Low Z / M FCC catalysts prepared by in situ crystallization of pure alumina particles

Abstract

Disclosed herein is a fluid catalytic cracking (FCC) catalyst component comprising a zeolite crystallized in situ on pure alumina particles, the FCC catalyst component having a ratio of zeolite surface area (ZSA) to matrix surface area (MSA) of less than about 1.3. Also disclosed herein is an FCC catalyst composition comprising the FCC catalyst component, a method for preparing the FCC catalyst composition, a method for preparing the FCC catalyst component, and a method for using the FCC catalyst composition or the FCC catalyst component.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 270,462, 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] Certain FCC markets are experiencing a shift toward emphasis on light cycle oil (LCO) and liquefied petroleum gas (LPG, e.g., LPG olefins), which are precursors to diesel fuel, rather than FCC gasoline.

[0004] FCC catalyst components can address this trend by designing them to reduce the zeolite surface area to matrix surface area (Z / M). Existing low Z / M FCC catalysts include non-alumina, non-zeolite matrix materials such as clays. Without being limited thereto, it is believed that FCC catalyst components having non-alumina, non-zeolite matrix materials such as clays may exhibit higher coke yields compared to those exhibited by FCC catalyst components having alumina matrix materials. Summary of the Invention [Problem to be solved by the invention]

[0005] There remains a need to develop FCC catalyst components that exhibit improved LCO and LPG yields while minimizing coke formation. [Means for solving the problem]

[0006] The present disclosure provides a fluid catalytic cracking (FCC) catalyst component comprising a zeolite crystallized in-situ on pure alumina particles, the FCC catalyst component having a zeolite surface area (ZSA) to matrix surface area (MSA) ratio of less than about 1.3.

[0007] 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 zeolite may have a unit cell size of about 24.20 Å to about 24.70 Å.

[0008] The pure alumina particles 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, chi-alumina, delta-alumina, theta-alumina, kappa-alumina, alpha-alumina, rare earth modified versions thereof, alkaline earth metal modified versions thereof, bismuth modified versions thereof, or mixtures of two or more thereof.

[0009] In one embodiment, the pure alumina particles may be produced by first grinding an alumina precursor (e.g., dry or wet grinding, such as, but not limited to, chop milling, hammer milling, or ball milling), slurrying the ground alumina precursor, and spray drying the ground and slurried alumina precursor to produce alumina particles having a suitable average particle size. In another embodiment, the pure alumina particles may be unground and have a suitable average particle size. Suitable particle sizes of the pure alumina particles, whether ground or unground, may range from about 40 μm to about 150 μm, about 60 μm to about 120 μm, or about 80 μm to about 100 μm.

[0010] In certain embodiments, the pure alumina particles and / or zeolites may be modified with non-aluminous components 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.

[0011] 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 pure alumina particles, and the FCC catalyst component has a ZSA to MSA ratio of less than about 1.3. The zeolite can be any of the zeolites described herein. The pure alumina particles can be any of the pure alumina particles described herein.

[0012] In certain embodiments, the crystallization comprises mixing the pure alumina particles 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 at least about 5 wt.% of the zeolite, based on the total weight of the FCC catalyst components, to form zeolite microspheres.

[0013] In certain embodiments, the method includes forming pure alumina particles 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 particles of appropriate size as described herein.

[0014] In certain embodiments, the method of preparing any of the FCC catalyst components further comprises modifying the zeolite microspheres (after crystallization) and / or the pure 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 or contacting the zeolite microspheres and / or the pure alumina particles with a precursor solution of the selected non-alumina component (e.g., cerium nitrate, cerium acetate, lanthanum nitrate, lanthanum acetate).

[0015] In a particular embodiment, the present disclosure provides an FCC catalyst composition comprising a first FCC catalyst component according to any of the embodiments described herein and a second component compositionally different from the first FCC catalyst component. The second component may comprise a second zeolite and a second non-zeolitic matrix. The second zeolite may be 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 combinations thereof. The second matrix may comprise one or more of clay, spinel, mullite, boehmite, alumina, silica, titania, zirconia, magnesia, kaolin, metakaolin, halloysite, kaolinite, dickite, nacrite, anauxite, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, silica doped alumina, gamma-alumina, 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 thereof.

[0016] In certain embodiments, the present disclosure provides a method of preparing an FCC catalyst composition by combining a first FCC catalyst component according to any of the embodiments described herein with a second component that is compositionally different from the first FCC catalyst component.

[0017] 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 light cycle oil (LCO) yield, improved liquefied petroleum gas (LPG) yield, and / or reduced coke yield.

[0018] 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.

[0019] 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.

[0020] 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).

[0021] 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.

[0022] "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 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.

[0023] 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.

[0024] As used herein, "particles" may be in the form of microspheres that 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 catalytic components described herein may be particles in the form of microspheres.

[0025] 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.

[0026] 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.

[0027] As used herein, the term "intergrown zeolite" refers to a zeolite formed by an in situ crystallization process.

[0028] 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 the precursor microspheres such that the zeolites are uniformly distributed on the matrix or non-zeolitic material.

[0029] As used herein, the term "incorporated catalyst" refers to a process in which the zeolite component is crystallized and then incorporated into microspheres in a separate step.

[0030] As used herein, the term "preformed microspheres" or "precursor microspheres" refers to microspheres obtained by spray drying and calcining non-zeolitic components.

[0031] As used herein, the term "zeolite-containing microspheres" refers to microspheres obtained by in situ crystallization of zeolite material on preformed precursor microspheres or microspheres in which the zeolite components are crystallized separately and then mixed with precursor microspheres.

[0032] 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. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0033] The present disclosure relates, in certain embodiments, to a fluid catalytic cracking (FCC) catalyst component comprising in situ crystallized zeolite on pure alumina particles, the FCC catalyst component having a ratio of zeolite surface area (ZSA) to matrix surface area (MSA), which may also be referred to herein as Z / M ratio, of less than about 1.3. In certain embodiments, the Z / M ratio may 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 may range from any of about 0.2, about 0.3, about 0.4, about 0.5, or about 0.6 to any of 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. In one embodiment, the Z / M ratio of the FCC catalyst component is in the range of about 0.5 to about 1.3. In one embodiment, the Z / M ratio of the FCC catalyst component ranges from about 0.6 to about 1.3. In one embodiment, the Z / M ratio of the FCC catalyst component ranges from about 0.7 to about 1.3. Without being intended to be limiting, it is believed that light cycle oil (LCO) yield is a function of the Z / M of the FCC catalyst component such that for a given matrix technology, LCO yield increases as the Z / M ratio decreases. LCO is a precursor to diesel fuel and is of increasing interest in the FCC market.

[0034] In certain embodiments, the FCC catalyst component has a post-steaming Z / M ratio (sZ / M ratio) after being subjected to steaming conditions (e.g., 100% steaming at 800° C., e.g., for about 1 to 24 hours) of 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.

[0035] 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.

[0036] 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 2 In 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 150 m 2 / g ~ approx. 250m 2 / g range.

[0037] 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 75 m 2 / g ~ approx. 125m 2 / g range.

[0038] 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 75 m 2 / g ~ approx. 125m2 / g range.

[0039] 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.

[0040] 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 24.30 Å to about 24.40 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.

[0041] 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.

[0042] 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.

[0043] The pure alumina particles 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, 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. In certain embodiments, the pure 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 versions thereof, alkaline earth metal modified versions thereof, or mixtures of two or more thereof. In one embodiment, the pure alumina particles include lanthanum doped gamma alumina derived from the calcination of boehmite and / or pseudo-boehmite and modified with a lanthanum precursor. In one embodiment, the pure alumina particles include calcined flash calcined gibbsite, which may include chialumina, aluminas similar to gamma alumina, or combinations thereof.

[0044] 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 650°C to about 900°C, about 700°C to about 900°C, about 750°C to about 850°C, or about 800°C.

[0045] 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.

[0046] There are several reasons why a clay matrix is ​​inferior to a pure alumina particle matrix in minimizing coke.

[0047] 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 particles, 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.

[0048] Another reason why clay matrices are inferior to pure alumina particle matrices in minimizing coke is believed to be related to, but not limited to, the iron content in the clay. Under FCC riser conditions, the Fe(III) / Fe(II) redox couple is activated and iron can catalyze the initiation of radical reactions in addition to acid-catalyzed decomposition. Radical coupling of large hydrocarbon fragments leads to large hydrocarbon intermediates that do not desorb and are reported to the regenerator, constituting coke. Pure alumina particles may be free or substantially free of iron in certain embodiments (i.e., having 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 less than 0 wt% iron based on the total weight of the pure alumina particles).

[0049] The pure alumina particles may have an average particle size of about 40 μm to about 150 μm, about 60 μm to about 120 μm, or about 80 μm to about 100 μm. In one embodiment, the particle size distribution of the pure alumina particles may be narrow, and the average particle size of the particles may range from about 70 μm to about 90 μm, or about 80 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), slurrying, and / or spray drying to arrive at an average particle size of about 40 μm to about 150 μm, about 60 μm to about 120 μm, about 80 μm to about 100 μm, or about 70 μm to about 90 μm. In another embodiment, the pure alumina particles may be wet milled and then spray dried to reach an average particle size of about 40 μm to about 150 μm, about 60 μm to about 120 μm, about 80 μm to about 100 μm, or about 70 μm to about 90 μm. In another embodiment, the pure alumina particles are unmilled and have an average particle size of about 40 μm to about 150 μm, about 60 μm to about 120 μm, about 80 μm to about 100 μm, or about 70 μm to about 90 μm. Pure alumina particles that are sufficiently coarse without milling, slurrying, and spray drying may be preferred in certain embodiments due to the elimination of costs that may be associated with additional process steps (such as milling, slurrying, and spray drying).

[0050] In some embodiments, the pure alumina particles are 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.

[0051] Any of the pure alumina particles 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, 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%, or about 15% 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 wt. % to about 12 wt. %, from about 1 wt. % to about 10 wt. %, from about 1 wt. % to about 5 wt. %, or from about 1 wt. % to about 3 wt. %, based on the total weight of the FCC catalyst component, or any subrange or single concentration value therein.

[0052] In one embodiment, the pure alumina particles and / or zeolite in the FCC catalyst component described herein are 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 pure alumina particles and / or zeolite in the FCC catalyst component described herein are modified with, for example, about 0.1% to about 15% by weight, about 3% to about 15% by weight, about 5% to about 15% by weight, or about 10% to about 15% by weight of cerium 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 are modified with, for example, about 0.1% to about 12% by weight, about 1% to about 10% by weight, about 1% to about 5% by weight, or about 1% to about 3% by weight of lanthanum based on the total weight of the FCC catalyst component. In one embodiment, the pure alumina particles and / or zeolites in the FCC catalyst components described herein are modified with lanthanum and cerium.

[0053] In certain embodiments, the modification of pure alumina particles with lanthanum can beneficially promote bottoms conversion to light cycle oil (LCO) and contribute to the improved LCO yield exhibited by the FCC catalyst components contemplated herein.

[0054] In one embodiment, the pure alumina particles and / or zeolite in the FCC catalyst component described herein are 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 pure alumina particles and / or zeolite in the FCC catalyst component described herein are modified with strontium.

[0055] 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 pure alumina particles. 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 pure alumina particles described herein above.

[0056] In certain embodiments, the FCC catalyst component exhibits a pore volume, as measured by mercury porosimetry using, for example, a mercury porosimeter such as a Micromeritics Autopore IV or a Micromeritics Autopore V, of at least about 0.15 mL / g, at least about 0.20 mL / g, at least about 0.25 mL / g, at least about 0.30 mL / g, at least about 0.35 mL / g, at least about 0.40 mL / g, at least about 0.45 mL / g, or any range defined therebetween (e.g., from about 0.15 mL / g to about 0.45 mL / g).

[0057] In certain embodiments, the method of preparing any of the FCC catalyst components may further include preparing pure alumina particles prior to crystallization. In one embodiment, the preparation of the pure alumina particles includes grinding an alumina precursor (e.g., precipitated alumina made from boehmite or pseudo-boehmite), preparing 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 80 μm to about 100 μm. In another embodiment, the preparation of the pure alumina particles may not involve grinding and spray drying steps, for example, if the pure alumina particles are already sufficiently coarse to have an average particle size of about 40 μm to about 150 μm, about 60 μm to about 120 μm, or about 80 μm to about 100 μm.

[0058] In certain embodiments, the preparation of the pure alumina particles may further include modifying the pure alumina particles with one or more of a rare earth element, bismuth, or an alkaline earth element. In one embodiment, the preparation of the pure alumina particles includes modifying the pure alumina particles 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 pure alumina particles includes modifying the pure alumina particles with cerium. Modifying the pure alumina particles with cerium may include impregnating the pure alumina particles with a cerium precursor, such as cerium nitrate or cerium acetate. In one embodiment, the preparation of the pure alumina particles includes modifying the pure alumina particles with lanthanum. Modifying the pure alumina particles with lanthanum may include impregnating the pure alumina particles with a lanthanum precursor, such as lanthanum nitrate or lanthanum acetate.

[0059] In certain embodiments, the preparation of the pure alumina particles may further include modifying the pure alumina particles 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 pure alumina particles includes modifying the pure alumina particles with strontium. Modifying the pure alumina particles with strontium may include impregnating the pure alumina particles with a strontium precursor, such as strontium nitrate or strontium acetate.

[0060] In certain embodiments, preparing the pure alumina particles can further include calcining the pure alumina particles (e.g., at about 700° C. to about 900° C., or about 750° C. to about 850° C., or about 800° C.). Calcining the pure alumina particles can occur before the particles are modified (e.g., impregnated) with a rare earth precursor, an alkaline earth precursor, or a bismuth precursor, after the particles are modified with any of the above, or both before and after the particles are modified with any of the above.

[0061] For the crystallization step in the method of preparing the FCC catalyst component described herein, any of the pure alumina particles 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 at least about 5 wt.% of the zeolite based on the total weight of the FCC catalyst component 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.%, or about 25 wt.% based on the total weight of the FCC catalyst component, or any subrange or single phase composition therein.

[0062] Suitable sacrificial aluminum sources for zeolite crystallization include, but are not limited to, metakaolin, sodium aluminate, or combinations thereof.

[0063] 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 period of time sufficient to convert the kaolinite to metakaolin without forming spinel. In one embodiment, the aluminum source is metakaolin.

[0064] When preparing sacrificial aluminum source particles by calcining kaolinite, in certain instances iron may be introduced into the FCC catalyst component. In certain embodiments, a high iron content may be less desirable as it may contribute to coke production. Thus, in certain embodiments, the sacrificial aluminum source is iron-free, such as, but not limited to, sodium aluminate. Although not intended to be limiting, when sodium aluminate was used as the sacrificial aluminum source for Y zeolite crystallization, it was observed that if sodium aluminate was added all at once, Y zeolite did not grow. If sodium aluminate was added slowly over time, Y zeolite grew. Thus, when sodium aluminate sol is used for zeolite crystallization, it is added slowly (thereby also mimicking the slow dissolution of metakaolin that occurs during the crystallization of Y zeolite using metakaolin as the sacrificial aluminum source). It is believed that the slow addition of sodium aluminate sol provides better control of the zeolite phase and its hydrothermal stability.

[0065] 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 a second source of silicon is required in addition to metakaolin to promote the growth of zeolite Y.

[0066] 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.

[0067] 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 GNE zeolite structures).

[0068] 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.

[0069] 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, a Y zeolite is ion exchanged to reduce 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.% Na2O based on the total weight of the FCC catalyst component. Ion exchange can be performed once, twice, three times, four times, five times, six times, or as many times as necessary to reach the target sodium content.

[0070] 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.

[0071] 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 reduces the sodium content of the zeolite microsphere material from about 1% Na2O by weight to about 2% Na2O by weight based on the total weight of the FCC catalyst component.

[0072] 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 0.1% to about 12%, about 1% to about 5%, or about 2% to about 3% 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%, 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 0.5% to about 7% by weight, from about 1% to about 6% by weight, or from about 2% to about 5% by weight, based on the total weight of the FCC catalyst component.

[0073] 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.

[0074] 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. In one or more embodiments, the ion exchange step is performed such that the resulting FCC catalyst component contains less than about 0.2 wt. % Na2O (e.g., about 0.02 wt. % Na2O to about 0.2 wt. % Na2O) based on the total weight of the FCC catalyst component. After ion exchange, the microspheres may be calcined again (e.g., at a temperature of about 500° C. to about 750° C.).

[0075] 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. In some embodiments, the final step is carried out in a rotary calciner. In some embodiments, the final step is carried out in a fluidized bed calciner.

[0076] Although the crystallization techniques described herein refer to in situ techniques in which the zeolite is crystallized on and / or in preformed pure alumina particles, FCC catalyst components may be prepared via incorporation techniques in which the zeolite is crystallized separately and then incorporated into the pure alumina particles in a separate step.

[0077] The zeolite may be incorporated into a binder comprising any of the pure alumina particles described herein. In some embodiments, a slurry containing the zeolite and a binder comprising any of the pure alumina particles described herein is prepared and spray dried to obtain FCC catalyst component microspheres having an average particle size ranging from about 40 μm to about 150 μm, from about 60 μm to about 120 μm, or from about 80 μm to about 100 μm.

[0078] The crystal size of the zeolite material in the FCC catalyst varies greatly depending on the manufacturing method, materials, etc. The FCC catalyst materials of the present disclosure were analyzed for crystal size using two methods: X-ray diffraction (XRD) and scanning electron microscope (SEM) analysis.

[0079] The crystallite size and anisotropy measured by XRD can be expressed by two equations for the isotropic and anisotropic sizes, where the isotropic and anisotropic size parameters describe the crystalline properties. The average isotropic size S i is given by the following formula:

number

number

[0080] The XRD isotropic crystal size of the FCC catalyst components of the present disclosure can be from about 300 Å to about 550 Å. In some embodiments, the XRD isotropic crystal size can be from about 350 Å to about 450 Å. The XRD anisotropic parameter p of the fresh (e.g., before steaming) catalyst can be amay have a magnitude of about 3.5 to about 5.

[0081] An interesting feature of the FCC catalyst components disclosed herein is the shift in crystallite size upon steam deactivation. Experimental XRD evidence indicates that the isotropic crystallite size does not change significantly (i.e., within experimental error) upon steaming. However, the catalysts disclosed herein change shape upon deactivation, and the steamed catalysts exhibit anisotropic parameters p within zero experimental error. a Conventional catalysts do not exhibit this behavior upon steam treatment.

[0082] In certain embodiments, the XRD anisotropy parameter p of the steam-treated FCC catalyst component a is less than about 1.0, less than about 0.9, less than about 0.8, less than about 0.7, less than about 0.6, or less than about 0.5.

[0083] As used herein, strain (S, in %) is calculated according to the following formula:

number

number

number

[0084] FCC catalyst composition In certain embodiments, the present disclosure relates to an FCC catalyst composition comprising any of the FCC catalyst components contemplated by the present disclosure (e.g., comprising a zeolite crystallized in situ on pure alumina particles and having a Z / M ratio of about 1.3 or less) and a second component compositionally distinct from the FCC catalyst component. In certain embodiments, the second component comprises a second zeolite and a second non-zeolitic matrix.

[0085] The second zeolite may be selected from zeolites having the structure BEA, MSE, -SVR, FAU, MOR, CON, SOF, MFI, IMF, FER, MWW, MTT, TON, EUO, MRE, NAT, CHA, EMT, or combinations thereof.

[0086] In certain embodiments, the second zeolite is (1) a large pore zeolite (e.g., having a pore opening of greater than about 7 Angstroms), such as USY, REY, silicoaluminophosphate SAPO-5, SAPO-37, SAPO-40, MCM-9, metalloaluminophosphate MAPO-36, aluminophosphate VPI-5, or mesoporous crystalline material MCM-41; REUSY, zeolite Z, zeolite Y, dealuminated zeolite Y, silica-reinforced dealuminated zeolite Y, zeolite beta, ZSM-3, ZSM-4. , ZSM-18, ZSM-20, and EMT, (2) medium pore zeolites (e.g., those having pore openings of about 4 Angstroms to about 7 Angstroms), such as ZSM-5, MCM-68, ZSM-11, ZSM-5, ZSM-11 intermediate, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-57, silicoaluminophosphate SAPO-31, and (3) small pore zeolites (e.g., those having pore openings less than about 4 Angstroms), such as erionite and ZSM-34.

[0087] In certain embodiments, the second zeolite can include zeolite A, zeolite B, zeolite F, zeolite H, zeolite KG, zeolite L, zeolite M, zeolite Q, zeolite R, zeolite T, mordenite, erionite, offretite, ferrierite, chabazite, clinoptilolite, gmelinite, phillipsite, and faujasite.

[0088] Hydrothermally and / or chemically modified forms of many of the components listed above may also be suitable as the second component in the FCC catalyst compositions contemplated herein.

[0089] In certain embodiments, the second non-zeolitic matrix in the second component may include one or more of clay, spinel, mullite, boehmite, alumina, silica, titania, zirconia, magnesia, kaolin, metakaolin, halloysite, kaolinite, dickite, nacrite, anauxite, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, silica-doped alumina, gamma-alumina, 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 thereof.

[0090] In certain embodiments, the second component may further comprise a rare earth element, an alkaline earth element, bismuth, or a mixture of two or more such elements as part of the second zeolite and / or as part of the second non-zeolitic matrix. Suitable rare earth elements include ytterbium, gadolinium, cerium, lanthanum, praseodymium, neodymium, or a mixture of two or more thereof. Suitable alkaline earth elements include barium, calcium, strontium, magnesium, or a mixture of two or more thereof.

[0091] Any of the FCC catalyst components contemplated by the present disclosure may be included in the FCC catalyst composition in an amount ranging from any of 1 weight percent, about 5 weight percent, about 10 weight percent, about 15 weight percent, about 20 weight percent, or about 25 weight percent to any of about 50 weight percent, about 60 weight percent, about 70 weight percent, about 80 weight percent, about 90 weight percent, or about 95 weight percent, or any subrange or single value therein, based on the total weight of the FCC catalyst composition.

[0092] Any second component described herein may be included in the FCC catalyst composition in an amount ranging from any of 5 weight percent, about 10 weight percent, about 20 weight percent, about 30 weight percent, about 40 weight percent, or about 50 weight percent to any of about 75 weight percent, about 80 weight percent, about 85 weight percent, about 90 weight percent, about 95 weight percent, or about 99 weight percent based on the total weight of the FCC catalyst composition, or any subrange or single value therein.

[0093] An FCC catalyst composition can be formed by combining, such as by blending or mixing (e.g., physical mixing), any of the FCC catalyst components contemplated by this disclosure with any of the second components described herein.

[0094] 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., comprising in situ crystallized zeolite on pure alumina particles and having a Z / M ratio of about 1.3 or less) or any of the FCC catalyst compositions described herein.

[0095] In certain embodiments, the methods of cracking a hydrocarbon feedstock described herein result in improved light cycle oil (LCO) yields. For example, it is believed that LCO yields are a function of Z / M ratio, and for a given matrix technology, as Z / M decreases, LCO yields increase. Thus, in certain embodiments, the methods described herein result in LCO yields that are greater than the LCO yields that would result from contacting a hydrocarbon feedstock with an FCC catalyst component having a Z / M ratio of about 1.3 or greater (otherwise identical except for the Z / M ratio).

[0096] 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 24.50 Å (otherwise identical except for the unit cell size dimension).

[0097] 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 pure 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 comprising a non-zeolitic matrix that includes clay in place of at least a portion of the pure alumina particles (otherwise identical except for the non-zeolitic matrix material). EXAMPLES

[0098] 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.

[0099] Example 1: In situ crystallization of Y-zeolite on pure lanthanum-doped gamma-alumina particles The Y zeolite was crystallized in situ on previously spray-dried pure alumina particles, which were lanthanum-doped gamma alumina. The lanthanum-doped gamma alumina is a precipitated alumina made from pseudoboehmite and contained about 4 wt. % La2O3 based on the total weight of the lanthanum-doped gamma alumina. These pure alumina particles were screened to greater than 325 mesh (or 44 μm).

[0100] Coarse pure alumina particles having a particle size of 44 μm or greater were combined with seeds, sodium silicate, sacrificial iron-containing metakaolin microspheres (made by calcining kaolin clay to a temperature sufficient to convert kaolinite to metakaolin but at a calcination level low enough that no spinel was produced), caustic, and water to form three alkaline slurries. The alkaline slurries were heated at temperatures between about 82°C and 99°C for about 16-19 hours, which was sufficient to crystallize Y zeolite in situ on the coarse pure lanthanum-doped gamma alumina particles to form zeolite microspheres.

[0101] The zeolite microspheres were isolated from the alkaline slurry, washed, calcined and characterized. The properties of the resulting zeolite microspheres are summarized in Table 1 below.

[0102] [Table 1]

[0103] Example 2 Coarse gibbsite consisting of aggregates of hexagonal columnar gibbsite crystals with an average grain size of about 90 μm was flash-sintered. The flash-sintered gibbsite particles were calcined in a rotary kiln to a surface area of ​​about 100 m. 2 The particles were calcined to 10 ... As expected, Y zeolite grew in both fractions. On a mass basis, the majority of the zeolite grown was grown in the calcined crude flash calcined gibbsite fraction. Once the catalyst was treated and steamed, physical properties were measured. Most physical properties changed normally, except for the zeolite stability. After steam deactivation, nearly all of the Y zeolite in the catalyst was amorphized. This amorphization correlated with a low pore volume, and these particles did not have even the smallest acceptable pore volume.

[0104] The calcined crude flash-sintered gibbsite was milled to a 4 μm d using Premier Mill, monoclinic zirconia grinding media. 90 The microspheres were milled to 0.001 mm and spray dried with 6% sodium silicate (modulus 3.22). The resulting microspheres contained 91.4 wt. % alumina VF, 6.56 wt. % silica VF, and 2.18 wt. % Na2O VF. The resulting particles had a diameter of about 95 μm. 50 , about 140m 2The particles had a surface area of ​​1000 nm / g and a pore volume of about 0.42 ml / g (measured by Hg intrusion). The pore volume was about twice that of the parent FCA-90 particles. The macropore volume of the spray-dried particles can be larger than the total pore volume of the parent. These were crystallized using standard in situ FCC procedures at 88°C using separate metakaolin particles, sodium silicate, caustic, seeds, and water. Consistently, the yield was about 200% of the theoretical yield. An excessively high yield of Y zeolite would result in a higher Z / M ratio than intended. Surprisingly, the crystallization proceeded well if the separate metakaolin particles were omitted. Using only sodium silicate, caustic, seeds, and water, we were successful in obtaining a crystallized material with a useful Y zeolite content at 88°C. It is believed that prior to this application, Y zeolite had never been crystallized in situ without the use of calcined kaolin clay. This method repeatedly produced catalysts with usefully low Z / M. After ion exchange (with ammonium nitrate and enough lanthanum nitrate to obtain 1 wt. % La2O3 material), calcination, additional ammonium nitrate exchange, and a second calcination, which is a typical in situ process for converting NaY zeolite into fresh FCC catalyst, Z / M=0.9 (ZSA=94 m 2 A Z / M of 0.55 / g or equivalently 14 wt% Y zeolite and a total pore volume of 0.31 ml / g were achieved. After steaming (788°C, 100% steaming, 24 hours), the Z / M is reduced to 0.55 and the unit cell size is 24.351. The zeolite surface area stability from NaY was an acceptable 38%. This catalyst was tested in a fixed fluidized bed "ACE" reactor against a control catalyst with Z / M=0.38 and a unit cell size of 24.348 after steaming. The catalyst made without the calcined kaolin clay gave about 26% lower bottoms, 15% higher LCO / bottoms ratio, 24% higher propylene, about 18% higher C4 olefins, and equivalent gasoline and equivalent dry gas at constant coke versus the control catalyst.

[0105] The Y zeolite in the steamed catalyst was characterized by X-ray diffraction using the Rietveld method. The Rietveld analysis was performed using the GSAS described in A. C. Larson and R. B. Von Dreele, General Structure Analysis System (GSAS), Los Alamos National Laboratory Report LAUR 86-748 (2004). The characterization of the Y zeolite is most interesting in comparison with an in situ clay reference catalyst. The clay reference catalyst was prepared according to the method described in U.S. Pat. No. 6,656,347. SEM analysis shows a typical size of Y zeolite of about 2000 nm. In the NaY form, the Rietveld Y zeolite crystallite size was found to be about 1800 Å with a strain of about 0.17%. The ion exchange and calcination procedures involve ultrastabilization, a process shown by Beyerlein et al. (see Topics in Catalysis, vol 4, 27-42, 1997 and Studies in Surface Science and Catalysis, vol 134, 3-40, 2001) to result in the destruction of Y zeolite crystals and the formation of new internal grain boundaries where mesopores and alumina membranes (formed from alumina originally contained in the Y zeolite but liberated by dealuminization) form. Not surprisingly, this clay reference catalyst technique reduces the crystallite size (the size of the coherent diffraction domains). The fresh catalyst of this comparative material, after ion exchange with ammonium and lanthanum cations, calcination, ion exchange with ammonium ions, and calcination, has a Y zeolite isotropic size of about 690 Å and a strain of 0.62%. The steam-treated catalyst has the same Y zeolite isotropic size of about 665 Å and a strain of 0.37% as the fresh catalyst.

[0106] Catalysts made without clay during crystallization had fairly small crystallite sizes of about 467 Å for NaY, 368 Å after workup (ion exchange, calcination, ion exchange and calcination), and 316 Å after steaming. No distortion was detectable at any stage, and the best estimate was zero distortion. In zeolites, crystallite size and distortion have not previously been thought to be related. Without being bound by theory, distortion is thought to be an assessment of the defect density of the zeolite. Presumably, variations in the number of framework aluminum atoms in the unit cell across the crystallites, as well as other defects, can lead to distortion. If the crystallite size is relatively large, defects can occur within the crystallite. However, as the crystallite size decreases, these defects tend to collect on the crystallite surface, i.e., grain boundaries and outer surfaces, and to coalesce in some form. Thus, relatively small crystallites help to eliminate or reduce distortion.

[0107] The catalyst described in this example produces much lower bottoms at a given coke, higher LCO / bottoms and more LPG olefins than currently available catalysts. Without being bound by theory, it is believed that the reasons for this include the very small crystallite size of the Y zeolite in the experimental material and the very low level of distortion. The absence of an alumina matrix and a highly acidic clay matrix results in low coke selectivity, allowing for improved yields at a given coke. The unprecedented low Z / M for an in situ FCC catalyst in an alumina matrix allows for a desirably high LCO / bottoms. An unprecedented crystallization procedure without the use of calcined clay allows for the production of this low coke, high LCO / bottoms catalyst using an affordable alumina matrix. Calcined flash calcined gibbsite is a particularly economical way to produce an active matrix for FCC cracking catalysts.

[0108] For ease of explanation, embodiments of the methods of the present disclosure are depicted and described as a series of acts. However, acts in accordance with the present disclosure may occur in various orders and / or simultaneously and with other acts not shown and described herein. Moreover, not all illustrated acts may be required to implement a methodology in accordance with the disclosed subject matter. In addition, those skilled in the art will understand and appreciate that a methodology may alternatively be represented as a series of interrelated states via a state diagram or events.

[0109] In the preceding description, numerous specific details are set forth, such as specific 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.

[0110] The present disclosure has been described with respect to certain exemplary embodiments thereof. Accordingly, the specification is to be regarded in an illustrative rather than a restrictive sense. Various modifications of the present 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. A fluid catalytic cracking (FCC) catalyst component comprising a zeolite crystallized in situ on pure alumina particles, the component having a zeolite surface area (ZSA) to matrix surface area (MSA) ratio of less than about 1.

3.

2. 2. The FCC catalyst component of claim 1, wherein the pure alumina particles 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, chi-alumina, delta-alumina, theta-alumina, kappa-alumina, alpha-alumina, rare earth-modified versions thereof, alkaline earth metal-modified versions thereof, bismuth-modified versions thereof, or mixtures of two or more thereof.

3. 10. The FCC catalyst component of claim 1, wherein the pure alumina particles are unground.

4. The pure alumina particles have an average particle size of about 40 μm to about 150 μm, about 60 μm to about 120 μm, or about 80 μm to about 100 μm, and the pure alumina particles grinding an alumina precursor; preparing a slurry from the alumina precursor; spray drying the slurried alumina precursor to arrive at pure alumina particles having said average particle size; 10. The FCC catalyst component of claim 1 prepared by:

5. 2. The FCC catalyst component of claim 1, wherein the zeolite is selected from zeolites having the structure BEA, MSE, -SVR, FAU, MOR, CON, SOF, MFI, IMF, FER, MWW, MTT, TON, EUO, MRE, NAT, CHA, EMT, or a mixture of two or more thereof.

6. 2. The FCC catalyst component of claim 1, wherein 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 a mixture of two or more thereof.

7. 2. The FCC catalyst component of claim 1, wherein the zeolite is a Y-zeolite.

8. 8. The FCC catalyst component of claim 7, wherein the Y-zeolite is present at less than about 20 wt. %.

9. 8. The FCC catalyst component of claim 7, wherein the Y-zeolite phase composition is in the range of about 5 wt%, about 6 wt%, about 7 wt%, or about 8 wt%, based on the total weight of the FCC catalyst component, to about 15 wt%, about 17 wt%, about 20 wt%, about 25 wt%, or any subrange or single phase composition therein.

10. 7. The FCC catalyst component of claim 6, wherein the zeolite has a unit cell size of about 24.50 Å to about 24.80 Å.

11. 7. The FCC catalyst component of claim 6, wherein the zeolite has a unit cell size of about 24.40 Å or less.

12. 10. The FCC catalyst component of claim 1, wherein the pure alumina particles have an average particle size of about 40 μm to about 150 μm, about 60 μm to about 120 μm, or about 80 μm to about 100 μm.

13. 10. The FCC catalyst component of claim 1, wherein the pure alumina particles are modified with a non-alumina component selected from rare earth elements, bismuth, alkaline earth elements, or a mixture of two or more thereof.

14. 10. The FCC catalyst component of claim 1, wherein the pure alumina particles are modified with a rare earth element.

15. 15. The FCC catalyst component of claim 14, wherein the rare earth element comprises ytterbium, gadolinium, cerium, lanthanum, or a mixture of two or more thereof.

16. 15. The FCC catalyst component of claim 14, wherein the rare earth element comprises cerium.

17. 15. The FCC catalyst component of claim 14, wherein the rare earth element comprises lanthanum.

18. 10. The FCC catalyst component of claim 1, wherein the pure alumina particles are modified with an alkaline earth element.

19. 20. The FCC catalyst component of claim 18, wherein the alkaline earth element comprises barium, strontium, calcium, magnesium, or a mixture of two or more thereof.

20. 10. The FCC catalyst component of claim 1, wherein the pore volume of the FCC catalyst component is at least about 0.15 mL / g as measured by mercury porosimetry.

21. 10. The FCC catalyst component of claim 1, wherein the pore volume of the FCC catalyst component is from about 0.15 mL / g to about 0.45 mL / g as measured by mercury porosimetry.

22. 10. The FCC catalyst component of claim 1, wherein the zeolite has an isotropic crystal size of from about 300 Å to about 550 Å.

23. 2. The FCC catalyst component of claim 1, wherein the isotropic size of the zeolite in the deactivated form of the FCC catalyst component is substantially similar to the isotropic size of the zeolite before deactivation, and the XRD anisotropy parameter of the deactivated catalyst is less than about 1.

0.

24. 10. The FCC catalyst component of claim 1, wherein the zeolite has a crystallographic distortion of less than about 0.25% as determined from LY parameters of a GSAS Rietveld refinement of X-ray diffraction data.

25. 1. A method for preparing a fluid catalytic cracking (FCC) catalyst component, comprising in situ crystallizing a zeolite on pure alumina particles, wherein the FCC catalyst component has a zeolite surface area (ZSA) to matrix surface area (MSA) ratio of less than about 1.

3.

26. 26. The method of claim 25, wherein the pure alumina particles 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, chi-alumina, delta-alumina, theta-alumina, kappa-alumina, alpha-alumina, rare earth modified versions thereof, alkaline earth metal modified versions thereof, bismuth modified versions thereof, or mixtures of two or more thereof.

27. 26. The method of claim 25, wherein the pure alumina particles are not crushed prior to the crystallization.

28. The method further includes preparing pure alumina particles, the preparing comprising: grinding an alumina precursor; preparing a slurry from the alumina precursor; spray drying the slurried alumina precursor to arrive at pure alumina particles having an average particle size of about 40 μm to about 150 μm, about 60 μm to about 120 μm, or about 80 μm to about 100 μm; 26. The method of claim 25, comprising:

29. 30. The method of claim 28, wherein the slurry further comprises a sodium silicate sol.

30. 26. The method of claim 25, wherein the zeolite is selected from zeolites having the structure BEA, MSE, -SVR, FAU, MOR, CON, SOF, MFI, IMF, FER, MWW, MTT, TON, EUO, MRE, NAT, CHA, EMT, or a mixture of two or more thereof.

31. 26. The method of claim 25, wherein 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 a mixture of two or more thereof.

32. 26. The method of claim 25, wherein the zeolite is a Y-zeolite.

33. 33. The method of claim 32, wherein the zeolite has a unit cell parameter of about 24.20 Å to about 24.70 Å or about 24.30 Å to about 24.40 Å.

34. 30. The method of claim 28, wherein the pure alumina particles have an average particle size of about 40 μm to about 150 μm, about 60 μm to about 120 μm, or about 80 μm to about 100 μm.

35. Crystallization is mixing the pure alumina particles with an aluminum source, a silicon source, optionally sodium hydroxide, and water to obtain an alkaline slurry; heating the alkaline slurry to a temperature and for a time sufficient to crystallize at least about 5 wt. % of the zeolite, based on the total weight of the FCC catalyst component, to form zeolite microspheres; 29. The method of claim 28, comprising:

36. 36. The method of claim 35, wherein the aluminum source comprises metakaolin, sodium aluminate, or a combination thereof.

37. 36. The method of claim 35, wherein the silicon source comprises sodium silicate, quartz, silica gel, silica sol, sodium silicate sol, and combinations thereof.

38. 36. The method of claim 35, wherein the aluminum source comprises metakaolin obtained from calcining kaolinite at a temperature and for a period of time sufficient to convert the kaolinite to metakaolin without forming spinel.

39. 36. The method of claim 35, further comprising separating the zeolite microspheres from the alkaline slurry.

40. 36. The method of claim 35, further comprising calcining the zeolite microspheres.

41. 36. The method of claim 35, further comprising modifying the zeolite microspheres or the pure alumina particles with a non-alumina component, wherein the non-alumina component is selected from rare earth elements, bismuth, alkaline earth elements, or a mixture of two or more thereof.

42. 42. The method of claim 41, wherein the non-alumina component comprises a rare earth element.

43. 43. The method of claim 42, wherein the rare earth element comprises ytterbium, gadolinium, cerium, lanthanum, or a mixture of two or more thereof.

44. 43. The method of claim 42, wherein the rare earth element comprises cerium.

45. 45. The method of claim 44, wherein modifying the zeolite microspheres or the pure alumina particles with cerium comprises impregnating the zeolite microspheres or the pure alumina particles with a cerium precursor selected from cerium nitrate or cerium acetate.

46. 43. The method of claim 42, wherein the rare earth element comprises lanthanum.

47. 47. The method of claim 46, wherein modifying the zeolite microspheres or the pure alumina particles with lanthanum comprises impregnating the zeolite microspheres or the pure alumina particles with a lanthanum precursor selected from lanthanum nitrate or lanthanum acetate.

48. 42. The method of claim 41, wherein the non-alumina component comprises an alkaline earth element.

49. 49. The method of claim 48, wherein the alkaline earth element comprises barium, strontium, calcium, magnesium, or a mixture of two or more thereof.

50. 49. The method of claim 48, wherein the alkaline earth element comprises strontium.

51. A first FCC catalyst component, the FCC catalyst component being the FCC catalyst component of claim 1 or prepared according to the method of claim 25; a second component compositionally different from the first FCC catalyst component; 1. A fluid catalytic cracking (FCC) catalyst composition comprising:

52. 52. The FCC catalyst composition of claim 51, wherein the second component comprises a second zeolite and a second non-zeolitic matrix.

53. 53. The FCC catalyst composition of claim 52, wherein the second zeolite is selected from zeolites having the structure BEA, MSE, -SVR, FAU, MOR, CON, SOF, MFI, IMF, FER, MWW, MTT, TON, EUO, MRE, NAT, CHA, EMT, or combinations thereof.

54. 53. The FCC catalyst composition of claim 52, wherein the second non-zeolitic matrix comprises one or more of clay, spinel, mullite, boehmite, alumina, silica, titania, zirconia, magnesia, kaolin, metakaolin, halloysite, kaolinite, dickite, nacrite, anauxite, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, silica-doped alumina, gamma-alumina, chi-alumina, delta-alumina, theta-alumina, kappa-alumina, alpha-alumina, rare earth modified versions thereof, alkaline earth metal modified versions thereof, bismuth modified versions thereof, or mixtures thereof.

55. A method for preparing the FCC catalyst composition of claim 51, comprising combining the first FCC catalyst component with the second component.

56. 52. A method for cracking a hydrocarbon feedstock, comprising contacting the feedstock with an FCC catalyst component according to claim 1, or an FCC catalyst component prepared by the method of claim 26, or an FCC catalyst composition according to claim 51, or an FCC catalyst composition prepared by the method of claim 55.

57. 1. A method for cracking a hydrocarbon feedstock, comprising contacting the feedstock with an FCC catalyst component comprising in situ crystallized Y zeolite on pure alumina particles, the FCC catalyst component having a zeolite surface area (ZSA) to matrix surface area (MSA) ratio of less than about 1.

3.

58. 58. The method of claim 57, wherein the method results in a light cycle oil (LCO) yield greater than the LCO yield obtained from contacting the feed with an FCC catalyst component having a ZSA / MSA ratio of about 1.3 or greater.

59. 58. The method of claim 57, wherein the Y-zeolite has a unit cell size of about 24.50 Å to about 24.80 Å.

60. 60. The method of claim 59, wherein the method results in a liquefied petroleum gas (LPG) yield greater than the LPG yield obtained from contacting the feedstock with an FCC catalyst component having a zeolite having a unit cell size of less than 24.50 Å.

61. 60. The method of claim 59, wherein the method results in a coke yield that is lower than the coke yield obtained from contacting the feedstock with an FCC catalyst component comprising a non-zeolitic matrix that comprises clay in place of at least a portion of the pure alumina particles.

62. A method for preparing a fluid catalytic cracking (FCC) catalyst comprising in situ crystallizing a zeolite on alumina particles in the absence of clay.

63. 63. The method of claim 62, wherein the FCC catalyst has a zeolite surface area (ZSA) to matrix surface area (MSA) ratio of less than about 1.

0.

64. 63. The method of claim 62, wherein the pore volume of the FCC catalyst is from about 0.15 mL / g to about 0.45 mL / g as measured by mercury porosimetry.

65. 63. The method of claim 62, wherein the alumina particles comprise flash-calcined gibbsite.

66. 63. The method of claim 62, wherein the zeolite has an isotropic crystal size of about 250 Å to about 500 Å.

67. 63. The method of claim 62, wherein the crystallographic distortion of the zeolite is less than about 0.25% as determined from the LY parameters of a GSAS Rietveld refinement of X-ray diffraction data.

68. 63. The method of claim 62, wherein the zeolite has a unit cell size of about 24.20 Å to about 24.70 Å.