Fluid catalytic cracking process and catalyst

Abstract

The present invention provides a process for fluid catalytic cracking of a feedstock, the process comprising contacting a fluid catalytic cracking catalyst composition with a feedstock comprising an oxygenated feedstock and optionally a hydrocarbon feedstock, the oxygenated feedstock comprising at least one oxygenate containing at least carbon, hydrogen, and oxygen.

Description

[Technical field]

[0001] The present invention relates to a process for fluid catalytic cracking of a feedstock comprising one or more oxygenates, optionally together with a hydrocarbon feedstock as part of the feedstock. [Background technology]

[0002] Fluid catalytic cracking unit (FCCU) limitations related to the formation of coke and hydrogen are known problems in the fluid catalytic cracking of hydrocarbon feedstocks. Various methods have been attempted to reduce coke and hydrogen, such as including small amounts of additives with the fluid catalytic cracking catalyst, modifying the active ingredients forming the fluid catalytic cracking catalyst, minimizing the use of hydrocarbon feedstocks with reduced carbon residues or reduced amounts of metal contaminants, and modifying the operating parameters, such as feed throughput and reaction temperature. Further improvements in coke reduction and hydrogen reduction by the fluid catalytic cracking process are desirable. Summary of the Invention

[0003] The present invention provides a process for catalytic cracking a feedstock that includes one or more oxygenates, optionally and preferably with a hydrocarbon feedstock as part of the feedstock. The process of the present invention typically produces less coke and reduces hydrogen production. Additional benefits provided by the process of the present invention may include one or more of the following: reduced bottoms, reduced LCO (light cycle oil) yield, improved gasoline yield, improved propylene yield, increased naphtha yield, and increased olefinicity. In at least some embodiments, the benefits obtained, particularly the reduction in coke and hydrogen, are greater than those that may be attributed to the dilution and / or additive effects of the oxygenate(s).

[0004] One embodiment of the present invention is a fluid catalytic cracking process comprising contacting a fluid catalytic cracking catalyst composition with a feedstock comprising an oxygen-containing feedstock and, optionally, a hydrocarbon feedstock. The oxygen-containing feedstock comprises at least one oxygen-containing compound containing at least carbon, hydrogen, and oxygen. The fluid catalytic cracking catalyst composition comprises one or more Y-type zeolites, one or more ZSM-5 zeolites, a rare earth component, a phosphorus component, and an alumina comprising boehmite and / or pseudo-boehmite. Alternatively, the fluid catalytic cracking catalyst composition comprises one or more Y-type zeolites, a rare earth component, a phosphorus component, and an alumina comprising boehmite and / or pseudo-boehmite.

[0005] Another embodiment of the present invention is a fluid catalytic cracking catalyst composition comprising one or more Y-type zeolites, one or more ZSM-5 zeolites, a rare earth component, and an alumina comprising boehmite and / or pseudo-boehmite; alternatively, the fluid catalytic cracking catalyst composition comprises one or more Y-type zeolites, a rare earth component, and an alumina comprising boehmite and / or pseudo-boehmite.

[0006] These and other embodiments and features of the present invention will become further apparent from the subsequent description and appended claims. [Brief description of the drawings]

[0007] [Figure 1] 1 is a graph comparing predicted and measured hydrogen and coke yields for Comparative Catalyst A of Example 1. [Diagram 2] 1 is a graph comparing predicted and measured hydrogen and coke yields for Catalyst B of Example 1.

[0008] The figures depict embodiments of certain aspects of the invention and are not intended to impose limitations on the scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The terms "ZSM-5" and "ZSM-5 zeolite" are used interchangeably throughout this document.

[0010] As used throughout this document, the expression "fluid catalytic cracking composition" is used interchangeably with the expression "catalyst composition."

[0011] Throughout this document, amounts of catalysts, catalyst additives, and their components are reported on a dry basis or relative to other dry ingredients or components of the catalyst or catalyst additive, unless otherwise specified.

[0012] As used throughout this document, the phrase "expressed as its oxides" and similar expressions for rare earths and phosphorus refer to the amount of rare earth element or phosphorus, and the numerical value is the amount of the respective oxide(s) of the rare earth element(s), or phosphorus, phosphorus pentoxide (P 2 O 5 ) When multiple rare earth elements are present, the amount refers to the sum of all of the rare earth elements present as their oxides, unless otherwise indicated.

[0013] In some embodiments, the fluid cracking catalyst composition used in the process of the invention contains components including one or more Y-type zeolites, one or more ZSM-5 zeolites, a rare earth component, alumina with boehmite and / or pseudo-boehmite, optionally phosphorus, optionally silica, and optionally clay. In other embodiments, the fluid cracking catalyst composition used in the process of the invention contains components including one or more Y-type zeolites, a rare earth component, alumina with boehmite and / or pseudo-boehmite, optionally phosphorus, optionally silica, and optionally clay. Other optional components may be present in the fluid cracking catalyst composition used in the practice of the invention.

[0014] In fluid cracking catalysts, the dry components that form the catalyst composition include the zeolite, the alumina, the optional phosphorus component, the optional silica component, the optional clay component, and any other dry components that were used in the preparation of the catalyst composition and remain in the catalyst composition.

[0015] Y-type zeolites are large pore zeolites. Y-type zeolites suitable for the practice of the present invention include Y zeolite, ultrastable Y zeolite (USY), HY zeolite, and dealuminated Y zeolite. In some embodiments, preferred Y-type zeolites include ultrastable Y zeolite and Y zeolite.

[0016] In fluid cracking catalyst compositions containing ZSM-5 zeolite, the Y-type zeolite is typically present in the catalyst composition in an amount of about 0.5 wt% or more, based on the total weight of the catalyst composition. In some embodiments, the amount of Y-type zeolite in the catalyst composition containing ZSM-5 zeolite is about 2.5 wt% or more, preferably about 5 wt% or more, based on the total weight of the catalyst composition. Typically, in catalyst compositions containing ZSM-5 zeolite, the Y-type zeolite is present in an amount of about 0.5 wt% to about 50 wt%, preferably about 2.5 wt% to about 45 wt%, more preferably about 5 wt% to about 40 wt%, based on the total weight of the catalyst composition.

[0017] In fluid cracking catalyst compositions that do not contain ZSM-5 zeolite, the Y-type zeolite is typically present in the catalyst composition in an amount of about 5 wt% or more, based on the total weight of the catalyst composition. In some embodiments, the preferred amount of Y-type zeolite in the ZSM-5 zeolite-free catalyst composition is about 7.5 wt% or more, particularly about 10 wt% or more, based on the total weight of the catalyst composition. Typically, in catalyst compositions that do not contain ZSM-5 zeolite, the Y-type zeolite is present in an amount of about 5 wt% to about 60 wt%, preferably about 7.5 wt% to about 55 wt%, more preferably about 10 wt% to about 55 wt%, based on the total weight of the catalyst composition.

[0018] Pentasil zeolites are small or medium pore zeolites. ZSM-5 zeolites are pentasil zeolites that are used in the practice of the present invention.

[0019] In some embodiments where the fluid cracking catalyst composition comprises a ZSM-5 zeolite, the ZSM-5 zeolite is typically present in the catalyst composition in an amount of about 1 wt% or more, preferably about 2 wt% or more, and more preferably about 5 wt% or more, based on the total weight of the catalyst composition. Typically, in catalyst compositions comprising a ZSM-5 zeolite, the ZSM-5 zeolite is present in an amount of about 1 wt% to about 50 wt%, preferably about 2 wt% to about 45 wt%, and more preferably about 5 wt% to about 40 wt%, based on the total weight of the catalyst composition.

[0020] In other embodiments where the fluid cracking catalyst composition comprises a ZSM-5 zeolite, the ZSM-5 zeolite is typically present in the catalyst composition in an amount of about 2.5 wt% or more, preferably about 5 wt% or more, based on the total weight of the catalyst composition. In some preferred embodiments, the ZSM-5 zeolite is present in an amount of about 2.5 wt% to about 50 wt%, preferably about 5 wt% to about 45 wt%, more preferably about 5 wt% to about 40 wt%, based on the total weight of the catalyst composition.

[0021] In yet other embodiments in which the fluid cracking catalyst composition comprises a ZSM-5 zeolite, the ZSM-5 zeolite is typically present in the catalyst composition in an amount of at least about 15 wt.%, often from about 15 wt.% to about 50 wt.%, preferably from about 15 wt.% to about 45 wt.%, and more preferably from about 15 wt.% to about 40 wt.%, based on the total weight of the catalyst composition.

[0022] In fluid cracking catalyst compositions containing ZSM-5 zeolite, the Y zeolite and the ZSM-5 zeolite are present in a combined amount of about 15 wt% or more, preferably about 20 wt% or more, and more preferably about 25 wt% or more, based on the total weight of the catalyst composition. In some embodiments, the Y zeolite and the ZSM-5 zeolite are present in a combined amount of about 15 wt% to about 75 wt%, preferably about 20 wt% to about 60 wt%, and more preferably about 25 wt% to about 50 wt%, based on the total weight of the catalyst composition.

[0023] In fluid cracking catalyst compositions comprising ZSM-5 zeolite, the weight ratio of the Y zeolite to the ZSM-5 zeolite is at least about 0.25:1, preferably at least about 0.3:1. In some embodiments, the weight ratio of the Y zeolite to the ZSM-5 zeolite is from about 0.25:1 to about 2.75:1, and in other embodiments, the weight ratio of the Y zeolite to the ZSM-5 zeolite is from about 0.3:1 to about 2.5:1, preferably from about 0.3:1 to about 1.5:1.

[0024] In other embodiments where the fluid cracking catalyst composition comprises a ZSM-5 zeolite, the weight ratio of the Y zeolite to the ZSM-5 zeolite is at least about 1.5:1, preferably at least about 2:1. In some embodiments, the weight ratio of the Y zeolite to the ZSM-5 zeolite is from about 1.5:1 to about 8:1, and in other embodiments, the weight ratio of the Y zeolite to the ZSM-5 zeolite is from about 2:1 to about 8:1.

[0025] In the practice of the present invention, other large pore zeolites and / or other small or medium pore zeolites may be present in the fluid cracking catalyst composition. Large pore zeolites have ring structures with 12 or more members within the zeolite framework. In small or medium pore zeolites, the largest ring structure within the zeolite framework is less than 12 members. Some zeolites have characteristics that allow them to be classified as both large pore zeolites and small or medium pore zeolites, and these zeolites can be used in the present invention.

[0026] Other suitable large pore zeolites that may be part of the fluid cracking catalyst composition include faujasite, beta zeolite, mordenite, X zeolite, AFI, AFR, BEC, BOG, EMT, EON, ETR, EWT, IFT, IFU, IRR, ISV, IWR, IWS, IWW, LTL, MEI, MOR, MOZ, MSE, OFF, SSZ-31, and / or SSZ-60. Any of these rare earth-containing large pore zeolites can also be used.

[0027] Other suitable small or medium pore zeolites that may be part of the fluid cracking catalyst composition include ZSM-4, ZSM-11, ZSM-12, ZSM-18, ZSM-20, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-50, ZSM-57, beta zeolite, chabazite, mazzite, mordenite, natrolite, offretite, stilbite, Li-A zeolite, zeolite Na-P1, zeolite Na-P2, zeolite A, zeolite L, zeolite Q (or zeolite KI or Linde Q), zeolite T, zeolite RHO, AIPO-18, CIT-5, CIT-7, ECR-1, EMC-2, EMM-10, EMM-26, EU-1 , IPC-4, IM-5, MCM-22, MCM-35, MCM-36, MCM-49, MCM-56, MCM-58, MCM-68, NU-87, SSZ-13, SSZ-23, SSZ-35, SSZ-36, SSZ-48, SSZ-61, SUZ-4, TNU-9, UZM-4, UZM-8, ITQ zeolites (e.g., ITQ-2, ITQ-3, ITQ-4, ITQ-7, ITQ-12, ITQ-13, ITQ-30, ITQ-39, and ITQ-51), silicoaluminophosphate zeolites (SAPO) (e.g., SAPO-5, SAPO-11, SAPO-18, SAPO-31, SAPO-34, and SAPO-41), and aluminophosphate zeolites (ALPO). More than one small or medium pore zeolite can be used. Preferred small or medium pore zeolites include pentasil zeolites, including beta zeolite, IM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, and ZSM-57.

[0028] The fluid cracking catalyst composition used in the practice of the present invention includes a rare earth component. The rare earth element can be yttrium or any of the lanthanide series (e.g., lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, and ytterbium). In some embodiments, the rare earth element can be yttrium, lanthanum, cerium, and / or praseodymium, preferably lanthanum and / or cerium; lanthanum is often more preferred.

[0029] In some embodiments, the rare earth component is present in the fluid cracking catalyst composition in an amount of about 0.25 wt% or more, preferably about 0.5 wt% or more, expressed as rare earth oxide(s), based on the total weight of the catalyst composition. In other embodiments, the rare earth component is present in the catalyst composition in an amount of about 0.25 wt% to about 20 wt% expressed as rare earth oxide(s), based on the total weight of the catalyst composition. In other embodiments, the rare earth component is present in an amount of about 0.5 wt% to about 15 wt%, preferably about 0.5 wt% to about 10 wt%, more preferably about 0.5 wt% to about 7.5 wt%, expressed as rare earth oxide(s), based on the total weight of the catalyst composition. The rare earth oxides may be any of their common oxides (e.g., for lanthanum, La 2 O 3 , for cerium, CeO 2 When multiple rare earth elements are present in the catalyst composition, the amount of rare earth component in the catalyst composition is the sum of the amounts of the individual rare earth oxides.

[0030] In some embodiments, the rare earth component is present in a Y-type zeolite prior to combination with other catalyst components. When the rare earth component is present in a Y-type zeolite, the rare earth element may be incorporated into the Y-type zeolite by any convenient method, such as ion exchange into the Y-type zeolite or impregnation into the Y-type zeolite.

[0031] In embodiments in which a rare earth component is present in the catalyst composition other than a Y-type zeolite, the rare earth component can be introduced at any convenient point during the preparation of the catalyst composition (e.g., when combining one or more components or after combining the other catalyst components).

[0032] In other embodiments, a portion of the rare earth component is present in the Y zeolite prior to combination with other catalyst components, and a portion of the rare earth component is present in the catalyst composition other than the Y zeolite.

[0033] In some embodiments, when the optional phosphorus component is present in the fluid cracking catalyst composition, the phosphorus is present in an amount of about 0.1 wt.% or more, preferably about 0.2 wt.% or more, expressed as phosphorus pentoxide, based on the total weight of the catalyst composition. In other embodiments in which phosphorus is present, the phosphorus component is present in an amount of about 0.1 wt.% to about 10 wt.%, preferably about 0.1 wt.% to about 7.5 wt.%, more preferably about 0.2 wt.% to about 7.5 wt.%, and even more preferably about 0.2 wt.% to about 5 wt.%, expressed as phosphorus pentoxide, based on the total weight of the catalyst composition.

[0034] In some embodiments in which the fluid cracking catalyst composition comprises a ZSM-5 zeolite and phosphorus is present, the phosphorus component is present within the ZSM-5 zeolite prior to combination with the other catalyst components. If an optional phosphorus component is present in the ZSM-5 zeolite, the phosphorus component may be incorporated into the ZSM-5 zeolite by any convenient method, such as by impregnation into the ZSM-5 zeolite.

[0035] In embodiments where the fluid cracking catalyst composition comprises a ZSM-5 zeolite, where an optional phosphorus component is present in the catalyst composition other than the ZSM-5 zeolite, the phosphorus component can be introduced at any convenient point during preparation of the catalyst composition (e.g., when combining one or more components or after combining the other catalyst components).

[0036] In other embodiments, a portion of the optional phosphorus component is present in the ZSM-5 zeolite prior to combination with other catalyst components, and a portion of the optional phosphorus component is present in the catalyst composition other than the ZSM-5 zeolite.

[0037] For the introduction of the phosphorus component, suitable sources of phosphorus include phosphoric acid, pyrophosphoric acid, polyphosphoric acid, hypophosphoric acid, hypophosphorous acid, ammonium phosphate, phosphorus oxides (e.g., phosphorus pentoxide), and phosphates (e.g., metal phosphates). When the fluid cracking catalyst composition comprises a ZSM-5 zeolite, commercially available phosphorus-containing ZSM-5 zeolites can also be used in the practice of the present invention.

[0038] In some embodiments, all of the components of the fluid cracking catalyst composition are present in a single particle. In other embodiments, the components of the fluid cracking catalyst composition are present in multiple particles, optionally in two or more particles, preferably in two particles. The zeolites may be in the same particle or dispersed in separate particles; if dispersed in separate particles, the separate particles may contain the same zeolite(s) and / or different zeolites.

[0039] In some embodiments where the fluid cracking catalyst composition comprises ZSM-5 zeolite, at least a portion of the Y-type zeolite and rare earth components are present in one particle and the ZSM-5 zeolite is present in another particle. At least a portion of the optional phosphorus component, if present, is present in the particles containing the ZSM-5 zeolite. Typically, a portion of the alumina is present in each particle.

[0040] In other embodiments where the fluid cracking catalyst composition comprises ZSM-5 zeolite, the components of the catalyst composition may be dispersed throughout the particles, with a portion of either or both of the Y and ZSM-5 zeolite in multiple particles. A suitable distribution is to include all of the Y zeolite and a portion of the ZSM-5 zeolite in one particle and the remaining portion of the ZSM-5 zeolite in another particle; all of the ZSM-5 zeolite and a portion of the Y zeolite in one particle and the remaining portion of the Y zeolite in another particle. In those embodiments where the catalyst composition is dispersed throughout the particles, with a portion of either or both of the Y and ZSM-5 zeolite in multiple particles, a portion of the alumina is present in each particle; and at least a portion of the rare earth component is present with at least a portion of the Y zeolite. In a preferred embodiment, if phosphorus is present, at least a portion of the optional phosphorus component is present with at least a portion of the ZSM-5 zeolite.

[0041] The alumina in the fluid cracking catalyst composition is in the form of boehmite and / or pseudo-boehmite. The boehmite and pseudo-boehmite can be in microcrystalline or crystalline form. Preferably, the alumina comprises boehmite or comprises boehmite and pseudo-boehmite. Preferably, the boehmite is crystalline or microcrystalline and the pseudo-boehmite is microcrystalline. More preferably, the alumina comprises boehmite or comprises boehmite and pseudo-boehmite, the boehmite is crystalline or microcrystalline and the pseudo-boehmite is microcrystalline.

[0042] The total amount of boehmite and pseudo-boehmite in the catalyst composition is generally about 1 wt% to about 50 wt%, preferably about 5 wt% to about 45 wt%, more preferably about 10 wt% to about 45 wt%, and even more preferably about 15 wt% to about 45 wt%, based on the total weight of the catalyst composition, which does not include alumina derived from zeolite components or other sources.

[0043] The fluid cracking catalyst composition may optionally contain other aluminum-containing components. Other aluminum-containing components, when present, include polyaluminum chlorides, such as aluminum chlorohydrates, polyaluminum nitrates, and polyaluminum sulfates. A mixture of two or more other aluminum-containing components of the same or different types may be used. In some embodiments in which one or more other aluminum-containing components are present, the total amount of alumina and other aluminum-containing components is about 20 wt% or more, preferably about 30 wt% or more, more preferably about 50 wt% or more, based on the total weight of the catalyst composition; these amounts do not include alumina from the zeolite component or other sources. In other embodiments in which one or more other aluminum-containing components are present, the total amount of alumina and other aluminum-containing components is about 20 wt% to about 80 wt%, preferably about 30 wt% to about 80 wt%, more preferably about 50 wt% to about 80 wt%, based on the total weight of the catalyst composition; these amounts do not include alumina from the zeolite component or other sources.

[0044] In the practice of the present invention, the zeolite and alumina are present in the fluid cracking catalyst composition in a combined amount of about 25 wt% or more, preferably about 30 wt% or more, and more preferably about 35 wt% or more, based on the total weight of the catalyst composition. In some embodiments, the zeolite and alumina are present in a combined amount of about 25 wt% to about 90 wt%, preferably about 30 wt% to about 85 wt%, and more preferably about 35 wt% to about 85 wt%, based on the total weight of the catalyst composition. These amounts do not include alumina from the zeolite component or other sources.

[0045] The optional silica component in the fluid cracking catalyst composition used in the process of the present invention can be one or more of inorganic silicates, organic silicates, (poly)silicic acid, organic chlorosilanes, fumed silica, or colloidal silica. Inorganic silicates include ammonium silicate, lithium silicate, sodium silicate, potassium silicate, magnesium silicate, calcium silicate, strontium silicate, barium silicate, zinc silicate, and phosphorus silicate; mixtures of two or more of these silicates can include the silica component. Suitable organic silicates are compounds containing a Si-OCO-Si structure, especially silicones, especially polyorganosiloxanes, such as polymethylphenylsiloxane and polydimethylsiloxane. Organic chlorosilanes include methylchlorosilane, dimethylchlorosilane, trimethylchlorosilane, and mixtures thereof. Preferably, the average particle size of the colloidal silica is about 1 nm to about 500 nm, more preferably, the average particle size of the colloidal silica is about 1.5 nm to about 100 nm, and even more preferably, the average particle size of the colloidal silica is about 1.5 nm to about 50 nm. The silica component in the practice of the present invention preferably has a low sodium content (e.g., about 1.5 wt% or less). Preferred silica components include sodium-stabilized colloidal silica, ammonium-stabilized colloidal silica, and acid-stabilized colloidal silica; mixtures of any two or all three of these stabilized colloidal silicas can be used.

[0046] The total amount of this silica component in the catalyst composition, if present, is generally from about 0.1 wt% to about 20 wt%, preferably from about 0.25 wt% to about 15 wt%, more preferably from about 0.5 wt% to about 10 wt%, and even more preferably from about 1 wt% to about 7.5 wt%, based on the total weight of the dry components forming the catalyst composition, which does not include silica from zeolite components or other sources (e.g., clays).

[0047] In some embodiments, the catalyst composition includes both an alumina component and a silica component.

[0048] Optionally, one or more clays may be present in the catalyst composition. In some embodiments, one or more clays are present in the catalyst composition. Clays suitable for the catalyst composition include kaolin, bentonite, saponite, sepiolite, attapulgite, laponite, laolinite, hectorite, halloysite, montmorillonite, English clay, anionic clays (e.g., hydrotalcite), and heat-treated or chemically treated clays (e.g., metakaolin). Preferred clays include kaolin, bentonite, and hydrotalcite.

[0049] When present, the total amount of clay in the catalyst composition is generally from about 0.1 wt % to about 75 wt %, preferably from about 5 wt % to about 65 wt %, and more preferably from about 10 wt % to about 60 wt %, based on the total weight of the catalyst composition.

[0050] For fluid catalytic cracking catalyst compositions in which all of the components of the catalyst composition are present in a single particle, the ratio of the zeolite surface area to the matrix surface area can be determined. For purposes of determining the surface area ratio, the matrix includes alumina, silica, if present, and clay. In some embodiments in which all of the components of the catalyst composition are present in a single particle, the ratio of the zeolite surface area to the matrix surface area is about 5:1 or less, preferably about 2:1 or less, more preferably about 1.5:1 or less. In other embodiments in which all of the components of the catalyst composition are present in a single particle, the ratio of the zeolite surface area to the matrix surface area is usually about 1.5:1 or less, preferably about 1.3:1 or less. In another embodiment in which all of the components of the catalyst composition are present in a single particle, the ratio of the zeolite surface area to the matrix surface area is about 0.25:1 to about 1.5:1, preferably about 0.45:1 to about 1.5:1, more preferably about 0.45:1 to about 1.4:1. In yet another embodiment in which all components of the catalyst composition are present in a single particle, the ratio of the zeolite surface area to the matrix surface area is less than or equal to about 1: 1. In yet another embodiment in which all components of the catalyst composition are present in a single particle, the ratio of the zeolite surface area to the matrix surface area is from about 0.25: 1 to about 1: 1, preferably from about 0.45: 1 to about 1: 1.

[0051] The fluid cracking catalyst composition can be prepared in a variety of ways. In some embodiments, the rare earth component is present in a Y-type zeolite; in other embodiments, the rare earth component is added separately from the Y-type zeolite. In some embodiments where the fluid cracking catalyst composition comprises a ZSM-5 zeolite, the phosphorus component is present in the ZSM-5 zeolite; in other embodiments, the phosphorus component is added separately from the ZSM-5 zeolite.

[0052] The feedstock for the process of the present invention comprises an oxygenated feedstock, which comprises at least one oxygenate and, optionally, a hydrocarbon feedstock. When a hydrocarbon feedstock is part of the feedstock, the oxygenated feedstock can be present in any amount, for example, from about 0.1 wt% to about 99.9 wt% of the feedstock. In some embodiments, the oxygenated feedstock comprises at least about 0.5 wt% of the feedstock, typically from about 0.5 wt% to about 60 wt% of the feedstock, preferably from about 1 wt% to about 50 wt% of the feedstock, more preferably from about 3 wt% to about 30 wt%, even more preferably from about 3 wt% to about 20 wt%, even more preferably from about 3 wt% to about 15 wt%, and even more preferably from about 3 wt% to about 10 wt%.

[0053] Another way to express the amount of oxygen-containing material or oxygen-containing compound(s) present in the feedstock is as the amount of oxygen present in the feedstock. In terms of oxygen present in the feedstock, the amount of oxygen is about 0.01 wt% or more of the feedstock, typically about 0.01 wt% to about 50 wt% of the feedstock, preferably about 0.1 wt% to about 40 wt% of the feedstock, more preferably about 0.1 wt% to about 25 wt%, even more preferably about 0.1 wt% to about 15 wt%, even more preferably about 0.1 wt% to about 10 wt%, and even more preferably about 0.1 wt% to about 5 wt%. Other preferred amounts of oxygen in the feedstock are greater than or equal to about 0.1 wt% of the feedstock, typically from about 0.1 wt% to about 12 wt% of the feedstock, preferably from about 0.1 wt% to about 6 wt% of the feedstock, more preferably from about 0.1 wt% to about 3 wt%, even more preferably from about 0.1 wt% to about 2 wt%, even more preferably from about 0.1 wt% to about 1.5 wt%, and even more preferably from about 0.1 wt% to about 1 wt%.

[0054] The oxygenate used in the process of the present invention contains at least carbon, hydrogen, and oxygen, and has one or more carbon atoms, one or more hydrogen atoms, and one or more oxygen atoms. Compounds containing only one carbon atom can be used; compounds containing only one oxygen atom can be used. Usually, there are two or more hydrogen atoms in the oxygenate, and often three or more hydrogen atoms.

[0055] Preferably, the oxygen content of the oxygen-containing compound is about 5 wt% or more, or about 5 wt% to about 75 wt%. More preferred are oxygen-containing compounds having a molecular weight of about 30 g / mol or more and an oxygen content of about 5 wt% or more, preferably about 5 wt% to about 60 wt%.

[0056] Suitable oxygenates include formaldehyde, methanol, ethanol, propanol, glycerol, polyols, phenolic compounds, furans, quinones, fatty acids, fatty acid methyl esters (FAMEs), triglycerides (including animal fats), such as soybean oil, palm oil, rapeseed oil (canola oil), other vegetable oils, other oils extracted from plants, distilled corn oil, used edible oils, and / or derivatives of any of these oxygenates, where "derivatives" refers to products, by-products, or by-products of physical or chemical processing or combinations thereof. Additional suitable oxygenates include biogenic pyrolysis oil, waste-derived pyrolysis oil, hot water liquid oil, sewage sludge-derived oil, plastic-derived oil, municipal waste-derived oil, or industrial waste-derived oil, and / or derivatives of any of these oxygenates, where "derivatives" refers to products, by-products, or by-products of physical or chemical processing or combinations thereof. Physical processing of these oxygenates may include distillation, filtration, and / or oil pressing and / or filtration. Chemical processing of these oxygenates may include contaminant removal and / or conversion processes; conversion processes typically include fermentation, esterification, saponification, and metathesis. Mixtures of any two or more oxygenates and / or their derivatives may be used. Preferred oxygenates include triglycerides, more preferably soybean oil, palm oil, rapeseed oil (canola oil), other vegetable oils, other oils extracted from plants, and used edible oils.

[0057] In some embodiments, the oxygenates are present as mixtures, particularly those derived from biological or waste sources. Biological sources include biomass, pyrolysis oils, algae, agricultural waste, animal waste and fats, and tall oil. Carbon-based waste sources include municipal waste, industrial waste, sewage sludge, domestic waste, and electronic waste. Oxygenated mixtures derived from biological or waste sources are products, by-products, and / or by-products of physical or chemical processing of biological or waste sources (often thermochemical or catalytic conversion of biological or waste sources). Exemplary processes that produce oxygenated mixtures include separation (e.g., distillation or extraction), various pyrolysis processes, gasification, hydrothermal liquefaction, roasting, polymerization, depolymerization, Fischer-Tropsch synthesis, and acid or base decomposition. Combinations of one or more processes can produce oxygenated compounds or oxygenated mixtures. Oxygenated compounds and / or oxygenated mixtures obtained by further processing, extraction, or chemical or physical modification of the products can also be used to produce oxygenated compounds or mixtures used in the process of the invention.

[0058] Additional oxygenates which may be produced as a mixture and used in the process of the present invention include aqueous phase liquids from the pyrolysis of an organic compound or mixture of organic compounds, and vapors from various processes performed on an organic compound or mixture of organic compounds, such as pyrolysis, hydrothermal liquefaction, or gasification.

[0059] Related materials that can be used for the oxygenated feedstock include pyrolysis oils that have been treated to reduce the oxygen and / or nitrogen content and / or to remove metals and / or other contaminants. Some of these materials, which occur as mixtures, contain one or more heteroatoms (in addition to oxygen) (e.g., nitrogen or sulfur), although a wide variety of other heteroatoms may also be present. Mixtures of these materials, which occur as mixtures with each other and / or with one or more oxygenates, can be used in the practice of the present invention.

[0060] When a hydrocarbon feedstock is part of the feedstock, the hydrocarbon feedstock may be a resid feedstock, light gas oil (LGO), heavy gas oil (HGO), vacuum gas oil (VGO), deep cut gas oil, thermal oil, cycle oil, hole top crude oil, tar sands oil, shale oil, synthetic fuel, naphtha, petroleum gas or liquefied petroleum gas (LPG), heavy hydrocarbon fractions (e.g., those obtained from the destructive hydrogenation of coal, tar, pitch, asphalt), and / or hydrotreated feedstocks obtained from any of the above.

[0061] The term "feedstock" as used throughout this document is not intended to limit the physical form of the feedstock (e.g., gas, liquid, suspension, slurry, emulsion). When the hydrocarbon feedstock and the oxygenate feedstock form a feedstock, there is no need for premixing or blending the feedstocks; these feedstocks can be introduced separately; the only requirement is that a portion of the hydrocarbon feedstock and a portion of the oxygenate feedstock are simultaneously present in the reaction chamber with the fluid catalytic cracking catalyst composition in the desired ratio.

[0062] As used throughout this document, the phrase "oxygenate" refers to a feedstock that contains one or more oxygen-containing compounds. The oxygenate may form the entire feedstock or may be included as part of the feedstock, with the hydrocarbon feed comprising another portion of the feedstock.

[0063] The process of the present invention is generally considered to be a fluid catalytic cracking process. In an FCC process, the catalyst is generally particulate with about 90 wt% or more of the particles having diameters in the range of about 5 to about 300 microns: in an FCC process, a hydrocarbon feedstock is gasified and conducted upwardly through a reaction zone such that the particulate catalyst enters and fluidizes the hydrocarbon feedstock stream, the catalyst contacts the gaseous hydrocarbon feedstock, and the gaseous hydrocarbon feedstock is cracked by the catalyst.

[0064] In the process of the invention, a feedstock is contacted with a fluid catalytic cracking composition under fluid catalytic cracking conditions to obtain a product. The catalyst to oil ratio is typically in the range of about 1 to about 15 (wt / wt). In some embodiments, the catalyst to oil ratio is typically in the range of about 2 to about 12 (wt / wt). The temperature of the fluid cracking reaction zone is typically in the range of about 300° C. to about 700° C., and often in the range of about 400° C. to about 650° C. In some embodiments, the temperature of the reaction zone is in the range of about 450° C. to about 575° C. The pressure of the fluid cracking reaction zone is typically in the range of about 14 pounds per square inch to about 45 pounds per square inch (0.097 MPa to 0.31 MPa). In some embodiments, the pressure in the reaction zone is in the range of about 14.5 pounds per square inch to about 29.4 pounds per square inch (0.1 MPa to 0.2 MPa). In other embodiments, the pressure in the reaction zone is atmospheric pressure. The contact time between the feedstock and the fluid catalytic cracking catalyst composition typically ranges from about 0.5 seconds to about 10 seconds. In some embodiments, the contact time ranges from about 1 second to about 5 seconds. In other embodiments, the contact time ranges from about 1 second to about 3 seconds. The reaction outlet temperature in the process of the present invention is generally from about 400° C. to about 650° C. In some embodiments, the reaction zone temperature ranges from about 450° C. to about 600° C. In other embodiments, the reaction zone temperature ranges from about 500° C. to about 575° C.

[0065] The process of the invention includes contacting a fluid cracking catalyst composition with a feedstock comprising at least one oxygenate and, optionally, a hydrocarbon feedstock. In some embodiments, the fluid cracking catalyst composition contains one or more Y-type zeolites, one or more ZSM-5 zeolites, a rare earth component, a phosphorus component, and an alumina comprising boehmite and / or pseudo-boehmite. In other embodiments, the fluid cracking catalyst composition contains one or more Y-type zeolites, a rare earth component, a phosphorus component, and an alumina comprising boehmite and / or pseudo-boehmite.

[0066] Another embodiment of the invention is a fluid cracking catalyst composition comprising one or more Y-type zeolites, one or more ZSM-5 zeolites, a rare earth component, a phosphorus component, and an alumina containing boehmite and / or pseudo-boehmite, the characteristics of these components, the amounts thereof, and preferences for all of these are as described above.

[0067] Yet another embodiment of the present invention is a fluid cracking catalyst composition comprising one or more Y-type zeolites, a rare earth component, a phosphorus component, and an alumina containing boehmite and / or pseudo-boehmite, the characteristics of these components, the amounts thereof, and preferences for all of these and the preferences for each of these components being as described above.

[0068] The following examples are offered for illustrative purposes and are not intended to limit the scope of the invention. EXAMPLES

[0069] Example 1 Various feedstocks were subjected to fluid catalytic cracking using various fluid catalytic cracking catalysts (mixed with 15-19.5 wt% ZSM-5). For the phosphorus-containing catalysts, phosphorus was added by the addition of H 3 PO 4 It was introduced as an aqueous solution of

[0070] Catalysts C, E, and A are for comparison. Catalyst C is composed of 25-35 wt% Y zeolite; 25-35 wt% alumina (boehmite and / or pseudoboehmite); 1-3 wt% silica; and lanthanum oxide (La) present in the Y zeolite. 2 O 3 The catalyst contained 0.2-2 wt% rare earths as catalyst catalysts, the remainder being mineral clays. The catalyst had a fresh surface area of ​​200 m 2 / g~300m 2 / g, with a zeolite to matrix surface area of ​​0.5:1 to 1.5:1. Catalyst E was composed of 25-35 wt% Y zeolite; 25-35 wt% alumina (boehmite and / or pseudoboehmite); 1-3 wt% silica; 0.2-2 wt% rare earths as lanthanum oxide present in the Y zeolite; P 2 O 5 The catalyst contained 0.2-2 wt% phosphorus as a catalyst, with the remainder being mineral clay. The catalyst had a fresh surface area of ​​275 m 2 / g~350m 2 / g with a zeolite to matrix surface area of ​​0.5:1-1.5:1. Catalyst A contained 2.5-5 wt% ZSM-5; 15-25 wt% Y zeolite; 25-35 wt% alumina (boehmite and / or pseudo-boehmite); 1.5-5 wt% silica; 1-3 wt% rare earths as lanthanum oxides present in the Y zeolite with the balance being mineral clay. This catalyst had a fresh surface area of ​​200 m 2 / g~300m 2 / g, with the zeolite to matrix surface area being 1:1 to 1.7:1. The amounts of components in Catalysts C, E, and A are listed in Table 1A.

[0071] Catalysts D, F and B are related to the invention. Catalyst D is composed of 5-10 wt% ZSM-5; 25-35 wt% Y zeolite; 25-35 wt% alumina (boehmite and / or pseudo-boehmite); 1-3 wt% silica; La present in the Y zeolite. 2 O 3 % of rare earths as catalysts, with the remainder being mineral clays. The catalysts had a zeolite to matrix surface area ratio of 0.5:1 to 1.3:1. Catalyst F was composed of 5-10 wt% ZSM-5; 25-35 wt% Y zeolite; 25-35 wt% alumina (boehmite and / or pseudo-boehmite); 1-3 wt% silica; La present in the Y zeolite. 2 O 3 1.5~3.5wt% rare earths as P 2 O 5% ZSM-5, 0.2-2 wt. % phosphorus as lanthanum oxide, and the balance being mineral clay. The catalyst had a zeolite to matrix surface area ratio of 0.5:1 to 1.2:1. Catalyst B consisted of a) 70 wt. % catalyst containing 2.5-5 wt. % ZSM-5, 15-35 wt. % Y zeolite, 20-35 wt. % alumina (boehmite and / or pseudo-boehmite), 1.5-5 wt. % silica, 1.3 wt. % rare earths as lanthanum oxides present in the Y zeolite, and the balance being mineral clay, and b) 50-75 wt. % ZSM-5, 2-20 wt. % alumina (boehmite and / or pseudo-boehmite), 2-10 wt. % silica, and P 2 O 5 % of the additive, containing 2-15 wt. % phosphorus as the additive. Catalyst B was prepared by physically mixing the powders of part a) and part b). The amounts of the components of catalysts D, F, and B are listed in Table 1B.

[0072] Catalysts A-F were subjected to Advanced Cracking Evaluation Technology (ACE Technology®; Kayser Technology, Inc.) using feedstocks with varying ratios of soybean oil and VGO. The hydrocarbon feed was a vacuum gas oil (VGO) feed and the oxygenated feed was refined, bleached, degummed, and deodorized soybean oil containing about 8 wt% to about 11 wt% oxygen. The feedstocks ranged in amount of VGO from 0 to 100 wt% and in amount of soybean oil from 0 to 100 wt%. When both soybean oil and VGO were present in the feedstock, the soybean oil and VGO were mixed and fed as a single stream. Catalyst-to-oil ratio (CTO) (calculated as the total weight of catalyst divided by the total weight of feedstock oil introduced into the reactor in a given run). CTO ratios were varied from 2 to 10 grams catalyst / gram feed. Testing was performed in an ACE Technology® unit according to ASTM D7964 / D7964M-19 (Standard Test Method for Measuring Activity of Fluidized Catalytic Cracking (FCC) Catalysts in a Fluidized Bed). The reaction zone temperature was 480° C.-540° C., and the reaction zone pressure was 14.5 psia-25 psia (0.1 MPa-0.17 MPa). The VGO feedstock properties are listed in Table 2. The relative amounts of soybean oil and VGO, as well as the results of the ACE Technology® testing, are summarized in Tables 3A-3B and 4A-4B. [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7]

[0073] In the above runs, coke reduction of nearly 1 wt% was achieved at low catalyst to oil ratios (e.g., about 3:1 by weight) for Catalyst B compared to Catalyst A. When the fluid cracking catalyst composition contained about 15 wt% or more ZSM-5 zeolite, a net coke reduction of about 1.5 wt% was observed relatively consistently at the various catalyst to oil ratios evaluated and for all oxygenated feed ratios tested.

[0074] In Figure 1, the actual hydrogen and coke yields of Comparative Catalyst A of Example 1 are compared to the predicted hydrogen and coke yields for various soybean oil to VGO ratios at a constant catalyst to oil ratio of 4. In Figure 2, the actual hydrogen and coke yields of Catalyst B of Example 1 are compared to the predicted hydrogen and coke yields for various soybean oil to VGO ratios at a constant catalyst to oil ratio of 4. In both Figures 1 and 2, the predicted yields were calculated from a linear combination of the expected coke and hydrogen yield contributions from VGO alone and soybean oil alone. In equation form, the predicted yield calculation is expressed as follows, where SBO is soybean oil and X is either hydrogen or coke: Expected yield of X, wt% = (Yield of X, wt%) 100%VGO × (VGO in raw material (wt%)) + (yield of X (wt%)) 100%SBO × (SBO in raw material (wt%)) The actual yields are lower than would be predicted from the feed additive or dilution effect on both coke and hydrogen yields, indicating a synergistic effect of a feed containing both VGO and oxygenates (herein soybean oil) when cracked over either catalyst. For Catalyst B, the greater reduction in both coke and hydrogen yields indicates that a higher amount of pentasil zeolite component (phosphorus-containing ZSM-5 zeolite) as part of the Catalyst B fluid cracking catalyst composition improves the reduction in the amount of coke and hydrogen produced.

[0075] In addition to the observed reduction in coke and hydrogen, other improvements in the amount of products obtained from the fluid catalytic cracking process according to the present invention include reduction in bottoms, reduction in dry gas volume at similar dry gas mass yield, gasoline yield, propylene yield, and / or C 4 Improvements in olefin yields, including those that can be achieved with higher percentages of oxygen-containing components (about 2.5 wt% or more oxygen in the feed) when a small or medium pore zeolite (particularly a pentasil zeolite, typically ZSM-5, often a phosphorus-containing ZSM-5 zeolite) is present in the fluid cracking catalyst composition in an amount of about 15 wt% or more. Another improvement in product quantities obtained when a pentasil zeolite additive (typically ZSM-5, often a phosphorus-containing ZSM-5 zeolite) is present with the fluid cracking catalyst composition in an amount of about 15 wt% or more and the oxygen-containing components provide about 2.5 wt% or more oxygen in the feed is increased olefinicity of the liquefied petroleum gas (LPG) due to increased formation of product components (e.g., propylene and butylene) without increasing the amount of LPG produced. Yet another improvement obtained when a small or medium pore zeolite, particularly a pentasil zeolite (usually ZSM-5, often a phosphorus-containing ZSM-5 zeolite), is present in the fluid cracking catalyst composition in an amount of about 15 wt % or greater, further significantly reduces the amount of dry gas produced.

[0076] The present invention allows for the use of hydrocarbon feedstocks without reducing the residual carbon in the hydrocarbon feedstock or reducing the amount of metal contaminants in the hydrocarbon feedstock.

[0077] The presence of oxygenated components allows the FCC process to be run at higher conversions and catalyst-to-oil ratios, and higher throughputs, than could otherwise be achieved. Reduced hydrogen production allows operation at higher (catalytic) temperatures, increasing product throughput and / or conversion levels while producing more liquefied petroleum gas (LPG) and LPG-range olefins.

[0078] In turn, reduced dry gas production reduces wet gas compressor limitations, allowing for increased light olefin production or increased unit throughput.

[0079] A component referred to by chemical name or formula anywhere in this specification or claims, whether referred to in the singular or plural, is identified as being present prior to contact with another substance referred to by chemical name or chemical type (e.g., another component, solvent, etc.). It does not matter what chemical changes, transformations, and / or reactions (if any) occur in the resulting mixture or solution, because such changes, transformations, and / or reactions are the natural result of bringing together the specified components under the conditions required in accordance with this disclosure. Thus, the components are identified as components that are brought together in connection with performing a desired operation or in forming a desired composition. Also, even if the claims herein may refer to substances, components, and / or ingredients in the present tense (e.g., "comprising," "is," etc.), the reference refers to the substance, component, or ingredient that was present immediately prior to being first contacted, blended, or mixed with one or more other substances, components, and / or ingredients in accordance with this disclosure. Thus, the fact that a substance, component, or ingredient may have lost its original identity by chemical reaction or change in the course of a contacting, blending, or mixing operation, when carried out in accordance with this disclosure and within the ordinary skill of a chemist, is of no practical importance.

[0080] The present invention may comprise, consist of, or consist essentially of the materials and / or procedures recited herein.

[0081] As used herein, the term "about" modifying the amount of a component in the composition or used in the method of the present invention refers to variations in the numerical amount that may occur due to, for example, typical measuring procedures and liquid handling procedures used to make concentrates or use solutions in the real world, inadvertent errors in these procedures, differences in manufacture, source, or purity of the components used to make the composition or carry out the method, etc. The term "about" also encompasses amounts that differ due to different equilibrium conditions of the composition resulting from a particular initial mixture. Whether or not modified by the term "about," the claims include the equivalent of the amount.

[0082] Unless expressly indicated otherwise, the article "a" or "an" as used herein is not intended, and should not be construed as, limiting the description or claims to the single element to which the article refers. Rather, the article "a" or "an" as used herein is intended to cover one or more such elements, unless the context expressly indicates otherwise.

[0083] This invention is susceptible to considerable variation in its practice, therefore the foregoing description is not intended to limit, and should not be construed as limiting, the invention to the particular exemplifications presented hereinabove.

Claims

1. 1. A process for fluid catalytic cracking of a feedstock, comprising contacting a fluid catalytic cracking catalyst composition with a feedstock comprising an oxygenated feedstock and, optionally, a hydrocarbon feedstock, wherein the oxygenated feedstock comprises at least one oxygenate containing at least carbon, hydrogen, and oxygen, and wherein the fluid catalytic cracking catalyst composition is a) one or more Y-type zeolites, one or more ZSM-5 zeolites, a rare earth component, and an alumina containing boehmite and / or pseudoboehmite, or b) one or more Y-type zeolites, rare earth components, and alumina, including boehmite and / or pseudoboehmite The process comprising:

2. 2. The process of claim 1, wherein the Y-type zeolite is a Y zeolite or an ultrastable Y zeolite.

3. In a), the amount of said Y-type zeolite is about 0.5 wt % or more; the amount of ZSM-5 zeolite is greater than or equal to about 1 wt. %; and / or the amount of said rare earth constituent is greater than or equal to about 0.25 wt. % as rare earth oxide(s); 3. The process of claim 1 or 2, wherein the amount is relative to the total weight of the catalyst composition.

4. 4. The process of claim 1, wherein in a) the zeolite is in a weight ratio of Y-type zeolite to ZSM-5 zeolite of about 0.25:1 or greater.

5. In b), the amount of the Y-type zeolite is greater than or equal to about 5 wt %; and / or the amount of said rare earth constituent is greater than or equal to about 0.25 wt. % as rare earth oxide(s); 3. The process of claim 1 or 2, wherein the amount is relative to the total weight of the catalyst composition.

6. The process of any one of claims 1 to 5, wherein the rare earth component comprises yttrium, lanthanum, cerium, and / or praseodymium.

7. The process according to any of claims 1 to 6, wherein the alumina is boehmite, or boehmite and pseudo-boehmite, and / or the amount of the alumina is from 0.1 to 50 wt %, based on the total weight of the catalyst composition.

8. The process of any one of claims 1 to 7, wherein the combined amount of zeolite and alumina is about 25 wt% or more, based on the total weight of the catalyst composition.

9. The process of any of claims 1 to 8, wherein silica is present in an amount of from about 0.1 wt% to about 20 wt%, based on the total weight of the catalyst composition.

10. 10. The process of any of claims 1 to 9, wherein clay is present in an amount of from about 0.1 wt% to about 75 wt%, based on the total weight of the catalyst composition.

11. A phosphorus component is present, and the amount of the phosphorus component is based on the total weight of the catalyst composition.

11. The process of any one of claims 1 to 10, wherein the phosphorus pentoxide is about 0.1 wt% or more.

12. The process of any one of claims 1 to 11, wherein the oxygen-containing feed consists of one oxygenate having an oxygen content of about 5 wt% or more.

13. 13. The process of any of claims 1 to 12, wherein the oxygenated feed consists of one oxygenate having a molecular weight of about 30 grams / mole or greater and an oxygen content of about 5 wt.% or greater.

14. The process of any of claims 1 to 13, wherein the oxygenate is soybean oil.

15. The process of any of claims 1 to 14, wherein the feedstock comprises a hydrocarbon feedstock and the oxygenated feedstock is about 0.5 wt% or more of the feedstock.

16. The process of any of claims 1 to 15, wherein oxygen is present in an amount of about 0.3 wt% or greater of the feedstock.

17. 1. A fluid catalytic cracking catalyst composition comprising: a) one or more Y-type zeolites, one or more ZSM-5 zeolites, a rare earth component, and an alumina containing boehmite and / or pseudoboehmite, or b) one or more Y-type zeolites, rare earth components, and alumina, including boehmite and / or pseudoboehmite The fluid catalytic cracking catalyst composition comprising:

18. 18. The composition of claim 17, wherein the Y-type zeolite is a Y zeolite or an ultrastable Y zeolite.

19. In a), the amount of said Y-type zeolite is about 0.5 wt % or more; the amount of ZSM-5 zeolite is greater than or equal to about 1 wt. %; and / or the amount of said rare earth constituent is greater than or equal to about 0.25 wt. % as rare earth oxide(s); 19. The composition of claim 17 or 18, wherein the amount is relative to the total weight of the catalyst composition.

20. 20. The composition of claim 17, wherein in a) the zeolite is in a weight ratio of Y-type zeolite to ZSM-5 zeolite of about 0.25:1 or greater.

21. In b), the amount of the Y-type zeolite is greater than or equal to about 5 wt %; and / or the amount of said rare earth constituent is greater than or equal to about 0.25 wt. % as rare earth oxide(s); 19. The composition of claim 17 or 18, wherein the amount is relative to the total weight of the catalyst composition.

22. 22. The composition of any of claims 17 to 21, wherein the rare earth component comprises yttrium, lanthanum, cerium, and / or praseodymium.

23. The alumina is boehmite, or boehmite and pseudoboehmite, and / or 23. The composition according to claim 17, wherein the amount of said alumina is from 0.1 to 50 wt %, based on the total weight of said catalyst composition.

24. 24. The composition of any one of claims 17 to 23, wherein the combined amount of the zeolite and alumina is about 25 wt% or more, based on the total weight of the catalyst composition.

25. 25. The composition of any of claims 17 to 24, wherein silica is present in an amount of from about 0.1 wt % to about 20 wt %, based on the total weight of the catalyst composition.

26. 26. The composition of any of claims 17 to 25, wherein a clay is present in an amount of from about 0.1 wt % to about 75 wt %, based on the total weight of the catalyst composition.

27. 27. The composition of any of claims 17 to 26, wherein a phosphorus component is present and the amount of said phosphorus component is about 0.1 wt. % or more as phosphorus pentoxide, based on the total weight of said catalyst composition.

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