Catalytic cracking of hydrocarbons using fluidizable particles containing emm-17

Abstract

EMM-17 may be utilized during catalytic cracking of a hydrocarbon feed to afford increased production of butylenes while maintaining high C4- olefinicity. Such methods may comprise: introducing a hydrocarbon feed to a reactor containing a cracking aid comprising a plurality of fluidizable particles comprising at least EMM-17, the EMM-17 being a zeolite having an X-ray powder diffraction pattern characterized by at least the following 2θ scattering angles, as determined using Cu Kα radiation: 7.6+0.2, 8.0+0.2, 8.4+0.2, 10.4+0.2, 14.7+0.2, 15.6+0.2, 22.6+0.2, and 23.2+0.2; exposing the hydrocarbon feed to catalytic cracking conditions in the reactor in the presence of the cracking aid; and obtaining a cracked hydrocarbon product having a weight ratio of propylene to butylenes of about 1.5 or less and a C4- olefinicity of about 80% or more.

Description

CATALYTIC CRACKING OF HYDROCARBONS USING FLUIDIZABLE PARTICLES CONTAINING EMM-17FIELD

[0001] The present disclosure relates to catalytic cracking of hydrocarbons, and more particularly, methods for catalytically cracking hydrocarbons with improved selectivity toward butylenes production.BACKGROUND

[0002] Catalytic cracking, including fluid catalytic cracking (FCC), is a widely used process in the petroleum industry to convert heavy, high-boiling hydrocarbons into more valuable, lower-boiling products such as gasoline and diesel fuel. FCC processes begin with a feedstock, typically a heavy crude oil or vacuum gas oil, that may be preheated and introduced into a reactor and mixed with fluidizable catalyst particles. The fluidizable catalyst particles may comprise at least one zeolite as a catalytic material. As long-chain hydrocarbons in the feedstock break apart due to high temperatures in the reactor, the resulting cracked molecular fragments contact the catalytic material and undergo further cracking and rearrangement into smaller hydrocarbons. FCC processes may be tailored to maximize the yield of particular light hydrocarbons, commonly propylene, through manipulation of the hydrocarbon feedstock composition, the properties of the catalyst, and various reaction conditions.

[0003] Cracking aids for FCC may include a primary cracking catalyst and a secondary cracking catalyst, each being located upon a plurality of fluidizable particles. USY zeolite is a common primary cracking catalyst. Common secondary cracking catalysts for FCC may include MFI zeolites (e.g., ZSM-5), NU-86, MEL zeolites, MTW zeolites, TON zeolites, or MTT zeolites. Cracking aids including these secondary cracking catalysts are usually prone to producing propylene in preference to butylenes. In addition, butylenes are more likely than propylene under FCC conditions to be saturated forming butanes and may tend to undergo further cracking to form even smaller light ends or byproducts such as coke, thereby lowering the butylenes yield even further.

[0004] Although propylene is frequently more readily produced by catalytic cracking than are butylenes and may often be the desired primary cracking product, there are instances when it may be desirable to produce butylenes preferentially. Butylenes are commonly used in the production of high- octane gasoline, which is more valuable than conventional gasoline. Additionally, butylenes are a precursor to other valuable chemicals, including methyl tert-butyl ether (MTBE), a gasoline additive, and butadiene, which is used in the production of synthetic rubber and other industrial materials. At present, catalytic cracking processes may not be capable of producing butylenes reliably or insufficient yields. Catalytic cracking processes suitable for producing butylenes in preference to propylene would therefore be desirable.SUMMARY

[0005] In some aspects, catalytic cracking methods of the present disclosure comprise: introducing a hydrocarbon feed to a reactor containing a cracking aid comprising a plurality of fluidizable particles comprising at least EMM-17, the EMM-17 being a zeolite having an X-ray powder diffraction pattern characterized by at least the following 20 scattering angles, as determined using Cu Kot radiation: 7.6+0.2, 8.0+0.2, 8.4+0.2, 10.4+0.2, 14.7+0.2, 15.6+0.2, 22.6+0.2, and 23.2±0.2; exposing the hydrocarbon feed to catalytic cracking conditions in the reactor in the presence of the cracking aid; and obtaining a cracked hydrocarbon product having a weight ratio of propylene to butylenes of about 1.5 or less and a C4- olefini city of about 80% or more.

[0006] In some aspects, methods for producing fluidizable catalyst particles comprising EMM- 17 comprise: combining EMM-17 and a dispersant to form a first EMM-17 slurry, the EMM-17 being a zeolite having an X-ray powder diffraction pattern characterized by at least the following 20 scattering angles, as determined using Cu Koc radiation: 7.6+0.2, 8.0+0.2, 8.4+0.2, 10.4+0.2, 14.7+0.2, 15.6+0.2, 22.6+0.2, and 23.2+0.2; combining the first EMM-17 slurry with a homogenizer and a binder to obtain a second EMM- 17 slurry; spray drying the second EMM- 17 slurry to form a plurality of fluidizable particles comprising the EMM-17; and calcining the plurality of fluidizable particles.

[0007] In some aspects, cracking catalysts suitable for performing fluid catalytic cracking comprise: a first plurality of fluidizable particles comprising a primary cracking catalyst; and a second plurality of fluidizable particles comprising EMM- 17 as a secondary cracking catalyst; wherein the fluidizable particles further comprise a binder and a homogenizer.

[0008] These and other features and attributes of the disclosed methods of the present disclosure and their advantageous applications and / or uses will be apparent from the detailed description which follows.BRIEF DESCRIPTION OF THE DRAWINGS

[0009] To assist those of ordinary skill in the relevant art in making and using the subject matter hereof, reference is made to the appended drawings. The following figures are included to illustrate certain aspects of the disclosure, and should not be viewed as exclusive configurations. The subject matter disclosed is capable of considerable modifications, alterations, combinations, and equivalents in form and function, as will occur to those skilled in the art and having the benefit of this disclosure.

[0010] FIG. 1 is a graph of the X-ray diffraction pattern of EMM-17 after exposure to various steaming conditions.

[0011] FIG. 2 is a graph of product yield composition for cracking performed with a 75 wt% USY :25 wt% EMM-17 cracking aid in comparison to that of a 75 wt% USY :25 wt% ZSM-5 cracking aid.

[0012] FIG. 3 is a graph of C3 / C4 olefin ratio as a function of the C3+C4 olefin yield for cracking performed with a 75 wt% USY:25 wt% EMM-17 cracking aid in comparison to that of a reference 75 wt% USY:25 wt% ZSM-5 cracking aid.

[0013] FIG. 4 is a graph of C4- olefinicity as a function of the volume of C4- produced per volume of feed for cracking performed with a 75 wt% USY:25 wt% EMM-17 cracking aid in comparison to that of a reference 75 wt% USY:25 wt% ZSM-5 cracking aid.DETAILED DESCRIPTION

[0014] The present disclosure relates to catalytic cracking of hydrocarbons, and more particularly, methods for catalytically cracking hydrocarbons with improved selectivity toward butylenes production.

[0015] As indicated above, catalytic cracking of a hydrocarbon feedstock may often form propylene in preference to butylenes. Catalytic cracking methods of the present disclosure may produce butylenes with improved selectivity relative to propylene in comparison to conventional FCC processes. In the present disclosure, EMM- 17 may be combined as a secondary cracking catalyst with a primary cracking catalyst, such as a USY zeolite, to provide a cracking aid suitable for performing catalytic cracking, preferably fluid catalytic cracking. The primary cracking catalyst and the EMM- 17 may be located on a plurality of fluidizable particles when accomplishing the foregoing. EMM- 17 is an aluminosilicate zeolite having three-dimensional intersecting H xlOx lO-ring channels, as discussed further below and described in more detail in U.S. Patent 9,452,423, incorporated herein by reference, which may facilitate cracking of a hydrocarbon feedstock in combination with a suitable primary cracking catalyst. Surprisingly, the combination of EMM-17 and a primary cracking catalyst, such as USY zeolite, may afford improved selectivity toward butylenes production than is typically realized in FCC. In addition, such cracking aids comprising EMM-17 may surprisingly improve C4- olefinicity of the resulting cracked hydrocarbon product as well, thereby affording more efficient hydrocarbon feedstock utilization and less product loss as paraffinic light ends and dry gas.

[0016] EMM-17 also offers the additional advantage of excellent thermal stability when incorporated within a cracking aid for catalytic cracking. The crystallinity and active sites of EMM-17 may be preserved even after the zeolite has been exposed to high temperatures and conditions comparable to those of an FCC environment. The thermal stability of EMM-17 may reduce the extent of catalytic deactivation, thus decreasing system downtime and lowering the amount of fresh catalyst that needs to be replenished in the reactor to maintain the butylenes yield, as well as the yield of total olefins, over extended run times.

[0017] In addition, as discussed further herein, EMM-17 may be readily incorporated within fluidizable particles that are highly suitable for performing catalytic cracking. Such fluidizable particles may be combined in various ratios with other fluidizable particles containing the primary cracking catalyst (e.g. , USY zeolite) to promote tailoring of the cracking process. Because the EMM- 17 and the primary cracking catalyst may be located within separate fluidizable particles, the primary cracking catalyst and the EMM-17 may be easily mixed in various ratios to alter the EMM-17:USY zeolite ratio. Altering the EMM-17:USY zeolite ratio may allow further tailoring of the composition obtained within the resulting cracked hydrocarbon product.Definitions

[0018] Various specific embodiments, versions and examples of the present disclosure will now be described, including preferred embodiments and definitions that are adopted herein for purposes of understanding the claimed invention. While the following detailed description gives specific preferred embodiments, those skilled in the art will appreciate that these embodiments are exemplary only, and that the invention may be practiced in other ways. For purposes of determining infringement, the scope of the present disclosure will refer to any one or more of the appended claims, including their equivalents, and elements or limitations that are equivalent to those that are recited. Any reference to the “invention” may refer to one or more, but not necessarily all, of the inventions defined by the claims.

[0019] As used herein, the indefinite article “a” or “an” shall mean “at least one” unless specified to the contrary or the context clearly indicates otherwise.

[0020] Unless otherwise indicated, all numbers indicating quantities in this disclosure are to be understood as being modified by the term “about” in all instances. It should also be understood that the precise numerical values used in the specification and claims constitute specific embodiments.

[0021] The term “and / or” as used in a phrase such as “A and / or B” herein is intended to include “A and B,” “A or B,” “A,” and “B.”

[0022] As used herein, “wt%” means percentage by weight, “vol%” means percentage by volume, “mol%” means percentage by mole, “ppm” means parts per million, and “ppm wt” and “wppm” areused interchangeably and mean parts per million on a weight basis. All concentrations herein, unless otherwise stated, are expressed on the basis of the total amount of the composition in question.

[0023] For the purposes of this disclosure, the nomenclature of elements is pursuant to the NEW NOTATION version of the Periodic Table of Elements as provided in Hawley's Condensed Chemical Dictionary, 16thEd., John Wiley & Sons, Inc., (2016), Appendix V unless otherwise noted.

[0024] As used herein, the terms “optional” or “optionally” mean that the subsequently described event or circumstance does or does not occur (or an element is or is not present) and that the description includes instances where said event or circumstance occurs and instances where said event or circumstance does not occur.

[0025] Following synthesis and calcination, EMM-17 may be characterized by an X-ray diffraction pattern having at least the following 20 scattering angles, as determined using Cu Koc radiation: 7.6+0.2, 8.0+0.2, 8.4+0.2, 10.4+0.2, 14.7±0.2, 15.6±0.2, 22.6+0.2, and 23.2±0.2. The X-ray diffraction data reported herein were collected with a Bruker D8 Endeavor diffraction system using Cu K-oc radiation and a fixed 0.25 degrees divergence slit. The scattering angles were recorded by step-scanning at 0.017 degrees of 20, where 0 is the Bragg angle, and a counting time of 20 seconds for each step. The interplanar spacings, d-spacings, were calculated in Angstrom units, and the relative peak area intensities of the lines, I / I(O) is one-hundredth of the intensity of the strongest line, above background, were determined with the MDI Jade peak profile-fitting algorithm. The intensities are uncorrected for Lorentz and polarization effects. It should be understood that diffraction data listed for this sample as single lines may consist of multiple overlapping lines which under certain conditions, such as differences in crystallographic changes, may appear as resolved or partially resolved lines. Typically, crystallographic changes can include minor changes in unit cell parameters and / or a change in crystal symmetry, without a change in the structure. These minor effects, including changes in relative intensities, can also occur as a result of differences in cation content, framework composition, nature and degree of pore filling, crystal size and shape, preferred orientation, and thermal and / or hydrothermal history. Sample orientation within the powder X-ray diffractometer may also play a role. It is to be appreciated that additional peaks associated with EMM-17 may also be present in the X-ray diffraction pattern.

[0026] Moreover, it is to be appreciated that EMM-17 suitable for use in the disclosure herein may contain up to about 20 wt% of one or more additional phases. Additional phases that may be present in combination with EMM-17 include zeolite phases such as, for example, ZSM-5, beta, mordenite,ZSM-22, NU-86, or other dense phases such as quartz, cristobalite, or layered phases such as kenyaite or magadiite.

[0027] EMM- 17 crystals may feature a large pore volume and surface area to promote a high reaction rate. In non-limiting examples, EMM-17 may have a total BET surface area of about 400 m2 / g to about 600 m2 / g, or about 400 m2 / g to about 550 m2 / g, or about 400 m2 / g to about 500 m2 / g, or about 400 m2 / g to about 450 m2 / g, or about 450 m2 / g to about 600 m2 / g, or about 450 m2 / g to about 550 m2 / g, or about 450 m2 / g to about 500 m2 / g, or about 500 m2 / g to about 600 m2 / g, or about 500 m2 / g to about 550 m2 / g, or about 550 m2 / g to about 600 m2 / g, according to ISO 9277:2010 or procedures similar thereto. The samples were degassed at 350°C for 4 hours under vacuum before nitrogen absorption was carried out. In some or other non-limiting examples, the micropore surface area of EMM-17 may range from about 350 m2 / g to about 550 m2 / g, or about 350 m2 / g to about 500 m2 / g, or about 350 m2 / g to about 450 m2 / g, or about 350 m2 / g to about 400 m2 / g, or about 400 m2 / g to about 550 m2 / g, or about 400 m2 / g to about 500 m2 / g, or about 400 m2 / g to about 450 m2 / g, or about 450 m2 / g to about 550 m2 / g, or about 450 m2 / g to about 500 m2 / g, or about 500 m2 / g to about 550 m2 / g), according to ISO 9277:2010 or modified procedures similar thereto. Similarly, the external surface area of EMM-17 may range from about 10 m2 / g to about 50 m2 / g, or about 10 m2 / g to about 40 m2 / g, or about 10 m2 / g to about 30 m2 / g, or about 10 m2 / g to about 20 m2 / g, or about 20 m2 / g to about 50 m2 / g, or about 20 m2 / g to about 40 m2 / g, or about 20 m2 / g to about 30 m2 / g, or about 30 m2 / g to about 50 m2 / g, or about 30 m2 / g to about 40 m2 / g, or about 40 m2 / g to about 50 m2 / g, according to ISO 9277:2010 or modified procedures similar thereto. The foregoing demonstrates that the pores of EMM-17 may account for greater than about 95% of the zeolite’s total surface area, or greater than about 96%, or greater than about 97%, or greater than about 98%, or greater than about 99%.

[0028] When EMM- 17 is exposed to steam at high temperatures, such as the temperatures commonly encountered within an FCC reactor, the EMM- 17 may show no or only a very low amount of crystal degradation. For example, when exposed to temperatures of 1000°F (537.8°C) or higher for at least four hours, the total surface area of EMM- 17 may decrease by less than about 10%, or by less than about 9%, or by less than about 8%, or by less than about 7%, or by less than about 6%, or by less than about 5%, or by less than about 4%, or by less than about 3%, or by less than about 2%, or by less than about 1%. Thus, in any embodiment, the EMM-17 or a cracking aid comprising EMM- 17 may be steamed at a temperature up to 1000°F (537.8°C) up to a period of at least about 4 hours prior to being provided to catalytic cracking conditions. Stability in the typical FCC regeneration range of about 1300°F (704.4°C) to about 1500°F (815.6°C) may also be realized.

[0029] To prepare a cracking aid suitable for FCC applications, the EMM-17 may be processed into fluidizable particles, which are then calcined. In addition to the EMM- 17, the fluidizable particles may comprise at least a homogenizer and a binder. The binder may provide structure integrity and bulk to define the macrostructure of the fluidizable particles containing the EMM- 17. Optionally, the binder may be omitted. The homogenizer may adjust the microstructure of the fluidizable particles by providing porosity and regulating density. The fluidizable particles may optionally be prepared in the presence of a dispersant, which is then lost in the course of the fluidizable particles undergoing calcination. The dispersant may facilitate spray drying by maintaining the particles in a suitable form and discouraging particle settling prior to or during spray drying and subsequent calcination. Suitable examples of the foregoing components are provided hereinafter.

[0030] The fluidizable particles may contain components that are resistant to the temperatures and other conditions encountered during catalytic cracking processes, such as FCC. Such materials may include inorganic materials such as clays, silica, and / or metal oxides such as alumina. Any of the foregoing may be either naturally occurring in the form of gelatinous precipitates or gels, sometimes including mixtures of silica and metal oxides. Use of one or more catalytically inactive components in conjunction with EMM- 17 may change the conversion and / or selectivity of the catalyst during a catalytic cracking process. Catalytically inactive materials may suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained in an economic and orderly manner without employing other means for controlling the rate of reaction. Naturally occurring clays (e.g., bentonite and / or kaolin) and other inorganic materials may improve the particle attrition or crush strength of the catalyst under commercial operating conditions to prevent the fluidizable particles from breaking down into powder-like materials.

[0031] In non-limiting examples, the dispersant may comprise any organic material that is readily removed by calcination, preferably an organic salt. In one example, the dispersant may comprise a sodium lignosulfonate salt. Another suitable dispersant can be polyvinylpyrollidone (PVP). The fluidizable particles may be substantially free of dispersant following calcination. It is to be appreciated by persons having ordinary skill in the art, however, that traces of residual dispersant may remain in the fluidizable particles in some instances.

[0032] In non-limiting examples, the homogenizer may comprise a clay. Naturally occurring clays that may be combined with EMM- 17 in the course of producing fluidizable particles may include, for example, clays from the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia, and Florida clays, orothers in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, and / or anauxite. Such clays may be used in the raw state as originally mined or initially subjected to calcination, acid treatment, and / or chemical modification. The amount of homogenizer in the fluidizable particles comprising EMM-17 may range from 10 wt% to about 40 wt%, or about 20 wt% to about 35 wt%, or about 25 wt% to about 40 wt%, based on a total mass of the fluidizable particles comprising EMM- 17.

[0033] In non-limiting examples, the binder may comprise an inorganic oxide. Examples of inorganic oxide binders suitable for use in preparation of fluidizable particles of the present disclosure include, but are not limited to, silica, alumina, silica-alumina, silica-magnesia, silica-zirconia, silica- thoria, silica-beryllia, silica-titania, as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, and any combination thereof. The amount of binder in the fluidizable particles comprising EMM-17 may range from about 0.1 wt% to about 5 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 40 wt%, or about 20 wt% to about 35 wt%, or about 25 wt% to about 40 wt%, based on a total mass of the fluidizable particles comprising EMM-17. The binder may be optionally omitted in some cases.

[0034] A non-limiting example method for preparing fluidizable particles comprising EMM-17 for use as a secondary cracking catalyst in a cracking aid may comprise combining EMM- 17 and a dispersant (e.g., a sodium lignosulfonate salt) to form a first EMM- 17 slurry. The first EMM- 17 slurry may then be combined with a homogenizer and an optional binder to obtain a second EMM- 17 slurry that may be further processed to form the fluidizable particles comprising EMM- 17. In non-limiting examples, the second EMM- 17 slurry may be spray dried to form a plurality of fluidizable particles, which may then be further calcined to remove the dispersant and ready the fluidizable particles for further use, as described hereinafter.

[0035] The concentration of EMM- 17 in the second EMM- 17 slurry may, for example, be about 1 wt% to about 50 wt%, or about 1 wt% to about 15 wt%, or about 1 wt% to about 10 wt%, or about 1 wt% to about 5 wt%, or about 5 wt% to about 40 wt%, or about 5 wt% to about 30 wt%, or about 5 wt% to about 20 wt%, or about 5 wt% to about 15 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 40 wt%, or about 10 wt% to about 30 wt%, or about 10 wt% to about 20 wt%, or about 10 wt% to about 15 wt%, or about 20 wt% to about 40 wt%, or about 30 wt% to about 40 wt%, based on a total mass of the second EMM- 17 slurry.

[0036] The concentration of the dispersant in the second EMM-17 slurry may, for example, be about 0.001 wt% to about 1 wt%, or about 0.001 wt% to about 0.1 wt%, or about 0.001 wt% to about 0.01wt%, or about 0.01 wt% to about 1 wt%, or about 0.01 wt% to about 0.1 wt%, or about 0.1 wt% to about 1 wt%, based on a total mass of the second EMM- 17 slurry.

[0037] The concentration of the homogenizer in the second EMM- 17 slurry may, for example, be about 1 wt% to about 50 wt%, or about 1 wt% to about 15 wt%, or about 1 wt% to about 10 wt%, or about 1 wt% to about 5 wt%, or about 5 wt% to about 40 wt%, or about 5 wt% to about 30 wt%, or about 5 wt% to about 20 wt%, or about 5 wt% to about 15 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 40 wt%, or about 10 wt% to about 30 wt%, or about 10 wt% to about 20 wt%, or about 10 wt% to about 15 wt%, or about 20 wt% to about 40 wt%, or about 30 wt% to about 40 wt%, based on a total mass of the second EMM- 17 slurry. Up to about 50 wt% total solids may be present in the second EMM- 17 slurry.

[0038] The concentration of the binder in the second EMM- 17 slurry may, for example, be about 0.1 wt% to about 1 wt%, or about 1 wt% to about 50 wt%, or about 1 wt% to about 15 wt%, or about 1 wt% to about 10 wt%, or about 1 wt% to about 5 wt%, or about 5 wt% to about 40 wt%, or about 5 wt% to about 30 wt%, or about 5 wt% to about 20 wt%, or about 5 wt% to about 15 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 40 wt%, or about 10 wt% to about 30 wt%, or about 10 wt% to about 20 wt%, or about 10 wt% to about 15 wt%, or about 20 wt% to about 40 wt%, or about 30 wt% to about 40 wt%, based on a mass of total solids in the second EMM- 17 slurry. Optionally, the binder may be omitted from the second EMM-17 slurry.

[0039] Following the addition of the binder, the pH of the second EMM-17 slurry may be adjusted to ensure proper interaction between the EMM- 17 and the binder. In non-limiting examples, the pH may range from about 2 to about 7 or about 2 to about 5, which may be applicable to alumina and alumina-type binders. For silica binders, the pH may range from about 8 to about 10.

[0040] The preparation of the fluidizable particles comprising EMM-17 may further comprise grinding the second EMM- 17 slurry before spray drying the second EMM- 17 slurry to form the fluidizable particles containing EMM- 17. The second EMM- 17 slurry may be ground with, for example, a ball mill, an autogenous mill, a buhrstone mill, high-pressure grinding rolls, a pebble mill, a rod mill, a SAG mill, a tower mill, a VSI mill, or any combination thereof.

[0041] Spray drying may form fluidizable particles from the second EMM-17 slurry. One or more high-pressure single-fluid nozzles and / or two-fluid nozzles may be used to spray dry the second EMM- 17 slurry. Depending on the type of nozzle used, the pressure at which spray drying takes place may be from about 700 psi to about 4500 psi, or about 700 psi to about 3500 psi, or about 700 psi to about 2500 psi, or about 700 psi to about 1500 psi, or about 1500 psi to about 4500 psi, or about 1500psi to about 3500 psi, or about 1500 psi to about 2500 psi, or about 2500 psi to about 4500 psi, or about 2500 psi to about 3500 psi, or about 3500 psi to about 4500 psi for high-pressure single-fluid nozzles, or from about 14 psi to about 110 psi, or about 14 psi to about 90 psi, or about 14 psi to about 70 psi, or about 14 psi to about 50 psi, or about 14 psi to about 30 psi, or about 30 psi to about 110 psi, or about 30 psi to about 90 psi, or about 30 psi to about 70 psi, or about 30 psi to about 50 psi, or about 50 psi to about 110 psi, or about 50 psi to about 90 psi, or about 50 psi to about 70 psi, or about 70 psi to about 110 psi, or about 70 psi to about 90 psi, or about 90 psi to about 110 psi for two-fluid nozzles. An inlet temperature of the spray dryer may range from about 150°C to about 250°C, or about 175°C to about 225°C, or about 200°C to about 250°C. An ultrasonic nozzle, single orifice, wheel, or other similar type of nozzle may be used to facilitate the spray drying process.

[0042] The fluidizable particles comprising EMM- 17 may be calcined after spray drying to ready the fluidizable particles for further use in cracking. Calcination may, for example, occur for up to about 8 hours, such as about 15 minutes to about 30 minutes, or about 30 minutes to about 45 minutes, or about 30 minutes to about 1 hour, or about 1 hour to about 2 hours, or about 2 hours to about 6 hours, or about 2 hours to about 4 hours, or about 4 hours to about 8 hours, or about 4 hours to about6 hours, or about 6 hours to about 8 hours, or about 2 hours to about 16 hours under heating conditions suitable to prepare the fluidizable particles for use. In non-limiting examples, suitable temperatures may range from about 500°C to about 600°C, or about 500°C to about 580°C, or about 500°C to about 560°C, or about 500°C to about 540°C, or about 500°C to about 520°C, or about 520°C to about600°C, or about 520°C to about 580°C, or about 520°C to about 560°C, or about 520°C to about540°C, or about 540°C to about 600°C, or about 540°C to about 580°C, or about 540°C to about560°C, or about 560°C to about 600°C, or about 560°C to about 580°C, or about 580°C to about600°C. Calcination may be conducted under inert atmosphere or in the presence of air.

[0043] The fluidizable particles comprising EMM- 17 may be used as a secondary cracking catalyst in an FCC process in combination with a primary cracking catalyst. A non-limiting example of the FCC process may include introducing a hydrocarbon feed to a reactor containing a cracking aid comprising a plurality of fluidizable particles comprising at least EMM-17. The EMM-17 may have an X-ray powder diffraction pattern characterized by at least the 20 scattering angles specified above. The cracking aid may further comprise a primary cracking catalyst (e.g., a USY zeolite). In addition, one or more additional secondary cracking catalysts including, but not limited to, an MFI zeolite (e.g., ZSM-5), NU-86 zeolite, a MEL zeolite, a MTW zeolite, a TON zeolite, a MTT zeolite, a MSE zeolite, or any combination thereof, may be optionally added to the cracking aid in combination with theEMM-17. The primary cracking catalyst and the secondary cracking catalyst may be located upon separate fluidizable particles. That is, the primary cracking catalyst may be located upon a first plurality of fluidizable particles, and the secondary cracking catalyst may be located upon a second plurality of fluidizable particles. When one or more additional secondary cracking catalysts are used, the one or more additional secondary cracking catalysts may be located upon the same fluidizable particles as the EMM- 17, upon the same fluidizable particles as the primary cracking catalyst, or upon different fluidizable particles altogether.

[0044] Accordingly, the present disclosure also provides cracking aids comprising a first plurality of fluidizable particles comprising a primary cracking catalyst, and a second plurality of fluidizable particles comprising EMM-17 as a secondary cracking catalyst. The fluidizable particles within the first and second pluralities of fluidizable particles each further comprise a binder and a homogenizer, which may individually be in the amounts described above. Preferably, the primary cracking catalyst may comprise a USY zeolite.

[0045] Preferably, the EMM- 17 and the primary cracking catalyst may be located upon separate fluidizable particles so that the ratio between the primary cracking catalyst and the secondary cracking catalyst may be easily adjusted to regulate the cracking reaction under specified catalytic cracking conditions.

[0046] Within the cracking aid, the concentration of EMM- 17 relative to a total mass of the fluidizable particles may range from about 20 wt% to about 50 wt%, or about 20 wt% to about 45 wt%, or about 20 wt% to about 40 wt%, or about 20 wt% to about 35 wt%, or about 20 wt% to about 30 wt%, or about 20 wt% to about 25 wt%, or about 25 wt% to about 50 wt%, or about 25 wt% to about 45 wt%, or about 25 wt% to about 40 wt%, or about 25 wt% to about 35 wt%, or about 25 wt% to about 30 wt%, or about 30 wt% to about 50 wt%, or about 30 wt% to about 45 wt%, or about 30 wt% to about 40 wt%, or about 30 wt% to about 35 wt%, or about 35 wt% to about 50 wt%, or about 35 wt% to about 45 wt%, or about 35 wt% to about 40 wt%, or about 40 wt% to about 50 wt%, or about 40 wt% to about 45 wt%, or about 45 wt% to about 50 wt%. In the case where a binder is omitted, the concentration of EMM-17 relative to the total mass of the fluidizable particles may range from about 70 wt% to about 80 wt%.

[0047] The EMM-17 may be exposed to the catalytic cracking conditions in combination with a primary catalyst, such as USY zeolite, more preferably with the EMM-17 and the USY being located upon separate fluidizable particles when exposed to the catalytic cracking conditions. The mass ratio of EMM-17 to the primary cracking catalyst (e.g., USY zeolite) in the cracking aid may range fromabout 1 :6 to about 6:1 , or about 1 :6 to about 3: 1, or about 1 :6 to about 1 : 1, or about 1 : 1 to about 6: 1, or about 1 :1 to about 3: 1, or about 3:1 to about 6: 1. Preferably, the primary cracking catalyst is present in the cracking aid as a majority component, such as at a ratio of primary cracking catalyst to EMM-17 of about 1 : 1 to 6: 1, or 2: 1 to 4: 1, for example. Alternately, however, the primary cracking catalyst may be omitted, and the cracking aid may include the EMM- 17 particles alone. For example, in the case of easily cracked feeds, such as naphtha, the primary cracking catalyst may be omitted.

[0048] In non-limiting examples, fluidizable particles suitable for performing fluid catalytic cracking may have a particle size ranging from about 10 pm to about 200 pm, or about 20 pm to about 120 pm, or about 30 pm to about 90 pm. The bulk density of the fluidizable particles may range from about 0.6 g / cm3to about 0.8 g / cm3. The surface area of the fluidizable particles may range from about 150 m2 / g to about 400 m2 / g, or about 150 m2 / g to about 250 m2 / g, or about 250 m2 / g to about 400 m2 / g. The foregoing values may be applicable to both fluidizable particles comprising EMM-17 and fluidizable particles comprising a primary cracking catalyst.

[0049] Examples of hydrocarbon feeds suitable for the methods disclosed herein may include, but are not limited to, straight-run gas oil, vacuum gas oil, heavy feedstocks such as heavy oil, atmospheric residuum, vacuum residuum, extra-heavy oil, tar sand bitumen, bio-oxygenated feeds, the like, and any combination thereof.

[0050] After introducing the hydrocarbon feed to the reactor containing the cracking aid, the hydrocarbon feed may be exposed to catalytic cracking conditions in the reactor in the presence of the cracking aid. Catalytic cracking may, for example, occur at a temperature of about 500°C to about700°C, or about 500°C to about 650°C, or about 500°C to about 600°C, or about 500°C to about550°C, or about 550°C to about 700°C, or about 55O°C to about 650°C, or about 550°C to about600°C, or about 600°C to about 700°C, or about 600°C to about 650°C, or about 650°C to about700°C. A residence time in the reactor may, for example, be about 5 minutes or less, or about 4 minutes or less, or about 3 minutes or less, or about 2 minutes or less, or about 1 minute or less, or about 45 seconds of less, or about 30 seconds or less, or about 20 seconds or less, or about 15 seconds or less, or about 10 seconds or less, or about 5 seconds or less, such as a residence time ranging from about 1 second to about 10 seconds, or about 10 seconds to about 30 seconds, or about 30 seconds to about 1 minute, or about 45 seconds to about 2 minutes, or about 2 minutes to about 5 minutes, or about 1 second to about 10 seconds, or about 5 seconds to about 20 seconds, or about 2 seconds to about 12 seconds.

[0051] Exposing the hydrocarbon feed to catalytic cracking conditions in the reactor in the presence of the cracking aid may result in the formation of a hydrocarbon product that may be subsequently obtained from the reactor. By utilizing EMM- 17 according to the disclosure herein, the cracked hydrocarbon product may, for example, have a weight ratio of propylene to butylene of about 2.0 or less, or about 1.5 or less, or about 1.25 or less, or about 1 or less, or about 0.75 or less, or about 0.5 or less, or about 0.25 or less, and a C4- olefinicity of about 70% or more, or about 75% or more, or about 80% or more, or about 85% or more, or about 90% or more, or about 95% or more. In nonlimiting examples, the weight ratio of propylene to butylene may range from about 0.5 to about 2, or about 0.5 to about 1.5, or about 0.5 to about 1.0. In some or other non-limiting examples, the C4- olefinicity may range from about 80% to about 95%, or about 80% to about 90%, or about 85% to about 95%. As used herein, the term “C4- olefinicity” refers to the ratio of total C4- olefinic hydrocarbons (ethylene+propylene+butylenes) to total C4- hydrocarbon fractions, including hydrogen and methane.

[0052] The present disclosure is further directed to the following non-limiting embodiments:

[0053] Embodiment 1. A method comprising: introducing a hydrocarbon feed to a reactor containing a cracking aid comprising a plurality of fluidizable particles comprising at least EMM-17, the EMM-17 being a zeolite having an X-ray powder diffraction pattern characterized by at least the following 20 scattering angles, as determined using Cu Ka radiation: 7.6+0.2, 8.0+0.2, 8.4+0.2, 10.4+0.2, 14.7+0.2, 15.6+0.2, 22.6+0.2, and 23.2+0.2; exposing the hydrocarbon feed to catalytic cracking conditions in the reactor in the presence of the cracking aid; and obtaining a cracked hydrocarbon product having a weight ratio of propylene to butylenes of about 1.5 or less and a C4- olefinicity of about 80% or more.

[0054] Embodiment 2. The method of embodiment 1, wherein the cracking aid comprises a primary cracking catalyst, and the EMM- 17 is a secondary cracking catalyst.

[0055] Embodiment s. The method of embodiment 2, wherein the primary cracking catalyst comprises a USY zeolite.

[0056] Embodiment 4. The method of embodiment 3, wherein a mass ratio of EMM-17 to the USY zeolite in the cracking aid is about 1 :6 to about 6: 1.

[0057] Embodiment 5. The method of any one of embodiments 2-4, wherein a concentration of EMM-17 in the cracking aid is about 20 wt% to about 50 wt%.

[0058] Embodiment 6. The method of any one of embodiments 2-5, wherein the primary cracking catalyst is located on a first plurality of fluidizable particles, and the secondary cracking catalyst is located on a second plurality of fluidizable particles.

[0059] Embodiment 7. The method of any one of embodiments 1-6, wherein a residence time of the hydrocarbon feed in the reactor is about 1 minute or less.

[0060] Embodiment s. The method of any one of embodiments 1-7, wherein the catalytic cracking conditions comprise a temperature of about 500°C to about 700°C.

[0061] Embodiment 9. The method of any one of embodiments 1-8, wherein at least a portion of fluidizable particles comprise the EMM- 17, a homogenizer, and a binder.

[0062] Embodiment 10. The method of embodiment 9, wherein the homogenizer comprises a clay.

[0063] Embodiment 11. The method of embodiment 9 or embodiment 10, wherein the binder comprises silica, alumina, alumina-silica, or any combination thereof.

[0064] Embodiment 12. The method of any one of embodiments 1-11, wherein the EMM-17 has a BET surface area of about 400 m2 / g to about 600 m2 / g, according to ISO 9277:2010.

[0065] Embodiment 13. The method of any one of embodiments 1-12, wherein the EMM- 17 has a micropore surface area of about 350 m2 / g to about 550 m2 / g, according to ISO 9277:2010.

[0066] Embodiment 14. The method of any one of embodiments 1-13, wherein the catalytic cracking conditions comprise fluid catalytic cracking conditions.

[0067] Embodiment 15. A method comprising: combining EMM- 17 and a dispersant to form a first EMM- 17 slurry, the EMM- 17 being a zeolite having an X-ray powder diffraction pattern characterized by at least the following 20 scattering angles, as determined using Cu Ka radiation: 7.6+0.2, 8.0+0.2, 8.4+0.2, 10.4+0.2, 14.7+0.2, 15.6+0.2, 22.6+0.2, and 23.2+0.2; combining the first EMM- 17 slurry with a homogenizer and a binder to obtain a second EMM- 17 slurry; spray drying the second EMM- 17 slurry to form a plurality of fluidizable particles comprising the EMM- 17; and calcining the plurality of fluidizable particles.

[0068] Embodiment 16. The method of embodiment 15, further comprising: grinding the second EMM- 17 slurry before spray drying to form the plurality of fluidizable particles.

[0069] Embodiment 17. The method of embodiment 15 or embodiment 16, wherein a concentration of EMM-17 in the second EMM-17 slurry is about 1 wt% to about 20 wt%, based on total mass of the second EMM-17 slurry.

[0070] Embodiment 18. The method of any one of embodiments 15-17, wherein a concentration of the dispersant is about 0.001 wt% to about 1 wt%, a concentration of the homogenizer is about 1 wt% to about 20 wt%, and a concentration of the binder is about 1 wt% to about 20 wt%, each based on a total mass of the second EMM- 17 slurry.

[0071] Embodiment 19. The method of any one of embodiments 15-18, wherein the dispersant comprises a sodium lignosulfonate salt, the homogenizer comprises a clay, and the binder comprises a silica, an alumina, an alumina-silica, or any combination thereof.

[0072] Embodiment 20. The method of any one of embodiments 15-19, wherein the fluidizable particles are calcined for up to about 8 hours at a temperature of about 500°C to about 600°C.

[0073] Embodiment 21. A cracking aid comprising: a first plurality of fluidizable particles comprising a primary cracking catalyst; and a second plurality of fluidizable particles comprising EMM- 17 as a secondary cracking catalyst; wherein the fluidizable particles further comprise a binder and a homogenizer.

[0074] Embodiment 22. The cracking aid of embodiment 21, wherein the primary cracking catalyst comprises a USY zeolite.

[0075] To facilitate a better understanding of the embodiments of the present disclosure, the following examples of preferred or representative embodiments are given. In no way should the following examples be read to limit, or to define, the scope of the invention.EXAMPLES

[0076] Example 1: Synthesis of EMM-17 Crystals. EMM- 17 crystals were synthesized in a similar manner to the procedure in U.S. Patent 9,452,423 or by the following procedure.

[0077] The starting gel composition (molar ratios) was 0.5 NH4F : 0.5 SDA : 0.01 AI2O3 : SiCh : 28.7 H2O, which was lowered to a H2O : SiCh ratio of 3 - 5 after mixing, either through evaporation or freeze drying (SDA is a 20 wt% solution of l-methyl-4-(pyrrolidin-l-yl)pyridinium hydroxide). Solid aluminum nitrate (159.2 g, nonahydrate) was dissolved in l-methyl-4-(pyrrolidin-l- yl)pyridinium hydroxide (10,157.7 g, 20 wt% solution). LUDOX AS-40 (3,188.6 g, 40% SiO2 colloidal silica sol) was added to the solution and stirred for 20 minutes. An aqueous solution ofammonium fluoride (1 ,310.2 g, 30%) was slowly added to the aluminosilicate solution and stirred for 45 minutes. The mixture was then dried at 50-70°C until the weight of the slurry reached approximately 4900 g in total. At this point additional water (440 g) was added to achieve the desired H2O : SiO? ratio required to minimize impurity formation. The resulting slurry was transferred to a horizontal stirred reactor and heated at 160°C for 3-4 days. The product was collected via vacuum filtration, washed thoroughly with deionized water, and dried in an oven at 120°C. Phase analysis by powder X-ray diffraction confirmed that the reaction product was EMM- 17, as compared against the pre-cal cination XRD peaks provided in U.S. Patent 9,452,423.

[0078] Calcination of the product was conducted in a furnace by heating at a rate of 5°F / min to a final temperature of 1000°F in five volumes of dry air / volume of EMM-17 crystals for 6 hours to produce a white solid. The XRD pattern obtained after calcination was consistent with the postcalcination XRD peaks provided in U.S. Patent 9,452,423. Elemental analysis by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) after dissolution of the calcined aluminosilicate EMM-17 in hydrofluoric acid gave 69.2% SiO , 1.01% AI2O3, <0.01% Na, and 0.01% K for an SiO2:AhO3 ratio of 116.

[0079] The calcined aluminosilicate EMM- 17 was exposed to steam and at high temperatures (1000°F, 1400°F, and 1500°F) for various lengths of time to assess the zeolite’s hydrothermal stability. X-ray diffraction and nitrogen physisorption measurements were used to evaluate the crystallinity and BET surface area of the EMM-17 before and after steaming. FIG. 1 is a graph of the X-ray diffraction pattern of EMM-17 after exposure to various steaming conditions. Table 1 summarizes the total BET surface area of the EMM- 17 and the micropore and external surface areas.Table 1

[0080] The X-ray diffraction and BET results demonstrate the hydrothermal stability of EMM-17 under conditions similar to those encountered during fluid catalytic cracking. The XRD patternshowed no significant crystallinity loss or destruction. The BET surface area similarly showed almost no change upon steaming at elevated temperatures, thus demonstrating an absence of crystal destruction and / or pore blockage and loss of surface area due to framework de-alumination.

[0081] Example 2: Preparation of Fluidizable Particles Containing EMM-17. A slurry of calcined aluminosilicate EMM- 17 and Marasperse N-22 dispersant was prepared and ball milled for between 3 hours and 12 hours. The total solid content of the EMM- 17 slurry was 20 wt%, with a dispersant content of 0.25 wt% on an EMM- 17 solid basis. Kaolin clay was added to the EMM- 17 slurry and mixed to obtain a well-dispersed and homogeneous suspension. A binder slurry of silica, alumina, or alumina-silica was prepared and the pH was adjusted accordingly for proper interaction between the EMM- 17 and the binder. The binder slurry was added to the combined EMM- 17 and clay slurry, and the final slurry was milled before spray drying. The final slurry had a total solid content of 20 wt% comprising 35% EMM-17, 30% binder, and 35% clay on a dry solids basis. The final slurry was spray-dried using a bench-scale spray dryer to form fluidizable particles. The resulting spray-dried catalyst was calcined at 550°C with a soak time of 4 hours. The calcined catalyst was then sized and steamed at 1450°F for four hours prior to further use. The final cracking aid was prepared as a combination of the fluidizable particles containing EMM- 17 and similarly prepared fluidizable particles containing USY zeolite. The mass ratio of USY to EMM-17 in the cracking aid was 3: 1.

[0082] Example 3: Cracking Activity. The experimental cracking aid and a control cracking aid comprising 3 : 1 mass ratio of USY :ZSM-5 zeolite were evaluated in an advanced cracking evaluation (ACE) unit. Permian atmospheric tower bottoms (ATB) were used as a hydrocarbon feed. The amount of feed introduced to the unit was fixed and the catalyst-to-oil ratio (C / O) was changed by altering the load of cracking aid in the reactor. The total cracking time was 42 seconds with a feed rate of 1.82 g / min, a C / O molar ratio of 8.6, and a cracking temperature of 1100°F. The collected gaseous products were analyzed by gas chromatography, and the liquid fraction collected in the downstream cold trap was analyzed using simulated distillation (SimDis). FIG. 2 is a graph of product yield composition for cracking performed with a 75 wt% USY:25 wt% EMM-17 cracking aid in comparison to that of a reference 75 wt% USY:25 wt% ZSM-5 cracking aid. As shown in FIG. 2, there was a decrease in C3 and C4 paraffin production in addition to a lower dry gas yield (H2, methane, ethane, and ethylene), hence a higher olefini city when EMM- 17 was present within the cracking aid. This result is indicative of less undesired hydrogen transfer occurring on the surface of EMM- 17 compared to ZSM-5.

[0083] Table 2 summarizes the total propylene and butylenes yield, the propylene-to-butylenes mass ratio, and the C4- olefinicity for light ends obtained using each of the cracking aids.Table 2

[0084] FIG. 3 is a graph of C3 / C4 olefin ratio as a function of the C3+C4 olefin yield for cracking performed with a 75 wt% USY:25 wt% EMM-17 cracking aid in comparison to that of a reference 75 wt% USY:25 wt% ZSM-5 cracking aid. FIG. 4 is a graph of C4- olefinicity as a function of the volume of C4- produced per volume of feed for cracking performed with a 75 wt% USY:25 wt% EMM-17 cracking aid in comparison to that of a reference 75 wt% USY:25 wt% ZSM-5 cracking aid. As shown, by using EMM-17 in combination with a primary FCC catalyst (e.g., USY) a higher olefin yield with a lower propylene-to-butylenes ratio (z.e., more butylenes production) was obtained.

[0085] All documents described herein are incorporated by reference herein for purposes of all jurisdictions where such practice is allowed, including any priority documents and / or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the disclosure. Accordingly, it is not intended that the disclosure be limited thereby. For example, the compositions described herein may be free of any component, or composition not expressly recited or disclosed herein. Any method may lack any step not recited or disclosed herein. Likewise, the term “comprising” is considered synonymous with the term “including.” Whenever a method, composition, element or group of elements is preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

[0086] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the present specification and associated claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification andattached claims are approximations that may vary depending upon the desired properties sought to be obtained by one or more embodiments described herein. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claim, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0087] Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee. Moreover, the indefinite articles “a” or “an,” as used in the claims, are defined herein to mean one or more than one of the element that it introduces.

[0088] One or more illustrative embodiments are presented herein. Not all features of a physical implementation are described or shown in this application for the sake of clarity. It is understood that in the development of a physical embodiment of the present disclosure, numerous implementationspecific decisions must be made to achieve the developer's goals, such as compliance with system- related, business-related, government-related and other constraints, which vary by implementation and from time to time. While a developer's efforts might be time-consuming, such efforts would be, nevertheless, a routine undertaking for one of ordinary skill in the art and having benefit of this disclosure.

[0089] Therefore, the present disclosure is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present disclosure may be modified and practiced in different but equivalent manners apparent to one having ordinary skill in the art and having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered, combined, or modified and all such variations are considered within the scope and spirit of the present disclosure. The embodiments illustratively disclosed herein suitably may be practiced in the absence of any element that is not specifically disclosed herein and / or any optional element disclosed herein.

Claims

CLAIMSThe invention claimed is:

1. A method comprising: introducing a hydrocarbon feed to a reactor containing a cracking aid comprising a plurality of fluidizable particles comprising at least EMM-17, the EMM-17 being a zeolite having an X-ray powder diffraction pattern characterized by at least the following 26 scattering angles, as determined using Cu Koc radiation: 7.6+0.2, 8.0+0.2, 8.4+0.2, 10.4+0.2, 14.7+0.2, 15.6+0.2, 22.6+0.2, and 23.2+0.2; exposing the hydrocarbon feed to catalytic cracking conditions in the reactor in the presence of the cracking aid; and obtaining a cracked hydrocarbon product having a weight ratio of propylene to butylenes of about 1.5 or less and a C4- olefini city of about 80% or more.

2. The method of claim 1, wherein the cracking aid comprises a primary cracking catalyst, and the EMM-17 is a secondary cracking catalyst.

3. The method of claim 2, wherein the primary cracking catalyst comprises a USY zeolite.

4. The method of claim 3, wherein a mass ratio of EMM-17 to the USY zeolite in the cracking aid is about 1 :6 to about 6: 1.

5. The method of claim 2, wherein a concentration of EMM-17 in the cracking aid is about 20 wt% to about 50 wt%.

6. The method of claim 2, wherein the primary cracking catalyst is located on a first plurality of fluidizable particles, and the secondary cracking catalyst is located on a second plurality of fluidizable particles.

7. The method of any preceding claim, wherein a residence time of the hydrocarbon feed in the reactor is about 1 minute or less.

8. The method of any preceding claim, wherein the catalytic cracking conditions comprise a temperature of about 500°C to about 700°C.

9. The method of any preceding claim, wherein at least a portion of fluidizable particles comprise the EMM- 17, a homogenizer, and a binder.

10. The method of claim 9, wherein the binder comprises silica, alumina, alumina-silica, or any combination thereof.

11. The method of any preceding claim, wherein the EMM- 17 has:(i) a BET surface area of about 400 m2 / g to about 600 m2 / g, according to ISO 9277:2010;(ii) a micropore surface area of about 350 m2 / g to about 550 m2 / g, according to ISO 9277:2010; or,(iii) both (i) and (ii).

12. A method comprising: combining EMM- 17 and a dispersant to form a first EMM- 17 slurry, the EMM- 17 being a zeolite having an X-ray powder diffraction pattern characterized by at least the following 20 scattering angles, as determined using Cu Kot radiation: 7.6+0.2, 8.0+0.2, 8.4+0.2, 10.4+0.2, 14.7+0.2, 15.6+0.2, 22.6+0.2, and 23.2+0.2; combining the first EMM- 17 slurry with a homogenizer and a binder to obtain a second EMM- 17 slurry; spray drying the second EMM- 17 slurry to form a plurality of fluidizable particles comprising the EMM- 17; and calcining the plurality of fluidizable particles.

13. The method of claim 12, further comprising: grinding the second EMM- 17 slurry before spray drying to form the plurality of fluidizable particles.

14. The method of claim 12, wherein a concentration of EMM-17 in the second EMM-17 slurry is about 1 wt% to about 20 wt%, based on total mass of the second EMM-17 slurry.

15. The method of claim 15, wherein: a concentration of the dispersant is about 0.001 wt% to about 1 wt% and wherein the dispersant comprises a sodium lignosulfonate salt, a concentration of the homogenizer is about 1 wt% to about 20 wt% and the homogenizer comprises a clay, and a concentration of the binder is about 1 wt% to about 20 wt% and binder comprises a silica, an alumina, an alumina-silica, or any combination thereof, each based on a total mass of the second EMM- 17 slurry.

16. A cracking aid comprising: a first plurality of fluidizable particles comprising a primary cracking catalyst; and a second plurality of fluidizable particles comprising EMM-17 as a secondary cracking catalyst; wherein the fluidizable particles further comprise a binder and a homogenizer.

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