WO2023212011A1

WO2023212011A1 - Method for new fcc catalyst formulations using pre-milling techniques

Info

Publication number: WO2023212011A1
Application number: PCT/US2023/019918
Authority: WO
Inventors: Wathudura Indika Namal DE SILVA; William T. OWENS; Charles F. KEWESHAN; Gary M. Smith
Original assignee: BASF Corp
Current assignee: BASF Corp
Priority date: 2022-04-26
Filing date: 2023-04-26
Publication date: 2023-11-02
Anticipated expiration: 2024-10-26

Abstract

A microspherical fluid catalytic cracking (FCC) catalyst that passivates nickel during catalytic cracking of heavy hydrocarbon feed stocks, reducing contaminant coke and hydrogen yields is provided. The microspherical fluid catalytic cracking catalyst includes a matrix and a zeolite, wherein the catalyst has a high fraction of porosity in a radius range of about 150 A to about 1100 A. The high fraction of porosity is created by the method of prepanng the microspherical FCC catalyst with wet milling a preformed microsphere.

Description

METHOD FOR NEW FCC CATALYST FORMULATIONS USING PREMILLING TECHNIQUES

CROSS REFERENCE TO RELATED APPLICATION(S)

[0001] The present application claims priority to U.S. Provisional Patent No. 63/334,789 filed on April 26, 2022. The entire contents of which are incorporated herein in its entirety.

TECHNICAL FIELD

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

BACKGROUND

[0003] Catalytic cracking is a petroleum refining process that is applied commercially on a very large scale. Catalytic cracking, and particularly fluid catalytic cracking (FCC), is routinely used to convert heavy hydrocarbon feedstocks to lighter products, such as gasoline and distillate range fractions. In FCC processes, a hydrocarbon feedstock is injected into the riser section of a FCC unit, where the feedstock is cracked into lighter, more valuable products upon contacting hot catalyst circulated to the riser-reactor from a catalyst regenerator.

[0004] Excessive coke and hydrogen are undesirable in commercial catalytic cracking processes. Even small increases in the yields of these products relative to the yield of gasoline can cause significant practical problems. For example, increases in the amount of coke produced can cause undesirable increases in the heat that is generated by burning off the coke during the highly exothermic regeneration of the catalyst. Conversely, insufficient coke production can also distort the heat balance of the cracking process. In addition, in commercial refineries, expensive compressors are used to handle high volume gases, such as hydrogen. Increases in the volume of hydrogen produced, therefore, can add substantially to the capital expense of the refinery.

[0005] Since the 1960s, most commercial fluid catalytic cracking catalysts have contained zeolites as an active component. Such catalysts have taken the form of small particles, called microspheres, containing both an active zeolite component and a nonzeolite component in the form of a high alumina, silica-alumina (aluminosilicate) matrix. The active zeolitic component is incorporated into the microspheres of the catalyst by one of general techniques known in the art, such as those in U.S. Pat. No. 4,482,530 or U.S. Pat. No. 4,493,902.

SUMMARY

[0006] The present disclosure is directed in certain embodiments to a microspherical fluid catalytic cracking (FCC) catalyst composition that includes a matrix and a zeolite, wherein the catalyst has a high fraction of porosity in a radius range of about 150 A to about 1100 A .

[0007] In some embodiments of the catalyst, the matrix may also include a clay, a rare earth-doped alumina, aluminosilicate (SiCh-AhOs) matrix, a silica-doped alumina, /-alumina, “ -alumina. 5- alumina 0-alumina, K-alumina, or boehmite. In some embodiments, the matrix may also include gamma-alumina. In some embodiments of the catalyst, the gamma-alumina may be rare-earth doped.

[0008] In some embodiments of the catalyst, the clay may include a kaolin clay. In some embodiments, the kaolin clay may include metakaolin.

[0009] In some embodiments of the catalyst, the zeolite may include Y-zeolite. [0010] In certain embodiments, the catalyst may further include an incorporated catalyst or an in-situ catalyst.

[0011] In certain embodiments, the zeolite may be in situ crystallized in and/or on a surface of the matrix.

[0012] In some embodiments, the zeolite may be included in an amount of 10 wt% to about 50 wt% based on a total weight of the catalyst. In some embodiments, the catalyst may include at least about 10 wt%, at least 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, or at least about 60 wt% Y-zeolite, based on total weight.

[0013] In some embodiments, an air jet attrition rate (AJAR) of the catalyst is less than about 5 wt%/hr, less than about 4.5 wt%/hr, less than about 4 wt%/hr, less than about 3.5 wt%/hr, less than about 3 wt%/hr, less than about 2.5 wt%/hr, or less than about 1.5 wt%/hr. [0014] In some embodiments, the catalyst may include a zeolite to matrix (Z/M) ratio of about 0.5 to about 3, about 0.5 to about 2.5, about 0.5 to about 2, about 0.5 to about 1.5, or about 0.5 to about 1.

[0015] In some embodiments, the Y-zeolite may have been ion-exchanged to reduce the sodium content to less than 0.7 wt%, or to less than 0.5 wt% Na2O, based on total weight of the ion-exchanged Y -zeolite. In some embodiments, the Y -zeolite may have been ion exchanged to include a rare earth element. In some embodiments, the rare earth element may include one or more lanthanum, cerium, praseodymium, neodymium or yttrium.

[0016] In another embodiment of the present disclosure, a method for producing a microspherical fluid catalytic cracking (FCC) catalyst is also provided. The method may include wet milling a preformed microsphere to obtain a slurry, mixing the slurry with alumina and a clay to obtain a feed slurry, spray drying the feed slurry to form a microsphere, calcining the microsphere at a temperature of from about 420°C to 875°C, and applying a caustic material to the microsphere to obtain the microsphencal FCC catalyst.

[0017] In some embodiments, the method may further include forming an in- situ catalyst from a metakaolin-containing microsphere, an alumina-containing matrix contained in the metakaolin-containing microsphere, wherein the alumina-containing matrix may be obtained by calcination of a dispersible cry stalline boehmite and a hydrous kaolin at a temperature of about 730°C to about 815°C.

[0018] In certain embodiments, the method may further include forming the catalyst by incorporation or in-situ. In some embodiments, forming the catalyst in-situ may include pre-forming precursor microspheres including the matrix; and in-situ crystallizing zeolite on the pre-formed precursor microspheres to form the microspherical FCC catalyst.

[0019] In some embodiments, the in-situ crystallizing may include mixing the pre-formed precursor microspheres with sodium silicate, sodium hydroxide, and water to obtain an alkaline slurry; and heating the alkaline slurry to a temperature, and for a time, sufficient to crystallize at least about 15 wt% Na Y-zeolite, or at least about 40 wt% in or on the pre-formed precursor microspheres, based on total weight of the preformed precursor microspheres. [0020] In some embodiments, the matrix may include gamma-alumina and optionally one or more of clay, rare earth-doped alumina, SiCh-AhOi matrix, and silica- doped alumina, y-alumina, /-alumina, 6-alumina, 9-alumina, K-alumina, or boehmite.

[0021] In some embodiments, the method may further include separating a zeolitic microspheric material from at least a major part of the alkaline slurry; exchanging sodium cations in the zeolitic microspheric material with ammonium ions and thereafter rare earth ions.

[0022] In some embodiments, the method may further include calcining the zeolitic microspheric material; and further exchanging the zeolitic microspheric material with ammonium ions such that the NazO content is reduced to below 0.2%.

[0023] In some embodiments, the matrix may further include kaolin that has been subjected to calcination through an exotherm. In some embodiments, the hydrous clay may include a slurry of kaolin clay. In some embodiments, the clay may include calcined kaolin. In some embodiments, the alumina may include alumina slurry.

[0024] In some embodiment of the method, the catalyst may include a zeolite to matrix (Z/M) ratio of about 0.5 to about 3, about 0.5 to about 2.5, about 0.5 to about 2, about 0.5 to about 1.5, or about 0.5 to about 1.

[0025] In some embodiments of the method, the calcining may occur at a temperature of about 730°C.

[0026] In another embodiment, a method of cracking a hydrocarbon feed may include contacting the feed with the catalyst according to the present disclosure. In some embodiments, the amount of coke produced may be less than about 12% at about 55% to about 95% conversion. In some embodiments, the amount of hydrogen produced may be less than about 0.6% at about 55% to about 95% conversion.

BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The present disclosure is illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings, in which:

[0028] FIG. I illustrates improved macroporosity of a catalyst according to one embodiment of the present disclosure.

[0029] FIG. 2 is a graph illustrating the coke verse conversion using a catalyst according to one embodiment of the present disclosure.

[0030] FIG. 3 is a graph illustrating the hydrogen verse conversion using a catalyst according to one embodiment of the present disclosure. [0031] FIG. 4 is a graph illustrating the dry gas selectivities verse conversion using a catalyst according to one embodiment of the present disclosure.

DETAILED DESCRIPTION

[0032] The present disclosure is directed in certain embodiments to a microspherical fluid catalytic cracking (FCC) catalyst composition that includes a matrix and a zeolite, wherein the catalyst has a high fraction of porosity in a radius range of about 150 A to about 1100 A. In other embodiments of the present disclosure, a method of preparing the FCC catalyst composition. In another embodiment, the present disclosure is also directed to a method of using the microspherical FCC catalyst when cracking a hydrocarbon feed, all without compromising the yield and selectivity of less desirable products, such as bottoms and coke.

[0033] Various embodiments are described hereinafter. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. One aspect described in conjunction with a particular embodiment is not necessanly limited to that embodiment and can be practiced with any other embodiment (s).

[0034] The use of the terms “a” and “an” and “the” and similar referents in the context of describing the elements (especially in the context of the following claims) are to be constmed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are 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 into the specification 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., “such as”) provided herein, is intended merely to better illuminate the embodiments and does not pose a limitation on the scope of the claims unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential.

[0035] As used herein, the term “about” in connection with a measured quantity, refers to the normal variations in that measured quantity', as expected by one of ordinary skill in the art in making the measurement and exercising a level of care commensurate with the objective of measurement and the precision of the measuring equipment. In certain embodiments, the term “about” includes the recited number ±10%, such that “about 10” would include from 9 to 11.

[0036] As used herein, the term “catalyst” or “catalyst composition” or “catalyst material” refers to a material that promotes a reaction.

[0037] As used herein, the term “fluid catalytic cracking” or “FCC” refers to a conversion process in petroleum refineries wherein high-boiling, high-molecular weight hydrocarbon fractions of petroleum crude oils are converted to more valuable gasoline, olefinic gases, and other products.

[0038] “Cracking conditions” or “FCC conditions” refers to typical FCC process conditions. Typical FCC processes are conducted at reaction temperatures of 450°C to 650°C with catalyst regeneration temperatures of 600°C to 850°C. Hot regenerated catalyst is added to a hydrocarbon feed at the base of a rise reactor. The fluidization of the solid catalyst particles may be promoted with a lift gas. The catalyst vaporizes and superheats the feed to the desired cracking temperature. During the upward passage of the catalyst and feed, the feed is cracked, and coke deposits on the catalyst. The coked catalyst and the cracked products exit the riser and enter a solidgas 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 heavier hydrocarbons may be recycled to the reactor.

[0039] As used herein, the term “feed” or “feedstock” refers to that portion of crude oil that has a high boiling point and a high molecular weight. In FCC processes, a hydrocarbon feedstock is injected into the riser section of an FCC unit, where the feedstock is cracked into lighter, more valuable products upon contacting hot catalyst circulated to the riser reactor from a catalyst regenerator.

[0040] As used herein, the terms “non-zeolitic component” or “matrix” refer to the components of an FCC catalyst that are not zeolites or molecular sieves. As used herein, the non-zeolitic component can comprise binder and filler.

[0041] As used herein, the term “zeolite” refers to is a crystalline aluminosilicate with a framework based on an extensive three-dimensional network of silicon, aluminum and oxygen ions and have a substantially uniform pore distribution. [0042] As used herein, the term “intergrown zeolite” refers to a zeolite that is formed by an in situ crystallization process. [0043] As used herein, the term “in situ crystallized” refers to the process in which a zeolite is grown or intergrown directly on/in a microsphere and is intimately associated with the matrix or non-zeolitic material, for example, as described in U.S. Pat. Nos. 4,493,902 and 6,656,347. The zeolite is intergrown within the macropores of the microsphere, such that the zeolite is uniformly dispersed on the matrix or non- zeolitic material. The zeolite is intergrown directly on/in the macropores of the precursor microsphere such that the zeolite is intimately associated and uniformly dispersed on the matrix or non-zeolitic material.

[0044] As used herein, the term “incorporated catalyst” refers to a process in which the zeolitic component is crystallized and then incorporated into microspheres in a separate step.

[0045] As used herein, the terms “preformed microspheres” or “precursor microspheres” refer to microspheres obtained by spray drying and calcining a non- zeolitic matrix component and a gamma-alumina.

[0046] As used herein, the term “zeolite-containing microsphere” refers to a microsphere obtained either by in situ crystallizing a zeolite material on pre-formed precursor microspheres or by microspheres in which the zeolitic component is crystallized separately and then mixed with the precursor microspheres.

[0047] Recitation of ranges of values herein are 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 into the specification 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., “such as”) provided herein, is intended merely to illuminate certain materials and methods and does not pose a limitation on 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.

[0048] As used herein, the term “macroporosity” refers to pores greater than 50 nm in diameter. Flow through macropores is described by bulk diffusion. Further, the pore size may be understood using FIG. 1. That is, “macroporosity” refers to pores from about 150 A to about 1100 A pore radius using a scale of mercury porosimeter measurement. [0049] As used herein, the term “mesoporosity” refers to pores greater than 2 nm and less than 50 nm in diameter. Flow through mesopores is described by Knudsen diffusion. Using FIG. 1, “mesoporosity” refers to pores from about 50 A to about 150 A pore radius using a scale of mercury porosimeter measurement.

[0050] As used herein, the term “microporosity” refers to pores smaller than 2 nm in diameter. Movement in micropores is activated by diffusion. Using FIG. 1, “microporosity” refers to pores that are less than about 50 A pore radius using a scale of mercury porosimeter measurement.

[0051] Preparation of the microspherical FCC catalyst, in accordance with one embodiment of this disclosure, involves an initial step of preparing microspheres comprising hydrous kaolin clay and/or metakaolin, a dispersible crystalline boehmite (AhOs, H2O), optionally spinel and/or mullite, and a sodium silicate or silica sol binder. The microspheres are milled using a wet-milling process. By using a wet-mill process, the fluid cracking catalyst of the present disclosure has significantly improved attrition to dry -milled spinel products that are currently used.

[0052] The microspheres are then calcined to convert any hydrous kaolin component to metakaolin. The calcination process transforms the dispersible boehmite into a transitional alumina phase (e.g., gamma alumina). The calcination may be performed at lower temperatures then presently used in the industry. By using a lower calcination temperature, this eliminates an additional process step to eliminate external metakaolin

[0053] The calcined microspheres are reacted with an alkaline sodium silicate solution to crystallize zeolite Y and are ion-exchanged. The transitional alumina phase (that results from the dispersible crystalline boehmite during the preparative procedure) forms the matrix of the final catalyst and passivates the Ni that are deposited on to the catalyst during the cracking process, especially during cracking of heavy residuum feeds. The FCC catalyst further has an unexpected reduction in contaminant coke and hydrogen yields. Contaminant coke and hydrogen arise due to the presence of Ni and V and reduction of these byproducts significantly improves FCC operation.

[0054] The present inventors have found that when there is more gamma alumina phase in the matrix of the final catalyst, the Ni passivation is improved when compared to current FCC catalyst on the market. Preparing the microsphere using a wet-milling process for certain feed materials enables a new method of control of the final pore volume distribution of the catalyst. Furthermore, this novel approach delivers improved attrition resistance of the catalyst thus enabling lower temperature calcination and preservation of the gamma phase of alumina.

[0055] In view of this, it was found that by balancing the amount of spinel, boehmite and hydrous kaolin the spryer dryer feed, the porosity of the catalyst may be tailored very specifically.

[0056] Accordingly, in one embodiment, the spray dried microspheres, after calcination, may contain a metakaolin content of up to 50 wt. %. In another embodiment, the spray dried microspheres, after calcination, may contain a metakaolin content of up to 45 wt. %. In another embodiment, the spray dried microspheres, after calcination, may contain a metakaolin content of 30-40 wt. %. In another embodiment, the spray dried microspheres, after calcination, may contain a metakaolin content of about 20-30 wt.%. In yet another embodiment, the spray dried microspheres, after calcination, may contain a metakaolin content of about 15-20 wt.%.

[0057] FCC catalysts of the present disclosure may be made by spray drying a feed mixture of hydrous kaolin, metakaolin, and a binder such as silica sol or sodium silicate. In one embodiment, the spray-dried microspheres are acid-neutralized and washed to reduce sodium content. The spray-dried microspheres may be subsequently calcined to form precursor porous microspheres. In one embodiment, the hydrous kaolin is maintained as an inert component by calcining at lower temperatures so as to avoid the endothermic transformation of the hydrous kaolin component to metakaolin. Calcination temperatures of less than 1000° F, preferably less than 800° F, can be used to calcine the spray dried microspheres.

[0058] In one embodiment, any binder used contains only sodium, expressed as Na2O, which is easily removed. Although the silica or silicate binders traditionally used do bring these nutrients into the zeolite crystallization process, the binders are to provide mechanical strength to the microspheres sufficient to withstand processing up until crystallization. Therefore, a binder capable of fulfilling this role while not interfering with the other constraints described herein may be used. Aluminum chlorohydrol for example may be used as the binder.

[0059] In one embodiment of the present disclosure, a microspherical fluid catalytic cracking (FCC) catalyst is provided. The catalyst includes a matrix and a zeolite, wherein the catalyst has a high fraction of porosity in a radius range of about 150 A to about 1100 A . [0060] In some embodiments, the matrix may include alumina. In some embodiments, the matrix may further include clay, rare earth-doped alumina (e.g., selected from one or more of ytterbium-doped alumina, gadolinium-doped alumina, cerium-doped alumina, or lanthanum-doped alumina), SiCh-AhOa matrix, silica-doped alumina, gamma-alumina, /-alumina, 5- alumina 0-alumina, K-alumina, boehmite, or mixtures thereof. In some embodiments, the matrix may include gamma-alumina and one or more of /-alumina, 5- alumina, 0-alumina, K-alumina, or boehmite. In other embodiments, the matrix may include a mixture of gamma-alumina, /-alumina, 5- alumina, 0-alumina, K-alumina, or boehmite. In other embodiments, the matrix may include gamma-alumina.

[0061] In some embodiments, the gamma-alumina may further include a rare earth element, an alkaline earth element, or a mixture of any two or more such elements. For example, the gamma-alumina may include a rare earth element. In particular embodiments, the rare earth element may be ytterbium, gadolinium, cerium, lanthanum, or a mixture of any two or more thereof. In particular embodiments, the rare earth element is lanthanum. In some embodiments, the gamma-alumina includes alkaline earth metals. In further embodiments, the alkaline earth metal is at least one of barium, calcium, or magnesium, or a mixture of any two or more thereof. In particular embodiments, the alkaline earth metal is barium.

[0062] In some embodiments, the rare earth element may be present in an amount of about 0. 1 wt% to about 12 wt% based on total weight of the gamma-alumina. In some embodiments, the rare earth or alkaline earth elements are present in an amount of from any of about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 3 wt%, about 4 wt%, or about 5 wt% to any of about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, or about 12 wt%, based on total weight of the gamma-alumina. In certain embodiments, the rare earth or alkaline earth elements are present in an amount of about 0.1 wt% to about 12 wt%, based on total weight of the gamma-alumina. In some embodiments, the rare earth or alkaline earth elements are present in an amount of about I wt% to about 10 wt%, based on total weight of the gamma-alumina In a particular embodiment, the gamma-alumina includes about 1 wt% to about 5 wt% lanthanum. In a particular embodiment, the gamma-alumina includes about 1 wt% to about 3 wt% lanthanum. In particular embodiments, the gamma-alumina includes about 1 wt% to about 5 wt% barium. In a particular embodiment, the gamma-alumina includes about 1 wt% to about 3 wt% barium.

[0063] In some embodiments, the gamma-alumina, " -alumina. 5- alumina 0- alumina, K-alumina, or boehmite may further include a rare earth element, an alkaline earth element, or a mixture of any two or more such elements as described herein in any embodiment. For example, the gamma-alumina, /-alumina, 6- alumina 0-alumina, K-alurmna, or boehmite in the catalyst may include a rare earth element, including but not limited to, ytterbium, gadolinium, cerium, lanthanum, or a mixture of any two or more thereof. In particular embodiments, the rare earth element may include lanthanum. In some embodiments, the gamma-alumina, /-alumina, 5- alumina 0-alumina, K- alumina, or boehmite may include an alkaline earth element. In some embodiments, the alkaline earth element may include barium, calcium, magnesium, or a mixture of any two or more thereof. In particular embodiments, the alkaline earth metal includes barium. In particular embodiments, the rare earth elements or alkaline earth elements are present in an amount of about 0.1 wt% to about 12 wt%, about 1 wt% to about 10 wt%, about 1% to about 5 wt%, or about 1 wt% to about 3 wt%, based on total weight of the gamma-alumina.

[0064] In some embodiments, the catalyst includes about 1 wt% to about 80 wt% of the gamma-alumina. In some embodiments, the catalyst includes about 5 wt% to about 55 wt% of the gamma-alumina. In other embodiments, the catalyst includes about 1 about 10 wt% to about 40 wt%, about 20 wt% to about 35 wt%, about 25 wt% to about 30 wt% of the gamma-alumina. In other embodiments, the catalyst includes at least about 1 wt%, at least about 3 wt%, at least about 5 wt%, at least about 8 wt%, at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about 25 wt%, at least about 30 wt%, at least about 35 wt%, at least about 40 wt%, at least about 45 wt%, at least about 50 wt%, at least about 55 wt%, at least about 60 wt%, at least about 65 wt%, at least about 70 wt%, at least about 75 wt%, or at least about 80 wt%, or any sub-range or single value therein, based on total weight of the catalyst.

[0065] In some embodiments, the matrix may be derived from a kaolin calcined through its characteristic exotherm. The matrix may also include metakaolin.

[0066] In some embodiments, the catalyst of the present disclosure may include at least 10 wt% zeolite, at least 20 wt% zeolite, at least 30 wt% zeolite, at least 40 wt% zeolite, at least 50 wt% zeolite, or at least 60 wt% zeolite based on total weight of the catalyst. In some embodiments, the catalyst may include from about 10 wt% zeolite to about 50 wt% zeolite.

[0067] In some embodiments, the catalyst has a phase composition, wherein the zeolite may be a Y-zeolite. In some embodiments, the catalyst may have a phase composition including at least about 10 wt% Y-zeolite based on total weight of the catalyst. In some embodiments, the catalyst has a phase composition that includes at least about 20 wt% Y-zeolite based on total weight of the catalyst. In some embodiments, the catalyst has a phase composition that includes at least about 30 wt% Y-zeolite of the catalyst. In some embodiments, the catalyst has a phase composition that includes at least about 40 wt% Y-zeolite of the catalyst. In some embodiments, the catalyst has a phase composition that includes at least about 50 wt% Y-zeolite of the catalyst. In some embodiments, the catalyst has a phase composition that includes at least about 60 wt% Y-zeolite of the catalyst.

[0068] In some embodiments, the cataly st may include Y-zeolite, wherein the Y-zeolite in the first component includes Y-zeolite that has been ion-exchanged to reduce the sodium content to less than 0.7 wt%, or to less than 0.5 wt% Na2O, based on total weight of the ion-exchanged Y-zeolite. In some embodiments, the Y-zeolite has been ion exchanged to include a rare earth element.

[0069] In some embodiments, the Y-zeolite may be crystallized as a layer on the surface of a matrix, wherein the matrix comprises gamma-alumina. In some embodiments, the matrix also includes kaolin that has been subjected to calcination through an exotherm. In further embodiments, the matrix includes about 10 wt% to about 60 wt% kaolin that has been subjected to calcination through an exotherm. In particular embodiments, the matrix includes about 30 wt% kaolin that has been subjected to calcination through an exotherm.

[0070] In some embodiments, the Y-zeolite may further include a rare earth element in the range of 0.1 wt% to 12 wt%, based on total weight of the catalyst. In some embodiments, the rare earth element may be lanthanum, cerium, praseodymium, neodymium, yttrium, or a mixture of any two or more. In particular embodiments, the rare earth element may be lanthanum. In certain embodiments, the rare earth element may be yttrium. In further particular embodiments, the Y-zeolite may be ion-exchanged to include the rare earth element. In some embodiments, the catalyst includes a lanthanum-exchanged zeolite crystallized in-situ in a porous kaolin matrix. [0071] In some embodiments, the catalyst may have an air jet attrition rate (AJAR) of less than about 5 wt%/hr, less than about 4.5 wt%/hr, less than about 4 wt%/hr, less than 3.5 wt%/hr, less than about 2.5 wt%/hr, less than about 2 wt%/hr, less than about 1.5 wt%/hr, or less than about 1 wt%/hr.

[0072] In some embodiments, the catalyst may include a zeolite to matrix (Z/M) ratio of about 0.5 to about 3.0, about 0.75 to about 2.75, about 1 to about 2.5, about 1.25 to about 2.25, or about 1.5 to about 2.

[0073] In some embodiments, the catalyst may have a matrix that comprises about 15% to about 20% gamma-alumina, about 15% to about 20% of metakaolin, and about 60% to about 70% of wet-milled spinelin another embodiment of the present disclosure, a method of making the microspherical FCC catalyst is also provided. The method includes wet milling a preformed microsphere to obtain a slurry, mixing the clay slurry with alumina and a clay to obtain a feed slurry, spray drying the feed slurry to form a microsphere, calcining the microsphere at a temperature from about 425°C to about 875°C and applying a caustic material to the microsphere to obtain the microspherical FCC catalyst.

[0074] In some embodiments, the method may further include forming the catalyst by incorporation or in situ.

[0075] In some embodiments, the method may include forming in situ catalyst from a metakaolin-containing microsphere and an alumina-containing matrix is contained in the metakaolin-containing calcined microsphere, wherein the aluminacontaining matrix is obtained by calcination of a dispersible crystalline boehmite and a hydrous kaolin at a temperature of about 725°C to about 825°C. In another embodiment, forming the catalyst in-situ may include pre-forming precursor microspheres including the matrix; and in-situ crystallizing zeolite on the pre-formed precursor microspheres to form the microspherical FCC catalyst.

[0076] In some embodiments, the in situ crystallizing includes mixing the preformed precursor microspheres with sodium silicate, sodium hydroxide, and water to obtain an alkaline slurry; and heating the alkaline slurry to a temperature, and for a time, sufficient to crystallize at least about 15 wt% NaY-zeolite, or at least about 40 wt% in or on the pre-formed precursor microspheres, based on total weight of the preformed precursor microspheres.

[0077] In some embodiments, the alkaline slurry is heated for a time sufficient to crystallize at least about 10 wt%, Y-zeolite in or on the pre-formed microspheres, or at least about 20 wt%, Y-zeolite in or on the pre-formed microspheres, at least about 30 wt%, Y-zeolite in or on the pre-formed microspheres, or at least about 40 wt%, Y- zeolite in or on the pre-formed microspheres.

[0078] In some embodiments of the method, the matrix may include alumina. In some embodiments, the alumina may be a clay, such as a kaolin clay, gammaalumina, /-alumina. 5- alumina 0-alumina, K-alumina, boehmite, or mixtures thereof. In some embodiments, the matrix may include gamma-alumina and one or more of /- alumina, 5- alumina, 0-alumina, K-alumina, or boehmite. In other embodiments, the matrix may include a mixture of gamma-alumina, /-alumina, 5- alumina, 9-alumina, K- alumina, or boehmite.

[0079] In some embodiments, the method may further include separating a zeolitic microspheric material from at least a major part of the alkaline slurry; exchanging sodium cations in the zeolitic microspheric material with ammonium ions or ammonium ions and thereafter rare earth ions.

[0080] In some embodiments, the method may further include calcining the zeolitic microspheric material; further exchanging the zeolitic microspheric material with ammonium ions such that the Na2O content is reduced to below 0.2%; and further calcining the first zeolitic microspheric material.

[0081] In some embodiments of the method, the matrix may include kaolin that has been subjected to calcination through an exotherm.

[0082] In other embodiments of the method, a Y-zeolite may be included that has been ion-exchanged to reduce the sodium content to less than 0.7 wt%, or to less than 0.5 wt% Na2O based on total weight of the ion-exchanged Y-zeolite. In some embodiments, the Y-zeolite has been ion exchanged to include a rare earth element. The rare earth element in the rare earth element ion-exchanged Y-zeohte may include one or more lanthanum, cerium, praseodymium, neodymium or ytrrium.

[0083] In the method of the present disclosure, a hydrous clay may include a slurry of kaolin clay. In another embodiment of the method, the clay may include calcined kaolin. In one embodiment of the method, the alumina may include an alumina slurry.

[0084] In one embodiment of the method, the catalyst may include a zeolite to matrix (Z/M) ratio of about 0.5 to about 3.0, about 0.75 to about 2.75, about 1 to about 2.5, about 1.25 to about 2.25, or about 1.5 to about 2. [0085] In one embodiment of the method, the calcining of the microsphere may occur at a temperature of about 730°C to about 735°C.

[0086] In certain embodiments, a method of cracking a hydrocarbon feed is provided including contacting the feed with a microspherical FCC catalyst of the present disclosure. In some embodiments, the amount of coke produced in the method of cracking a hydrocarbon feed is less than about 12% at about 55% to about 95% conversion. In some embodiments, the amount of hydrogen produced in the method of cracking a hydrocarbon feed is less than about 0.6% at about 55% to about 95% conversion.

ILLUSTRATIVE EXAMPLES

[0087] The following examples are set forth to assist in understanding the disclosure and should not be construed as specifically limiting the invention described and claimed herein. Such variations of the invention, including the substitution of all equivalents now known or later developed, which would be within the purview of those skilled in the art, and changes in formulation or minor changes in experimental design are to be considered to fall within the scope of the invention incorporated herein.

Preparation of Catalyst

[0088] A catalyst according to the present invention was prepared using 18 wt% hydrous kaolin, 18 wt% cry stalline boehmite, and 64 wt% wet-milled spinel in the spray dryer feed. After spray drying, the material was calcined at 800°C for two hours. The reactors were formulated assuming all hydrous kaolin was converted to metakaolin during calcination, such that greater than 99% theoretical zeolite yield was achieved. A comparative catalyst was prepared by ion exchange of the reactor product using methods familiar to those skilled in the art. The pore structure of the catalysts were analyzed and are shown in FIG. 1.

Performance of Catalyst in Hydrocarbon process

[0089] The catalyst prepared above were used in a hydrocarbon feed. The performance of the catalysts are illustrated in FIGS. 2 to 4. As can be seen in FIG. 2, the Example of the present application has 12% lower coke at 78% conversion when compared to Comparative Example. FIG. 3 illustrates that the Example had 21% lower H2 at 78% conversion in comparison to the Comparative Example. As can be seen in FIG. 4, the Example had improved dry gas selectivities. [0090] For simplicity of explanation, the embodiments of the methods of this disclosure are depicted and described as a series of acts. However, acts in accordance with this disclosure can occur in various orders and/or concurrently, and with other acts not presented and described herein. Furthermore, not all illustrated acts may be required to implement the methods in accordance with the disclosed subject matter. In addition, those skilled in the art will understand and appreciate that the methods could alternatively be represented as a series of interrelated states via a state diagram or events.

[0091] In the foregoing description, numerous specific details are set forth, such as specific materials, dimensions, processes parameters, etc., to provide athorough understanding of the present invention. The particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments. The words “example” or “exemplary” are used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as “example” or “exemplary ” is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the words “example” or “exemplary” is intended to present concepts in a concrete fashion. As used in this application, the term “or” is intended to mean an inclusive “or” rather than an exclusive “or”. That is, unless specified otherwise, or clear from context, “X includes A or B” is intended to mean any of the natural inclusive permutations. 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 foregoing instances. Reference throughout this specification to “an embodiment”, “certain embodiments”, or “one embodiment” means 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 phrase “an embodiment”, “certain embodiments”, or “one embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment.

[0092] The present disclosure has been described with reference to specific exemplary embodiments thereof. The specification and drawings are, accordingly, 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

What is claimed is:

1. A microspherical fluid catalytic cracking (FCC) catalyst comprising a matrix and a zeolite, wherein the catalyst has a high fraction of porosity in a radius range of about 150 A to about 1100 A .

2. The catalyst of claim 1 , wherein the matrix further comprises a clay, a rare earth- doped alumina, aluminosilicate (SiCh-AhCh) matrix, a silica-doped alumina, y- alumina, /-alumina, 5- alumina 0-alumina, K-alumina, or boehmite.

3. The catalyst of claim 1, wherein the matrix comprises gamma-alumina.

4. The catalyst of claim 3, wherein the gamma-alumina is rare-earth doped.

5. The catalyst of claim 2, wherein the clay comprises a kaolin clay.

6. The catalyst of claim 5, wherein the kaolin clay comprises metakaolin.

7. The catalyst of claim 1, wherein the zeolite comprises Y-zeolite.

8. The catalyst of claim 1, further comprising an incorporated catalyst or an in-situ catalyst.

9. The catalyst of claim 1, wherein the zeolite is in situ crystallized in and/or on a surface of the matrix.

10. The catalyst of claim 1, wherein the zeolite is included in an amount of 10 wt% to about 50 wt% based on a total weight of the catalyst.

11. The catalyst of claim 7, wherein the catalyst comprises at least about 10 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, or at least about 60 wt% Y-zeolite, based on total weight.

12. The catalyst of claim 1 , wherein an air jet attrition rate (AJAR) of the catalyst is less than about 5 wt%/hr, less than about 4.5 wt%/hr, less than about 4 wt%/hr, less than about 3.5 wt%/hr, less than about 3 wt%/hr less than about 2.5 wt%/hr, or less than about 1.5 wt%/hr. The catalyst of claim 1, wherein the catalyst comprises a zeolite to matrix (Z/M) ratio of about 0.5 to about 3, about 0.5 to about 2.5, about 0.5 to about 2, about 0.5 to about 1.5, or about 0.5 to about 1. The catalyst of claim 7, wherein the Y-zeolite has been ion-exchanged to reduce the sodium content to less than 0.7 wt%, or to less than 0.5 wt% Na2O, based on total weight of the ion-exchanged Y-zeolite. The catalyst of claim 7, wherein the Y-zeolite has been ion exchanged to include a rare earth element. The catalyst of claim 15, wherein the rare earth element comprises one or more of lanthanum, cerium, praseodymium, neodymium or yttrium. A method for producing a microspherical fluid catalytic cracking (FCC) catalyst comprising: wet milling a preformed micropshere to obtain a slurry; mixing the slurry with alumina and a clay to obtain a feed slurry; spray drying the feed slurry to form a microsphere; calcining the microsphere at a temperature of from about 420°C to 875°C; applying a caustic material to the microsphere to obtain the microspherical FCC catalyst. The method of claim 17, further comprising forming an in-situ catalyst from: a metakaolin-containing microsphere, an alumina-containing matrix contained in the metakaolin-containing microsphere, wherein the aluminacontaining matrix is obtained by calcination of a dispersible crystalline boehmite and a hydrous kaolin at a temperature of about 730°C to about 815°C.

19. The method of claim 17 or 18, forming comprising forming the catalyst by incorporation or in-situ.

20. The method of claim 19, wherein forming the catalyst in-situ comprises preforming precursor microspheres comprising the matrix; and in-situ crystallizing zeolite on the pre-formed precursor microspheres to form the microspherical FCC catalyst.

21. The method of claim 19, wherein the in-situ crystallizing comprises: mixing the pre-formed precursor microspheres with sodium silicate, sodium hydroxide, and water to obtain an alkaline slurry; and heating the alkaline slurry to a temperature, and for a time, sufficient to crystallize at least about 15 wt% Na Y-zeolite, or at least about 40 wt% in or on the pre-formed precursor microspheres, based on total weight of the pre-formed precursor microspheres.

22. The method of any one of claims 17 to 21, wherein the matrix comprises gamma-alumina and optionally one or more of clay, rare earth-doped alumina, SiC -AhCh matrix, and silica-doped alumina, /-alumina, /-alumina. 5- alumina 0-alumina, K-alumina, or boehmite.

23. The method of any one of claims 17 to 22, further comprising separating a zeolitic microspheric material from at least a major part of the alkaline slurry; exchanging sodium cations in the zeolitic microspheric material with ammonium ions and thereafter rare earth ions.

24. The method of claim 17, further comprising calcining the zeolitic microspheric material; and further exchanging the zeolitic microspheric material with ammonium ions such that the Na2O content is reduced to below 0.2%.

25. The method of any one of claims 17 to 22, wherein the matrix further comprises kaolin that has been subjected to calcination through an exotherm.

26. The method of any one of claims 17 to 25, wherein the hydrous clay comprises a slurry of kaolin clay. The method of any one of claims 17 to 25, wherein the clay comprises calcined kaolin. The method of any one of claims 17 to 27, wherein the alumina comprises alumina slurry. The method of any one of claims 17 to 28, wherein the catalyst comprises a zeolite to matrix (Z/M) ratio of about 0.5 to about 3, about 0.5 to about 2.5, about 0.5 to about 2, about 0.5 to about 1.5, or about 0.5 to about 1. The method of claim 17, wherein the calcining occurs at a temperature of about 730°C. A method of cracking a hydrocarbon feed comprising contacting the feed with the catalyst of claim 1. The method of claim 31 , wherein an amount of coke produced is less than about 12% at about 55% to about 95% conversion. The method of claim 31, wherein an amount of hydrogen produced is less than about 0.6% at about 55% to about 95% conversion.