55 weight percent, about 60 weight percent, about 65 weight percent, about 70 weight percent, or about 75 weight percent to about 80 weight percent, about 85 weight percent, about 90 weight percent, or about 95 weight percent, or any subrange or single concentration value therein, based on the total weight of the FCC catalyst component.

[0048] Any of the pure aluminas and / or zeolites in the FCC catalyst components described herein may be further modified with non-alumina components, such as, but not limited to, rare earth elements, bismuth, alkaline earth elements, oxides thereof, or mixtures of two or more thereof. In some embodiments, the non-alumina components are present in the FCC catalyst component in an amount ranging from about 0.1%, about 0.5%, about 1%, about 2%, about 3%, about 4%, or about 5% by weight to about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, or about 18% by weight based on the total weight of the FCC catalyst component, or any subrange or single concentration value therein. In certain embodiments, the non-alumina component is present in the FCC catalyst component in an amount ranging from about 0.1% to about 18% by weight, from about 3% to about 18% by weight, from about 5% to about 18% by weight, or from about 10% to about 17% by weight, based on the total weight of the FCC catalyst component, or any subrange or single concentration value therein.

[0049] In one embodiment, the alumina and / or zeolite in the FCC catalyst component described herein is modified with a rare earth element. Suitable rare earth elements include, but are not limited to, ytterbium, gadolinium, cerium, lanthanum, or a mixture of two or more thereof. In one embodiment, the alumina particles and / or zeolite in the FCC catalyst component described herein is modified with cerium, for example, from about 0.1% to about 15% by weight, from about 3% to about 15% by weight, from about 5% to about 15% by weight, or from about 10% to about 15% by weight, based on the total weight of the FCC catalyst component. In one embodiment, the pure alumina particles and / or zeolite in the FCC catalyst component described herein is modified with lanthanum, for example, from about 0.1% to about 18% by weight, from about 1% to about 18% by weight, from about 5% to about 18% by weight, or from about 10% to about 17% by weight, of lanthanum oxide, based on the total weight of the FCC catalyst component. In one embodiment, the alumina particles and / or zeolites in the FCC catalyst components described herein are modified with lanthanum and cerium.

[0050] In certain embodiments, modifying the alumina matrix with lanthanum may beneficially promote bottoms conversion to light cycle oil (LCO) and contribute to the improved LCO yield exhibited by the FCC catalyst components contemplated herein.

[0051] In one embodiment, the pure alumina and / or zeolite in the FCC catalyst component described herein is modified with an alkaline earth element. Suitable alkaline earth elements include, but are not limited to, barium, strontium, calcium, magnesium, or a mixture of two or more thereof. In one embodiment, the alumina particles and / or zeolite in the FCC catalyst component described herein is modified with strontium.

[0052] In certain embodiments, the present disclosure relates to a method for preparing any of the FCC catalyst components having a Z / M ratio of less than about 1.3 described herein by in situ crystallization of a zeolite on alumina microspheres. In certain embodiments, the Z / M ratio can be less than about 1.2, less than about 1.1, less than about 1.0, less than about 0.9, less than about 0.8, or less than about 0.7. In certain embodiments, the Z / M ratio can be in the range of about 0.2, about 0.3, about 0.4, about 0.5, or about 0.6 to about 0.7, about 0.8, about 0.9, about 1.0, about 1.1, about 1.2, or about 1.3, or any subrange or single Z / M value therein. Any of the zeolites described herein above can be crystallized on any of the alumina microspheres described herein above.

[0053] In certain embodiments, the method of preparing any of the FCC catalyst components may further include preparing alumina-containing microspheres prior to crystallization. In one embodiment, preparing the alumina microspheres includes grinding an alumina precursor (e.g., precipitated alumina made from boehmite or pseudo-boehmite), producing a slurry of the ground alumina precursor and optional sodium silicate sol, and spray drying the slurried and ground alumina precursor and optional sodium silicate sol to reach an average particle size of about 40 μm to about 150 μm, about 60 μm to about 120 μm, or about 70 μm to about 90 μm.

[0054] In certain embodiments, the preparation of the alumina microspheres may further include modifying the alumina with one or more of a rare earth element, bismuth, or an alkaline earth element. In one embodiment, the preparation of the alumina microspheres includes modifying pure alumina with a rare earth element. Suitable rare earth elements include, but are not limited to, ytterbium, gadolinium, cerium, lanthanum, or a mixture of two or more thereof. In one embodiment, the preparation of the alumina microspheres includes modifying the alumina with cerium. Modifying the alumina with cerium may include impregnating the alumina with a cerium precursor, such as cerium nitrate or cerium acetate. In one embodiment, the preparation of the alumina microspheres includes modifying the alumina with lanthanum. Modifying the alumina with lanthanum may include impregnating the alumina with a lanthanum precursor, such as lanthanum nitrate or lanthanum acetate.

[0055] In certain embodiments, the preparation of the alumina microspheres may further include modifying the alumina with an alkaline earth element. Suitable alkaline earth elements include, but are not limited to, barium, strontium, calcium, magnesium, or a mixture of two or more thereof. In one embodiment, the preparation of the alumina microspheres includes modifying the alumina with strontium. Modifying the alumina with strontium may include impregnating the alumina with a strontium precursor, such as strontium nitrate or strontium acetate.

[0056] In certain embodiments, preparing the alumina microspheres can further include calcining the alumina microspheres (eg, at about 700° C. to about 900° C., or about 750° C. to about 850° C., or about 800° C.).

[0057] For the crystallization step in the method of preparing the FCC catalyst component described herein, any of the alumina-containing microspheres described herein can be mixed with an aluminum source, a silicon source, water, and optionally sodium hydroxide to obtain an alkaline slurry. Seeds (such as those described in U.S. Pat. No. 4,631,262, the teachings of which are incorporated by reference in their entirety) can be added to the slurry. The alkaline slurry can then be heated to a temperature and for a time sufficient to crystallize the desired weight percent of the zeolite to form zeolite microspheres. The phase composition of the zeolite (e.g., zeolite Y) can range from about 5 wt%, about 6 wt%, about 7 wt%, or about 8 wt%, to about 15 wt%, about 17 wt%, about 20 wt%, about 25 wt%, or about 30 wt%, based on the total weight of the FCC catalyst component, or any subrange or single phase composition therein.

[0058] Suitable sacrificial aluminum sources for zeolite crystallization include, but are not limited to, metakaolin, sodium aluminate, or combinations thereof.

[0059] In certain embodiments, the method for preparing the FCC catalyst component described herein also includes preparing sacrificial aluminum source particles. In one embodiment, the aluminum source particles are obtained from calcining kaolinite at a temperature and for a time sufficient to convert the kaolinite to metakaolin without forming spinel. In one embodiment, the aluminum source is metakaolin.

[0060] Kaolinite (and the resulting metakaolin) contains aluminum and silicon with an atomic ratio of Si / Al of 1.0, but metakaolin alone may provide insufficient silicon to crystallize certain zeolites with Si / Al ratios greater than 1.0. For example, zeolite Y has an atomic ratio of Si / Al of 2.5 and requires a second source of silicon in addition to metakaolin to promote the growth of zeolite Y.

[0061] Suitable sacrificial silicon sources for zeolite crystallization may include, but are not limited to, sodium silicate, quartz, silica gel, silica sol, sodium silicate sol, and combinations thereof. In one embodiment, the silicon source used includes sodium silicate sol (e.g., a mostly water-based solution containing sodium silicate, which may be made by dissolving solid sodium silicate in water). In one embodiment, the silicon source used includes silica gel. In one embodiment, the silicon source used includes quartz.

[0062] When using sodium silicate sol as a sacrificial silicon source for Y-zeolite crystallization, it can be added at once at the beginning of the zeolite crystallization or zeolite growth reaction. Other sacrificial silicon sources, such as, but not limited to, silica gel or quartz, can be used to provide more flexibility in adjusting the amount of sodium and silica present in the zeolite crystallization, since they do not introduce sodium into the zeolite crystallization reaction and the two components (sodium and silica) can be added separately. In contrast, sodium silicate (or sodium silicate sol) already contains sodium in it, and provides less flexibility in adjusting the amount of sodium and silica present during zeolite crystallization. This may pose some challenges or result in additional process steps, since the sodium to silica ratio in sodium silicate (or sodium silicate sol) is high, which may contribute to the rapid growth of the zeolite. The rapid growth of the zeolite may be less favorable, since it may adversely affect the hydrothermal stability of the crystallized zeolite and / or contribute to the growth of less favorable zeolite phases (such as GIS or GME zeolite structures).

[0063] After the crystallization step in the preparation method of the FCC catalyst component described herein, in certain embodiments, the method further comprises isolating or separating the zeolite microspheres from the alkaline slurry. The isolation or separation of the zeolite microspheres can be carried out by commonly used methods such as filtration. In certain embodiments, the zeolite microspheres can be washed or contacted with water or other suitable liquid to remove residual crystallization liquid.

[0064] In certain embodiments, the method of preparing the FCC catalyst component described herein further comprises ion exchanging a zeolite (e.g., ion exchanging a Y-zeolite) to reduce the sodium content in the FCC catalyst component and / or replace sodium ions with other more preferred ions. For example, in one embodiment, the Y-zeolite reduces the sodium content of the FCC catalyst component to less than about 0.7 wt.%, less than about 0.5 wt.%, or less than about 0.3 wt.%, based on the total weight of the FCC catalyst component. 2 The sodium content of the ion-exchanged solution is reduced to 0. The ion-exchange can be performed 1, 2, 3, 4, 5, 6 or as many times as necessary to reach the target sodium content.

[0065] In certain embodiments, the sodium ions can be replaced with other ions, for example by ion-exchanging with ammonium cations, rare earth metals, or combinations thereof, to obtain an FCC catalyst component comprising a zeolite modified with a more preferred cation.

[0066] In some embodiments, the method may further include mixing the zeolite microsphere material with an ammonium nitrate solution before or after contacting the zeolite in the sodium form prior to mixing with the ammonium nitrate solution. In some embodiments, mixing with the ammonium nitrate solution is carried out at acidic pH conditions. In some embodiments, mixing with the ammonium nitrate solution is carried out at a pH of about 3 to about 3.5. In some embodiments, mixing with the ammonium nitrate solution is carried out at a temperature above room temperature. In some embodiments, mixing with the ammonium nitrate solution is carried out at a temperature of at least about 80° C. to about 100° C., including increments therein. In certain embodiments, ion-exchanging the zeolite microsphere material with ammonium cations increases the sodium content of the zeolite microsphere material to about 1 wt. % Na, based on the total weight of the FCC catalyst component. 2 O to about 2% by weight of Na 2 Decreased to O.

[0067] In some embodiments, the ammonium-exchanged microsphere material is further ion-exchanged with a rare earth ion solution. In some embodiments, the rare earth ion is a nitrate of ytterbium, neodymium, samarium, gadolinium, cerium, lanthanum, or a mixture of any two or more such nitrates. In some embodiments, the rare earth ion is derived from a lanthanide or yttrium. In some embodiments, the microspheres are contacted with a solution of lanthanum nitrate or yttrium nitrate. In certain embodiments, the microspheres are contacted with a solution of lanthanum nitrate. Rare earth concentrations ranging from about 5% to about 18%, about 10% to about 17%, or about 10% to about 15% by weight based on the total weight of the FCC catalyst components are contemplated. In certain embodiments, the amount of rare earth added to the catalyst as rare earth oxide ranges from about 1% to about 5% by weight, or about 2% to about 3% by weight of rare earth oxide (REO) based on the total weight of the FCC catalyst components. In one embodiment, the FCC catalyst component comprises lanthana in a concentration ranging from about 5% to about 18% by weight, from about 10% to about 17% by weight, or from about 10% to about 15% by weight, based on the total weight of the FCC catalyst component.

[0068] The lanthana content of the catalyst material can be estimated by chemical analysis (e.g., ICP chemical analysis). For fresh (i.e., unsteamed) FCC catalyst materials disclosed herein, substantially all of the lanthana (i.e., 100% within experimental error) is found in the zeolitic material.

[0069] In certain embodiments, the method further comprises calcining the zeolite microspheres. The calcination may be carried out for at least about 2 hours. In certain embodiments, the calcination may be carried out at a temperature of about 500° C. to about 750° C. In certain embodiments, the calcination may be carried out in the presence of about 25% v / v steam.

[0070] In certain embodiments, after calcination, the FCC catalyst component may be subjected to an additional ammonium nitrate solution ion exchange to further reduce the sodium content in the FCC catalyst component.

[0071] In one or more embodiments, the ion exchange step is performed such that the resulting FCC catalyst component has less than about 0.2 wt. % Na, based on the total weight of the FCC catalyst component. 2 O (e.g., about 0.02% by weight Na 2 O ~ about 0.2% by weight Na 2 O).

[0072] After ion exchange, the microspheres may be calcined again (eg, at a temperature of about 500° C. to about 750° C.).

[0073] In certain embodiments, the methods of preparing an FCC catalyst component described herein further include steaming the FCC catalyst component. In some embodiments, the steaming is carried out at a temperature of at least about 700° C. (e.g., about 750° C. or about 800° C.). In some embodiments, the steaming is carried out for at least about 4 hours. In some embodiments, the steaming is carried out for about 1 hour to about 24 hours.

[0074] The crystallite size and distribution of zeolite materials in FCC catalysts varies widely depending on the manufacturing method, materials, etc. The FCC catalyst materials of this disclosure were analyzed for crystallite size using a scanning electron microscope (SEM).

[0075] The zeolite crystal size of the catalyst disclosed herein can also be characterized by SEM. The crystal size measured by SEM ranges from 1000 Å to 3000 Å. SEM measurements provide the number weight average crystal size.

[0076] SEM analysis of the zeolite catalyst materials disclosed herein also shows another distinct feature: the presence of isolated crystals with few or no intergrown crystals. Without wishing to be bound by theory, it is believed that isolated crystals grown on the matrix material allow greater access of the feedstock to the matrix surface than is the case for highly intergrown catalyst materials. The alumina matrix material promotes the cracking of larger molecules in the feedstock, and the increased available matrix surface area is believed to contribute to the lower coke / higher conversion of the catalyst materials disclosed herein.

[0077] How to use In certain embodiments, the present disclosure relates to a method of cracking a hydrocarbon feedstock by contacting the feedstock with any of the FCC catalyst components contemplated by the present disclosure (e.g., those comprising zeolite crystallized in situ on alumina particles and having a Z / M ratio of the deactivated catalyst of about 1.0 or less) or any of the FCC catalyst compositions described herein.

[0078] In certain embodiments, the method for cracking a hydrocarbon feedstock described herein results in improved bottoms upgrading performance. Forming the non-zeolitic matrix of the FCC catalyst component from alumina rather than the traditional clay matrix is ​​believed to improve bottoms conversion. Thus, in certain embodiments, the method described herein results in a bottoms yield that is lower than the bottoms yield produced by contacting a hydrocarbon feedstock with an FCC catalyst component that includes a non-zeolitic matrix that includes clay instead of at least a portion of the alumina (otherwise identical except for the non-zeolitic matrix material).

[0079] In certain embodiments, the methods for cracking a hydrocarbon feedstock described herein result in a reduced coke yield. It is believed that forming the non-zeolitic matrix of an FCC catalyst component from alumina particles rather than a traditional clay matrix results in less coke. Thus, in certain embodiments, the methods described herein result in a lower coke yield than that produced by contacting a hydrocarbon feedstock with an FCC catalyst component that includes a non-zeolitic matrix that includes clay instead of at least a portion of pure alumina (otherwise identical except for the non-zeolitic matrix material).

[0080] In certain embodiments, the methods of cracking a hydrocarbon feedstock described herein result in improved light cycle oil (LCO) yields. For example, LCO yields are a function of the Z / M ratio, and for a given matrix technology, it is believed that as Z / M decreases, the LCO yield increases. Thus, in certain embodiments, the methods described herein result in an LCO yield that is greater than the LCO yield that would result from contacting a hydrocarbon feedstock with an FCC catalyst component having a Z / M ratio of the steam deactivated catalyst of about 1.0 or greater (otherwise identical except for the Z / M ratio).

[0081] In certain embodiments, the methods of cracking a hydrocarbon feedstock described herein provide improved liquefied petroleum gas (LPG) yields. For example, a relatively large effective unit cell parameter is believed to provide increased LPG yields. As such, in certain embodiments, the methods described herein provide higher LPG yields than those provided by contacting a hydrocarbon feedstock with an FCC catalyst component having a unit cell size that is less than 24.3 Å (otherwise identical except for the unit cell size dimension). EXAMPLES

[0082] The following examples are provided to aid in the understanding of the present disclosure and should not be construed as specifically limiting the invention described and claimed herein. Such variations of the invention and modifications in formulations or minor modifications in experimental design, including the substitution of all equivalents now known or later developed that would be within the scope of those skilled in the art, should be considered to fall within the scope of the invention incorporated herein.

[0083] Example 1: In situ crystallization of Y-zeolite on rare earth doped gamma alumina A microspheres Y zeolite was crystallized in situ on the microspheres of mainly alumina. The alumina was rare earth doped gamma alumina A. 4 wt% rare earth doped gamma alumina A was ground to a D90 of about 5 μm. 94 parts of ground gamma alumina A in the form of a 40% solids slurry was mixed with 6 parts SiO in the form of a sodium silicate solution. 2 The mixture was spray dried to form microspheres having an average particle size of about 80 μm. The microspheres were calcined at 1500° F. for 2 hours.

[0084] The alumina microspheres were combined with sodium silicate solution, zeolite-Y seeds, water and sacrificial metakaolin microspheres. The metakaolin microspheres were prepared by calcining spray-dried kaolin clay microspheres to a temperature and for a time sufficient to convert the kaolin to metakaolin but insufficient to convert it to spinel. The mixture was added to a reactor and heated to a temperature of 190°F for crystallization. The crystallization temperature was maintained for 10-14 hours with stirring. The resulting zeolite microspheres were then filtered and washed to produce sodium ion type Y-zeolite FCC catalyst (NaY type).

[0085] The zeolite microspheres were then subjected to ion exchange to replace the sodium ions with lanthanum ions. The ion-exchanged microspheres were then steamed at 1450°F for 24 hours. The resulting catalyst was designated "Catalyst A." Characterization of certain properties of Catalyst A was performed at the NaY stage, after ion exchange, and after steam deactivation. The properties of Catalyst A are shown in Table 1 below.

[0086] Example 2: In situ crystallization of Y-zeolite on gamma alumina B Y zeolite was crystallized in situ on spray-dried microspheres using gamma alumina B without rare earth dopant. Gamma alumina B was ground to a D90 of about 5 μm. 94 parts of ground gamma alumina B in the form of a 40% solids slurry was mixed with 6 parts SiO in the form of a sodium silicate solution. 2 The mixture was spray dried to form microspheres having an average particle size of about 80 μm. The microspheres were calcined at 1500° F. for 2 hours.

[0087] The alumina microspheres were combined with sodium silicate solution, zeolite-Y seeds, water, caustic and sacrificial metakaolin microspheres. The metakaolin microspheres were prepared by calcining spray-dried kaolin clay microspheres to a temperature and for a time sufficient to convert the kaolin to metakaolin but insufficient to convert it to spinel. The mixture was added to a reactor and heated to a temperature of 190°F for crystallization. The crystallization temperature was maintained for 10-14 hours with stirring. The resulting zeolite microspheres were then filtered and washed to produce sodium ion type Y-zeolite FCC catalyst (NaY type).

[0088] The zeolite microspheres were then subjected to ion exchange to replace the sodium ions with lanthanum ions. The ion-exchanged microspheres were then steamed at 1450°F for 24 hours. The resulting catalyst was designated "Catalyst B." Characterization of certain properties of Catalyst B was performed at the NaY stage, after ion exchange, and after steam deactivation. The properties of Catalyst B are shown in Table 1 below.

[0089] Catalyst B was also scaled up using 15 Kg of Microspheres B in a 25 gallon crystallization reactor. The sample underwent the same ion exchange and steaming process. The properties of this sample are summarized in Table 2 below.

[0090] Example 3: In situ crystallization of Y-zeolite on alumina C and clay particles Y zeolite was crystallized in situ primarily on alumina microspheres. This alumina was Alumina C. Alumina C was ground to a D90 of about 5 μm. 83 parts of ground Alumina C in the form of a 40% solids slurry was mixed with 11 parts hydrous kaolin in the form of a 60% solids slurry and 6 parts SiO in the form of a sodium silicate solution. 2 The mixture was spray dried to form microspheres having an average particle size of about 80 μm. The microspheres were calcined at 1500° F. for 2 hours.

[0091] Alumina and clay microspheres were combined with sodium silicate solution, zeolite-Y seeds, water and caustic. The mixture was added to a reactor and heated to a temperature of 190°F for crystallization. The crystallization temperature was maintained for 10-14 hours with stirring. The resulting zeolite microspheres were then filtered and washed to produce sodium ion type Y-zeolite FCC catalyst (NaY type).

[0092] The zeolite microspheres were then subjected to ion exchange to replace the sodium ions with lanthanum ions. The ion-exchanged microspheres were then steamed at 1450°F for 24 hours. The resulting catalyst was designated "Catalyst C." Characterization of certain properties of Catalyst C was performed at the NaY stage, after ion exchange, and after steam deactivation. The properties of Catalyst C are shown in Table 1 below.

[0093] Catalyst C was also scaled up using 15 Kg of Microspheres C in a 25 gallon crystallization reactor. The sample underwent the same ion exchange and steaming process. The properties of this sample are summarized in Table 2 below.

[0094] Tables 2, 3 and Figure 1 contain data from the reference catalysts. The reference catalysts are commercially available. The reference microspheres were spray dried using 25% hydrous clay, 25% clay calcined at 2300°F and 50% alumina-A. The zeolite material was then crystallized in situ and ion-exchanged according to conventional methods.

[0095] Table 1 shows a comparison of the properties of example catalysts A, B and C. The surface area is m 2 / g, unit cell size (UCS) in Å, composition in wt.%. Table 2 shows a comparison of the properties of the scaled-up samples and the reference material, with the same units as in Table 1.

[0096] [Table 1]

[0097] [Table 2]

[0098] FIG. 1 shows performance data measured in a circulating riser unit (CRU) for scaled-up catalyst B, scaled-up catalyst C, and the reference material. As shown in FIG. 1, at a given coke yield, catalysts B and C convert more feed (bottoms) to products than the reference material. At a given bottoms conversion level, catalysts B and C produce less coke than the reference material. The CRU tests were performed after steaming. Catalyst B showed a 22% improvement in coke selectivity at constant bottoms conversion and a 20% improvement in bottoms upgrading at constant coke compared to the reference material. Catalyst C showed an 11% improvement in coke selectivity at constant bottoms conversion and an 8% improvement in bottoms upgrading at constant coke compared to the reference material.

[0099] Figure 2 shows SEM images of catalyst B and the reference material (scale bar is 500 nm). In catalyst B, the zeolite crystals are grown on the matrix material, and free matrix material between the zeolite crystals is clearly observed. In the reference catalyst, there is a high degree of crystal intergrowth, rather than the well-dispersed crystals of catalyst B. The crystals of catalyst B are also smaller than those of the reference material.

[0100] Table 3 shows the amount of various products produced in the fluid catalytic cracking process for catalyst B, catalyst C and the reference material. The tests were carried out at 80% gasoline conversion. Catalyst B improved LPG, gasoline yield, LCO (light cycle oil), LOC / HCO (light cycle oil / heavy cycle oil) ratio and coke selectivity compared to the reference catalyst.

[0101] [Table 3]

[0102] In the preceding description, numerous specific details are set forth, such as particular materials, dimensions, process parameters, etc., to provide a detailed understanding of the present invention. Particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments. The term "example" or "exemplary" is used herein to mean serving as an example, illustration, or illustration. Any aspect or design described herein as "example" or "exemplary" is not necessarily construed as preferred or advantageous over other aspects or designs. Rather, use of the word "example" or "exemplary" is intended to present concepts in a specific manner. As used in this application, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." That is, unless otherwise stated or clear from the context, "X includes A or B" is intended to mean any of the natural inclusive arrangements. That is, if X includes A; X includes B; or X includes both A and B, then "X includes A or B" is satisfied under any of the preceding examples. Throughout this specification, references to "an embodiment," "a particular embodiment," or "one embodiment" mean that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases "an embodiment," "a particular embodiment," or "one embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment.

[0103] The present disclosure has been described with respect to certain exemplary embodiments thereof. Accordingly, the specification and drawings are to be regarded in an illustrative rather than a restrictive sense. Various modifications of the disclosure in addition to those shown and described herein will become apparent to those skilled in the art and are intended to fall within the scope of the appended claims.

Claims

1. 1. A fluid catalytic cracking catalyst comprising an in situ crystallized zeolite material and a matrix material, wherein the deactivated catalyst has a ratio of zeolite surface area to matrix surface area (Z / M) of less than about 1 and a unit cell size of the deactivated catalyst of at least about 24.3 Å.

2. The catalyst of claim 1 , wherein the zeolite material further comprises a rare earth element.

3. 3. The catalyst of claim 2, wherein the rare earth element is present on the zeolite as a rare earth oxide in an amount of about 10% to 17% by weight.

4. The catalyst of claim 3 , wherein the rare earth element comprises lanthanum.

5. 5. The catalyst of claim 4, wherein substantially all of the lanthanum comprising the catalyst is in the zeolite material.

6. 10. The catalyst of claim 1, wherein the zeolitic material consists essentially of Y-zeolite.

7. 10. The catalyst of claim 1, wherein the zeolite material contains substantially isolated crystals and is substantially free of intergrown crystals.

8. 10. The catalyst of claim 1, wherein the zeolitic material is crystallized on particles comprising at least about 70% by weight pure alumina.

9. 9. The catalyst of claim 8, wherein the pure alumina comprises at least one of alumina A, alumina B, alumina C, or alumina D.

10. A fluid catalytic cracking catalyst comprising an in situ crystallized zeolite material and a matrix material, the fluid catalytic cracking catalyst having a zeolite content of less than about 30 wt. % without zeolite intergrowth.

11. The catalyst of claim 10, wherein the crystallite size measured by SEM is about 1000-3000 Å.

12. 1. A method for producing a fluid catalytic cracking catalyst comprising a zeolitic material, comprising: Preforming precursor microspheres comprising alumina together with less than 20% clay; crystallizing in situ zeolite on said preformed microspheres to less than about 30 weight percent; A method comprising:

13. The crystallization is mixing the preformed precursor microspheres, metakaolin-containing microspheres, sodium silicate solution, and zeolite seeds to form a slurry; heating the slurry to a temperature and for a time sufficient to crystallize the zeolite; 13. The method of claim 12, comprising:

14. 14. The method of claim 13, further comprising exchanging sodium cations in the zeolite material with other ions, the ion-exchanged product having a weight percent of sodium oxide of less than about 0.2%.

15. 14. The method of claim 13, further comprising deactivating the catalyst by steaming the catalyst at about 1350-1550°F for about 15-30 hours.

16. 16. The method of claim 15, wherein the ratio of zeolite surface area to matrix surface area of ​​the deactivated catalyst (post-steaming Z / M) is less than about 1 and the post-steaming unit cell size (SUCS) of the deactivated catalyst is at least about 24.3 Å.

17. 13. The method of claim 12, wherein the zeolitic material further comprises a rare earth element.

18. 18. The method of claim 17, wherein the rare earth element is present on the zeolite as a rare earth oxide in an amount of about 10% to 17% by weight.

19. 20. The method of claim 18, wherein the rare earth element comprises lanthanum.

20. 20. The method of claim 19, wherein substantially all of the lanthanum comprising the catalyst is in the zeolite material.

21. 13. The method of claim 12, wherein the zeolitic material consists essentially of Y-zeolite.

22. 13. The method of claim 12, wherein the zeolite material contains substantially discrete crystals and is substantially free of intergrown crystals.

23. 13. The method of claim 12, wherein the zeolitic material is crystallized on particles comprising at least about 70% by weight pure alumina.

24. 24. The method of claim 23, wherein the pure alumina comprises at least one of alumina A, alumina B, alumina C, or alumina D.

25. 10. A method for cracking a hydrocarbon feedstock comprising contacting said feedstock with the catalyst of claim 1.

26. 10. The catalyst of claim 1, which exhibits at least 5% lower coke yield compared to conventional catalysts at a constant bottoms conversion.

27. 10. The catalyst of claim 1, which exhibits at least 10% lower coke yield compared to conventional catalysts at a constant bottoms conversion.

28. 10. The catalyst of claim 1, which exhibits at least 15% lower coke yield compared to conventional catalysts at a constant bottoms conversion.

29. 10. The catalyst of claim 1, wherein the bottoms upgrade is increased by at least 5% compared to a conventional catalyst at a constant coke yield.

30. 10. The catalyst of claim 1, wherein the bottoms upgrade is increased by at least 10% compared to a conventional catalyst at a constant coke yield.

31. 10. The catalyst of claim 1, which when used in an FCC process performs with less than 5% residual bottoms at a constant coke yield of 6 wt.%.

32. 10. The catalyst of claim 1, which when used in an FCC process performs with less than 5.5% residual bottoms at a constant coke yield of 6 wt.%.

33. 10. The catalyst of claim 1, which when used in an FCC process performs with no more than 5% residual bottoms at a constant coke yield of 6 wt.%.

34. 10. The catalyst of claim 1, which when used in an FCC process performs with less than 6% coke yield at a constant bottoms residue of 5 wt.%.

35. 10. The catalyst of claim 1, which when used in an FCC process performs at a constant bottoms residue of 5 wt.% with a coke yield of less than 5.5%.

36. 10. The catalyst of claim 1, which when used in an FCC process performs at a constant bottoms residue of 5 wt.% with a coke yield of less than 5%.

37. 10. The catalyst of claim 1, which when used in an FCC process exhibits a cracking selectivity such that the gasoline yield is at least 56 at 80% gasoline conversion.

38. 10. The catalyst of claim 1, which when used in an FCC process exhibits a cracking selectivity such that the LCO yield at 80% gasoline conversion is at least 12.

7.

39. 10. The catalyst of claim 1, which when used in an FCC process exhibits a cracking selectivity such that the LCO / HCO ratio is at least 3 at 80% gasoline conversion.

40. 10. The catalyst of claim 1, which when used in an FCC process exhibits a cracking selectivity such that coke yield is less than 6.5 at 80% gasoline conversion.

41. 10. The catalyst of claim 1, which when used in an FCC process exhibits cracking selectivity such that coke formation is less than 6 at 80% gasoline conversion.

42. 10. The catalyst of claim 1, which when used in an FCC process exhibits a cracking selectivity such that coke yield at 80% gasoline conversion is less than 5.9.

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