Toluene disproportionation using reinforced UZM-44 aluminosilicate zeolite

Abstract

A toluene disproportionation method using a treated UZM-44 zeolite is described. This method produces an effluent stream containing para-xylene and benzene. The molar ratio of benzene to xylene in the effluent stream (Bz / X) may be in the range of 1.00 to 1.14, the molar ratio of para-xylene to xylene in the effluent stream (pX / X) may be in the range of 0.80 to 1.0, and the conversion rate of toluene may be 20% to 40%.

Description

Technology Field

[0001] Priority statement

[0002] This application claims priority from U.S. Application No. 16 / 793,530 filed February 18, 2020, which is incorporated herein in its entirety. Background Technology

[0003] Zeolites are microporous crystalline aluminosilicate compositions formed from corner-sharing AlO2 and SiO2 tetrahedra. Numerous zeolites, both naturally occurring and synthetically produced, are used in various industrial processes. Synthetic zeolites are produced via hydrothermal synthesis using suitable Si sources, Al sources, and structure-directing agents, such as alkali metals, alkaline earth metals, amines, or organic ammonium cations. The structure-directing agent is present within the zeolite pores and is the primary cause of the specific structure ultimately formed. These chemical species balance the framework charge associated with aluminum and can also act as space fillers. Zeolites are characterized by having pore openings of uniform dimensions, possessing a significant ion exchange capacity, and being able to reversibly desorb an adsorbed phase dispersed throughout the internal voids of the crystal without significantly displacing any atoms constituting the permanent zeolite crystal structure. Zeolites can be used as catalysts for hydrocarbon conversion reactions, and hydrocarbon conversion reactions can occur not only on the outer surface but also on the inner surface within the pores.

[0004] One other specific zeolite IM-5 was first disclosed in 1996 by Benazzi et al. describing the synthesis of IM-5 from 1,5-bis(N-methylpyrrolidinium)pentane dibromide or 1,6-bis(N-methylpyrrolidinium)hexane dibromide, which are flexible divalent cationic structure-directing agents, in the presence of sodium (French Patent No. 96 / 12873; International Patent Publication WO98 / 17581). After the structure of IM-5 was elucidated by Baerlocher et al. (reference [Science, 2007, 315, 113-6]), the International Zeolite Association Structure Commission assigned an IMF code to this zeolite structure type; refer to the Atlas of Zeolite Framework Types managed by the International Zeolite Association Structure Commission at http: / / www.iza-structure.org / databases / . The IMF structure type also revealed that each channel contains a set of three mutually orthogonal channels defined by a decadal ring of tetrahedral coordination atoms. However, connections in the third dimension are interrupted every 2.5 nm; thus, diffusion is somewhat restricted. Additionally, multiple decadal ring channels of different sizes exist in the structure.

[0005] The applicant has successfully manufactured a new family of materials named UZM-44. The topology of this material is similar to that observed for IM-5. The material is manufactured using a mixture of simple commercially available structure-directing agents such as 1,5-dibromorphentane and 1-methylpyrrolidine and is described in U.S. Patent No. 8,609,920 and U.S. Patent No. 8,623,321. UZM-44 has been used as a catalyst in various reactions including methane conversion (U.S. Patent No. 8,921,634), dehydrocyclodimerization (U.S. Patent No. 8,889,939), catalytic pyrolysis (U.S. Patent No. 8,609,911 and U.S. Patent No. 8,701,285), transalkylation (U.S. Patent No. 8,609,921 and U.S. Patent No. 8,704,026), and aromatic modification (U.S. Patent No. 8,609,919, U.S. Patent No. 8,748,685, and U.S. Patent No. 8,716,540). UZM-44 can be used as a catalyst in the toluene disproportionation reaction.

[0006] Xylene isomers are produced in large quantities from petroleum as feedstocks for various important industrial chemicals. The most important of the xylene isomers is para-xylene, a major feedstock for polyester that continues to experience high growth due to high basic demand. Ortho-xylene is used to produce phthalic anhydrides; while production is high, the market is mature. Meta-xylene is used in products such as plasticizers, azo dyes, and wood preservatives; although in small quantities, its use is increasing.

[0007] Among aromatic hydrocarbons, the overall importance of xylene is comparable to that of benzene as a feedstock for industrial chemicals. Neither xylene nor benzene is produced from petroleum by reforming naphtha in sufficient quantities to meet demand. Therefore, the conversion of other hydrocarbons is required to increase the production of xylene and benzene. Often, toluene is selectively disproportioned to produce benzene and C8 aromatics, from which individual xylene isomers are recovered.

[0008] Para-selective toluene disproportionation is a method commercialized in the 1980s for the purpose of converting toluene into benzene and xylene, typically with a high molar ratio of para-xylene to total xylene (pX / X molar ratio) exceeding 0.85. This technology is particularly required in cases where there is demand for polyesters and other chemicals derived from para-xylene but limited demand for other xylenes. Initially, high pX / X was achieved by the "selection" of catalysts using carbon and / or coke to narrow the MFI pore size and cover acid sites on the outer surface of the MFI crystals. Later, it was found that depositing silica on the catalyst achieved similar results.

[0009] U.S. Patent No. 4,016,219 B1 (Kaeding) discloses a method for disproportioning toluene using a catalyst comprising a zeolite modified by the addition of an amount of phosphorus of 0.5 mass% or more. The zeolite crystal is brought into contact with a phosphorus compound to cause a reaction between the zeolite and the phosphorus compound. Subsequently, the modified zeolite may be incorporated into a indicated matrix material.

[0010] U.S. Patent No. 4,097,543 B1 (Haag et al.) teaches toluene disproportionation for the selective production of para-xylene using a zeolite that has undergone controlled pre-coking. The zeolite can be ion-exchanged with various elements ranging from Group IB to Group VIII and can be composited with various clays and other porous matrix materials.

[0011] U.S. Patent No. 6,114,592 B1 (Gajda et al.) teaches an improved process combination for the selective disproportionation of toluene. This combination comprises the selective hydrogenation of a toluene feedstock followed by contact with an oil-dropped zeolite catalyst in an aluminum phosphate binder to achieve high yield of para-xylene.

[0012] U.S. Patent No. 6,429,347 B1 (Boldingh) teaches toluene disproportion for the selective production of para-xylene using a catalyst comprising an MFI zeolite combined with alumina phosphate after selectively pre-coking the catalyst by contacting the catalyst with a coke-forming feed under pre-coking conditions.

[0013] In this process, the selected zeolite was ZSM-5 with an MFI framework. Using this catalyst, the molar ratio of para-xylene to xylene (pX / X) can be increased from the equilibrium level of 0.24 to above 0.90 by the deposition of a sufficient amount of coke or silica. This increases the pX / X molar ratio but is always accompanied by an increase in the molar ratio of benzene to xylene (Bz / X) to significantly exceed the theoretical value of 1. The higher the pX / X molar ratio, the higher the Bz / X molar ratio.

[0014] Although we do not wish to be bound by theory, an increase in the Bz / X molar ratio appears to be attributed to a loss in total xylene yield. Generally, as the para-xylene yield increases beyond a certain level, the total xylene yield typically decreases. This is considered inevitable, and there are many studies aimed at optimizing the use of coke or silica to minimize the Bz / X molar ratio. When the pX / X molar ratio is increased above 0.90 using the best silica deposition technology, it is very common to see Bz / X molar ratio values ​​of up to 1.4 under disproportionation conditions of 30% toluene conversion, H2 / HC = 2, and WHSV = 4 at a pressure of 400 psig.

[0015] Therefore, an improved toluene disproportionation method is required in which the pX / X molar ratio is high (e.g., 0.70 or higher) and the Bz / X molar ratio is less than 1.2. Brief explanation of the drawing

[0016] Figure 1 is an example of one embodiment of a toluene disproportionation method. Figure 2 is a graph showing the Bz / X molar ratio as a function of the pX / X molar ratio for various catalysts at a 30% conversion rate. Figure 3 is a graph showing the selectivity for xylene as a function of the pX / X molar ratio for various catalysts at a 30% conversion rate. Figure 4 is a graph showing the selectivity for light fractions (C1-C6) as a function of the pX / X molar ratio for various catalysts at a 30% conversion rate. Figure 5 is a graph showing the temperature required to achieve a 30% conversion rate for various catalysts, plotted against the achieved pX / X molar ratio. Specific details for implementing the invention

[0017] One aspect of the present invention is a toluene disproportionation method. In one embodiment, the method comprises the step of contacting a feed containing toluene with a microporous crystalline zeolite under disproportionation conditions to produce an effluent stream containing para-xylene and benzene, wherein the molar ratio of benzene to xylene in the effluent stream (Bz / X) is in the range of 1.00 to 1.14, the molar ratio of para-xylene to xylene in the effluent stream (pX / X) is in the range of 0.80 to 1.0, and the conversion rate of toluene is 20% to 40%.

[0018] The present invention relates to the use of an aluminosilicate zeolite named UZM-44 as a catalyst. UZM-44 is a material having a three-dimensional framework of at least AlO2 and SiO2 tetrahedral units and having an experimental composition expressed by the following empirical formula, both as synthesized and on an anhydrous basis:

[0019] Na n M m k+ T t Al 1-x E x Si y O z

[0020] Here, "n" is the molar ratio of Na to (Al + E) and has a value of 0.05 to 0.5, M represents at least one metal selected from the group consisting of zinc, Group 1 (IUPAC 1), Group 2 (IUPAC 2), Group 3 (IUPAC 3), the lanthanide series of the periodic table, and any combination thereof, "m" is the molar ratio of M to (Al + E) and has a value of 0 to 0.5, "k" is the average charge of the metal or metals M, T is an organic structure inducer or organic structure inducers derived from reactants R and Q, where R is an A,Ω-dihalogen-substituted alkane having 5 carbon atoms and Q is at least one neutral monoamine having 6 or fewer carbon atoms, "t" is the molar ratio of N from the organic structure inducer or organic structure inducers to (Al + E) and has a value of 0.5 to 1.5, E is gallium, An element selected from the group consisting of iron, boron, and combinations thereof, where "x" is the mole fraction of E and has a value from 0 to 1.0, "y" is the molar ratio of Si to (Al + E) and varies from greater than 9 to 25, and "z" is the molar ratio of O to (Al + E), and Equation:

[0021] z = (n + k m + 3 + 4 It has a value determined by y) / 2.

[0022] UZM-44 as synthesized is characterized by an X-ray diffraction pattern having at least the d-spacing and relative intensity presented in Table A below. In this specification, the diffraction pattern refers to the K of copper. αLines were obtained using a typical laboratory powder diffractometer with a high-intensity X-ray tube operating at 45 kV and 35 mA using Cu K alpha. Flat compressed powder samples were scanned continuously from 2° to 56° (2θ). From the positions of the diffraction peaks indicated by the angle 2θ (2θ), the characteristic interplanar distance d of the sample was determined using the Bragg equation. hkl It can be calculated. As is understood by those skilled in the art, the determination of the parameter 2θ is affected by both human and mechanical errors, which, when combined, can introduce an uncertainty of ±0.4° to each reported value of 2θ. Of course, this uncertainty also appears in the reported values ​​of the d-interval calculated from the 2θ values. Such inaccuracies are common throughout the art and are not sufficient to exclude distinguishing current crystalline materials from one another and from compositions of the prior art.

[0023] Intensity is calculated based on a relative intensity scale in which a value of 100 is assigned to the line representing the strongest peak in the X-ray diffraction pattern, where very weak (vw) means less than 5; weak (w) means less than 15; medium (m) means a range of 15 to 50; strong (s) means a range of 50 to 80; and very strong (vs) means greater than 80. Intensity may also be expressed in the above comprehensive ranges. The X-ray diffraction pattern from which data (d interval and intensity) is obtained features a large number of reflections, some of which are broad peaks or peaks forming shoulders on peaks of higher intensity. Some or all of the shoulders may not be resolved. This may be the case for samples of low crystallinity of specific coherently grown composite structures, or for samples having crystals small enough to cause significant broadening of the X-rays. This may also be the case where the equipment or operating conditions used to generate the diffraction pattern are significantly different from those used in this case.

[0024] The zeolite may further feature an X-ray diffraction pattern having at least the d-spacing and relative intensity presented in Table A.

[0025] [Table A]

[0026]

[0027] As shown, the zeolite in one embodiment is 600 o Exceeding C, 800 in other embodiments o It is thermally stable up to temperatures above C.

[0028] When synthesized, UZM-44 material will contain some exchangeable or charge-balanced cations within its pores. These exchangeable cations can be exchanged for other cations, or, in the case of organic cations, removed by heating under controlled conditions. It is also possible to remove some organic cations from UZM-44 zeolite directly by ion exchange. UZM-44 zeolite can be modified in many ways to suit use in specific applications. As outlined for the case of UZM-4M in U.S. Patent No. 6,776,975 B1 incorporated by reference in its entirety, modification includes calcination, ion-exchange, steaming, various acid extraction, ammonium hexafluorosilicate treatment, or any combination thereof. The conditions may be harsher than those set forth in U.S. Patent No. 6,776,975. Characteristics to be modified include porosity, adsorption, Si / Al ratio, acidity, thermal stability, etc.

[0029] The modified microporous crystalline zeolite UZM-44, after calcination, ion-exchange, and calcination and on an anhydrous basis, is

[0030] M1 a N+ Al (l-x) E x Si y' O z"

[0031] The experimental composition in the form of hydrogen is expressed by the empirical formula and has a three-dimensional framework of at least AlO2 and SiO2 tetrahedral units, where M1 is at least one exchangeable cation selected from the group consisting of alkali, alkaline earth metals, rare earth metals, ammonium ions, hydrogen ions, and combinations thereof; "a" is the molar ratio of M1 to (Al + E) and varies from 0.05 to 50; "N" is the weighted average valence of M1 and has a value of +1 to +3; E is an element selected from the group consisting of gallium, iron, boron, and combinations thereof; x is the mole fraction of E and varies from 0 to 1.0; y' is the molar ratio of Si to (Al + E) and varies from greater than 9 to virtually pure silica; z" is the molar ratio of O to (Al + E) and Formula:

[0032] z" = (a N + 3 + 4 It has a value determined by y') / 2.

[0033] After calcination to remove NH3 in the hydrogen form, ion-exchange, and calcination, the modified UZM-44 (UZM-44M) exhibits an X-ray diffraction pattern with at least the d-spacing and intensity presented in Table B. These characteristic peaks of UZM-44 are shown in Table B. Additional peaks, particularly those of very weak intensity, may also be present. All peaks of intermediate or higher intensity present in UZM-44 are shown in Table B.

[0034] [Table B]

[0035]

[0036] The surface area, micropore volume, and total pore volume can be determined by N2 adsorption using conventional BET analysis methods combined with t-plot analysis of adsorption isotherms, such as as implemented in, for example, Micromeritics ASAP 2010 software (reference [J. Am. Chem. Soc., 1938, 60, 309-16]). The t-plot is a mathematical representation of multilayer adsorption and enables the determination of the amount of N2 adsorbed in the micropores of the zeolite material under analysis. In particular, for the material described herein, the slope of the t-plot line is determined using points at 0.45, 0.50, 0.55, 0.60, and 0.65 P / P0, the intercept of which is the micropore volume. The total pore volume is determined at 0.98 P / P0. The UZM-44 used in the present invention has a micropore volume of less than 0.155 mL / g, typically less than 0.150 mL / g, and often less than 0.145 mL / g. Additionally, looking at the dV / dlog D versus pore diameter plot (differential volume of adsorbed nitrogen as a function of pore diameter), the UZM-44 used in the present invention does not include a feature of approximately 200 to 300 Å. The UZM-44 has an adsorption feature occurring at greater than 450 Å. In one embodiment, greater than 0.1 mL N2 / gÅ is differentially adsorbed at a pore diameter of 475 Å. Preferably, greater than 0.1 mL N2 / gÅ is differentially adsorbed at a pore diameter greater than 475 Å, where differential adsorption indicates that a differential volume of nitrogen is adsorbed at a specific pore diameter.

[0037] In specifying the proportion of zeolite source material or the adsorption characteristics of zeolite products in this specification, the "anhydrous state" of the zeolite is intended unless otherwise stated. The term "anhydrous state" is used in this specification to refer to a zeolite that is substantially free of both physically adsorbed water and chemically adsorbed water.

[0038] UZM-44 or UZM-44M can be enhanced to increase the pX / X ratio achieved during toluene disproportionation. Enhancement is intended to represent a step that increases the pX / X molar ratio significantly higher than the equilibrium value of 0.24 during toluene disproportionation. Three known examples are carbon deposition, treatment with silica, and steaming after carbon and / or silica deposition.

[0039] Surprisingly, UZM-44, which underwent an intensification step until the pX / X molar ratio achieved during disproportionation conditions exceeded 0.6, was found to have a unique combination of a high pX / X molar ratio and high total xylene selectivity without the generation of excess benzene.

[0040] The catalyst may further comprise a refractory binder or matrix to facilitate the preparation of the disproportionate catalyst, provide strength, reduce manufacturing costs, or a combination thereof. The binder may have a uniform composition and may be relatively refractory for the conditions used in the process. Suitable binders may include one or more of inorganic oxides, such as alumina, magnesia, zirconia, chromia, titania, boria, thoria, zinc oxide, and silica. Alumina and / or silica are preferred binders. The amount of zeolite present in the bound catalyst may vary considerably, but is usually present in an amount of 30 to 90 mass%, preferably 50 to 80 mass%, of the catalyst.

[0041] An exemplary reinforcement step for depositing silica includes a calcination step after exposing the zeolite to a silicon reagent such as tetraethyl orthosilicate (TEOS). Exemplary reinforcement by silica treatment incorporates silica onto the zeolite. Reinforcement by silica deposition can be performed by treating the zeolite, on the zeolite before bonding with a refractory oxide, or on a bonded catalyst.

[0042] In one embodiment, UZM-44 may be extruded with a metal oxide binder before reinforcement. The ion-exchanged zeolite powder may be extruded into a cylindrical or trilobe shape having a refractory metal oxide comprising SiO2, TiO2, ZrO2, Al2O3, or a mixture thereof. In one embodiment, the refractory metal oxide may be SiO2. The relative loading amounts of zeolite and refractory metal oxide may vary. The zeolite content in the catalyst extrude may be greater than 50 wt%, or greater than 55 wt%, or greater than 60 wt%, or greater than 65 wt%, or less than 95 wt%, or less than 90 wt%, or less than 80 wt%. The size and shape of the extrude may vary within the known technical range, and cylindrical and trilobe shapes of 1.6 mm are preferred. The width of the extrude may be from 0.75 mm to 4 mm, or from 1.0 mm to 3 mm.

[0043] The dried extruded material may be calcined in air at a temperature ranging from 350°C to 600°C for 5 minutes to 6 hours. A time of 15 minutes to 4 hours, or 30 minutes to 3 hours, may be acceptable. A temperature of 400°C to 550°C, or 450°C to 550°C, may be acceptable. Optionally, the extruded material may be ion-exchanged at 75°C for 1 hour using a weight ratio of water:ammonium nitrate:extruded material of 10:1:1. If ion-exchanged, the extruded material will be rinsed multiple times with deionized H2O. If used, ion-exchange may be repeated if necessary. Subsequently, the final dried extruded material may be calcined as described above.

[0044] Reinforcement treatment with silica can be carried out by placing the sample in a container and adding an organic solvent. In one embodiment, the amount of organic solvent added can be determined from Table 1. The container may be heated at the reflux temperature of the organic solvent for 1 hour, during which time water may be removed from the system. Subsequently, a silicon reagent may be added to the container. In one embodiment, the silicon reagent includes, but is not limited to, silicon alkoxides. Suitable silicon alkoxides include, but are not limited to, tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), tetrapropyl orthosilicate (TPOS), tetraisopropyl orthosilicate (TiPOS), and tetrabutyl orthosilicate (TBOS). The silicon reagent may be a partially hydrolyzed silicon alkoxide or a siloxane. A suitable source may be one of the Dynaslan® Silbond® series products available from Evonik. The silicon reagent may be a chlorosilane. The concentration of the silicon reagent used may be in the range of 5 to 25 weight percent based on the weight of the sample.

[0045] Once the silicon reagent is added, the contents of the vessel may be reacted under reflux for 5 minutes to 8 hours, or 30 minutes to 4 hours. After reflux, the solvent may be removed from the sample. Suitable solvent removal methods may include gradient separation, distillation, or vacuum distillation. Subsequently, the sample may be exposed to a heat treatment step at 175°C to 600°C to form an enhanced catalyst. The enhancement treatment may be repeated as many times as necessary to achieve the desired pX / X selectivity.

[0046] Enhancement by carbon deposition can be performed under conditions for a subsequent disproportionation step comprising one or more of higher temperatures, lower pressures, higher space velocities, or higher hydrogen-to-hydrocarbon ratios. These carbon deposition conditions are a pressure of 100 kPa to 4 MPa, and 0.2 to 10 hr -1 It may include a liquid hourly space velocity. The conditions may include an inlet temperature at least 50°C higher than the reaction temperature; and a pressure at least 100 kPa lower than the reaction pressure, or preferably less than half the pressure used in the subsequent disproportionation step. Preferably, the molar ratio of free hydrogen to the feedstock coke-forming hydrocarbon is less than half that used in the subsequent disproportionation step. Lower pressure and / or a lower hydrogen / hydrocarbon ratio will limit the temperature rise by lowering the rate of exothermic aromatic-saturation reactions; the result will be a relatively flat temperature profile. Thus, a typical temperature range will be 300°C to 700°C, and a typical hydrogen to coke-forming feedstock range will be 0.01 to 5. Enhancement by carbon deposition may result in a catalytic carbon content of 5 to 40 mass% carbon, preferably 10 to 30 mass% carbon. The coke-forming feed for carbon deposition may include a feedstock to a disproportionation step as described below. In one embodiment, toluene, or other specific hydrocarbons or mixtures known in the art, preferably including aromatics, may be used as the coke-forming feed.

[0047] UZM-44 may be reinforced one or more times with carbon and / or silica. Reinforcement may involve incorporating carbon or silica into a catalyst comprising a zeolite. "Into" means "into or on the surface of" and is intended to indicate that carbon or silica reinforcement may deposit the material onto the outer surface of the zeolite crystal and / or on the outer surface of any refractory oxide present and / or within the pore structure. Without being bound by theory, "into" does not describe the deposition of the material within the micropores of the zeolite. In one embodiment, reinforcement may be performed on the zeolite, or on the zeolite prior to bonding with the refractory oxide, or on a bonded catalyst comprising UZM-44 or UZM-44M. Individual reinforcement steps may be repeated until the desired selectivity is achieved under disproportionation conditions. In one sun, the reinforcement step can be performed until pX / X becomes greater than 0.6, or greater than 0.7, or greater than 0.8, or greater than 0.85, or greater than 0.9.

[0048] After reinforcement by carbon deposition or silica deposition, the reinforced UZM-44 may optionally undergo a steaming treatment. Steaming after reinforcement can increase the pX / X achieved during disproportionation. However, steaming can also reduce the activity of the zeolite or catalyst. In one embodiment, steaming treatment conditions may be a temperature of 100°C to 750°C, or 200°C to 700°C, or 450°C to 650°C; a partial pressure of water of 0.1 to 0.5, or 0.15 to 0.35; and a time of 10 minutes to 26 hours, or 30 minutes to 6 hours. In one embodiment, a high pX / X ratio during disproportionation may be achieved by a reinforcement step or steps, or by a reinforcement step or steps and a steaming step or a combination of steps. The steaming and reinforcement steps may be performed in any order found to achieve a high pX / X.

[0049] The enhanced UZM-44 zeolite of the present invention can be used as a catalyst or catalyst support in a toluene disproportionation method.

[0050] A toluene disproportionation method comprises the step of contacting a feed stream containing toluene with a catalyst containing zeolite under disproportionation conditions to produce an effluent stream containing benzene and xylene. In a selective disproportionation method such as in the present invention, the catalyst may be enhanced by one or more treatment steps to increase the molar ratio of para-xylene to xylene (pX / X) from an equilibrium level of 0.24 to 0.60 or higher by the deposition of a sufficient amount of coke or silica. While this enhancement increases the pX / X molar ratio, it was previously accompanied by an increase in the molar ratio of benzene to xylene (Bz / X) to significantly exceed the theoretical value of 1. When the pX / X molar ratio is increased to 0.90 or higher using the best silica deposition technique, at a pressure of 2.8 MPa(g), a 30% toluene conversion rate, H2 / HC = 2, and WHSV = 4 hr -1It was common to see a maximum Bz / X molar ratio value of 1.4 under disproportionate conditions that may include.

[0051] Ideally, the toluene disproportionation method operates at the highest possible toluene conversion rate while maximizing the xylene yield from the reaction. In one sun, the toluene conversion rate may be greater than 20 wt%, or greater than 25 wt%, or greater than 28 wt%, or greater than 30 wt%, or greater than 32 wt%, or greater than 35 wt%, or less than 50 wt%, or less than 40 wt%, or less than 35 wt%.

[0052] The feed for the disproportionation reaction may comprise toluene, optionally combined with C9 aromatics, and is suitably derived from one or various sources. The feed may be synthesized, for example, by catalytic reforming from naphtha or by producing an aromatic-rich product by hydrotreatment after pyrolysis. The feed may be derived from the product to a suitable purity by the extraction of aromatic hydrocarbons from a mixture of aromatic and non-aromatic hydrocarbons and the fractionation of the extract. For example, aromatics may be recovered from reformate. The feed may comprise more than 80 mass% toluene, or more than 85% toluene, or more than 90% toluene, or more than 95% toluene, or even more than 98.5% toluene. The feed may contain more than 90 mass% of aromatic compounds, or more than 95% of aromatic compounds, or more than 98% of aromatic compounds, or more than 99% of aromatic compounds, or even more than 99.5% of aromatic compounds. In one embodiment, the feed may contain 10 mass% or less of non-aromatic compounds. In one embodiment, the feed may contain 10 mass% or less of benzene. In one embodiment, the feed may contain 10 mass% or less of xylene. In one embodiment, the feed may contain 10 mass% or less of A9 aromatic compounds. Preferably, the non-aromatic compounds, benzene, xylene, and A9 aromatic compounds are close to 0 mass%. In one embodiment, all or a combination of any of the conditions listed in this paragraph may be applied to the characterization of the feed.

[0053] The disproportionation reaction conditions may include temperatures ranging from 200°C to 600°C, or from 300°C to 450°C, or from 350°C to 425°C. The pressure may be in the range of 1.0 MPa to 7.0 MPa, or from 1.4 MPa(g) to 4.5 MPa(g), or from 2.0 MPa(g) to 3.5 MPa(g). The disproportionation reaction may be carried out over a wide range of space velocities, where higher space velocities achieve a higher proportion of para-xylene at the expense of conversion. The weight hourly space velocity (WHSV) is 0.5 to 10 hr⁻¹ -1 , or 1.0 to 7 hr -1 , or 1.0 to 5 hr -1 The ratio of hydrogen to hydrocarbons may be in the range. The ratio of hydrogen to hydrocarbons is calculated based on the molar ratio of free hydrogen to feedstock hydrocarbons. A periodic increase in hydrogen to hydrocarbons greater than 0.5, preferably in the range of 1 to 5, can enable catalyst regeneration by hydrogenation of soft coke. The ratio of hydrogen to hydrocarbons may be in the range of 0.25 to 10, or 0.5 to 5.

[0054] The molar ratio of para-xylene to xylene (pX / X) in the effluent is an important factor in the selective toluene disproportionation method. Since the equilibrium pX / X is 0.24 under toluene disproportionation conditions, the para-selective toluene disproportionation method produces effluent containing a pX / X greater than 0.25 or greater than 0.30. The effluent from the toluene disproportionation method may have a pX / X molar ratio greater than 0.60, greater than 0.70, greater than 0.75, greater than 0.80, greater than 0.85, or greater than 0.90, and less than 0.98, less than 0.96, or less than 0.94.

[0055] Ideally, the toluene disproportionation method operates with a molar ratio of benzene to xylene (Bz / X) of 1.00 in the effluent. A Bz / X of 1.00 indicates that 1 mole of xylene is produced for every 1 mole of benzene produced. A Bz / X ratio close to 1.00 is preferred, and in one sun, the Bz / X molar ratio may be less than 1.20, or less than 1.16, or less than 1.12, or less than 1.08, or less than 1.06, or less than 1.05, or less than 1.04, or less than 1.03, or less than 1.02, or less than 1.01, or greater than 1.00, or greater than 0.99, or greater than 0.98. For example, in some embodiments, the Bz / X molar ratio is in the range of 0.98 to 1.20 over the pX / X molar ratio in the range of 0.25 to 0.95. In some embodiments, the Bz / X molar ratio is in the range of 0.98 to 1.16 over the pX / X molar ratio in the range of 0.25 to 0.95. In some embodiments, the Bz / X molar ratio is in the range of 0.98 to 1.12 over the pX / X molar ratio in the range of 0.25 to 0.95. In some embodiments, the Bz / X molar ratio is in the range of 0.98 to 1.08 over the pX / X molar ratio in the range of 0.25 to 0.95. In some embodiments, the Bz / X molar ratio is in the range of 0.98 to 1.06 over the pX / X molar ratio in the range of 0.25 to 0.90. In some embodiments, the Bz / X molar ratio is 0.98 to 1.05 over a pX / X molar ratio in the range of 0.25 to 0.85. In some embodiments, the Bz / X molar ratio is in the range of 0.98 to 1.02 over a pX / X molar ratio in the range of 0.25 to 0.85. In some embodiments, the Bz / X molar ratio is in the range of 0.98 to 1.01 over a pX / X molar ratio in the range of 0.25 to 0.80. In some embodiments, the Bz / X ratio is in the range of 1.00 to 1.20 over a pX / X molar ratio in the range of 0.80 to 0.95. In some embodiments, the Bz / X ratio is 1. over a pX / X molar ratio in the range of 0.80 to 0.95.The range is from 00 to 1.16. In some embodiments, the Bz / X molar ratio is in the range of 1.00 to 1.12 over a pX / X molar ratio in the range of 0.80 to 0.95. In some embodiments, the Bz / X ratio is in the range of 1.00 to 1.08 over a pX / X molar ratio in the range of 0.80 to 0.95. In some embodiments, the Bz / X ratio is in the range of 1.00 to 1.06 over a pX / X molar ratio in the range of 0.80 to 0.90.

[0056] If the feed contains benzene or xylene, the Bz / X ratio and pX / X ratio are determined by subtracting the amount of benzene, xylene, or para-xylene in the feed from the amount of product. That is,

[0057] Bz / X molar ratio = (Bz 생성물 - Bz 공급물 ) / (X 생성물 - X 공급물 ).

[0058] Additionally, the molar ratio of para-xylene to total xylene is pX / X molar ratio = (pX 생성물 - pX 공급물 ) / (X 생성물 - X 공급물 ) = can be determined by PXX.

[0059] There is a relationship between the molar ratio of benzene to xylene Bz / X and the molar ratio of para-xylene to xylene pX / X such that Bz / X increases as pX / X increases. Surprisingly, catalysts containing UZM-44 suffer significantly less from this problem than previously known catalysts. Thus, when pX / X is in the range of 0.60 to 1.0, Bz / X can be in the range of 1.00 to 0.375*PXX + 0.825, where PXX is the molar ratio of para-xylene to xylene. Without being bound by theory, a person skilled in the art can calculate from this equation that at a pX / X of 0.60, Bz / X can be in the range of 1.00 to 1.05. At a pX / X of 0.80, Bz / X can be in the range of 1.00 to 1.13. At pX / X of 0.90, Bz / X may be in the range of 1.00 to 1.16.

[0060] Even at pX / X molar ratios greater than 0.8, very high selectivity for xylene can be achieved at all pX / X molar ratios using an enhanced catalyst prepared with UZM-44. Selectivity for xylene may be greater than 52% at pX / X molar ratios in the range of 0.3 to 0.9 or greater, greater than 53% at pX / X molar ratios in the range of 0.3 to 0.85 or greater, greater than 54% at pX / X molar ratios in the range of 0.3 to 0.85 or greater, or greater than 55% at pX / X molar ratios in the range of 0.3 to 0.8 or greater. In one embodiment, all or a combination of any of the conditions listed in this paragraph may be applied to pX / X molar ratios in the range of 0.6 to 0.95 or to pX / X molar ratios in the range of 0.8 to 0.95.

[0061] Very low selectivity for light fractions (e.g., C1-C6 hydrocarbons) can be achieved using an enhanced catalyst prepared with UZM-44 at all pX / X molar ratios, even at pX / X molar ratios greater than 0.8. Selectivity for light fractions may be less than 3.5 wt% at pX / X molar ratios in the range of 0.3 to 0.9 or greater, less than 3 wt% at pX / X molar ratios in the range of 0.3 to 0.9 or greater, less than 2 wt% at pX / X molar ratios in the range of 0.3 to 0.85 or greater, less than 1.5 wt% at pX / X molar ratios in the range of 0.3 to 0.8 or greater, or even less than 1 wt% at pX / X molar ratios in the range of 0.3 to 0.8 or greater. In one sun, all or any combination of the conditions listed in this paragraph may be applied to a pX / X molar ratio in the range of 0.6 to 0.95 or a pX / X molar ratio in the range of 0.8 to 0.95.

[0062] The enhanced catalyst of the present invention may have a low ring loss rate. The ring loss rate can be calculated by subtracting the moles of single-ring aromatic compounds in the product from the moles of single-ring aromatics in the feed, dividing the result by the moles of single-ring aromatics in the feed, and multiplying by 100. Therefore, ring loss rate = (Ar 생성물 - Ar 공급물 ) / (Ar 공급물) *100. Monocyclic aromatics may include benzene, toluene, xylene, 9-carbon aromatic molecules, 10-carbon aromatic molecules, etc. Monocyclic aromatics do not include naphthalene. Without being bound by theory, due to cracking, selectivity for light fractions and ring loss rate may be proportional. That is, a catalyst having high selectivity for light fractions may also have a high ring loss rate. Light fractions represent non-aromatic hydrocarbons having 1 to 6 carbon atoms. In one aspect, methane, ethane, propane, butane, pentane, hexane, and cyclohexane may constitute light fractions. In one sun, the ring loss rate may be less than 1.5%, or less than 1.4%, or less than 1.3%, or less than 1.2%, or less than 1.1%, or less than 1.0%, or less than 0.8%, or less than 0.65%, or less than 0.5%.

[0063] In one embodiment, the industry desires the retention of methyl groups during disproportionation. For example, benzene has 0 moles of methyl groups per mole of benzene, toluene has 1 mole of methyl groups per mole of toluene, xylene has 2 moles of methyl groups per mole of xylene, and so on. The ratio of methyl to phenyl in a stream can be calculated by dividing the number of moles of methyl groups in the stream by the number of moles of mono-ring aromatics in the stream. In one embodiment, the ratio of methyl to phenyl in the product may be similar to the ratio of methyl to phenyl in the feed. The MPP is calculated by dividing the ratio of methyl to phenyl in the product stream by the ratio of methyl to phenyl in the feed stream. The MPP may be greater than 0.96, or 0.97, or 0.98, or 0.99, and less than 1.0.

[0064] Enhanced UZM-44 zeolite can be used in a toluene disproportionation method such as that illustrated in FIG. 1. The toluene disproportionation method may comprise a plurality of modules. In one embodiment, a feed stream (100) containing toluene is combined with a second stream (304) to form a combined feed stream (102), which is delivered to a reaction zone (200). During the disproportionation method, the feed stream or the combined feed stream may first be heated by indirect heat exchange with the effluent of the reaction zone and then further heated in a combustion heater. Subsequently, the resulting vapor stream may pass through a reaction zone that may comprise one or more individual reactors. The feed preferably contains less than 10 mass% of benzene, less than 10 mass% of xylene, less than 10 mass% of A9 aromatic compounds, and less than 10 mass% of non-aromatic compounds. Benzene, xylene, A9 aromatic compounds, and non-aromatic compounds may be less than 5 mass% in the combined feed stream (102). Preferably, all of these are close to 0 mass%.

[0065] The reaction zone (200) may include one or more reactors. The one or more reactors may be a fixed-bed reactor in which a fixed bed of a catalyst containing UZM-44 or fixed beds are located. While the use of a single reaction vessel having a cylindrical fixed bed of the catalyst is preferred, other reaction configurations using a moving bed of the catalyst or a radial flow reactor may be used if desired. The reaction conditions in the reaction zone (200) may include disproportionate reaction conditions as described above.

[0066] The passage of the combined feed stream (102) through the reaction zone affects the generation of a vapor effluent (204) containing hydrogen, product hydrocarbons, and unconverted feed hydrocarbons. An effluent (204) is generated from the reaction zone (200), wherein the effluent (204) has a higher concentration of pX than that present in the combined stream (102). In one sun, the pX may be greater than 0.6 or greater than 0.7, or greater than 0.8, or greater than 0.85, or greater than 0.9. The effluent (204) may be transferred to a separation zone (300) to separate unreacted toluene from the product benzene and xylene. This effluent is typically cooled by indirect heat exchange with the stream entering the reaction zone, and then further cooled using air or cooling water. The temperature of the effluent stream can be lowered sufficiently by heat exchange to achieve condensation of substantially all of the feed and product hydrocarbons having more than 6 carbon atoms per molecule. The resulting mixed-phase stream can be transferred to a vapor-liquid separator, where the two phases are separated, and hydrogen-rich vapor from thereon is recirculated from the first recirculation stream to the reaction zone.

[0067] The separation zone (300) may include one or more distillation columns. Condensate from the separator may be transferred to a stripping column, and substantially all C5 and lighter hydrocarbons present in the effluent are concentrated into an overhead stream and removed from the process. An aromatic-rich stream, referred to as the disproportionate effluent stream, may be recovered as net stripper bottoms. In one embodiment, a benzene column and a toluene column may be present. The disproportionate effluent stream may be fed from the separation zone to the benzene column and the toluene column. A first stream (302) containing benzene may be separated and used for other reaction operations in the aromatic complex or sent to a tank for sale. In one embodiment, the first stream (302) may be an overhead stream from the benzene column. A second stream (304) containing toluene may be separated. In one embodiment, all or part of the second stream (304) may be recirculated to the reaction zone as part of the combined feed stream (102). In one embodiment, the second stream (304) contains less than 10 mass% benzene, or less than 5 mass% benzene, or less than 3 mass% benzene, or less than 1 mass% benzene. In one embodiment, the second stream (304) is essentially free of benzene. “Essentially free” means less than 0.1 mass%. In one embodiment, the second stream (304) contains less than 10 mass% xylene, or less than 5 mass% xylene, or less than 3 mass% xylene, or less than 1 mass% xylene. In one embodiment, the second stream (304) is essentially free of xylene. In one embodiment, the second stream (304) may be the overhead stream of a toluene column. In one sun, the downstream from the benzene column can feed the toluene column. A third stream (306) containing xylene can be separated.

[0068] The third stream (306) may be used as is, depending on the desired para-xylene purity, or may be transferred to a pX purification section (400). In one embodiment, the separation section or pX purification section may also include a catalytic alkyl-aromatic section for ethylbenzene conversion and dealkylation. The purification section (400) may include one or more pX purification devices. Many pX purification devices are known and include, but are not limited to, crystallization processes and adsorption separation processes such as the Parex™ process available from UOP. In each case, a purified pX stream (404) containing up to 100% pX may be formed. The purification section (400) may also produce a reject stream (402) containing meta-xylene (mX) and ortho-xylene (oX). The reject stream (402) may also contain ethylbenzene (EB). The reject stream may be purged from the process. An exemplary use of the removal stream may be as a feed to a xylene isomerization process, such as the Isomar™ process available from UOP. The xylene isomerization product may be recycled back to the purification section (400).

[0069] One aspect of the present invention is a toluene disproportionation method. In one embodiment, the method comprises the step of contacting a feed containing toluene with a catalyst containing a microporous crystalline zeolite under disproportionation conditions to produce an effluent stream containing para-xylene and benzene, wherein the molar ratio of benzene to xylene in the effluent stream is in the range of 1.00 to 1.14, the molar ratio of para-xylene to xylene in the effluent stream is in the range of 0.80 to 1.0, and the conversion rate of toluene is 20% to 40%.

[0070] In some embodiments, the molar ratio of benzene to xylene is in the range of 1.00 to 1.08.

[0071] In some embodiments, the microporous crystalline zeolite is

[0072] M1 a N+ Al (l-x) E x Si y' O z"

[0073] The experimental composition in the form of hydrogen expressed by the empirical formula and comprises a three-dimensional framework of at least AlO2 and SiO2 tetrahedral units, wherein M1 is at least one exchangeable cation selected from the group consisting of alkali, alkaline earth metals, rare earth metals, zinc, ammonium ions, hydrogen ions, and combinations thereof; "a" is the molar ratio of M1 to (Al + E), varying from 0.05 to 50; "N" is the weighted average valence of M1, having a value of +1 to +3; E is an element selected from the group consisting of gallium, iron, boron, and combinations thereof; "x" is the mole fraction of E, varying from 0 to 1.0; y' is the molar ratio of Si to (Al + E), varying from greater than 9 to virtually pure silica; and z" is the molar ratio of O to (Al + E), and Formula:

[0074] z" = (a N + 3 + 4 y') / 2

[0075] Having a value determined by, the zeolite is characterized by having an X-ray diffraction pattern having at least the d-spacing and intensity presented in Table B:

[0076] [Table B]

[0077]

[0078] .

[0079] In some embodiments, the catalyst is reinforced with at least one reinforcement treatment step.

[0080] In some embodiments, at least one reinforcement treatment step includes at least one treatment for incorporating silica.

[0081] In some embodiments, the catalyst is steamed after at least one reinforcement treatment step.

[0082] In some embodiments, the molar ratio of benzene to xylene is in the range of 1.00 to 1.08 compared to the molar ratio of para-xylene to xylene in the range of 0.80 to 0.95.

[0083] In some embodiments, when the molar ratio of para-xylene to xylene is in the range of 0.80 to 0.9, the selectivity for xylene is greater than 52%.

[0084] In some embodiments, when the molar ratio of para-xylene to xylene is in the range of 0.80 to 0.9, the selectivity for the light fraction is less than 3.5%.

[0085] In some embodiments, the disproportionation conditions are a temperature in the range of 200°C to 600°C; a pressure in the range of 1.4 to 4.5 MPa(g); and 0.1 to 10 hr -1 It includes one or more of a weight-hour space velocity in the range; or a hydrogen-to-hydrocarbon ratio in the range of 0.25:1 to 10:1.

[0086] In some embodiments, the ring loss rate is less than 1.5%.

[0087] Another aspect of the present invention is a toluene disproportionation method. In one embodiment, the method comprises the step of contacting a feed containing toluene with a catalyst containing a microporous crystalline zeolite under disproportionation conditions to produce an effluent stream containing para-xylene and benzene, wherein the molar ratio of benzene to xylene in the effluent stream is in the range of 1.00 to 1.20, the molar ratio of para-xylene to xylene in the effluent stream is in the range of 0.60 to 1.0, and the zeolite

[0088] M1 a N+ Al (l-x) E x Si y' O z"

[0089] The experimental composition in the form of hydrogen is expressed by the empirical formula and has a three-dimensional framework of at least AlO2 and SiO2 tetrahedral units, where M1 is at least one exchangeable cation selected from the group consisting of alkali, alkaline earth metals, rare earth metals, zinc, ammonium ions, hydrogen ions, and combinations thereof; "a" is the molar ratio of M1 to (Al + E) and varies from 0.05 to 50; "N" is the weighted average valence of M1 and has a value from +1 to +3; E is an element selected from the group consisting of gallium, iron, boron, and combinations thereof; "x" is the mole fraction of E and varies from 0 to 1.0; y' is the molar ratio of Si to (Al + E) and varies from greater than 9 to virtually pure silica; z" is the molar ratio of O to (Al + E) and Formula:

[0090] z" = (a N + 3 + 4 y') / 2

[0091] Having a value determined by, the zeolite is characterized by having an X-ray diffraction pattern having at least the d-spacing and intensity presented in Table B:

[0092] [Table B]

[0093]

[0094] .

[0095] In some embodiments, the conversion rate of toluene is 20% to 40%.

[0096] In some embodiments, the zeolite is reinforced by at least one reinforcement selected from a treatment for carbon deposition, a treatment for silica deposition, or both.

[0097] In some embodiments, the catalyst is steamed after at least one reinforcement treatment step.

[0098] In some embodiments, the molar ratio of benzene to xylene is in the range of 1.00 to 1.08 compared to the molar ratio of para-xylene to xylene in the range of 0.80 to 0.95.

[0099] In some embodiments, when the molar ratio of para-xylene to xylene is in the range of 0.80 to 0.9, the selectivity for xylene is greater than 52%.

[0100] In some embodiments, when the molar ratio of para-xylene to xylene is in the range of 0.80 to 0.9, the selectivity for the light fraction is less than 3.5%.

[0101] In some embodiments, the disproportionation conditions are a temperature in the range of 200°C to 600°C; a pressure in the range of 1.4 to 4.5 MPa(g); and 0.1 to 10 hr -1 It includes one or more of the following: a space velocity per unit weight per hour in the range; or a ratio of hydrogen to hydrocarbons in the range of 0.25 to 10.

[0102] Another aspect of the present invention is a toluene disproportionation method. In one embodiment, the method comprises the step of contacting a feed containing toluene with a catalyst containing a microporous crystalline zeolite under disproportionation conditions to produce an effluent stream containing para-xylene and benzene, wherein PXX is the molar ratio of para-xylene to xylene in the effluent stream, BX is the molar ratio of benzene to xylene in the effluent stream, and when PXX is in the range of 0.60 to 1.0, BX is in the range of 1.00 to 0.375*PXX + 0.825.

[0103] In certain cases, the purity of the synthesized product can be evaluated by referring to its X-ray powder diffraction pattern. Thus, for example, if a sample is referred to as pure, this merely means that there are no lines attributable to crystalline impurities in the sample's X-ray pattern, not that amorphous material is absent.

[0104] To further fully illustrate the invention, the following examples are described. It should be understood that the examples are for illustrative purposes only and are not intended to be an excessive limitation to the broad scope of the invention as described in the appended claims.

[0105] Examples

[0106] UZM-44 zeolite material with a SiO2 / Al2O3 ratio of 28 was prepared according to the procedures described in U.S. Patents No. 8,609,920 and No. 8,623,321. MFI #1 is an MFI zeolite with a SiO2 / Al2O3 ratio of 38 available from UOP. MFI #2 is an MFI zeolite with a SiO2 / Al2O3 ratio of 23 available from Zeolyst.

[0107] Standard catalytic extrusion

[0108] Zeolite was typically extruded prior to strengthening. Unless otherwise noted, ion-exchanged zeolite powder was extruded into 1 / 16" cylindrical or trilobate shapes having 35 wt% SiO2 and dried overnight. Subsequently, the dried extruder was calcined in air at 550°C for 2 to 4 hours. In some cases, the extruder was ion-exchanged at 75°C for 1 hour using a 10:1:1 weight ratio of water:ammonium nitrate:extruder. When ion-exchanged, the sample was rinsed multiple times with deionized H2O. Ion-exchange was repeated three times, and the final dried extruder was calcined in air at 450 to 500°C for 4 hours.

[0109] General reinforcement procedure:

[0110] The sample to be strengthened was placed in a glass round-bottom flask, and an appropriate amount of organic solvent from Table 1 was added. A Dean-Stark trap and condenser were attached to the round-bottom flask, filled with additional solvent, and insulated with aluminum foil. After heating the flask under reflux for 1 hour using a heating mantle, the Dean-Stark trap was drained and removed from the flask. Tetraethyl orthosilicate or other silicon reagent was added to the flask at 14 wt% based on the sample weight, unless otherwise specified. The condenser was reattached, and the contents of the flask were reacted under reflux for 2 hours. Subsequently, the solvent was removed from the sample by gradient separation, distillation, or vacuum distillation. The sample was then passed through a heat treatment step of 175°C or higher to form the strengthened catalyst. The strengthening treatment was repeated several times as needed to achieve the desired pX / X selectivity.

[0111] [Table 1]

[0112]

[0113] Example 1. UZM-44 was used in the standard preparation using a 3-cycle treatment cycle in which rotary evaporation was used as the solvent removal method.

[0114] Example 2. UZM-44 was used in the standard preparation using a 6-cycle treatment method using rotary evaporation as the solvent removal method.

[0115] Example 3. UZM-44 was used in the standard preparation using a 5-cycle treatment method in which rotary evaporation was used as the solvent removal method.

[0116] Example 4. UZM-44 was used in the preparation of a standard using rotary evaporation as a solvent removal method, with 6 treatment cycles at a 14% TEOS concentration and a 7th treatment cycle at a 6% TEOS concentration.

[0117] Comparative Examples 5 to 31. Examples 5 to 24 are prepared using MFI #1. Examples 25 to 31 are prepared using MFI #2.

[0118] Comparative Example 5. MFI #1 was used in the preparation of a 3-step treatment cycle using hexane as a solvent.

[0119] Comparative Example 6. MFI #1 was used in a standard manufacturing process with a 3-cycle treatment.

[0120] Comparative Example 7. MFI #1 was used in a standard manufacturing process with a 3-cycle treatment.

[0121] Comparative Example 8. MFI #1 was used in a standard manufacturing process with a 4-cycle treatment.

[0122] Comparative Example 9. MFI #1 was used in a standard manufacturing process with a 3-cycle treatment.

[0123] Comparative Example 10. MFI #1 was used in a standard manufacturing process with a 4-cycle treatment.

[0124] Comparative Example 11. MFI #1 was used in a standard manufacturing process with a 3-cycle treatment.

[0125] Comparative Example 12. MFI #1 was used in a standard manufacturing process with a 4-cycle treatment.

[0126] Comparative Example 13. MFI #1 was used in the standard preparation using a 3-step treatment cycle to remove the solvent by distillation.

[0127] Comparative Example 14. MFI #1 was extruded with TiO2 at a 70% zeolite content and treated with 4 standard treatment cycles.

[0128] Comparative Example 15. MFI #1 was used in a standard manufacturing process with a 3-cycle treatment.

[0129] Comparative Example 16. MFI #1 was used in a standard manufacturing process with a 2-cycle treatment.

[0130] Comparative Example 17. MFI #1 was used in the standard preparation prior to a 3-cycle treatment using 20% ​​TEOS in hexane.

[0131] Comparative Example 18. MFI #1 was used in a standard preparation using a heating step of 190°C after a three-cycle treatment using hexane as a solvent.

[0132] Comparative Example 19. MFI #1 was used in the preparation of a standard using a 3-step treatment cycle in which hexane was used as the solvent and distillation was used as the solvent removal method.

[0133] Comparative Example 20. MFI #1 was used in the preparation of a standard using a two-step treatment cycle in which n-octane was used as the solvent and gradient separation was used as the solvent removal method.

[0134] Comparative Example 21. MFI #1 was used to prepare a standard using a 3-step treatment cycle in which n-decane was used as the solvent and gradient separation was used as the solvent removal method.

[0135] Comparative Example 22. MFI #1 was used to prepare a standard 3-cycle treatment cyclo using 10.2% TMOS in cyclohexane.

[0136] Comparative Example 23. MFI #1 was used in the preparation of a standard using a two-cycle treatment using 14% TBOS in toluene and rotary evaporation as the solvent removal method.

[0137] Comparative Example 24. MFI #1 was used in the standard preparation of Dynaslan Silbond, a TEOS-derived product available from Evonik, in a 4-cycle treatment.

[0138] Comparative Example 25. MFI #2 was used in a standard manufacturing process with a 3-cycle treatment.

[0139] Comparative Example 26. MFI #2 was used in a standard manufacturing process with a 3-cycle treatment.

[0140] Comparative Example 27. MFI #2 was prepared in a spherical form with 70% zeolite content containing ZrO2 using the method described in U.S. Patent No. 4,629,717. Subsequently, 70 / 30 MFI / ZrO2 spheres were strengthened by three treatment cycles.

[0141] Comparative Example 28. MFI #2 was used in the standard preparation using a one-step treatment cycle that uses rotary evaporation as a solvent removal method.

[0142] Comparative Example 29. MFI #2 was used in the standard preparation using a two-cycle treatment method in which rotary evaporation was used as the solvent removal method.

[0143] Comparative Example 30. MFI #2 was used in the standard preparation using a 3-cycle treatment cycle in which rotary evaporation was used as the solvent removal method.

[0144] Comparative Example 31. MFI #2 was used to prepare a standard in a single cycle using 14% TEOS in mesitylene (1,3,5-trimethylbenzene) as the solvent and gradient separation as the solvent removal method.

[0145] Catalyst Test Procedure:

[0146] The catalyst was tested in a disproportionation reaction using a feed of 100 wt% toluene nominally. The disproportionation reaction conditions were 4 hr -1 The WHSV was 2, the molar ratio of hydrogen to the feed was 2, the pressure was 2.8 MPa (g) (400 psig), and the temperature was 350°C to 460°C. The achieved results are shown in Table 2 and compared at a target total toluene conversion rate of 30 wt%.

[0147] Figure 2 illustrates the results of Table 2 plotted as the molar ratio of benzene to xylene in the product (Bz / X) versus the achieved molar ratio of para-xylene (pX / X). The catalyst prepared using MFI#1 is indicated by a black circle along the dark black trend line, that prepared using MFI#2 is indicated by an open circle along the gray trend line, and the catalyst of the present invention prepared with UZM-44 is indicated by an open square along the dotted trend line. At all pX / X ratios, the enhanced catalyst prepared using UZM-44 exhibits a very low Bz / X ratio even at pX / X greater than 0.8. The catalyst prepared using MFI zeolite has a Bz / X ratio greater than 1.17 at pX / X greater than 0.85.

[0148] Figure 3 illustrates the results of Table 2 plotted as xylene selectivity versus achieved para-xylene molar ratio (pX / X) in the product. The catalyst prepared using MFI#1 is shown as a black circle along the dark black trend line, the one prepared using MFI#2 is shown as an open circle along the gray trend line, and the catalyst of the present invention prepared using UZM-44 is shown as an open square along the dotted trend line. At all pX / X ratios, the enhanced catalyst prepared using UZM-44 exhibits very high selectivity for xylene even at pX / X greater than 0.8. The catalyst prepared using UZM-44 may have selectivity for xylene greater than 52%, greater than 53%, or greater than 54% at pX / X greater than 0.8, greater than 0.85, or greater than 0.9.

[0149] Figure 4 illustrates the results of Table 2 plotted as selectivity for light fractions (C1-C6 non-aromatic hydrocarbons) in the product versus the achieved para-xylene molar ratio (pX / X). The catalyst prepared using MFI#1 is indicated by a black circle along the dark black trend line, that prepared using MFI#2 is indicated by an open circle along the gray trend line, and the catalyst of the present invention prepared with UZM-44 is indicated by an open square along the dotted trend line. At all pX / X ratios, the enhanced catalyst prepared using UZM-44 exhibits very low selectivity for light fractions, even at pX / X greater than 0.8. The catalyst prepared using UZM-44 may have a selectivity for light fractions at a pX / X greater than 0.8, greater than 0.85, or greater than 0.9 of less than 3.5 wt%, less than 3 wt%, less than 2 wt%, less than 1.5 wt%, or even less than 1 wt%.

[0150] Figure 5 illustrates the results of Table 2 plotted as the achieved para-xylene molar ratio (pX / X) versus the temperature required to reach a 30% conversion rate of toluene. The catalyst prepared using MFI#1 is shown as a black circle along the dark black trend line, the one prepared using MFI#2 is shown as an open circle along the gray trend line, and the catalyst of the present invention prepared with UZM-44 is shown as an open square along the dotted trend line.

[0151] The enhanced UZM-44 catalyst is completely unique. In addition to its surprisingly low Bz / X molar ratio, it exhibits a higher total xylene yield, a lower ring loss rate, lower light fractions (e.g., C1-C6 hydrocarbons), and a better methyl / phenyl retention rate than any other catalyst with a similar pX / X molar ratio.

[0152] [Table 2]

[0153]

[0154]

[0155] Specific implementation form

[0156] Although the following is described in relation to specific embodiments, it will be understood that this description is for illustrative purposes only and is not intended to limit the scope of the foregoing description and the appended claims.

[0157] A first embodiment of the present invention is a toluene disproportionation method comprising the step of contacting a feed containing toluene with a catalyst containing a microporous crystalline zeolite under disproportionation conditions to produce an effluent stream containing para-xylene and benzene, wherein the molar ratio of benzene to xylene in the effluent stream is in the range of 1.00 to 1.14, the molar ratio of para-xylene to xylene in the effluent stream is in the range of 0.80 to 1.0, and the conversion rate of toluene is 20% to 40%. An embodiment of the present invention is any embodiment, or any embodiment, of any of the prior embodiments of this paragraph up to the first embodiment of this paragraph, wherein the molar ratio of benzene to xylene is in the range of 1.00 to 1.08. An embodiment of the present invention is such that the microporous crystalline zeolite

[0158] M1 a N+ Al (l-x) E x Si y' O z"

[0159] The experimental composition in the form of hydrogen expressed by the empirical formula and comprises a three-dimensional framework of at least AlO2 and SiO2 tetrahedral units, wherein M1 is at least one exchangeable cation selected from the group consisting of alkali, alkaline earth metals, rare earth metals, zinc, ammonium ions, hydrogen ions, and combinations thereof; "a" is the molar ratio of M1 to (Al + E), varying from 0.05 to 50; "N" is the weighted average valence of M1, having a value of +1 to +3; E is an element selected from the group consisting of gallium, iron, boron, and combinations thereof; "x" is the mole fraction of E, varying from 0 to 1.0; y' is the molar ratio of Si to (Al + E), varying from greater than 9 to virtually pure silica; and z" is the molar ratio of O to (Al + E), and Formula:

[0160] z" = (a N + 3 + 4 y') / 2

[0161] It is an embodiment of any or any of the prior embodiments of this paragraph up to the first embodiment of this paragraph, characterized in that the zeolite has a value determined by, and has an X-ray diffraction pattern having at least the d-spacing and intensity presented in Table B:

[0162] [Table B]

[0163]

[0164] One embodiment of the present invention is one, any, or all of the prior embodiments of this paragraph up to the first embodiment of this paragraph, wherein the catalyst is reinforced by at least one reinforcement treatment step. One embodiment of the present invention is one, any, or all of the prior embodiments of this paragraph up to the first embodiment of this paragraph, wherein the at least one reinforcement treatment step includes at least one treatment for incorporating silica. One embodiment of the present invention is one, any, or all of the prior embodiments of this paragraph up to the first embodiment of this paragraph, wherein the catalyst is steamed after at least one reinforcement treatment step. One embodiment of the present invention is one, any, or all of the prior embodiments of this paragraph up to the first embodiment of this paragraph, wherein the molar ratio of benzene to xylene is in the range of 1.00 to 1.08 compared to the molar ratio of para-xylene to xylene in the range of 0.80 to 0.95. One embodiment of the present invention is one, any, or all of the prior embodiments of this paragraph up to the first embodiment of this paragraph, wherein the selectivity for xylene is greater than 52% when the molar ratio of para-xylene to xylene is in the range of 0.80 to 0.9. One embodiment of the present invention is one, any, or all of the prior embodiments of this paragraph up to the first embodiment of this paragraph, wherein the selectivity for light fractions is less than 3.5% when the molar ratio of para-xylene to xylene is in the range of 0.80 to 0.9. One embodiment of the present invention is one of the prior embodiments of this paragraph up to the first embodiment of this paragraph, wherein the disproportionation conditions are a temperature in the range of 200°C to 600°C; a pressure in the range of 1.4 to 4.5 MPa(g); and 0.1 to 10 hr -1It is an embodiment of any or any of the prior embodiments of this paragraph up to the first embodiment of this paragraph, comprising one or more of a weight-hour space velocity in the range of; or a ratio of hydrogen to hydrocarbon in the range of 0.251 to 101. An embodiment of the present invention is an embodiment of any or any of the prior embodiments of this paragraph up to the first embodiment of this paragraph, comprising a ring loss rate of less than 1.5%.

[0165] A second embodiment of the present invention is a toluene disproportionation method comprising the step of contacting a feed containing toluene with a catalyst containing a microporous crystalline zeolite under disproportionation conditions to produce an effluent stream containing para-xylene and benzene, wherein the molar ratio of benzene to xylene in the effluent stream is in the range of 1.00 to 1.20, the molar ratio of para-xylene to xylene in the effluent stream is in the range of 0.60 to 1.0, and the zeolite is

[0166] M1 a N+ Al (l-x) E x Si y' O z"

[0167] The experimental composition in the form of hydrogen is expressed by the empirical formula and has a three-dimensional framework of at least AlO2 and SiO2 tetrahedral units, where M1 is at least one exchangeable cation selected from the group consisting of alkali, alkaline earth metals, rare earth metals, zinc, ammonium ions, hydrogen ions, and combinations thereof; "a" is the molar ratio of M1 to (Al + E) and varies from 0.05 to 50; "N" is the weighted average valence of M1 and has a value from +1 to +3; E is an element selected from the group consisting of gallium, iron, boron, and combinations thereof; "x" is the mole fraction of E and varies from 0 to 1.0; y' is the molar ratio of Si to (Al + E) and varies from greater than 9 to virtually pure silica; z" is the molar ratio of O to (Al + E) and Formula:

[0168] z" = (a N + 3 + 4 y') / 2

[0169] Having a value determined by, the zeolite is characterized by having an X-ray diffraction pattern having at least the d-spacing and intensity presented in Table B:

[0170] [Table B]

[0171]

[0172] One embodiment of the present invention is one embodiment of any embodiment, or any embodiment, of the prior embodiments of this paragraph up to the second embodiment of this paragraph, in which the conversion rate is 20% to 40%. One embodiment of the present invention is one embodiment of any embodiment, or any embodiment, of the prior embodiments of this paragraph up to the second embodiment of this paragraph, in which the zeolite is reinforced by at least one reinforcement selected from a treatment for carbon deposition, a treatment for silica deposition, or both. One embodiment of the present invention is one embodiment of any embodiment, or any embodiment, of the prior embodiments of this paragraph up to the second embodiment of this paragraph, in which the catalyst is steamed after at least one reinforcement treatment step. One embodiment of the present invention is one embodiment, any embodiment, or all embodiments of the prior embodiments of this paragraph up to the second embodiment of this paragraph, wherein the molar ratio of benzene to xylene is in the range of 1.00 to 1.08 compared to the molar ratio of para-xylene to xylene in the range of 0.80 to 0.95. One embodiment of the present invention is one embodiment, any embodiment, or all embodiments of the prior embodiments of this paragraph up to the second embodiment of this paragraph, wherein the selectivity for xylene is greater than 52% when the molar ratio of para-xylene to xylene is in the range of 0.80 to 0.9. One embodiment of the present invention is any or any of the prior embodiments of this paragraph up to the second embodiment of this paragraph, wherein the selectivity for the light fraction is less than 3.5% when the molar ratio of para-xylene to xylene is in the range of 0.80 to 0.9. One embodiment of the present invention is a disproportionation condition in which the temperature ranges from 200°C to 600°C; the pressure ranges from 1.4 to 4.5 MPa(g); and 0.1 to 10 hr -1It is an embodiment of any of the prior embodiments of this paragraph up to the second embodiment of this paragraph, or any embodiment, comprising a weight-hour space velocity in the range of; or a ratio of hydrogen to hydrocarbon in the range of 0.25 to 10.

[0173] A third embodiment of the present invention is a toluene disproportionation method comprising the step of contacting a feed containing toluene with a catalyst containing a microporous crystalline zeolite under disproportionation conditions to produce an effluent stream containing para-xylene and benzene, wherein PXX is the molar ratio of para-xylene to xylene in the effluent stream and BX is the molar ratio of benzene to xylene in the effluent stream, and when PXX is in the range of 0.60 to 1.0, BX is in the range of 1.00 to 0.375*PXX + 0.825.

[0174] It is understood that, without further detail, those skilled in the art can use the foregoing description to make full use of the invention and easily identify the essential features of the invention, and thus make various changes and modifications to the invention and adapt them to various uses and conditions without departing from the spirit and scope of the invention. Accordingly, the foregoing preferred specific embodiments should be interpreted merely as illustrative and not as limiting the remainder of this disclosure in any way, and are intended to include various modifications and equivalent arrangements that fall within the scope of the appended claims.

[0175] In the above, unless otherwise indicated, all temperatures are given in Celsius, and all parts and percentages are by weight.

Claims

Claim 1 A toluene disproportionation method comprising the step of contacting a feed containing toluene with a catalyst containing a microporous crystalline zeolite under disproportionation conditions to produce an effluent stream containing para-xylene and benzene, wherein the zeolite is UZM-44, the molar ratio of benzene to xylene in the effluent stream is in the range of 1.00 to 1.14, the molar ratio of para-xylene to xylene in the effluent stream is in the range of 0.80 to 1.0, the conversion rate of toluene is 20% to 40%, and the catalyst is enhanced by steaming after carbon and / or silica deposition, in a 6 or 7 treatment cycle using rotary evaporation as a solvent removal method. Claim 2 In claim 1, the microporous crystalline zeolite is M1 a N+ Al (l-x) E x Si y' O z" It comprises an experimental composition in the form of hydrogen expressed by the empirical formula and a three-dimensional framework of at least AlO2 and SiO2 tetrahedral units, wherein M1 is at least one exchangeable cation selected from the group consisting of alkali, alkaline earth metals, rare earth metals, zinc, ammonium ions, hydrogen ions, and combinations thereof; "a" is the molar ratio of M1 to (Al + E) and varies from 0.05 to 50; "N" is the weighted average valence of M1 and has a value of +1 to +3; E is an element selected from the group consisting of gallium, iron, boron, and combinations thereof; "x" is the mole fraction of E and varies from 0 to 1.0; y' is the molar ratio of Si to (Al + E) and varies from greater than 9 to virtually pure silica; z" is the molar ratio of O to (Al + E) and the formula: z" = (a N + 3 + 4 Method characterized by having a value determined by y') / 2, wherein the zeolite has an X-ray diffraction pattern having at least the d-spacing and intensity presented in Table B below: [Table B] . Claim 3 In paragraph 2, the method comprises at least one reinforcing treatment step including at least one treatment for incorporating silica. Claim 4 delete Claim 5 delete Claim 6 delete Claim 7 delete Claim 8 delete Claim 9 delete Claim 10 delete

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