Acid aromatization catalysts with improved activity and stability

Abstract

The title of the invention is Acidic aromatization catalysts with improved activity and stability. Disclosed herein are methods of producing supported catalysts containing a transition metal and a bound zeolite matrix. These methods utilize a step of impregnating the bound zeolite matrix with a transition metal, fluorine, and a high loading of chlorine. The resulting high-chlorine content supported catalysts have improved catalyst activity in aromatization reactions.

Description

[0001] This application is a divisional application of the patent application filed on September 7, 2017, with application number 201780054660X, entitled "Acidic aromatization catalyst with improved activity and stability".

[0002] Citation of relevant applications This application, filed on September 7, 2017, claims priority to U.S. Provisional Patent Application No. 62 / 384,746, filed on September 8, 2016, the disclosure of which is incorporated herein by reference in its entirety. Invention Field This disclosure relates to a method for producing a supported catalyst, and more particularly to an impregnation step using a catalyst having a high chlorine loading, to produce a supported aromatization catalyst containing a transition metal and a bound zeolite matrix. Background of the Invention The catalytic conversion of non-aromatic hydrocarbons to aromatic compounds (often referred to as aromatization or reforming) is an important industrial process that can be used to produce benzene, toluene, xylene, and other aromatic compounds. Aromatization or reforming processes are often carried out in a reactor system, which may contain one or more reactors with transition metal-based catalysts. These catalysts can increase the selectivity and / or yield of the desired aromatic compounds. Over time, these catalysts also slowly lose their activity, typically manifested as a loss of selectivity for the desired aromatic compounds and / or a decrease in conversion.

[0003] Catalysts with improved aromatization properties will be beneficial, providing high catalytic activity and selectivity, low fouling rate, and stability over long-term production operation. Therefore, this disclosure primarily relates to these objectives. Invention Overview This document discloses and describes supported catalysts that can be used in aromatization processes. In one aspect, these catalysts may comprise a bound zeolite matrix and, based on the total weight of the supported catalyst, approximately 0.3 wt.% to approximately 3 wt.% of a transition metal, approximately 1.8 wt.% to approximately 4 wt.% of chlorine, and approximately 0.4 wt.% to approximately 1.5 wt.% of fluorine. Typically, these supported catalysts are characterized by a peak reduction temperature on a temperature-programmed reduction curve in the range of approximately 580 °F to approximately 800 °F.

[0004] This document also discloses and describes a method for producing a supported catalyst. Such a method may include (a) impregnating a combined zeolite matrix with a transition metal precursor, a chlorine precursor, and a fluorine precursor to form an impregnated zeolite matrix; and (b) drying and subsequently calcining the impregnated zeolite matrix to produce the supported catalyst. Based on the total weight of the supported catalyst, the supported catalyst typically contains approximately 0.3 wt.% to approximately 3 wt.% of a transition metal, approximately 1.8 wt.% to approximately 4 wt.% of chlorine, and approximately 0.4 wt.% to approximately 1.5 wt.% of fluorine. The supported catalyst is characterized by a peak reduction temperature on a temperature-programmed reduction curve in the range of approximately 580 °F to approximately 800 °F.

[0005] The supported catalysts produced by the methods presented herein can be used in aromatization processes to generate aromatic compounds from non-aromatic hydrocarbons. These catalysts can exhibit an unexpected combination of high catalytic activity and reduced fouling, while maintaining excellent selectivity (e.g., for benzene and toluene).

[0006] The preceding overview and subsequent details are illustrative and for explanatory purposes only. Therefore, they should not be considered limiting. Moreover, other features or variations may be provided in addition to those described herein. For example, certain aspects may involve various combinations and sub-combinations of features described in the details. Brief description of the attached diagram Figure 1 shows the curves illustrating the amounts of F and Cl (wt.%) in the supported catalyst of Example 1.

[0007] Figure 2 shows the curve of surface area of ​​the supported catalyst versus Cl content (wt.%) in the supported catalyst in Example 1.

[0008] Figure 3 shows the curve of platinum dispersion of the supported catalyst versus Cl content (wt.%) in the supported catalyst in Example 1.

[0009] Figure 4 shows the curves illustrating the amount of N and Cl (wt.%) in the supported catalyst of Example 1.

[0010] Figure 5 shows the curves of molar aromatic selectivity and molar benzene + toluene selectivity of the supported catalyst in Example 2.

[0011] Figure 6 shows the yield correction temperature versus reaction time curve for the supported catalyst in Example 3.

[0012] Figure 7 shows the temperature-programmed reduction curve of the supported catalyst in Example 4.

[0013] Figure 8 shows the yield correction temperature and hydrogen purity versus reaction time curves for the supported catalyst in Example 5.

[0014] Figure 9 shows the "temperature programmed reduction" curve of the high-chlorine supported catalyst in Example 7.

[0015] Figure 10 shows the yield correction temperature versus reaction time curves for the control catalyst and the high-chlorine supported catalyst in Example 7.

[0016] definition To more clearly define the terms used herein, the following definitions are provided. Unless otherwise stated, the following definitions apply to this disclosure. If a term is used in this disclosure but is not specifically defined therein, the definition from the IUPAC General Catalogue of Chemical Terms, Second Edition (1997), may apply, provided that the definition does not conflict with any other disclosure or definition used herein, or if any claim using that definition is ambiguous or unenforceable. If any definition or usage provided in any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein shall prevail.

[0017] In this document, the characteristics of the subject matter are described in such a way that, in a particular aspect, combinations of different characteristics can be conceived. For each aspect and feature disclosed herein, all combinations are conceived that do not adversely affect the design, composition, process, or method described herein, while specific combinations may or may not be explicitly described. Furthermore, unless otherwise expressly stated, any aspect or feature disclosed herein can be combined to describe an inventive design, composition, process, or method consistent with this disclosure.

[0018] In this disclosure, although compositions and methods are often described by way of “comprising” various components or steps, compositions and methods may also be “substantially composed of various components or steps” or “consisting of therewith” unless otherwise stated.

[0019] The terms “a”, “an”, and “the” are intended to include plural alternatives, i.e., at least one. For example, unless otherwise specified, the disclosed “a transition metal” or “chlorine precursor” means containing one transition metal or chlorine precursor, a mixture thereof, or a combination of more than one transition metal or chlorine precursor.

[0020] Typically, using Chemical and Engineering News The numbering scheme indicated in the version of the periodic table published in 1985, 63(5), 27, indicates the group of elements. In some cases, the common name assigned to the group may be used to indicate the group of elements; for example, alkali metals indicate group 1 elements, transition metals indicate group 3-12 elements, and halogens or halides indicate group 17 elements.

[0021] For any particular compound or family disclosed herein, unless otherwise specified, any name or structure shown (generally or specifically) is intended to include all conformational isomers, positional isomers, stereoisomers, and mixtures thereof that can be produced from a particular set of substituents. Unless otherwise specified, the name or structure (generally or specifically) also includes all enantiomers, diastereomers, and other optical isomers (if any) – whether enantiomers or racemates, and mixtures of stereoisomers that a person skilled in the art would recognize. For example, the common names for p-hexane include n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane; the common names for p-butyl include n-butyl, sec-butyl, isobutyl, and tert-butyl.

[0022] On the one hand, a chemical “group” can be defined or described based on how it is theoretically derived from a reference or “parent” compound, for example, based on the number of hydrogen atoms removed from the parent compound to generate the group, even if the group is not actually synthesized in such a manner. These groups can function as substituents or coordinate with or bond to metal atoms. For example, an “alkyl” can be theoretically derived by removing a hydrogen atom from an alkane. Substituents, ligands, or other chemical parts can constitute the public information of a particular “group,” meaning that when the group is used as described, well-known chemical structures and bonding rules will be followed. When a group is described as “derived by…,” “derived from…,” “composed of…,” or “composed of…,” such terms are used in a formal sense unless otherwise specified or required by the context and are not intended to reflect any particular synthetic method or process.

[0023] Various numerical ranges are disclosed herein. Unless otherwise specified, when any type of range is disclosed or claimed herein, it is intended to disclose or claim each possible value that the range may reasonably include, including the endpoints of the range and any subranges and combinations thereof included therein. As a representative example, this application discloses that a supported catalyst may, in some respects, contain approximately 2 wt.% to approximately 3.8 wt.% chlorine based on the total weight of the supported catalyst. The disclosure that the chlorine content of the supported catalyst can be in the range of approximately 2 wt.% to approximately 3.8 wt.% is intended to illustrate that the chlorine content can be any amount within this range, for example, it may be equal to approximately 2 wt.%, approximately 2.2 wt.%, approximately 2.4 wt.%, approximately 2.6 wt.%, approximately 2.8 wt.%, approximately 3 wt.%, approximately 3.2 wt.%, approximately 3.4 wt.%, approximately 3.6 wt.%, or approximately 3.8 wt.%. Furthermore, the chlorine content can be in any range from about 2 wt.% to about 3.8 wt.% (e.g., the chlorine content can be in the range from about 2.5 wt.% to about 3.3 wt.%), and this also includes any combination of the ranges between about 2 wt.% and about 3.8 wt.%. Similarly, all other ranges disclosed herein should be interpreted in a similar manner to this example.

[0024] The term "about" means that quantities, sizes, formulations, parameters, and other quantities and characteristics are not accurate or do not need to be accurate, but can be approximate, including larger or smaller, reflecting tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art, as needed. Generally, whether explicitly stated or not, quantities, sizes, formulations, parameters, or other quantities or characteristics are "about" or "approximate." The term "about" also includes quantities that vary depending on the equilibrium conditions of the composition, said composition being produced from a particular initial mixture. Claims include equivalents of these quantities, whether or not modified by the term "about." The term "about" may mean within 10% of the reported value, preferably within 5% of the reported value.

[0025] As used herein, the term "hydrocarbon" refers to a compound containing only carbon and hydrogen atoms. Other identifiers may be used to indicate the presence of a specific group (if any) in a hydrocarbon (e.g., a halohydrocarbon indicates the presence of one or more halogen atoms that substitute for an equal number of hydrogen atoms in the hydrocarbon).

[0026] Aromatic compounds are compounds comprising a system of cyclic conjugated double bonds that follows Hückel's (4n+2) rule and contains (4n+2) π electrons, where n is an integer from 1 to 5. Aromatic compounds include "aromatic hydrocarbons" (aromatic compounds such as benzene, toluene, and xylene) and "heteroaromatic hydrocarbons" (heteroaromatic compounds theoretically derived from aromatic hydrocarbons by replacing one or more methylene (–C=) carbon atoms in the cyclic conjugated double bond system with trivalent or divalent heteroatoms, thereby maintaining the continuous π electron configuration of the aromatic system corresponding to the numerous out-of-plane π electrons of Hückel's (4n+2) rule). As disclosed herein, the term "substituted" can be used to describe aryl, aromatic, or heteroaromatic compounds, where, unless otherwise specified, the non-hydrogen portion theoretically replaces a hydrogen atom in the compound and is not intended to be limiting.

[0027] As used herein, the term "alkane" refers to a saturated hydrocarbon compound. Other identifiers may be used to indicate the presence of a specific group (if any) in an alkane (e.g., a haloalkane indicates the presence of one or more halogen atoms that have substituted an equal number of hydrogen atoms in the alkane). The term "alkyl" is used herein according to the definition given by IUPAC: a monovalent group formed by removing a hydrogen atom from an alkane. Unless otherwise specified, alkanes or alkyl groups may be straight-chain or branched.

[0028] "Cycloalkane" is a saturated cyclic hydrocarbon with or without side chains, such as cyclobutane, cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane. Other identifiers may be used to indicate the presence of a specific group (if any) in cycloalkanes (e.g., halocycloalkane indicates the presence of one or more halogen atoms that have substituted an equal number of hydrogen atoms in the cycloalkane).

[0029] As used herein, the terms "convertible hydrocarbon," "convertible C6 species," or "convertible C7 species" refer to hydrocarbon compounds that readily react to form aromatics under aromatization conditions. "Non-convertible hydrocarbon" refers to highly branched hydrocarbons that do not readily react to form aromatics under aromatization conditions. "Non-convertible hydrocarbons" include highly branched hydrocarbons having six or seven carbon atoms with an internal quaternary carbon, or hydrocarbons having six carbon atoms and two adjacent internal tertiary carbons, or mixtures thereof. "Convertible C6 species" are hydrocarbons containing six carbon atoms but without an internal quaternary carbon or two adjacent internal tertiary carbons, such as n-hexane, 2-methylpentane, 3-methylpentane, cyclohexane, and methylcyclopentane. "Convertible C7 species" are hydrocarbons containing seven carbon atoms but without an internal quaternary carbon, such as n-heptane, 2-methylhexane, 3-methylhexane, 2,3-dimethylpentane, 2,4-dimethylpentane, methylcyclohexane, and dimethylcyclopentane. Highly branched hydrocarbons having six or seven carbon atoms and an internal quaternary carbon can include 2,2-dimethylbutane, 2,2-dimethylpentane, 3,3-dimethylpentane, and 2,2,3-trimethylbutane, etc. Highly branched hydrocarbons having six carbon atoms and an adjacent internal tertiary carbon can, for example, include 2,3-dimethylbutane. Under aromatization conditions, highly branched hydrocarbons that are not readily convertible to aromatic products tend to convert to lighter hydrocarbons instead.

[0030] The term "halogen" has a common meaning. Examples of halogens include fluorine, chlorine, bromine, and iodine.

[0031] The definition of molar selectivity is as follows: Conversion rate is defined as the number of moles of "convertible" hydrocarbon converted per mole of input: In these equations, ṅ This indicates the molar flow rate in a continuous reactor or the number of moles in a batch reactor.

[0032] Although any methods and materials similar to or equivalent to those described herein may be used to practice or test the invention, general methods and materials are described herein.

[0033] For purposes of description and disclosure, all publications and patents mentioned herein are incorporated herein by reference, such as structures and methods described in publications, which may be used in conjunction with the invention currently described. Invention Details This paper discloses supported catalysts with high chlorine content, methods for producing such supported catalysts, and their applications in aromatization or reforming processes. Compared to conventional aromatization catalysts with low chlorine content, the high-chlorine-content supported catalysts described herein exhibit unexpectedly improved catalytic activity and stability, as well as lower scaling rates.

[0034] While not wishing to be bound by the following theories, it is believed that conventional chlorine loadings, using less than those of the high-chlorine-content supported catalysts disclosed herein, can lead to poor performance of aromatization catalysts, while using greater chlorine loadings can result in difficulties in successfully impregnating the zeolite matrix with the required amounts of transition metals, chlorine, fluorine, and water. Furthermore, conventional chlorine loadings are designed with the conventional notion that increasing the acidity of the catalyst will impair its activity and selectivity, in part referring to maintaining the non-acidic nature of the supported catalyst, thus making the high-chlorine-content supported catalysts described herein and their improved catalytic performance all the more surprising.

[0035] Supported catalysts Consistent with the aspects disclosed herein, the supported catalyst comprises (or is substantially composed of) a bound zeolite matrix, approximately 0.3 wt.% to approximately 3 wt.% of a transition metal, approximately 1.8 wt.% to approximately 4 wt.% of chlorine, and approximately 0.4 wt.% to approximately 1.5 wt.% of fluorine. These weight percentages are based on the total weight of the supported catalyst. The supported catalyst may be characterized by a peak reduction temperature on a temperature-programmed reduction (TPR) curve in the range of approximately 580 °F to approximately 800 °F. In general, the characteristics of any catalyst disclosed herein (e.g., bound zeolite matrix, transition metal and transition metal content, chlorine content, fluorine content, and TPR curve characteristics, etc.) are described independently herein, and these characteristics may be combined in any combination to further describe the disclosed supported catalyst.

[0036] First, the bound zeolite matrix is ​​mentioned. Any suitable bound zeolite matrix can be used with the high-chlorine-content supported catalysts disclosed herein. Typically, the bound zeolite matrix may contain inorganic oxides, examples of which include, but are not limited to, bound media and / or macroporous zeolites (aluminosilicates), amorphous inorganic oxides, and mixtures thereof. Macroporous zeolites often have an average pore size in the range of about 7 Å to about 12 Å, and non-limiting examples of macroporous zeolites include L-zeolites, Y-zeolites, mordenite, ω-zeolites, β-zeolites, etc. Mesoporous zeolites often have an average pore size in the range of about 5 Å to about 7 Å. Amorphous inorganic oxides include, but are not limited to, alumina, silica, titanium dioxide, and combinations thereof.

[0037] The term "zeolite" typically refers to a specific group of hydrated, crystalline metallic aluminum silicates. These zeolites exhibit SiO4 and AlO4 tetrahedral networks, in which aluminum and silicon atoms are cross-linked within a three-dimensional framework by sharing oxygen atoms. Within this framework, the ratio of oxygen atoms to the total number of aluminum and silicon atoms can be equal to 2. This framework exhibits a negative valence that can typically be balanced by incorporating cations (e.g., metals, alkali metals, and / or hydrogen) within the crystal.

[0038] In some respects, the bound zeolite matrix may include L-type zeolites. L-type zeolite supports are a subfamily of zeolite supports, wherein the zeolite support can be defined according to the following formula: M 2 / n OAl₂O₃xSiO₂yH₂O is an oxide containing a molar ratio of . In this formula, "M" refers to one or more exchangeable cations, such as barium, calcium, cerium, lithium, magnesium, potassium, sodium, strontium, and / or zinc, as well as nonmetallic cations, such as hydrated hydrogen ions and ammonium ions. These cations can be replaced by other exchangeable cations without causing a significant change in the basic crystal structure of the L-type zeolite. "n" in the formula represents the valence state of "M"; "x" is 2 or greater; and "y" is the number of water molecules contained in the channels or interconnected voids of the zeolite.

[0039] On the one hand, bound zeolite matrices can include potassium-bound L-type zeolites, also known as K / L-zeolites; on the other hand, bound zeolite matrices can include barium-exchanged L-zeolites. As used herein, the term "K / L-zeolite" refers to an L-type zeolite in which the major cation M incorporated into the zeolite is potassium. K / L-zeolites can be cation-exchanged (e.g., with barium) or impregnated with transition metals and one or more halides to produce transition metal-impregnated halide zeolites or K / L-supported transition metal-halide zeolite catalysts.

[0040] In a bound zeolite matrix, the zeolite can be bonded with a supporting matrix (or binder), and non-limiting examples of binders include, but are not limited to, inorganic solid oxides, clays, and combinations thereof. Zeolite can be bonded to a binder or supporting matrix using any method known in the art. For example, a bound zeolite matrix—comprising zeolite and a binder—can be produced by a process comprising mixing zeolite (e.g., K / L-zeolite) with a binder (e.g., silica sol), then extruding the mixture to form an extrudate, subsequently drying and calcining the extrudate to form a calcined matrix, and subsequently washing, drying, and calcining the calcined matrix to form a bound zeolite matrix.

[0041] In some aspects, the binder may include alumina, silica, magnesium oxide, boron oxide, titanium dioxide, zirconium oxide, oxides of the same or mixed thereof (e.g., aluminosilicates), or mixtures thereof; in other aspects, the binder may include montmorillonite, kaolin, cement, or combinations thereof. In certain aspects conceived herein, the binder may include silica, alumina, oxides of the same or mixed thereof; alternatively, silica; alternatively, alumina; or; or alternatively, silica-alumina. Accordingly, the bonded zeolite matrix may include silica-bonded L-zeolite, such as silica-bonded Ba / L-zeolite, silica-bonded barium ion-exchanged L-zeolite, or silica-bonded K / L-zeolite.

[0042] Without limitation, the bound zeolite matrix (or supported catalyst) as described herein may contain from about 3 wt.% to about 35 wt.% binder. For example, the bound zeolite matrix (or supported catalyst) may contain from about 5 wt.% to about 30 wt.% or from about 10 wt.% to about 30 wt.% binder. Depending on the context, these weight percentages are based on the total weight of the bound zeolite matrix or the total weight of the supported catalyst.

[0043] Illustrative examples of bound matrices and their use in supported catalysts are described in U.S. Patent Nos. 5,196,631, 6,190,539, 6,406,614, 6,518,470, 6,812,180, and 7,153,801, the disclosures of which are incorporated herein by reference in their entirety.

[0044] The supported catalyst may contain from about 0.3 wt.% to about 3 wt.% of a transition metal. For example, the supported catalyst may contain from about 0.5 wt.% to about 2.5 wt.%, from about 0.5 wt.% to about 2 wt.%, or from about 0.7 wt.% to about 1.5 wt.% of a transition metal. These weight percentages are based on the total weight of the supported catalyst.

[0045] Non-limiting examples of suitable transition metals may include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, gold, silver, copper, etc., or combinations of two or more transition metals. In one aspect, the transition metal may include Group 8-11 transition metals or Group 8-10 transition metals (one or more); in another aspect, the transition metal may include platinum (Pt). In yet another aspect, a bonded zeolite matrix may be impregnated with only one transition metal, and that transition metal is platinum.

[0046] When the transition metal includes platinum, the supported catalyst may contain about 0.3 wt.% to about 3 wt.% platinum; alternatively, about 0.5 wt.% to about 2.5 wt.% platinum; alternatively, about 0.5 wt.% to about 2 wt.% platinum; or alternatively, about 0.7 wt.% to about 1.5 wt.% platinum. In certain aspects conceived herein, the supported catalyst may contain platinum on K / L-zeolite.

[0047] Clearly, compared to conventional aromatization catalysts, the supported catalysts described herein exhibit relatively high chlorine (Cl) loadings, typically ranging from about 1.8 wt.% to about 4 wt.% based on the total weight of the supported catalyst. In one aspect, the supported catalyst may contain about 2 wt.% to about 3.8 wt.% chlorine. In another aspect, the supported catalyst may contain about 2.2 wt.% to about 3.6 wt.% chlorine. In yet another aspect, the supported catalyst may contain about 2.2 wt.% to about 3.4 wt.% chlorine. And in yet another aspect, the supported catalyst may contain about 2 wt.% to about 3.3 wt.% chlorine or about 2.5 wt.% to about 3.3 wt.% chlorine. Unexpectedly, the high chlorine loading in the supported catalyst has been found to provide improved catalyst activity and stability, as well as lower scaling rates.

[0048] The supported catalyst also contains fluorine (F) in the range of approximately 0.4 wt.% to about 1.5 wt.% or approximately 0.5 wt.% to about 1.5 wt.% by weight of the supported catalyst. For example, the supported catalyst may contain approximately 0.5 wt.% to about 1.3 wt.% of fluorine, approximately 0.5 wt.% to about 1.1 wt.% of fluorine, or approximately 0.6 wt.% to about 0.9 wt.% of fluorine.

[0049] Without limitation, high chlorine-supported catalysts may be characterized by a chlorine:fluorine weight ratio that typically falls within the range of about 1.5:1 to about 8:1, or about 2:1 to about 6:1. In some respects, the chlorine:fluorine weight ratio may range from about 2:1 to about 5:1, while in others it may range from about 3:1 to about 4.5:1.

[0050] Surprisingly, the high-chlorine-content supported catalysts described herein can exhibit “temperature-programmed reduction” (TPR) profiles that are distinctly different from those of conventional low-chlorine-content supported catalysts (e.g., with 0.3 wt.% to 1.5 wt.% Cl). For example, in one aspect, the high-chlorine-content supported catalysts disclosed herein can be characterized by peak temperatures on the TPR profile ranging from approximately 580 °F to approximately 800 °F. In another aspect, peak temperatures on the TPR profile can range from approximately 580 °F to 750 °F, approximately 600 °F to 730 °F, approximately 600 °F to approximately 720 °F, or approximately 630 °F to approximately 690 °F. The peak temperature on the TPR profile is the temperature of the highest peak on the TPR profile. As shown in subsequent examples, conventional low-chlorine-content supported catalysts exhibit much lower peak temperatures.

[0051] "Conventional low-chlorine-content supported catalysts" typically include aromatization catalysts as described herein, containing any amount of Cl ranging from 0.3 wt.% to 1.5 wt.% based on the total weight of the supported catalyst. Therefore, conventional low-chlorine-content supported catalysts can include supported catalysts having any Cl content ranging from 0.3 wt.% to 1.5 wt.% (e.g., from 0.3 wt.% to 1.2 wt.% Cl, or from 0.5 wt.% to 1.1 wt.% Cl). In addition, conventional low-chlorine supported catalysts can have Cl content of approximately 0.4 wt.%, approximately 0.5 wt.%, approximately 0.6 wt.%, approximately 0.7 wt.%, approximately 0.8 wt.%, approximately 0.9 wt.%, approximately 1 wt.%, approximately 1.1 wt.%, approximately 1.2 wt.%, approximately 1.3 wt.%, or approximately 1.4 wt.%.

[0052] For example, in one aspect, the high-chlorine-content supported catalyst disclosed herein may be characterized by a peak TPR temperature at least 100 °F higher than that of a conventional low-chlorine-content supported catalyst. In another aspect, the peak temperature on the TPR curve may be at least about 150 °F higher, at least about 200 °F higher, about 100 °F higher to about 400 °F higher, about 120 °F higher to about 300 °F higher, or about 100 °F higher to about 250 °F higher.

[0053] Furthermore, the high-chlorine-content supported catalysts disclosed herein are characterized by TPR curves with a lower temperature peak and a higher temperature peak (i.e., two peaks), with the higher temperature peak being greater in height than the lower temperature peak. As shown in the following examples, the opposite is true for low-chlorine-content supported catalysts—that is, the lower temperature peak is greater in height than the higher temperature peak.

[0054] Furthermore, the high-chlorine-content supported catalysts disclosed herein can have a higher total nitrogen (N) content than low-chlorine-content supported catalysts (e.g., with 0.3 wt.% to 1.5 wt.% Cl) under the same catalyst preparation conditions. In some cases, the total nitrogen content of the high-chlorine-content supported catalyst can be at least about 50%, at least about 100%, or at least about 200% higher than that of the low-chlorine-content supported catalyst, and often up to 500-1000%.

[0055] In some respects, the supported catalyst contains nitrogen (N), which typically ranges from about 0.4 wt.% to about 1.6 wt.% based on the total weight of the supported catalyst. For example, the supported catalyst may contain about 0.5 wt.% to about 1.4 wt.% nitrogen, about 0.6 wt.% to about 1.3 wt.% nitrogen, or about 0.7 wt.% to about 1.2 wt.% nitrogen.

[0056] Furthermore, the performance of the high-chlorine-content supported catalysts disclosed herein is improved in aromatization reactions. Surprisingly, these supported catalysts exhibit higher catalytic activity and stability, as discussed in more detail in subsequent examples. SOR (Starting operating temperature), T EOR The results are quantified by the operating end temperature (T0) and FR (fouling rate). Generally, when compared under the same catalyst preparation and aromatization reaction conditions, the high-chlorine-content supported catalysts described herein can exhibit lower T0 than low-chlorine-content supported catalysts (e.g., with 0.3 wt.% to 1.5 wt.% chlorine). SOR Lower T EOR And / or lower FR. Therefore, comparisons are made against supported catalysts that have the same platinum properties, fluorine properties and other compositional properties (except for chlorine content) and are prepared in the same manner and tested under the same aromatization reaction conditions (see Example 3 below).

[0057] High chlorine content supported catalysts can be characterized by the T described in this article. SOR(Operating start temperature), which can typically fall within the range of approximately 915 °F to approximately 935 °F, or approximately 915 °F to approximately 930 °F. Alternatively or additionally, these supported catalysts may be characterized by the T... described herein. EOR (End of operation temperature), which can typically fall within the range of approximately 920 °F to approximately 940 °F, or approximately 920 °F to approximately 930 °F. Additionally, or alternatively, these supported catalysts may be characterized by the FR (fouling rate) described herein, which can typically be less than approximately 0.12 °F / min, or less than approximately 0.1 °F / min.

[0058] Contrary to these improvements and unexpectedly, when compared under the same catalyst preparation conditions, the high-chlorine-content supported catalyst exhibits comparable surface area and platinum dispersion to the low-chlorine-content supported catalyst (e.g., with 0.3 wt.% to 1.5 wt.% chlorine). For example, when compared under the same catalyst preparation conditions, the high-chlorine-content supported catalyst can have substantially the same surface area and platinum dispersion as the low-chlorine-content supported catalyst. In these cases, "substantially" means within + / - 20%, more typically within + / - 15%, or within + / - 10%.

[0059] Furthermore, high-chlorine-content supported catalysts are characterized by having substantially the same aromatic selectivity (or benzene + toluene selectivity) as low-chlorine-content supported catalysts (with 0.3 wt.% to 1.5 wt.% chlorine) when compared under the same catalyst preparation and aromatization reaction conditions. In these cases, "substantially" means within a range of + / -10%, more typically + / -6%, or + / -4%.

[0060] Methods for producing supported catalysts This document discloses and describes various methods for producing supported catalysts (e.g., supported aromatization catalysts). Such a method for producing a supported catalyst may include (or substantially consist of) (a) impregnating a combined zeolite matrix with a transition metal precursor, a chlorine precursor, and a fluorine precursor to form an impregnated zeolite matrix; and (b) drying and subsequently calcining the impregnated zeolite matrix to produce the supported catalyst. Based on the total weight of the supported catalyst, the supported catalyst may contain approximately 0.3 wt.% to approximately 3 wt.% of a transition metal, approximately 1.8 wt.% to approximately 4 wt.% of chlorine, and approximately 0.4 wt.% to approximately 1.5 wt.% of fluorine. Additionally, the supported catalyst may be characterized by a peak reduction temperature on a temperature-programmed reduction curve in the range of approximately 580 °F to approximately 800 °F.

[0061] Generally, the characteristics of any method disclosed herein (e.g., bound zeolite matrix, transition metal precursor, transition metal and transition metal content, chlorine precursor, chlorine content, fluorine precursor, fluorine content, TPR curve characteristics, conditions for performing the impregnation step, conditions for drying and calcination, etc.) are described independently, and these characteristics may be combined in any combination to further describe the disclosed method for producing supported catalysts. Unless otherwise stated, other process steps may be performed before, during, and / or after any step listed in the disclosed method. Furthermore, supported catalysts (e.g., supported aromatization catalysts) produced according to any disclosed method / process fall within the scope of this disclosure and are included herein.

[0062] Now referring to step (a) of the supported catalyst production method (commonly referred to as the impregnation step), the bound zeolite matrix can be impregnated with transition metal precursors, chlorine precursors, and fluorine precursors to form an impregnated zeolite matrix. The bound zeolite matrix in step (a) can be produced by any technique known to those skilled in the art. The bound zeolite matrix—comprising zeolite and binder—can be produced by a process comprising mixing or combining the zeolite with the binder, then extruding the mixture to form an extrudate, subsequently drying and calcining the extrudate to form a calcined matrix, and subsequently washing, drying, and calcining the calcined matrix to form the bound zeolite matrix.

[0063] The transition metal precursors, chlorine precursors, and fluorine precursors in the impregnation step include any compound that can deposit a transition metal, chlorine, and / or fluorine into the interior or surface of a bound zeolite matrix to form the impregnated zeolite matrix. This description is intended to include (1) compounds that are a single material precursor – for example, ammonium chloride can be a chlorine precursor, and (2) compounds that are precursors to more than one material – for example, platinum(II) chloride can be a transition metal precursor of platinum and chlorine and a chlorine precursor, while chlorofluorocarbon compounds can be chlorine precursors of chlorine and fluorine and fluorine precursors.

[0064] Illustrative and non-limiting examples of transition metal precursors suitable for use in impregnating a platinum bonding matrix include, but are not limited to, tetraammineplatinum(II) chloride, tetraammineplatinum(II) nitrate, platinum(II) acetylacetonate, ammonium tetrachloroplatinate(II) nitrate, chloroplatinic acid, platinum(II) nitrate, and mixtures or combinations thereof. Illustrative and non-limiting examples of chlorine precursors include hydrochloric acid, carbon tetrachloride, tetrachloroethylene, chlorobenzene, chloromethane, dichloromethane, chloroform, allyl chloride, trichloroethylene, chloramine, chlorine oxides, chloric acid, chlorine dioxide, dichloride, dichlorhexyl chloride, chloric acid, perchloric acid, ammonium chloride, tetramethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, and combinations thereof. Illustrative and non-limiting examples of fluorine precursors include hydrofluoric acid, 2,2,2-trifluoroethanol, tetrafluoroethylene, tetrafluoromethane, trifluoromethane, fluoromethane, heptafluoropropane, decafluorobutane, hexafluoroisopropanol, tetrafluoropropanol, pentafluoropropanol, hexafluorophenylpropanol, perfluorobutanol, hexafluoro-2-propanol, pentafluoro-1-propanol, tetrafluoro-1-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, ammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, methyltriethylammonium fluoride, etc., and compositions thereof.

[0065] In the impregnation step, any suitable method or technique known to those skilled in the art that results in adequate dispersion of the transition metal on the supported catalyst can be used. This method involves mixing the bound zeolite matrix with any suitable transition metal precursor, wherein the transition metal precursor can be present in a solution of any suitable solvent (e.g., water). Similarly, for halogens, the impregnation step may include mixing the bound zeolite matrix with any suitable chlorine and / or fluorine precursor in any order or sequence. For example, the bound zeolite matrix can be mixed with a solution of a chlorine precursor, a solution of a fluorine precursor, or a solution of both chlorine and fluorine precursors in a suitable solvent. On one hand, the bound zeolite matrix can be mixed with the transition metal precursor, the chlorine precursor, and the fluorine precursor (i.e., all mixed together), for example, by mixing the bound zeolite matrix with an aqueous solution containing the transition metal precursor, the chlorine precursor, and the fluorine precursor. Initial wet impregnation techniques can be used. On the other hand, the combination of the transition metal precursor, the chlorine precursor, the fluorine precursor, and the bound zeolite matrix can be performed sequentially or in any order or combination.

[0066] However, in other respects, the combined zeolite matrix can be impregnated with chlorine and / or fluorine in the vapor phase. For example, the combined zeolite matrix can be contacted with a gas stream containing chlorine and / or fluorine precursors. Suitable chlorine and fluorine precursors may include the precursors listed above, as well as chlorine (Cl2) and fluorine (F2).

[0067] Now, regarding step (b), the impregnated zeolite matrix can be dried and then calcined to produce a supported catalyst. Any suitable temperature, pressure, time period, and environment can be used in both the drying and calcination steps.

[0068] In one aspect, the drying step may include contacting the impregnated zeolite matrix with a drying gas stream comprising (or substantially comprising) an inert gas (e.g., nitrogen), oxygen, air, or any mixture or combination thereof; alternatively, nitrogen; alternatively, helium; alternatively, neon; alternatively, argon; alternatively, oxygen; or alternatively, air. Without limitation, the drying step may generally be carried out at a drying temperature ranging from about 50 °C to about 200 °C; alternatively, from about 100 °C to about 200 °C; alternatively, from about 85 °C to about 175 °C; or alternatively, from about 80 °C to about 150 °C. In these and other aspects, these temperature ranges are also intended to include cases where the drying step is carried out at a range of different temperatures falling within their respective ranges, rather than at a single fixed temperature. In some respects, the drying step can be performed at atmospheric pressure or at any suitable sub-atmospheric pressure (e.g., less than about 150 Torr, less than about 125 Torr, less than about 100 Torr, or less than about 50 Torr).

[0069] The duration of the drying step is not limited to any specific time period. Typically, the drying step can be carried out over a period ranging from as short as 30 minutes to as long as 8 hours (or longer), but more typically, the drying step can be carried out over a period of approximately 1 hour to approximately 8 hours, for example, approximately 1 hour to approximately 7 hours, approximately 1 hour to approximately 6 hours, approximately 2 hours to approximately 7 hours, or approximately 2 hours to approximately 6 hours.

[0070] The calcination step can be performed at various temperatures and for a range of time periods. Typical peak calcination temperatures often fall within the range of approximately 200°C to approximately 600°C, for example, approximately 215°C to approximately 500°C, approximately 230°C to approximately 450°C, or approximately 230°C to approximately 350°C. In these and other respects, these temperature ranges are also intended to include cases where the calcination step is performed at a series of different temperatures falling within their respective ranges (e.g., initial calcination temperature, peak calcination temperature), rather than at a single fixed temperature. For example, the calcination step can begin at the same initial temperature as the drying temperature in the drying step. Thus, the calcination temperature can increase over time to the peak calcination temperature, for example, in the range of approximately 230°C to approximately 350°C.

[0071] The duration of the calcination step is not limited to any specific time period. Therefore, the calcination step can be carried out over a period ranging from as short as 30-45 minutes to as long as 10-12 hours or longer. The corresponding calcination time can depend, for example, on the initial / peak calcination temperature and the conditions of the drying step, as well as other variables. However, typically, the calcination step can be carried out over a time period that can be approximately 45 minutes to approximately 12 hours, for example, approximately 1 hour to approximately 12 hours, approximately 1 hour to approximately 10 hours, approximately 1 hour to approximately 5 hours, or approximately 1 hour to approximately 3 hours.

[0072] The calcination step can be carried out in a calcination gas stream containing (or substantially consisting of) an inert gas (e.g., nitrogen), oxygen, air, or any mixture or combination thereof. In some respects, the calcination gas stream may contain air, while in other respects, it may contain a mixture of air and nitrogen. However, in some respects, the calcination gas stream may be an inert gas, such as nitrogen and / or argon.

[0073] The method for preparing the supported catalyst disclosed herein may further include a reduction step following step (b) (i.e., after drying and calcining the impregnated zeolite matrix to produce the supported catalyst). This reduction step may include contacting the supported catalyst with a reducing gas stream containing hydrogen to produce a reduced (or activated) supported catalyst. Typically, the reducing gas stream comprises molecular hydrogen (alone or together with an inert gas, such as helium, neon, argon, nitrogen, etc.), and this reducing gas stream contains a combination of two or more of these inert gases. In some respects, the reducing gas stream may comprise (or consist essentially of) molecular hydrogen and nitrogen. Moreover, molecular hydrogen may be the major component of the reducing gas stream (greater than 50 mol%), while in other respects, molecular hydrogen may be a minor component (between 5-35 mol% or between 1-6 mol%). On the other hand, the reducing gas stream may comprise (or consist essentially of) molecular hydrogen and hydrocarbons.

[0074] The reduction step can be performed at a variety of temperatures and for a range of time periods. For example, the reduction step can be performed at reduction temperatures ranging from approximately 100 °C to approximately 700 °C; alternatively, from approximately 200 °C to approximately 600 °C; alternatively, from approximately 200 °C to approximately 575 °C; alternatively, from approximately 350 °C to approximately 575 °C; alternatively, from approximately 400 °C to approximately 550 °C; or alternatively, from approximately 450 °C to approximately 550 °C. In these and other respects, these temperature ranges are also intended to include cases where the reduction step is performed at a range of different temperatures falling within their respective ranges, rather than at a single fixed temperature.

[0075] The duration of the restoration step is not limited to any specific time period. Therefore, the restoration step can be performed over a period ranging from as short as 1 hour to as long as 48-72 hours or longer. For example, the restoration step can be performed over a time period that is approximately 1 hour to approximately 48 hours, approximately 3 hours to approximately 36 hours, approximately 5 hours to approximately 36 hours, approximately 2 hours to approximately 30 hours, or approximately 10 hours to approximately 30 hours.

[0076] In one respect, the reduction step can be performed off-site. In this respect, following the process described above, the high-chlorine-content supported catalyst is converted into a reduced (or activated) supported catalyst. This reduction can be carried out at the catalyst manufacturing site or elsewhere. The reduced (or activated) supported catalyst can then be packaged under air or an inert gas atmosphere and stored before being loaded into the aromatization reactor and used in the aromatization reactor system. Before use, a reduction step can be performed to reduce the supported catalyst that has become oxidized after the initial reduction, for example, during storage, transportation, and loading. The second reduction may require the same or shorter time as the in-situ reduction described below.

[0077] On the other hand, the reduction step can be performed in situ. In this regard, the high-chlorine-content supported catalyst is packaged after the calcination step. The high-chlorine-content supported catalyst can be stored for an extended period of time before being loaded into the aromatization reactor. After loading, the high-chlorine-content supported catalyst is subsequently converted into a reduced (or activated) supported catalyst according to the process described above.

[0078] Surprisingly, despite the high chlorine content of the supported catalysts disclosed herein, the reduced (or activated) supported catalysts can have significantly lower chlorine content after the reduction step. For example, the reduced (or activated) supported catalysts can contain approximately 0.2 wt.% to approximately 1.3 wt.% chlorine, approximately 0.2 wt.% to approximately 0.8 wt.% chlorine, or approximately 0.3 wt.% to approximately 1 wt.% chlorine. These weight percentages are based on the total weight of the reduced (or activated) supported catalyst.

[0079] Reforming process of aromatization catalyst This document also includes various processes for reforming hydrocarbons. Such a reforming process may include (or substantially consist of) contacting a hydrocarbon feedstock with a supported aromatization catalyst in a reactor system under reforming conditions to produce aromatic products. The supported aromatization catalyst used in the reforming process may be any supported catalyst disclosed herein (i.e., any high-chlorine-content supported catalyst disclosed herein) and / or may be produced by any method used to produce the supported catalyst disclosed herein.

[0080] Reactor systems and corresponding reforming conditions for reforming are well known to those skilled in the art and are described, for example, in U.S. Patent Nos. 4,456,527, 5,389,235, 5,401,386, 5,401,365, 6,207,042, and 7,932,425, the disclosures of which are incorporated herein by reference in their entirety.

[0081] Similarly, these references disclose typical hydrocarbon feedstocks. Typically, the hydrocarbon feedstock can be a naphtha stream or a light naphtha stream. In some respects, the hydrocarbon feedstock can include non-aromatic hydrocarbons, such as C6-C9 alkanes and / or cycloalkanes, C6-C8 alkanes and / or cycloalkanes (e.g., n-hexane, heptane, cyclohexane), and so on.

[0082] As described herein and surprisingly, the high-chlorine-content supported catalysts described herein can exhibit improved catalytic activity and stability and reduced scaling rates in aromatization or reforming reactions compared to low-chlorine-content supported catalysts (e.g., with 0.3 wt.% to 1.5 wt.% Cl).

[0083] Example The present invention is further illustrated by the following embodiments, which should not be construed as limiting the scope of the invention in any way. Various other aspects, modifications, and equivalents may be apparent to those skilled in the art upon reading the description herein, without departing from the spirit of the invention or the scope of the appended claims.

[0084] Unless otherwise stated, the weight percentages of Pt, Cl, F, and N were determined using X-ray fluorescence (XRF), and these weight percentages were based on the total weight of the supported catalyst. Surface area was determined using the BET method, and platinum dispersion was determined by CO chemisorption.

[0085] Unless otherwise specified, use the following general procedure to test the performance of supported catalysts in aromatization reactions. Grind and sieve the supported aromatization catalyst to 25–45 mesh (US), and place 1 cubic centimeter of the sieved supported catalyst in a 3 / 8-inch stainless steel reaction vessel in a temperature-controlled furnace. After reducing the supported catalyst under flowing molecular hydrogen, feed streams of aliphatic hydrocarbons and molecular hydrogen are introduced at a pressure of 100 psi, a hydrogen:hydrocarbon molar ratio of 1.3:1, and a liquid hourly space velocity (LHSV) of 12 hr. -1 The reaction vessel is introduced. The aliphatic hydrocarbon feed contains approximately 0.61 molar fractions of convertible C6 hydrocarbons and 0.21 molar fractions of convertible C7 hydrocarbons. The balance consists of aromatics, C8+, and non-convertible hydrocarbons. The reactor temperature is then adjusted to maintain the C5 content of the reactor effluent. + The target conversion of aromatic compounds in the fraction was 63 wt.%, as determined by gas chromatography. The quantities of various feed and product components (including benzene and toluene) were also recorded to calculate selectivity.

[0086] By plotting the temperature (yield-corrected catalyst temperature) required to maintain the total yield of aromatic substances (benzene and toluene) at 63 wt.% over time under the standard test conditions provided above, the operating start temperature (T0) of the supported catalyst sample was determined. SOR And scaling rate (abbreviated FR, unit °F / hour). As used herein, the term "yield-corrected temperature" refers to such a catalyst bed temperature in a laboratory-scale reactor system, which has been corrected to account for the reactor effluent at C5. + The sample was obtained when the fraction contained no 63 wt.% aromatics. Correction factors (e.g., °F / wt.%) were determined using previous experiments with similar catalysts. Linear regression analysis was performed on temperatures collected between 15 and 40 hours to obtain the formula T. adj = FR*t + T SOR T adj This is the temperature for yield correction, FR is the fouling rate, t is the time, and T is the temperature. SOR This is the start-of-run temperature (the temperature required to achieve a 63 wt.% aromatic content at assumed time zero). The total run time is 40 hours, and the end-of-run temperature (abbreviated as T) at 40 hours is also measured. EOR ); T EOR The temperature required to achieve a yield of 63 wt.% aromatic compounds at the end of a 40-hour run is [temperature missing]. Low initial conversion and catalyst break-in conditions were observed during the determination of T [temperature missing]. SOR The main reason why the temperature 15 hours prior was not included in the FR data.

[0087] Temperature-programmed reduction (TPR) is a method for testing the reducing power of catalytically active materials as a function of temperature in these hydrogen-using examples. For TPR testing, the calcined catalyst is ground and sieved to 25-45 mesh (US) and then placed in a sample container, which may be, for example, a simple U-tube. This sample container is then placed in a furnace equipped with temperature control and thermocouples to record the temperature of the catalyst bed. The sample container is first purged with an inert gas (e.g., argon or nitrogen). After a few minutes, 10% (by volume) of hydrogen is introduced into the inert gas flow using a flow regulator at a total gas flow rate of 50 cubic centimeters per minute. Before starting the measurement, the sample container is purged with the measuring gas at room temperature. The sample container is then heated in the furnace at a rate of 10 °C / min. The effluent from the sample container is fed to a thermal conductivity detector to determine the amount of hydrogen absorbed as a function of temperature.

[0088] Example 1 A standard KL-matrix consisting of approximately 17 wt.% silicone binder was used as the starting material for Example 1. The bound zeolite matrix was impregnated with Pt, Cl, and F using a wet impregnation technique by contacting the bound zeolite matrix with an aqueous solution containing ammonium chloroplatinate (Pt(NH3)4Cl2·xH2O), ammonium chloride, and ammonium fluoride. The impregnated matrix was then dried at 95 °C and calcined at 900 °F to form a supported aromatization catalyst.

[0089] In Example 1, supported catalysts containing approximately 1 wt.% Pt, 0.6 wt.% F, and a range of Cl contents were produced. Figure 1 illustrates the F and Cl contents of these supported catalysts, and the Cl content ranging from less than 1 wt.% to more than 3 wt.%. Despite this wide range of Cl contents, the surface area of ​​the supported catalysts remained substantially constant, as shown in Figure 2, and the platinum dispersion in the supported catalysts remained substantially constant, as shown in Figure 3. In contrast, Figure 4 shows that the N content of the supported catalysts increases linearly with the Cl content of the supported catalysts.

[0090] Example 2 In Example 2, a supported catalyst was produced as described in Example 1, with a Cl content ranging from 0.7 wt.% to 3.1 wt.%. These supported catalysts were compared to two standard supported catalysts: a large-scale control (0.98 wt.% Pt, 0.85 wt.% Cl, and 0.71 wt.% F) and a laboratory control (1.01 wt.% Pt, 0.87 wt.% Cl, and 0.61 wt.% F). The large-scale control and laboratory control were nearly identical supported catalysts; the large-scale control was a historical control catalyst produced on large-scale equipment commonly used by catalyst manufacturers, while the laboratory control was a control catalyst prepared in the laboratory at the same time and using the same equipment as the experimental catalyst.

[0091] The 40-hour testing procedure described above was used to determine the selectivity of each supported catalyst for aromatic compounds and for benzene + toluene. Figure 5 compares the average selectivity for aromatic compounds and the average selectivity for benzene + toluene of these supported catalysts. As shown in Figure 5, the supported catalysts with 0.7 wt.% to 3.1 wt.% Cl exhibited selectivity comparable to the standard catalyst, and the amount of Cl (high and low) did not significantly affect the selectivity of the supported catalysts.

[0092] Example 3 In Example 3, a supported catalyst was produced as described in Example 1, with Cl contents of 0.75 wt.%, 1.1 wt.%, 2.2 wt.%, 2.7 wt.%, and 3.1 wt.%. These supported catalysts were compared with two standard aromatization catalysts: a large-scale control and a laboratory control.

[0093] Figure 6 compares the yield correction temperature versus reaction time for each supported catalyst using the 40-hour test procedure described above. Table I summarizes the relevant catalyst performance parameters from Figure 6. As shown in the table and figure, the high chlorine content supported catalyst (2.2 to 3.1 wt.%) unexpectedly exhibits the best performance of all catalysts: highest catalyst activity (lowest T... SOR and T EOR And the lowest scaling rate. Interestingly, these beneficial results were achieved without significant changes in catalyst surface area, platinum dispersion, or catalyst selectivity (see Examples 1 and 2).

[0094] Table I. Example 3 – Summary of catalyst performance. Example 4 In Example 4, a supported catalyst was produced as described in Example 1, with Cl contents of 1.1 wt.%, 2.2 wt.%, 2.7 wt.%, and 3.1 wt.%. Figure 7 shows the temperature-programmed reduction (TPR) curves of the supported catalysts containing approximately 0.9 wt.% Cl (large-scale control), 1.1 wt.% Cl, 2.2 wt.% Cl, 2.7 wt.% Cl, and 3.1 wt.% Cl.

[0095] A comparison of high-chlorine-content supported catalysts (2.2–3.1 wt.%) and low-chlorine-content supported catalysts (0.9–1.1 wt.%) reveals some general trends. First, the peak temperatures (the highest peak temperatures on the curves) of the high-chlorine-content supported catalysts are significantly higher than those of the low-chlorine-content supported catalysts. Second, in terms of the relative height of the peaks, the higher temperature peaks of the high-chlorine-content supported catalysts are greater than the lower temperature peaks, while the opposite is true for the low-chlorine-content supported catalysts. Table II summarizes the corresponding peak temperatures and the temperatures of the second largest peak in Figure 7.

[0096] Table II. Summary of Example 4 – TPR Example 5 In Example 5, a supported catalyst was produced as described in Example 1, with a Cl content of 2.7 wt.%. The long-term activity and stability of this catalyst, as well as its scaling rate, were evaluated against a large-scale control catalyst (0.85 wt.% Cl). For this 2500-hour test, 80 cubic centimeters of the supported catalyst were reduced in 10 mol% hydrogen in nitrogen, and then a feed stream of aliphatic hydrocarbons and molecular hydrogen was introduced at a pressure of 65 psi, a hydrogen:hydrocarbon ratio of 2:1, and an LHSV of 1.6 hr. -1 A reactor containing the catalyst was introduced to obtain catalyst performance data over time. As described above, by adjusting the temperature to maintain the desired yield, the total yield of aromatic compounds remained at 83.5 wt.% during 2500 hours of operation.

[0097] Figure 8 compares the yield correction temperature versus reaction time for each catalyst. As shown in the figure, the high chlorine content supported catalyst (2.7 wt.%) unexpectedly exhibited superior performance: high catalyst activity throughout the 2500-hour operation (T0.05). SOR and T EOR The lower concentration of the catalyst and the lower scaling rate indicate higher catalyst stability.

[0098] Example 6 In Example 6, a supported catalyst was produced as described in Example 1, with a Cl content of 2.7 wt.%. This catalyst was evaluated against a large-scale control catalyst. These catalysts underwent a controlled reduction step at 950 °F for 1 hour using 100% H2 to determine the amount of Cl retained after the reduction step. Table III summarizes the results. While the F content remained relatively constant, the Cl and N contents were surprisingly significantly reduced from their corresponding amounts present in the supported aromatization catalyst prior to the reduction (or activation) step.

[0099] Table III. Example 6 – Summary of Catalyst Characteristics Example 7 In Example 7, a supported catalyst was produced as described in Example 1, with a Pt content of approximately 1 wt.% and a Cl content of 2.5 wt.%. Table IV summarizes the catalyst performance of the high-chlorine-content catalyst and the large-scale control catalyst. These catalysts had essentially the same platinum content, platinum dispersion, surface area, and F content, while the high-chlorine-content catalyst (2.5 wt.% Cl) had significantly higher Cl and N content. Figure 9 shows the temperature-programmed reduction (TPR) curves for the supported catalyst containing approximately 2.5 wt.% Cl. The peak temperature was approximately 668 °F, and the second largest peak temperature was approximately 490 °F. These temperatures are consistent with those of the high-chlorine-content catalyst evaluated in Example 4 (see Table II and Figure 7).

[0100] Figure 10 compares the yield correction temperature versus reaction time for the large-scale control catalyst and the high-chlorine-content catalyst (2.5 wt. % Cl). The 40-hour test procedure from Example 3 was used, with the exception that the total yield of aromatics (e.g., benzene and toluene) remained at 66 wt.% over time under standard test conditions. Table V summarizes the relevant catalyst performance parameters from Figure 10. As shown in the table and figure, the high-chlorine-content supported catalyst (2.5 wt. %) unexpectedly exhibits significantly superior performance compared to the control catalyst: higher catalyst activity (T... SOR and T EOR (Lower platinum content) and lower scaling rate. Interestingly, these beneficial results were achieved without significant changes in the catalyst's platinum content, platinum dispersion, surface area, and F content.

[0101] Table IV. Example 7 – Summary of Catalyst Characteristics Table V. Example 7 – Summary of Catalyst Performance The invention has been described above with reference to numerous aspects and specific embodiments. Based on the detailed description above, numerous variations will be apparent to those skilled in the art. All such apparent variations are within the full scope of the appended claims. Other aspects of the invention may include, but are not limited to, the following aspects (an aspect is described as "comprising," but alternatively, "substantially constitutes" or "comprises"): Aspect 1. A method for producing a supported catalyst, the method comprising: (a) Impregnating a combined zeolite matrix with transition metal precursors, chlorine precursors, and fluorine precursors to form an impregnated zeolite matrix; and (b) Drying and subsequently calcining the impregnated zeolite matrix to produce a supported catalyst; wherein, based on the total weight of the supported catalyst, the supported catalyst comprises: Approximately 0.3 wt.% to approximately 3 wt.% of transition metals; Approximately 1.8 wt.% to approximately 4 wt.% chlorine; Fluorine content of approximately 0.4 wt.% to approximately 1.5 wt.%; The supported catalyst is characterized by a peak reduction temperature on the temperature-programmed reduction curve ranging from approximately 580 °F to approximately 800 °F.

[0102] Aspect 2. The method defined in Aspect 1, wherein the bound zeolite matrix is ​​produced by a process comprising: Zeolite is combined with a binder to form a mixture, and the mixture is extruded to form an extrudate; The extrudate is dried and calcined to form a calcined matrix; The calcined matrix is ​​washed, dried, and calcined to form a bound zeolite matrix.

[0103] Aspect 3. The method as defined in Aspect 1 or 2, wherein the dried and subsequently calcined impregnated zeolite matrix comprises any suitable drying conditions or any drying conditions disclosed herein, for example, a drying temperature in the range of about 50 °C to about 200 °C or about 80 °C to about 150 °C, and drying at atmospheric or sub-atmospheric pressure (e.g., less than about 150 Torr or less than about 50 Torr).

[0104] Aspect 4. The method defined in any of the preceding aspects, wherein the dried and subsequently calcined impregnated zeolite matrix comprises any suitable calcination conditions or any calcination conditions disclosed herein, for example, a peak calcination temperature in the range of about 200 °C to about 500 °C, or about 230 °C to about 350 °C, and a calcination gas stream comprising nitrogen, oxygen, air, or any combination thereof.

[0105] Aspect 5. The method as defined in any of the preceding aspects, wherein the method further comprises a reduction step following drying and calcining the impregnated zeolite matrix, the reduction step comprising contacting the supported catalyst with any suitable reducing gas stream or any reducing gas stream disclosed herein (e.g., containing hydrogen) to produce a reduced (or activated) supported catalyst.

[0106] Aspect 6. The method defined in Aspect 5, wherein the reduction step is performed at any suitable reduction temperature or any reduction temperature disclosed herein (e.g., in the range of about 100 °C to about 700 °C, or about 200 °C to about 600 °C). Aspect 7. The method as defined in any of the preceding aspects, wherein impregnating the bound zeolite matrix with a transition metal precursor comprises mixing the bound zeolite matrix with any suitable transition metal precursor or any transition metal precursor disclosed herein, such as tetraammineplatinum(II), tetraammineplatinum(II), platinum(II) acetylacetonate, ammonium tetrachloroplatinate(II), ammonium chloroplatinate(II), chloroplatinic acid, platinum(II) nitrate, or combinations thereof.

[0107] Aspect 8. The method as defined in any of the preceding aspects, wherein impregnating the bound zeolite matrix with chlorine and fluorine precursors comprises mixing the bound zeolite matrix with any suitable chlorine and / or fluorine precursor or any chlorine and / or fluorine precursor disclosed herein, such as ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, ammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, methyltriethylammonium fluoride, or combinations thereof.

[0108] Aspect 9. The method as defined in any of the preceding aspects, wherein impregnating the bound zeolite matrix with a transition metal precursor, a chlorine precursor and a fluorine precursor comprises mixing the bound zeolite matrix with an aqueous solution containing the transition metal precursor, the chlorine precursor and / or the fluorine precursor.

[0109] Aspect 10. Supported catalysts obtained by the methods defined in any of the preceding aspects, for example, supported aromatization catalysts.

[0110] Aspect 11. Supported catalysts, including: Combined zeolite matrix; Approximately 0.3 wt.% to approximately 3 wt.% of transition metals; Approximately 1.8 wt.% to approximately 4 wt.% chlorine; Fluorine, ranging from approximately 0.4 wt.% to approximately 1.5 wt.%, with the weight percentage based on the total weight of the supported catalyst; wherein The supported catalyst is characterized by a peak reduction temperature on the temperature-programmed reduction curve ranging from approximately 580 °F to approximately 800 °F.

[0111] Aspect 12. The catalyst or method as defined in any of the preceding aspects, wherein the supported catalyst comprises any weight percentage of chlorine disclosed herein, for example, about 2 wt.% to about 3.8 wt.%, about 2.2 wt.% to about 3.6 wt.%, about 2.2 wt.% to about 3.4 wt.%, or about 2.5 wt.% to about 3.3 wt.%.

[0112] Aspect 13. The catalyst or method defined in any of the preceding aspects, wherein the supported catalyst comprises any weight percentage of fluorine disclosed herein, for example, from about 0.5 wt.% to about 1.3 wt.%, from about 0.5 wt.% to about 1.1 wt.%, or from about 0.6 wt.% to about 0.9 wt.%.

[0113] Aspect 14. The catalyst or method defined in any of the preceding aspects, wherein the bound zeolite matrix (or supported catalyst) comprises zeolite and binder.

[0114] Aspect 15. The catalyst or method as defined in Aspect 14, wherein the supported catalyst contains any weight percentage of binder disclosed herein, such as from about 3 wt.% to about 35 wt.% or from about 5 wt.% to about 30 wt.% of binder, based on the total weight of the bound zeolite matrix (or supported catalyst).

[0115] Aspect 16. The catalyst or method as defined in Aspect 14 or 15, wherein the binder comprises inorganic solid oxides, clays, or combinations thereof.

[0116] Aspect 17. The catalyst or method as defined in Aspect 14 or 15, wherein the binder comprises alumina, silica, magnesium oxide, boron oxide, titanium dioxide, zirconium oxide, oxides thereof, or mixtures thereof.

[0117] Aspect 18. The catalyst or method as defined in Aspect 14 or 15, wherein the binder comprises silica.

[0118] Aspect 19. The catalyst or method defined in any of the preceding aspects, wherein the bound zeolite matrix (or supported catalyst) includes bound L-zeolite.

[0119] Aspect 20. The catalyst or method defined in any of Aspects 1-18, wherein the bound zeolite matrix (or supported catalyst) comprises barium ion-exchanged bound L-zeolite.

[0120] Aspect 21. The catalyst or method defined in any one of Aspects 1-18, wherein the bound zeolite matrix (or supported catalyst) includes bound K / L-zeolite.

[0121] Aspect 22. Aspects 1-17 The catalyst or method defined in any one of them, wherein the bound zeolite matrix (or supported catalyst) includes silicon-bound K / L-zeolite.

[0122] Aspect 23. The catalyst or method defined in Aspect 22, wherein the bound zeolite matrix is ​​produced by a process comprising: K / L-zeolite was combined with silica sol to form a mixture, and then the mixture was extruded to form an extrudate; The extrudate is dried and calcined to form a calcined matrix; The calcined matrix is ​​washed, dried, and calcined to form a bound zeolite matrix.

[0123] Aspect 24. The catalyst or method defined in any of the preceding aspects, wherein the supported catalyst comprises any weight percentage of transition metal disclosed herein, for example, about 0.5 wt.% to about 2.5 wt.%, about 0.5 wt.% to about 2 wt.%, or about 0.7 wt.% to about 1.5 wt.%.

[0124] Aspect 25. The catalyst or method defined in any of the preceding aspects, wherein the transition metal includes platinum.

[0125] Aspect 26. The catalyst or method defined in any of the preceding aspects, wherein the supported catalyst comprises any weight percentage of platinum disclosed herein, for example, from about 0.5 wt.% to about 2.5 wt.%, from about 0.5 wt.% to about 2 wt.%, or from about 0.7 wt.% to about 1.5 wt.%.

[0126] Aspect 27. The catalyst or method defined in any of the preceding aspects, wherein the supported catalyst is characterized in that the peak temperature on the TPR curve is within any range disclosed herein (e.g., from about 580 °F to about 750 °F, from about 600 °F to about 730 °F, or from about 600 °F to about 720 °F).

[0127] Aspect 28. The catalyst or method defined in any of the preceding aspects, wherein the supported catalyst is characterized by a TPR curve comprising a lower temperature peak and a higher temperature peak, and wherein the higher temperature peak is greater in height than the lower temperature peak.

[0128] Aspect 29. The catalyst or method defined in any of the preceding aspects, wherein the supported catalyst comprises chlorine:fluorine in any weight ratio disclosed herein (e.g., from about 1.5:1 to about 8:1, from about 2:1 to about 5:1, or from about 3:1 to about 4.5:1).

[0129] The catalyst or method defined in any of the aspects 6-31, wherein the reduced (or activated) supported catalyst contains any weight percentage of chlorine disclosed herein, such as about 0.2 wt.% to about 1.3 wt.%, about 0.2 wt.% to about 0.8 wt.%, or about 0.3 wt.% to about 1 wt.% of chlorine, based on the total weight of the reduced (or activated) supported catalyst.

[0130] Aspect 31. The catalyst or method defined in any of the preceding aspects, wherein, under the same catalyst preparation conditions, the supported catalyst has substantially the same platinum dispersion as a catalyst having 0.3 wt.% to 1.5 wt.% chlorine.

[0131] Aspect 32. The catalyst or method defined in any of the preceding aspects, wherein, under the same catalyst preparation conditions, the supported catalyst has substantially the same platinum dispersion as a catalyst having 0.3 wt.% to 1.5 wt.% chlorine.

[0132] Aspect 33. The catalyst or method as defined in any of the preceding aspects, wherein, under the same catalyst preparation conditions, the total nitrogen content of the supported catalyst is greater than the total nitrogen content of the catalyst having 0.3 wt.% to 1.5 wt.% chlorine (reaching any amount disclosed herein, for example, at least about 50% more, at least about 100% more, or at least about 200% more).

[0133] Aspect 34. The catalyst or method defined in any of the preceding aspects, wherein the supported catalyst is characterized by T EOR The (end-of-run temperature) is reflected when it is within any range disclosed herein, such as approximately 920 °F to approximately 940 °F, or approximately 920 °F to approximately 930 °F.

[0134] Aspect 35. The catalyst or method defined in any of the preceding aspects, wherein the supported catalyst is characterized by T under the same catalyst preparation conditions and aromatization reaction conditions. EOR Less than T of catalysts containing 0.3 wt.% to 1.5 wt.% chlorine. EOR .

[0135] Aspect 36. The catalyst or method defined in any of the preceding aspects, wherein the supported catalyst is characterized by T SOR The (operation start temperature) is within any range disclosed herein (e.g., approximately 915 °F to approximately 935 °F, or approximately 915 °F to approximately 930 °F).

[0136] Aspect 37. The catalyst or method defined in any of the preceding aspects, wherein the supported catalyst is characterized by T under the same catalyst preparation conditions and aromatization reaction conditions. SOR Less than T of catalysts containing 0.3 wt.% to 1.5 wt.% chlorine. SOR .

[0137] Aspect 38. The catalyst or method defined in any of the preceding aspects, wherein the supported catalyst is characterized in that the fouling rate is within any range disclosed herein, for example, less than about 0.12 °F / min or less than about 0.1 °F / min.

[0138] Aspect 39. The catalyst or method defined in any of the preceding aspects, wherein the supported catalyst is characterized in that, under the same catalyst preparation conditions and aromatization reaction conditions, the scaling rate is less than that of a catalyst containing 0.3 wt.% to 1.5 wt.% chlorine.

[0139] Aspect 40. The catalyst or method defined in any of the preceding aspects, wherein the supported catalyst is characterized in that, under the same catalyst preparation conditions and aromatization reaction conditions, the selectivity for aromatic substances (or the selectivity for benzene + toluene) is substantially the same as that of a catalyst having 0.3 wt.% to 1.5 wt.% chlorine.

[0140] Aspect 41. A reforming process comprising contacting a hydrocarbon feedstock with a supported aromatization catalyst under reforming conditions in a reactor system to produce an aromatic product, wherein the supported aromatization catalyst is a supported catalyst (or a reducing or activated catalyst) as defined in any of the preceding aspects.

[0141] Aspect 42. The process defined in Aspect 41, wherein the hydrocarbon feed is any hydrocarbon feed disclosed herein, including, for example, non-aromatic hydrocarbons, including C6-C9 alkanes and / or cycloalkanes or including C6-C8 alkanes and / or cycloalkanes.

Claims

1. A supported catalyst, comprising: Combined zeolite matrix; Approximately 0.3 wt.% to approximately 3 wt.% of transition metals; Approximately 1.8 wt.% to approximately 4 wt.% chlorine; Fluorine of approximately 0.4 wt.% to approximately 1.5 wt.%, weight percentage based on the total weight of the supported catalyst; The supported catalyst is characterized by a peak reduction temperature on the temperature-programmed reduction (TPR) curve ranging from approximately 580 °F to approximately 800 °F.

2. The catalyst of claim 1, wherein the supported catalyst comprises about 2 wt.% to about 3.8 wt.% chlorine.

3. The catalyst according to claim 1 or 2, wherein the supported catalyst contains about 0.5 wt.% to about 1.3 wt.% fluorine.

4. The catalyst according to any one of the preceding claims, wherein the bound zeolite matrix comprises zeolite and binder.

5. The catalyst of claim 4, wherein the supported catalyst comprises from about 5 wt.% to about 30 wt.% binder based on the total weight of the supported catalyst.

6. The catalyst according to claim 4 or 5, wherein the binder comprises inorganic solid oxides, clay, or a combination thereof.

7. The catalyst according to claim 4 or 5, wherein the binder comprises alumina, silica, magnesium oxide, boron oxide, titanium dioxide, zirconium oxide, oxides thereof, or mixtures thereof.

8. The catalyst according to claim 4 or 5, wherein the binder comprises silica.

9. The catalyst according to any one of the preceding claims, wherein the supported catalyst comprises bound L-zeolite.

10. The catalyst according to any one of claims 1-9, wherein the supported catalyst comprises barium ion-exchanged bound L-zeolite.

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