MWW zeolite precursor nanoparticles having non-condensed layer structure and their manufacturing method

Abstract

Zeolite precursor nanoparticles can be formed by contacting a parent zeolite precursor, such as MCM-22 zeolite precursor, MCM-56 zeolite precursor, or EMM-10 zeolite precursor, with an aqueous base under temperature conditions where adjacent stacked layers in the MWW zeolite framework do not experience substantial condensation with each other. The zeolite precursor nanoparticles can be converted to zeolite nanoparticles after calcination. The zeolite nanoparticles can be formed into extrudates, optionally with a binder. Zeolite nanoparticles in unbound or extrudate form can be utilized to promote the alkylation of C6+ aromatic compounds.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 327,417, having a filing date of April 5, 2022, the disclosure of which is incorporated herein by reference in its entirety.

[0002] Field The present disclosure relates to zeolites and catalytic processes utilizing same. [Background technology]

[0003] background Zeolites are a diverse class of crystalline microporous framework materials that are widely used as molecular sieves, ion exchangers, and solid acid catalysts. Various zeolite framework structures recognized by the Structure Commission of the International Zeolite Association are maintained in a structure database accessible at http: / / www.iza-structure.org / databases / . The inorganic framework (framework structure) that defines a particular zeolite is characterized by a number of pores or channels of specific sizes present therein. The size of the pores or channels varies from zeolite to zeolite, and as a result, determines the extent of molecules that can reach the interior of a particular zeolite. Thanks to their defined porosity, zeolites can find utility as selective adsorbents and promote catalytic reactions suitable for various types of molecules that have a size that allows them to enter a given zeolite via the pores or channels.

[0004] Due to their crystalline nature, powder X-ray diffraction (XRD) can be used to characterize the structure of zeolites. Natural and synthetic zeolites are characterized by a rigid three-dimensional framework of SiO4 tetrahedra in which adjacent tetrahedra share oxygen atoms and in some cases some Si atoms may be replaced by other atoms. For example, at least some of the tetrahedra in a given zeolite may contain alternative atoms such as boron, gallium, aluminum, iron, titanium, zinc, vanadium, etc., instead of silicon. In tetrahedra that do not contain tetravalent elements, electroneutrality can be maintained by including cations such as hydrogen ions, alkali metal cations, or alkaline earth metal cations that are not part of the tetrahedral structure but are instead associated with the tetrahedral structure via electrostatic charge pairing.

[0005] Zeolites with MWW frameworks (MWW zeolites) are only one type of zeolite structure that has been extensively explored for use in catalysis. MWW zeolites include a variety of framework structures, such as fully condensed ordered layer structures (MCM-49), non-condensed ordered layer structures (MCM-22), and irregular single- or multi-layer structures (MCM-56 and EMM-10). Other types of MWW zeolites are also known, such as ITQ-1, ITQ-2, UZM-8, and UZM-8HS. A structure directing agent (SDA) can be used to facilitate the formation of the precursor into a given MWW zeolite framework structure. The SDA can be removed during calcination leaving empty pore space within the zeolite framework structure. If care is not taken, various MWW zeolite precursors can interconvert with each other, thereby resulting in a mixture of zeolites after calcination. In some cases, the fully condensed layer structure of MCM-49 can result.

[0006] FIG. 1 is a diagram showing powder X-ray diffraction data (XRD) characteristic of various types of MWW zeolite precursors and a pictorial description of the type of layer structure present therein. The peaks marked with an asterisk in FIG. 1 are characteristic peaks from the fully condensed ordered layer structure of MCM-49, and the in-growth and / or sharpening of these XRD peaks in other zeolite precursor samples may be characteristic of the interconversion of an initial non-condensed layer structure to at least a partially condensed layer structure type. The XRD peak at about 6.5° 2θ (Box A in FIG. 1) is characteristic of the interlayer distance. As MCM-49 is fully condensed and MCM-56 has a disordered stacking structure, both of which result in interlayer distance, these zeolites lack a peak at this position. The XRD peak at about 8°-10° 2θ (Box B in FIG. 1) is characteristic of the 101 and 102 crystallographic peaks, with the degree of stacking disorder embodied within this range. MCM-49 and MCM-22 have an ordered structure and exhibit sharp peaks in this range, while MCM-56 and EMM-10 are disordered and exhibit broad peaks as a result of their structures. Further characterization of the XRD patterns of MWW zeolites can be found in U.S. Patent Nos. 5,236,575 and 4,954,325, respectively, the contents of which are incorporated herein by reference.

[0007] Nanoparticle forms of zeolites are often desirable due to their potential to improve catalytic activity and selectivity, enhance substrate accessibility, and improve product desorption kinetics. Unfortunately, the direct synthesis of zeolite nanoparticles can be difficult, as can the conversion of as-produced zeolites or zeolite precursors to nanoparticle form. In the case of MWW zeolites, special polymer additives or multiple structure directing agents (SDAs) and / or multi-step synthesis may be required to directly synthesize MWW zeolite precursors in nanoparticle form and then calcinate to form the corresponding MWW zeolite nanoparticles. Another approach to produce MWW zeolite nanoparticles involves heating aqueous base with the MWW zeolite precursor at a temperature of about 70° C. or higher, preferably about 80° C. The aqueous base treatment promotes the fragmentation of the as-produced zeolite precursor crystals to the nanoparticle size range, resulting in MWW zeolite nanoparticles again after calcination. Unfortunately, the high reaction temperature at which fragmentation of the zeolite precursor crystals occurs can be problematic in terms of scalability and yield loss due to silicon loss. Additionally, conversion of at least a portion of the non-condensed MWW zeolite precursor to a fully condensed layer structure, such as that found in MCM-49, may occur at commonly used reaction temperatures to produce zeolite precursor nanoparticles from the parent zeolite. Summary of the Invention

[0008] summary In some embodiments, the present disclosure provides a composition comprising a plurality of zeolite nanoparticles formed from a parent zeolite precursor having an MWW framework and comprising a plurality of stacked layers, wherein the zeolite precursor nanoparticles are about 200 nm or less in size, adjacent stacked layers within the MWW framework remain substantially uncondensed with each other within the zeolite precursor nanoparticle, and the zeolite precursor nanoparticles contain up to one structure directing agent (SDA). In some embodiments, the disclosure provides a method for producing MWW zeolite nanoparticles, the method comprising: providing a parent zeolite precursor having an MWW framework comprising a plurality of stacked layers; and contacting the parent zeolite precursor with an aqueous base under conditions sufficient to subdivide the parent zeolite precursor into a plurality of zeolite precursor nanoparticles having a size of about 200 nm or less and that maintain the MWW framework without substantially inducing condensation between adjacent stacked layers within the MWW framework.

[0009] In yet another aspect, the present disclosure provides a process for aromatic alkylation comprising the steps of: providing an aromatic feed mixture comprising one or more C6+ aromatic hydrocarbons; providing extrudates comprising the composition of the present disclosure in a calcined form, the calcined form comprising zeolite nanoparticles devoid of a structure directing agent; contacting the aromatic feed mixture with the extrudates under alkylation conditions in the presence of an alkylating agent; and obtaining a product stream comprising one or more alkylated C6+ aromatic hydrocarbons after contacting the aromatic feed mixture with the composition under alkylation conditions. These and other features and properties of the disclosed methods and compositions of the present disclosure, as well as their advantageous applications and / or uses, will become apparent from the following detailed description. The following figures are included to illustrate certain aspects of the present disclosure and should not be considered as exclusive embodiments. The disclosed subject matter is susceptible to considerable modification, permutations, combinations, and equivalents, which will occur to those skilled in the art and having the benefit of this disclosure. To assist those skilled in the relevant art in making and using the subject matter in this regard, reference should be made to the accompanying drawings. [Brief description of the drawings]

[0010] [Figure 1] 1 is a chart showing powder X-ray diffraction data characteristic of various types of MWW zeolite precursors and a pictorial depiction of the types of layer structures present in the precursors. [Diagram 2]1 is a plot of overlaid powder X-ray diffraction patterns of MCM-22 zeolite precursor nanoparticles produced under various conditions according to Example 1. [Figure 3A] 1 shows SEM images of MCM-22 zeolite precursor nanoparticles produced under various conditions according to Example 1. [Figure 3B] 1 shows SEM images of MCM-22 zeolite precursor nanoparticles produced under various conditions according to Example 1. [Figure 3C] 1 shows SEM images of MCM-22 zeolite precursor nanoparticles produced under various conditions according to Example 1. [Figure 3D] 1 shows an SEM image of the parent MCM-22 zeolite precursor. [Figure 4] 1 shows a plot of overlaid powder X-ray diffraction patterns of EMM-10 zeolite precursor nanoparticles produced under various conditions according to Example 2. [Figure 5A] 1 shows SEM images of EMM-10 zeolite precursor nanoparticles produced under various conditions according to Example 2. [Figure 5B] 1 shows SEM images of EMM-10 zeolite precursor nanoparticles produced under various conditions according to Example 2. [Figure 5C] 1 shows an SEM image of the parent EMM-10 zeolite precursor. [Figure 6] FIG. 1 is a plot of the ratio [DIPB] / [IPB] versus the kinetic parameters (rate constants) for cumene alkylation using MCM-22 zeolite nanoparticles. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Detailed Description The present disclosure relates to zeolites, and more particularly to zeolite nanoparticles, precursors thereof, and catalytic reactions carried out therewith. definition Below, various specific embodiments, versions and examples of the present invention are described, including preferred embodiments and definitions adopted herein for the purpose of understanding the claimed invention. The detailed description below provides certain preferred embodiments, but those skilled in the art will recognize that these embodiments are merely exemplary and the present invention can be practiced in other ways. For purposes of determining infringement, the scope of the present invention refers to any one or more of the appended claims, including their equivalents and elements or limitations that are equivalent to those recited. Any reference to the "invention" may refer to one or more, but not necessarily all, of the invention defined by the claims.

[0012] In this disclosure, a process is described as including at least one "step." Each step should be understood to be an act or operation that may be performed once in the process or multiple times in a continuous or discontinuous manner. Unless otherwise specified or the context clearly indicates otherwise, the steps of the process may be performed consecutively in the order as described, with or without overlap with one or more other steps, or, in some cases, in any other order. Furthermore, one or more or even all steps may be performed simultaneously on the same or different batches of material. For example, in a continuous process, a first step of the process may be performed on raw material just fed at the beginning of the process, while a second step may be performed simultaneously on intermediate material resulting from the processing of raw material fed to the process at an earlier point in the first step. Preferably, the steps are performed in the order as described.

[0013] Unless otherwise indicated, all numbers indicating quantities in this disclosure should be understood to be modified in all cases by the term "about". It should also be understood that the exact numerical values ​​used in the specification and claims constitute specific embodiments. Efforts have been made to ensure the accuracy of the data in the examples. However, it should be understood that any measured data inherently contains a certain level of error due to the limitations of the techniques and / or instruments utilized to make the measurements. As used herein, the indefinite article "a" or "an" means "at least one" unless otherwise specified or the context clearly indicates otherwise. Thus, embodiments using "a fractionation column" include embodiments using one, two, or more than two fractionation columns, unless otherwise specified or the context clearly indicates that only one fractionation column is used. As used herein, "consisting essentially of" means a composition, feed, stream, or effluent that contains a given component or components in a concentration of at least about 60 wt%, preferably at least about 70 wt%, more preferably at least about 80 wt%, more preferably at least about 90 wt%, and even more preferably at least about 95 wt%, based on the total weight of the composition, feed, stream, or effluent.

[0014] For simplicity, the following abbreviations may be used herein: RT is room temperature (23° C. unless otherwise indicated), kPag is kilopascal gauge pressure, psig is pounds per square inch gauge pressure, psia is pounds per square inch absolute pressure, and WHSV is mass hourly space velocity. As used herein, "wt%" means weight percentage, "vol%" means volume percentage, "mol%" means mole percentage, "ppm" means parts per million, and "ppm wt" and "wppm" are used interchangeably to mean parts per million by weight. All concentrations herein are expressed based on the total amount of the composition in question. All ranges expressed herein are intended to include both endpoints as two specific embodiments, unless otherwise specified or indicated. The nomenclature of elements and groups used herein conforms to the periodic table used by the International Union of Pure and Applied Chemistry after 1988. An example of a periodic table is given in Advanced Inorganic Chemistry, 6 by F. Albert Cotton et al. (John Wiley & Sons, Inc., 1999). th As shown on the inside page of the front cover of the Edition.

[0015] As used herein, the term "hydrocarbon" means (i) any compound consisting of hydrogen atoms and carbon atoms, or (ii) any mixture of two or more of such compounds of (i). The term "Cn hydrocarbon" (where n is a positive integer) means (i) any hydrocarbon compound containing a total of n carbon atoms in its molecule, or (ii) any mixture of two or more of such hydrocarbon compounds of (i). Thus, C2 hydrocarbons can be ethane, ethylene, acetylene, or any mixture of at least two of these compounds in any ratio. "Cm~Cn hydrocarbon" or "Cm-Cn hydrocarbon" (where m and n are positive integers and m < n) means any one of Cm, Cm+1, Cm+2,..., Cn-1, Cn hydrocarbons, or any mixture of two or more of these. Thus, "C2~C3 hydrocarbon" or "C2-C3 hydrocarbon" can be ethane, ethylene, acetylene, propane, propene, propyne, propadiene, cyclopropane, and any mixture of two or more of these components in any ratio. "Saturated C2-C3 hydrocarbon" can be ethane, propane, cyclopropane, or any mixture of two or more of these in any ratio. "Cn+ hydrocarbon" means (i) any hydrocarbon compound containing at least n carbon atoms in total in its molecule, or (ii) any mixture of two or more of such hydrocarbon compounds of (i). "Cn- hydrocarbon" means (i) any hydrocarbon compound containing a maximum of n carbon atoms in total in its molecule, or (ii) any mixture of two or more of such hydrocarbon compounds of (i). "Cm hydrocarbon stream" means a hydrocarbon stream consisting essentially of Cm hydrocarbons. "Cm-Cn hydrocarbon stream" means a hydrocarbon stream consisting essentially of Cm-Cn hydrocarbons.

[0016] As used herein, "aromatic hydrocarbon" is a hydrocarbon containing an aromatic ring in its molecular structure. An "aromatic compound" can have a cyclic π electron cloud that satisfies Hückel's rule. "Non-aromatic hydrocarbon" means a hydrocarbon other than an aromatic hydrocarbon. As used herein, the term "lower aromatic hydrocarbon" refers to benzene, toluene, or a mixture of benzene and toluene. The term "selectivity" refers to the degree to which a particular reaction forms a particular product rather than another product. As used herein, the term "liquid phase" refers to reaction conditions in which the aromatic hydrocarbons present in the reactor are substantially in the liquid phase. By "substantially in the liquid phase" is meant that ≧about 90 wt.%, preferably ≧about 95 wt.%, preferably ≧about 99 wt.%, preferably all of the aromatic hydrocarbons are in the liquid phase.

[0017] As used herein, the term "gas phase" refers to reaction conditions in which the aromatic hydrocarbons present in the reactor are substantially in the gas phase. By "substantially in the gas phase" is meant that ≧90 wt.%, preferably ≧95 wt.%, preferably ≧99 wt.%, preferably all of the aromatic hydrocarbons are in the gas phase. As used herein, the term "alkylation" refers to a chemical reaction in which an alkyl group is transferred from an alkyl group source compound (alkylating agent), optionally with rearrangement to an aromatic ring as a substitute for a hydrogen atom on the aromatic ring in the transfer process. One or more alkyl groups may be transferred during the alkylation reaction. As used herein, the term "alkylated aromatic hydrocarbon" means an aromatic hydrocarbon containing at least one alkyl group attached to its aromatic ring. The alkyl group reacted with the aromatic hydrocarbon may be linear or branched.

[0018] Zeolite nanoparticles and their synthesis As mentioned above, zeolite nanoparticles are a desirable form for zeolite materials due to their potential to improve catalytic activity and selectivity, enhance substrate accessibility, and improve product desorption kinetics. However, both direct synthesis of zeolite nanoparticles and conversion of zeolite precursors to zeolite nanoparticles can be difficult. For example, to produce MWW zeolite in nanoparticle form by direct synthesis, special polymer additives or multiple structure directing agents and / or multi-step synthesis may be required to produce MWW zeolite precursor in nanoparticle form and then calcinate to form MWW zeolite nanoparticles. Alternatively, base-induced fragmentation of MWW zeolite precursor at high temperatures (above about 70° C.) can be performed, but this can be problematic in terms of scalability, yield loss, and crystallographic changes that occur at elevated reaction temperatures.

[0019] The present disclosure provides the surprising result that MWW zeolite precursor nanoparticles can be formed at temperatures lower than those previously believed to be suitable for promoting base-induced fragmentation of MWW zeolite precursors (i.e., about 70° C. or higher). That is, the present disclosure has found that reaction temperatures from about 60° C. to as low as room temperature can promote efficient formation of MWW zeolite precursor nanoparticles that can then be converted to the corresponding MWW zeolite after calcination. The formation of MWW zeolite nanoparticles via base-induced fragmentation of MWW zeolite precursors is believed to be advantageous because the process does not have to resort to multiple specialized SDA and / or multi-step zeolite syntheses, but rather allows for the use of non-nanoparticulate, commercially available MWW zeolite precursors as a convenient raw material. Furthermore, the low-temperature base-induced fragmentation conditions disclosed herein also tend to promote less yield loss than occurs at higher reaction temperatures, and may be more convenient to implement in large-scale production.

[0020] A further surprising and potentially advantageous benefit of the present disclosure is that the low-temperature base-induced fragmentation conditions can result in MWW zeolites with reduced (or no) undesired crystalline phases. At high-temperature base-induced fragmentation conditions (above about 70° C.) typically used to fragment MWW zeolite precursors, at least partial conversion of MWW zeolite precursors with non-condensed layer structures (e.g., MCM-22, MCM-56, and EMM-10) to condensed layer structures similar to that of MCM-49 can occur. At low-temperature base-induced fragmentation conditions disclosed herein, the formation of condensed zeolitic phases as contaminants during the formation of MWW zeolite precursor nanoparticles can be significantly suppressed or eliminated. By mitigating the formation of additional crystalline phases during MWW zeolite precursor fragmentation, a more intact MWW zeolite of a given type can be obtained upon calcination. Furthermore, by producing a more intact MWW zeolite nanoparticle of a given type, improved catalytic activity and / or reduced tendency to undesired catalytic side reactions driven by additional crystalline phases can be realized.

[0021] The zeolite nanoparticles disclosed herein can be easily extruded into various forms, either as self-bonded extrudates or with a suitable binder. The amount of zeolite nanoparticles in the extrudates can be adjusted to target specific ratios of products in catalytic processes. Furthermore, the catalytic activity of the zeolite nanoparticles in the extrudates can be higher than that obtained when unbound zeolite nanoparticles are utilized in similar catalytic reactions. Thus, a method for producing zeolite precursor nanoparticles includes the steps of providing a parent zeolite precursor having an MWW framework comprising a plurality of stacked layers, and contacting the parent zeolite precursor with an aqueous base under temperature conditions sufficient to break down the parent zeolite precursor into a plurality of zeolite precursor nanoparticles having a size of about 200 nm or less and maintaining the MWW framework without substantially inducing condensation between adjacent stacked layers in the MWW framework. Suitable temperature conditions are further defined below. Determining whether condensation between adjacent stacked layers has occurred may utilize suitable crystallographic techniques, in particular powder X-ray diffraction (XRD). Inward growth of XRD peaks characteristic of a fully condensed layered structure may be characteristic of condensation occurring between adjacent stacked layers. In the present disclosure, if no change in the powder XRD pattern occurs after base-promoted fragmentation, it is believed that no significant condensation has occurred between adjacent stacked layers.

[0022] Zeolite precursor nanoparticles produced according to the disclosure herein may be distinguished in several ways from those obtained by alternative production methods. In one example, the zeolite precursor nanoparticles may be distinguished by their substantial lack of fully condensed phases similar to those of MCM-49, as described above. In another example, the zeolite precursor nanoparticles may be distinguished by containing at most one SDA, resulting in a difference compared to zeolite precursor nanoparticles produced by alternative methods utilizing multiple small molecule SDAs and / or polymer-based SDAs in combination with small molecule SDAs. Thus, compositions resulting from the zeolite nanoparticle precursor synthesis described herein may include a plurality of zeolite precursor nanoparticles formed from a parent zeolite precursor having an MWW framework and including a plurality of stacked layers, the zeolite precursor nanoparticles being about 200 nm or less in size, adjacent stacked layers within the MWW framework remaining substantially uncondensed with one another within the zeolite precursor nanoparticle, and the zeolite precursor nanoparticles containing at most one SDA. The identity of the SDA, if any, within the zeolite precursor nanoparticles produced in accordance with the disclosure herein is not believed to be particularly limited.

[0023] In non-limiting examples, the zeolite precursor nanoparticles can range in size from about 50 nm to about 300 nm, or from about 50 nm to about 250 nm, or from about 100 nm to about 200 nm, or from about 100 nm to about 150 nm, or from about 150 nm to about 200 nm, or from about 150 nm to about 250 nm. Particle sizes are absolute ranges determined from scanning electron microscopy or similar imaging techniques. Suitable MWW zeolite precursors that may undergo base-promoted fragmentation according to the present disclosure include, but are not limited to, precursors that form (after appropriate calcination) MCM-22, MCM-56, EMM-10, or any combination thereof. Other suitable MWW zeolite precursors include ITQ-1, UZM-8, and the like. The MWW zeolite precursor may optionally contain SDA retained from the parent zeolite precursor synthesis, and the structure of the SDA is not believed to be particularly limited. The SDA may continue to be retained or may be lost during the formation of the zeolite precursor nanoparticles of the present disclosure. If still present after the formation of the zeolite precursor nanoparticles, the SDA may be removed during calcination (described below) to convert the zeolite precursor nanoparticles to zeolite nanoparticles.

[0024] The zeolite precursor nanoparticles, after their formation, may be grouped into aggregates, which may range in size from about 150 nm to about 2000 nm, or from about 200 nm to about 1000 nm, or from about 100 nm to about 800 nm, or from about 500 to about 1500 nm. In a non-limiting example, contacting the parent zeolite precursor with the aqueous base may include stirring the parent zeolite precursor with the aqueous base. The rate of stirring and the contact time are not believed to be particularly limited. Static contact between the parent zeolite precursor and the aqueous base may also be sufficient to produce zeolite precursor nanoparticles. The aqueous base may include an alkali metal hydroxide dissolved in water or other suitable aqueous solvent. Suitable alkali metal hydroxides include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, or any combination thereof. Preferably, the alkali metal hydroxide may include lithium hydroxide, sodium hydroxide, potassium hydroxide, or any combination thereof. Other suitable aqueous bases include, for example, alkali metal carbonates, tetraalkylammonium hydroxides, and the like.

[0025] Suitable base concentrations in the aqueous base may include any concentration in water or aqueous solvent that is sufficient to convert the parent zeolite precursor into zeolite precursor nanoparticles without inducing substantial condensation between adjacent stacked layers. Suitable base concentrations may range up to the solubility limit of the base, but are preferably lower. In non-limiting examples, suitable base concentrations in the aqueous base may be about 1.5M or less, or about 1.0M or less, or about 0.75M or less, or about 0.5M or less, such as about 0.2M to about 1.2M, or about 0.25M to about 1.0M, or about 0.3M to about 0.7M, or about 0.4M to about 0.8M, or about 0.2M to about 0.5M. Suitable temperature conditions for forming zeolite precursor nanoparticles in the present disclosure may include any temperature above the freezing point of the aqueous base and the temperature at which condensation of adjacent stacked layers begins to occur. In some embodiments, the temperature conditions may include temperatures of about 60° C. or less, or about 50° C. or less, or about 40° C. or less, or about 30° C. or less, or even below room temperature. Thus, suitable temperature conditions may range from the freezing point of the aqueous base to about room temperature, or to about 30° C., or to about 40° C., or to about 50° C., or to about 60° C. In another example, suitable temperature conditions may range from about room temperature to about 40° C., or to about 50° C., or to about 60° C. It should be understood that suitable temperature conditions may depend on the actual MWW zeolite precursor undergoing fragmentation, the aqueous base concentration, and the contact time, among other parameters.

[0026] The zeolite precursor nanoparticles produced according to the above disclosure may be converted to the corresponding zeolite nanoparticles by calcination in air, optionally before or after conversion to the hydrogen form, for example, by ammonium exchange. Thus, the method of the present disclosure may further include a step of calcining the plurality of zeolite precursor nanoparticles in air to form a plurality of zeolite nanoparticles. Suitable calcination conditions may at least remove SDA (if present) or residual organic compounds by pyrolysis, and convert other elements to their corresponding oxide forms that are retained in the zeolite nanoparticles. In non-limiting examples, suitable calcination temperatures may range from about 500°C to about 1000°C, or from about 550°C to about 750°C, or from about 500°C to about 650°C. After calcination, the resulting zeolite nanoparticles may be obtained in a similar size range to the zeolite precursor nanoparticles from which they were produced.

[0027] The method of the present disclosure may further include forming a shaped catalyst, such as pellets, extrudates, powders, etc., comprising the zeolite nanoparticles prepared as described above. The shaped catalyst may be self-bonded and thus essentially binder-free. The shaped catalyst may include a suitable binder. Thus, the zeolite precursor nanoparticles, or the mixture thereof without a binder, or the mixture with either or both suitable binders, may be processed to form a shaped catalyst using various methods known in the art, such as extrusion, casting, etc., optionally followed by ammonium exchange, optionally followed by drying, and optionally followed by calcination. Suitable binders that may be present in the extrudate are not believed to be particularly limited. In non-limiting examples, suitable binders include, for example, clay, alumina, silica, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, and silica-titania, as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia. The relative ratio of zeolite to binder can range from about 1:99 to about 99:1 by weight. In illustrative examples, zeolite nanoparticles (or zeolite precursor nanoparticles) can range from 10% to about 70% by weight of the extrudate, or from about 20% to about 50% by weight of the extrudate.

[0028] The extrudate and free powder (unbound) forms of the zeolite nanoparticles produced according to the above disclosure can be utilized in a variety of catalytic processes. The catalytic processes in which the zeolite nanoparticles can be utilized include any catalytic process in which regular (non-nanoparticle) MWW zeolite can be utilized. Illustrative examples of suitable catalytic processes in which MWW zeolite can be utilized are as follows: Aromatic alkylation processes using olefins that are normally liquid at room temperature can be facilitated by MWW zeolite nanoparticles. Aromatic compounds that can be alkylated include lower aromatic hydrocarbons, such as benzene and / or toluene, although other aromatic hydrocarbons can also be suitably alkylated. Illustrative reaction conditions include temperatures ranging from about 340° C. to about 500° C., pressures ranging from about atmospheric pressure to about 200 atmospheres, and reaction times of about 2 hours. -1 ~ Approx. 2000 hours -1 and an aromatics / olefin molar ratio in the range of about 1:1 to about 20:1.

[0029] Aromatic alkylation processes using olefins that are normally gases at room temperature can be facilitated by MWW zeolite nanoparticles. Aromatic compounds that can be alkylated include lower aromatic hydrocarbons, such as benzene and / or toluene, although other aromatic hydrocarbons can also be suitably alkylated. Illustrative reaction conditions include temperatures ranging from about 10° C. to about 240° C., or from about 20° C. to about 220° C., or from about 40° C. to about 200° C., or from about 50° C. to about 150° C., pressures ranging from about atmospheric pressure to about 30 atmospheres, and reaction times of about 5 hours. -1 ~ approx. 70 hours -1 Or about 2 hours -1 ~ approx. 50 hours -1 and an aromatic hydrocarbon / olefin molar ratio ranging from about 1:1 to about 20:1. In a non-limiting example, the aromatic compound may be alkylated with propylene to produce one or more isopropyl-substituted aromatic compounds, such as cumene and multi-isopropyl-substituted benzene. In another non-limiting example, the aromatic compound may be alkylated with ethylene to produce one or more ethyl-substituted aromatic compounds, such as ethylbenzene and multi-ethyl-substituted benzene. Phenol alkylation processes with olefins or alcohols can be promoted by MWW zeolite nanoparticles. Phenol or substituted phenols (e.g., o, m, or p-cresol) can be suitably alkylated. Illustrative reaction conditions include temperatures ranging from about 100° C. to about 300° C. or from about 200° C. to about 250° C., pressures ranging from about 10 atm to about 25 atm, and reaction times of about 2 hours. -1 ~ approx. 20 hours -1 Or about 2 hours -1 ~ approx. 10 hours -1 The mass hourly space velocity (WHSV) may range from 0.01 to 0.15.

[0030] Other types of catalytic reactions in which zeolite nanoparticles may be suitably used include, for example, conversion of light paraffins to olefins and / or aromatics, conversion of light olefins to gasoline hydrocarbons, hydrocracking, hydrocracking / dewaxing, ether formation from alcohols and olefins, toluene disproportionation, etc. Suitable reactor systems in which the zeolite nanoparticles or extrudate forms thereof may be present when used to promote the alkylation reaction include, but are not limited to, fixed bed reactors, moving bed reactors, fluidized bed reactors, and / or reactive distillation units. Furthermore, the reactor may contain a single alkylation reaction zone or multiple alkylation reaction zones therein. The alkylating agent may be injected at a single point in the alkylation reactor or at multiple points spaced along the alkylation reactor. The lower aromatic hydrocarbons, such as benzene and / or toluene, and the alkylating agent may be premixed or introduced separately prior to entering the alkylation reactor.

[0031] When used in a suitable catalytic process, the zeolite nanoparticles can optionally further comprise a metal element and / or be passivated with a passivating agent or treated with a selectivating agent to promote a desired type or degree of reactivity. In various examples, the zeolite nanoparticles can be in a desired form, e.g., H + form and can be used without further metal atom loading or passivation / selectivity agent modification. For example, alkylation of aromatic compounds with olefins or other electrophiles can take advantage of the acidity inherent within the pores of the framework structure of zeolite nanoparticles.

[0032] The embodiments disclosed in this specification include the following embodiments. A. Compositions Comprising Zeolite Precursor Nanoparticles The compositions comprise a plurality of zeolite precursor nanoparticles formed from a parent zeolite precursor having an MWW framework and comprising a plurality of stacked layers, the zeolite precursor nanoparticles being about 200 nm or less in size, adjacent stacked layers within the MWW framework remaining substantially uncondensed with one another within the zeolite precursor nanoparticles, and the zeolite precursor nanoparticles containing up to one structure directing agent (SDA). B. Method for making MWW zeolite nanoparticles The method includes providing a parent zeolite precursor having an MWW framework including a plurality of stacked layers, and contacting the parent zeolite precursor with an aqueous base under temperature conditions sufficient to break down the parent zeolite precursor into a plurality of zeolite precursor nanoparticles having a size of about 200 nm or less and that maintain the MWW framework without substantially inducing condensation between adjacent stacked layers within the MWW framework. C. Aromatic Alkylation Method. The method includes the steps of providing an aromatic feed mixture comprising one or more C6+ aromatic hydrocarbons, providing extrudates comprising the composition described in A in calcined form, the calcined form comprising zeolite nanoparticles devoid of a structure directing agent, contacting the aromatic feed mixture with the extrudates under alkylation conditions in the presence of an alkylating agent, and obtaining a product comprising one or more alkylated C6+ aromatic hydrocarbons after contacting the aromatic feed mixture with the composition under alkylation conditions.

[0033] Embodiments AC may include one or more of the following additional elements in any combination: Element 1: The zeolite precursor nanoparticles are about 50 nm to about 250 nm in size. Element 2A: Zeolite precursor nanoparticles include MCM-22 precursor. Element 2B: Zeolite precursor nanoparticles include EMM-10 precursor. Element 2C: The zeolite precursor nanoparticles include an MCM-56 precursor, an ITQ-1 precursor, or an UZM-8 precursor. Element 3: The zeolite precursor nanoparticles are grouped into aggregates. Element 4: The aqueous base comprises an alkali metal hydroxide. Element 5: The method further includes calcining the plurality of zeolite precursor nanoparticles in air to form a plurality of zeolite nanoparticles. Element 6: The method further includes combining a plurality of zeolite nanoparticles with a binder and forming an extrudate including a plurality of zeolite nanoparticles mixed with the binder. Element 7A: Temperature conditions include temperatures ranging from the freezing point of the aqueous base to about 60°C. Element 7B: Temperature conditions include temperatures ranging from the freezing point of the aqueous base to about 40°C. Element 8: The contacting step comprises stirring the parent zeolite precursor with an aqueous base. Element 9: The parent zeolite precursor contains a structure directing agent. Element 10: The zeolite nanoparticles in the extrudates are at least as active as the MWW parent zeolite in promoting the alkylation of one or more C6+ aromatic hydrocarbons. Element 11: C6+ aromatic hydrocarbons consist essentially of benzene. Element 12: The alkylating agent comprises propylene and the product stream comprises one or more isopropyl-functionalized C6+ aromatic hydrocarbons. Element 13: At least a majority of the product stream comprises isopropyl-functionalized C6+ aromatic hydrocarbons having one isopropyl group. Element 14: The zeolite nanoparticles in the extrudates form isopropyl-functionalized C6+ aromatic hydrocarbons with one isopropyl group with higher selectivity than do the unbound zeolite nanoparticles.

[0034] As non-limiting examples, exemplary combinations applicable to A-C include, but are not limited to, 1, and 2A, 2B or 2C; 1 and 3; and 2A, 2B or 2C, and 3. Non-limiting combinations applicable to B include any of the aforementioned combinations applicable to A-C further combined with one or more of 4-9. Further non-limiting combinations applicable to B include, but are not limited to, 4 and 5; 4 and 6; 4, and 7A or 7B; 4 and 8; 4 and 9; 5 and 6; 5, and 7A or 7B; 5 and 8; 5 and 9; 6, and 7A or 7B; 6 and 8; 6 and 9; 7A or 7B, and 8; 7A or 7B, and 9; and 8 and 9. Non-limiting combinations applicable to C include any of the aforementioned combinations applicable to A-C further combined with one or more of 10-14. Further non-limiting combinations applicable to C include, but are not limited to, 10 and 11, 10 and 12, 10-12; 10 and 13; 10 and 14; 10-13; 10-12 and 14; 11 and 12; 11-13; 11 and 14; 12 and 13; 12 and 14; and 13 and 14.

[0035] The present disclosure further relates to the following non-limiting embodiments. A1. A composition comprising a plurality of zeolite precursor nanoparticles formed from a parent zeolite precursor having an MWW framework and comprising a plurality of stacked layers, the zeolite precursor nanoparticles are about 200 nm or less in size, and adjacent stacking layers within the MWW framework remain substantially uncondensed with one another within the zeolite precursor nanoparticles; and The zeolite precursor nanoparticles contain up to one structure directing agent (SDA), composition. A2. The composition according to A1, wherein the zeolite precursor nanoparticles are from about 50 nm to about 250 nm in size. A3. The composition of A1 or A2, wherein the zeolite precursor nanoparticles comprise an MCM-22 precursor. A4. The composition of A1 or A2, wherein the zeolite precursor nanoparticles comprise an EMM-10 precursor. A5. The composition of A1 or A2, wherein the zeolite precursor nanoparticles comprise an MCM-56 precursor, an ITQ-1 precursor, or an UZM-8 precursor. A6. The composition according to any one of A1 to A5, wherein the zeolite precursor nanoparticles are grouped into aggregates.

[0036] B1. Providing a parent zeolite precursor having a MWW framework comprising a plurality of stacked layers; contacting the parent zeolite precursor with an aqueous base under temperature conditions sufficient to break down the parent zeolite precursor into a plurality of zeolite precursor nanoparticles having a size of about 200 nm or less and maintaining the MWW framework without substantially inducing condensation between adjacent stacked layers within the MWW framework; The method includes: B2. The method of B1, wherein the aqueous base comprises an alkali metal hydroxide. B3.Furthermore, The method of any one of B1 and B2, comprising calcining a plurality of zeolite precursor nanoparticles in air to form a plurality of zeolite nanoparticles. B4.Furthermore, combining a plurality of zeolite nanoparticles with a binder; forming an extrudate comprising a plurality of zeolite nanoparticles mixed with a binder; The method according to B3, comprising: B5. The method of any one of B1-B4, wherein the temperature conditions include a temperature ranging from the freezing point of the aqueous base to about 60° C. B6. The method of any one of B1-B4, wherein the temperature conditions include a temperature ranging from the freezing point of the aqueous base to about 40° C. B7. The method of any one of B1-B6, wherein the contacting step comprises stirring the parent zeolite precursor with an aqueous base. B8. The method of any one of B1-B7, wherein the zeolite precursor nanoparticles are in the size range of about 50 nm to about 250 nm. B9. The method of any one of B1-B8, wherein the parent zeolite precursor comprises an MCM-22 precursor. B10. The method of any one of B1-B8, wherein the parent zeolite precursor comprises an EMM-10 precursor. B11. The method of any one of B1-B8, wherein the parent zeolite precursor comprises an MCM-56 precursor, an ITQ-1 precursor, or an UZM-8 precursor. B12. The method of any one of B1-B11, wherein the plurality of zeolite precursor nanoparticles are grouped into agglomerates. B13. The method of any one of B1-B12, wherein the parent zeolite precursor contains a structure directing agent.

[0037] C1. Aromatic alkylation process comprising: providing an aromatic feed mixture comprising one or more C6+ aromatic hydrocarbons; Providing extrudates comprising a composition according to any one of A1 to A6 in calcined form, the calcined form comprising zeolite nanoparticles devoid of structure directing agents; contacting the aromatic feed mixture with the extrudates under alkylation conditions in the presence of an alkylating agent; obtaining a product stream comprising one or more alkylated C6+ aromatic hydrocarbons after contacting the aromatic feed mixture with the composition under alkylation conditions; A method comprising: C2. The aromatic alkylation process of C1, wherein the zeolite nanoparticles in the extrudate are at least as active as the MWW parent zeolite in promoting the alkylation of one or more C6+ aromatic hydrocarbons. The aromatic alkylation process according to C1 or C2, wherein the C3.C6+ aromatic hydrocarbon consists essentially of benzene. C4. The aromatic alkylation process according to any one of C1-C3, wherein the alkylating agent comprises propylene and the product stream comprises one or more isopropyl-functionalized C6+ aromatic hydrocarbons. C5. The aromatic alkylation process according to any one of C1-C4, wherein at least a majority of the product stream comprises isopropyl-functionalized C6+ aromatic hydrocarbons having one isopropyl group. C6. The aromatic alkylation process as described in C5, wherein the zeolite nanoparticles in the extrudate form isopropyl-functionalized C6+ aromatic hydrocarbons having one isopropyl group with higher selectivity than do unbound zeolite nanoparticles. EXAMPLES

[0038] In order to facilitate a better understanding of the embodiments of the present disclosure, the following examples of preferred or representative embodiments are given, which should not be construed in any way as limiting or defining the scope of the present invention. Example 1: General procedure for producing zeolite nanoparticles from MCM-22 zeolite precursor. Aqueous NaOH solution was introduced into a polytetrafluoroethylene vessel and heated in an oil bath under magnetic stirring conditions to the specified temperature (the concentrations and temperatures of the different runs are specified in Figure 2). The temperature of the solution was measured using a thermocouple probe. After reaching the specified temperature, MCM-22 zeolite precursor (MCM-22P) powder was added and the suspension was stirred for 2 hours. MCM-22P is a MWW zeolite with a non-condensed ordered layer structure. The volume:mass ratio of NaOH solution:zeolite precursor powder was fixed at 10 mL:1 g. The vessel was covered with aluminum foil to prevent evaporation. After 2 hours, the products of each run were collected by filtration or centrifugation. The zeolite precursor nanoparticles were further characterized by powder X-ray diffraction (see below) before calcination. The zeolite precursor nanoparticles were dried at 120 °C for more than 6 hours and then calcined at 550 °C in air for 6 hours. The calcined zeolite nanoparticles were then ion-exchanged three times with 1M NH4NO3 solution for 1 hour each. The ion-exchanged product was dried at 120°C for 6 more hours and calcined again in air at 550°C for 6 hours. For cumene alkylation studies (Example 3 below), the ion-exchanged product was further classified into 14 / 25 mesh size to maintain a constant particle size between runs.

[0039] Zeolite precursor nanoparticles prepared under various alkaline treatment conditions were analyzed by powder X-ray diffraction. FIG. 2 shows a plot of overlaid powder X-ray diffraction patterns of MCM-22 zeolite precursor nanoparticles produced according to Example 1 under various conditions. MCM-49 (lower XRD pattern) is provided as an example of MWW zeolite with fully condensed layer structure. As shown, peaks characteristic of MWW zeolite with fully condensed layer structure (corresponding to the peak positions of MCM-49) began to appear at treatment temperatures of 60° C. and above. In contrast, below 40° C., the XRD peaks were substantially overlapped with those of the MCM-22 parent zeolite precursor. This suggests that the formation of zeolite precursor nanoparticles at lower temperature treatments did not result in significant formation of fully condensed layer structure. Without being bound by theory or mechanism, it is believed that higher temperature treatments may result in significant decomposition of framework silicates, which may lead to interlayer condensation and corresponding yield loss.

[0040] The zeolite precursor nanoparticles were also characterized by scanning electron microscope (SEM) imaging. Figures 3A-3C show SEM images of MCM-22 zeolite precursor nanoparticles produced under various conditions according to Example 1. Figure 3D shows SEM images of the parent MCM-22 zeolite precursor. As shown in Figure 3D, the parent MCM-22 zeolite precursor formed nanosheet morphology with particle sizes ranging from 400-500 nm. Figure 3A shows the zeolite precursor nanoparticles of Example 1 produced at 80°C, which promotes at least partial interlayer condensation and is similar to the conditions used in conventional processes for forming MWW zeolite nanoparticles under alkaline milling conditions. The zeolite precursor nanoparticles were approximately 100-200 nm in size, and the zeolite precursor nanoparticles were agglomerated with each other. Figures 3B and 3C show the zeolite precursor nanoparticles of Example 1 produced at 16.4°C and 40°C, respectively. As can be seen, the particle size was comparable to that obtained at 80 °C (Figure 3A), and there was a similar degree of nanoparticle aggregation, but little interlayer condensation occurred (Figure 2).

[0041] Example 2: General procedure for producing zeolite precursor nanoparticles from EMM-10. The procedure of Example 1 was followed, except that an equal amount of EMM-10 zeolite precursor powder was used instead of MCM-22 zeolite precursor powder. EMM-10 is a MWW zeolite with multi-layered random stacking. The concentrations and temperatures of the various runs are demonstrated in FIG. 4. The EMM-10 zeolite precursor nanoparticles prepared under various alkaline treatment conditions were analyzed by powder X-ray diffraction. Figure 4 shows a plot of overlaid powder X-ray diffraction patterns for EMM-10 zeolite precursor nanoparticles produced under various conditions according to Example 2. MCM-49 (lower XRD pattern) is provided as an example of an MWW zeolite with a fully condensed layer structure. As shown, the XRD peaks were substantially overlapped with those of the EMM-10 parent zeolite precursor. This suggests that even at a treatment temperature of 80°C, little formation of a condensed layer structure occurred during the formation of the zeolite precursor nanoparticles. Also, a peak at 2θ=6.5° was still present after treatment at 80°C. This differs from the behavior observed when processing MCM-22 precursor under similar conditions (Example 1). The broad peak at 2θ=8-10° was also well preserved under these alkaline treatment conditions.

[0042] The zeolite precursor nanoparticles were also characterized by SEM imaging. Figures 5A and 5B show SEM images of EMM-10 zeolite precursor nanoparticles produced under various conditions according to Example 2. Figure 5C shows SEM images of the parent EMM-10 zeolite precursor. As shown in Figure 5C, the parent EMM-10 zeolite precursor exhibited an aggregated nanosheet morphology with particle sizes ranging from 300 to 500 nm. Figure 5A shows the zeolite precursor nanoparticles of Example 2 produced at 80°C, and Figure 5B shows the zeolite precursor nanoparticles of Example 2 produced at 40°C. Unlike MCM-22, the product morphology of these zeolite precursor nanoparticles appeared similar under both sets of reaction conditions, resulting in zeolite precursor nanoparticles in the size range of about 100 to 200 nm, respectively, with the zeolite precursor nanoparticles being further aggregated. The reaction temperature of 80°C resulted in a lower yield of zeolite precursor nanoparticles (about 40%) compared to the yield obtained at 40°C (about 80%).

[0043] Example 3: Alkylation of benzene to the product cumene (cumene alkylation). Unbound zeolite nanoparticles: MCM-22 zeolite nanoparticles were prepared under a series of conditions similar to those in Example 1 (see FIG. 6) and were subjected to benzene in an unbound form after being classified to a 14 / 25 mesh size. Propylene gas was used as the alkylating agent. The second order kinetic parameters (rate constants) for cumene alkylation and the amount of isopropylbenzene [IPB] (cumene) and diisopropylbenzene [DIPB] were determined. The rate constants were calculated using methods known to those skilled in the art. See "Principles and Practice of Heterogeneous Catalyst", JM Thomas, WJ Thomas, VCH, 1st Edition, 1997, the disclosure of which is incorporated herein by reference. Briefly, a mixture of benzene / propylene (3:1 mol / mol) was contacted with 0.5 g of catalyst in a stirred batch autoclave at 130° C. and 300 psig. Small aliquots of liquid were removed from the autoclave every 30 min for 3 h and analyzed off-line by gas chromatography. The rate constant values ​​(×10) corresponded to the pseudo-second-order rate constant for propylene consumption. 3 cm 3 Mole -1 time -1 g -1 The catalyst (diisopropylbenzene / isopropylbenzene) mass ratio was used to compare activity between runs, while the diisopropylbenzene / isopropylbenzene (DIPB / IPB) mass ratio was used to compare the selectivity of the catalyst towards the production of the desired product, cumene.

[0044] FIG. 6 is a plot of the ratio [DIPB] / [IPB] versus the kinetic parameters (rate constants) for cumene alkylation using MCM-22 zeolite nanoparticles. The preferred zeolite catalysts exhibited both high rate constants and low [DIPB] / [IPB] ratios (i.e., on the lower right side of the plot). Referring to FIG. 6, the parent MCM-22 zeolite resulted in poor [DIPB] / [IPB] selectivity and low rate constants. The zeolite nanoparticles, in contrast, resulted in significantly higher [DIPB] / [IPB] selectivity values, all in the range of about 24-25.5. The zeolite nanoparticles produced at 80° C., conditions conducive to at least partial formation of a condensed phase, resulted in slightly poorer (higher) [DIPB] / [IPB] ratios than the zeolite nanoparticles produced at 40° C. or 60° C. For the three zeolite nanoparticle samples produced at 80° C., the rate constants increased with increasing base concentration used to form the zeolite nanoparticles, likely due to more vigorous reaction conditions and the extent of fragmentation and desilation that resulted from them. For the zeolite nanoparticles formed at lower temperatures (40° C. and 60° C.), the rate constants were slightly lower than for two of the three samples formed at 80° C., but the [DIPB] / [IPB] ratios for these lower temperature samples were more favorable.

[0045] Zeolite Nanoparticle Extrudates. Extrudates were formed by combining parent MCM-22 zeolite or MCM-22 zeolite nanoparticles with V300 alumina in a muller and extruding the resulting blend through a 1 / 20" quadralobe die. Further details regarding the extrusion process can be found in U.S. Patent Application Publication No. 2008 / 0045765, the contents of which are incorporated herein by reference. The extrudates were subjected to ammonium exchange and then calcined at 540°C in air. The calcined extrudates were contacted with benzene under alkylation conditions to form cumene in a manner similar to that described above. Table 1 below provides catalytic data along with comparative data for parent MCM-22 and MCM-49 extrudates (DIPB=diisopropylbenzene, TIPB=triisopropylbenzene).

[0046] Table 1 [Table 1]

[0047] As shown, the MCM-22 zeolite nanoparticles gave comparable results to each other. All zeolite nanoparticle samples (entries 1-3) showed higher cumene alkylation activity values ​​than the MCM-22 parent zeolite. The cumene alkylation activity values ​​were improved compared to unbound zeolite nanoparticles (compare entries 3 and 4 in Table 2 with nanoparticles / 0.6M / 60°C and raw MCM-22 in Figure 6 from Example 1). Furthermore, by adjusting the amount of zeolite nanoparticles in the extrudate, the selectivity towards isopropylbenzene formation could be further clarified. When present at similar loadings in the extrudate, the selectivity towards isopropylbenzene was higher for the zeolite nanoparticles (compare entries 3 and 4).

[0048] In light of the foregoing description, numerous alternatives, modifications, and variations will be apparent to one of ordinary skill in the art without departing from the spirit or scope of the present disclosure, and it will also be apparent that when numerical limits and upper numerical limits are recited herein, ranges from any lower limit to any upper limit are contemplated. All documents described herein, including any priority documents and / or testing procedures, are incorporated by reference to the extent that they are not inconsistent with this text and are incorporated for all purposes for which such incorporation is permitted. As is apparent from the general description and specific embodiments above, forms of the disclosure have been illustrated and described, but various modifications can be made without departing from the spirit and scope of the disclosure. Thus, the disclosure is not intended to be limited thereby. For example, the compositions described herein may be free of any component or composition not expressly listed or disclosed herein. Any method may lack any step not listed or disclosed herein. Similarly, the term "comprising" is considered synonymous with the term "including." It is understood that whenever the transitional phrase "comprising" precedes a method, composition, element, or group of elements, we also contemplate the same composition or group of elements having the transitional phrase "consisting essentially of," "consisting of," "selected from the group of consisting of," or "is" preceding the recitation of the composition, element, or group of elements, and vice versa.

[0049] One or more illustrative embodiments incorporating one or more inventive elements are presented herein. For the sake of clarity, not all of the features of a physical implementation are described or shown in this application. It is recognized that in developing a physical embodiment incorporating one or more elements of the invention, implementation-specific numerical judgments must be made to achieve implementation-specific and time-varying goals of the developer, such as compliance with system-related, business-related, government-related and other constraints. While the developer's efforts may require significant time, the efforts would nevertheless be routine for one of ordinary skill in the art and having the benefit of this disclosure to undertake. Unless otherwise indicated, all numerical values ​​expressing quantities of ingredients, properties such as molecular weights, reaction conditions, and the like used in the specification and appended 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 and accompanying claims are approximations that may vary depending on the desired properties sought to be obtained by the embodiments of the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0050] Whenever a numerical range with a lower limit and an upper limit is disclosed, any numerical value and any subsumed range falling within that range are expressly disclosed, including the lower and upper limits. In particular, any range of values ​​disclosed herein (in the form, "about a to about b," or in other words, "about a to b," or in other words, "about a b") should be understood to specify any numerical value and range subsumed within the broader range of values. Additionally, the terms in the claims have their plain and ordinary meaning unless expressly and unambiguously defined by the patent owner. Additionally, the indefinite article "a" or "an" used in the claims is defined herein to mean one or more of the element it introduces.

[0051] Thus, the present disclosure is well adapted to attain the ends and advantages mentioned as well as those inherent therein. The specific embodiments described above are merely exemplary, as the present disclosure may be modified and practiced in different but equivalent manners apparent to those skilled in the art and having the benefit of the teachings herein. Moreover, no limitations are intended to the details of construction or design shown herein, other than as set forth in the following claims. It is therefore evident that the specific exemplary embodiments described above may be altered, combined or modified, and such variations are contemplated within the scope and spirit of the present disclosure. The embodiments disclosed herein as examples can be practiced in the absence of any element not specifically disclosed herein and / or any optional element disclosed herein.

Claims

1. 1. A composition comprising a plurality of zeolite precursor nanoparticles having a MWW framework and formed from a parent zeolite precursor comprising a plurality of stacked layers, the zeolite precursor nanoparticles are about 200 nm or less in size, and adjacent stacked layers within the MWW framework remain substantially uncondensed with one another within the zeolite precursor nanoparticles; and The zeolite precursor nanoparticles contain up to one structure directing agent (SDA); The composition.

2. 2. The composition of claim 1, wherein the zeolite precursor nanoparticles are about 50 nm to about 250 nm in size.

3. 3. The composition of claim 1 or claim 2, wherein the zeolite precursor nanoparticles comprise an MCM-22 precursor.

4. The composition of any one of claims 1 to 3, wherein the zeolite precursor nanoparticles comprise an EMM-10 precursor.

5. The composition of any one of claims 1 to 4, wherein the zeolite precursor nanoparticles comprise an MCM-56 precursor, an ITQ-1 precursor, or an UZM-8 precursor.

6. The composition according to any one of claims 1 to 5, wherein the zeolite precursor nanoparticles are grouped into aggregates.

7. Providing a parent zeolite precursor having a MWW framework comprising a plurality of stacked layers; contacting the parent zeolite precursor with an aqueous base under temperature conditions sufficient to break down the parent zeolite precursor into a plurality of zeolite precursor nanoparticles having a size of about 200 nm or less and maintaining the MWW framework without substantially inducing condensation between adjacent stacked layers within the MWW framework; The method includes:

8. 8. The method of claim 7, wherein the aqueous base comprises an alkali metal hydroxide.

9. moreover, calcining the plurality of zeolite precursor nanoparticles in air to form a plurality of zeolite nanoparticles. The method according to claim 7 or claim 8.

10. moreover, combining the plurality of zeolite nanoparticles with a binder; forming an extrudate comprising the plurality of zeolite nanoparticles mixed with the binder; Including, The method according to any one of claims 7 to 9.

11. 11. The method of any one of claims 7 to 10, wherein the temperature conditions comprise a temperature ranging from the freezing point of the aqueous base to about 60°C.

12. 12. The method of claim 11, wherein the temperature conditions include a temperature ranging from the freezing point of the aqueous base to about 40°C.

13. The method of any one of claims 7 to 12, wherein the contacting step comprises stirring the parent zeolite precursor with the aqueous base.

14. The method according to any one of claims 7 to 13, wherein the zeolite precursor nanoparticles are between about 50 nm and about 250 nm in size.

15. The method of any one of claims 7 to 14, wherein the parent zeolite precursor comprises an MCM-22 precursor.

16. 16. The method of any one of claims 7 to 15, wherein the parent zeolite precursor comprises an EMM-10 precursor.

17. 17. The method of any one of claims 7 to 16, wherein the parent zeolite precursor comprises an MCM-56 precursor, an ITQ-1 precursor, or an UZM-8 precursor.

18. The method according to any one of claims 7 to 17, wherein the zeolite precursor nanoparticles are grouped into aggregates.

19. A method according to any one of claims 7 to 18, wherein the parent zeolite precursor contains a structure directing agent.

20. 1. A process for aromatic alkylation comprising the steps of: providing an aromatic feed mixture comprising one or more C6+ aromatic hydrocarbons; Providing extrudates comprising the composition of claim 1 in calcined form, said calcined form comprising zeolite nanoparticles devoid of structure directing agents; contacting said aromatic feed mixture with said extrudates under alkylation conditions in the presence of an alkylating agent; obtaining a product stream comprising one or more alkylated C6+ aromatic hydrocarbons after contacting said aromatic feed mixture with said composition under said alkylation conditions; Including, The method.

21. the zeolite nanoparticles in the extrudates are at least as active as the MWW parent zeolite in promoting the alkylation of the one or more C6+ aromatic hydrocarbons; 21. The aromatic alkylation process of claim 20.

22. 22. The aromatic alkylation process of claim 20 or claim 21, wherein the C6+ aromatic hydrocarbons consist essentially of benzene.

23. 23. The aromatic alkylation process of any one of claims 20 to 22, wherein the alkylating agent comprises propylene and the product stream comprises one or more isopropyl-functionalized C6+ aromatic hydrocarbons.

24. 24. The aromatic alkylation process of any one of claims 20 to 23, wherein at least a majority of the product stream comprises isopropyl-functionalized C6+ aromatic hydrocarbons having one isopropyl group.

25. 25. The aromatic alkylation process of claim 24, wherein the zeolite nanoparticles in the extrudates form the isopropyl-functionalized C6+ aromatic hydrocarbons having one isopropyl group with a higher selectivity than do unbound zeolite nanoparticles.

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