Toluene disproportionation using reinforced UZM-39 aluminosilicate zeolite

Abstract

A toluene disproportionation process utilizing treated UZM-39 zeolite is described. The process produces an effluent stream containing para-xylene and benzene. The molar ratio of benzene to xylene (Bz / X) in the effluent stream can range from 1.00 to 1.14, the molar ratio of para-xylene to xylene (pX / X) in the effluent stream can range from 0.80 to 1.0, and the toluene conversion can be 20% to 40%.

Description

Technical Field

[0001] (Description of Priority) This application claims priority from U.S. Patent Application No. 16 / 793,527, filed on February 18, 2020, the entire disclosure of which is incorporated herein by reference.

Background Art

[0002] Zeolites are microporous, crystalline aluminosilicate compositions formed from the corners that share AlO2 and SiO2 tetrahedra. Zeolites, both naturally occurring and synthetically prepared, are used in a variety of industrial processes. Synthetic zeolites are prepared via hydrothermal synthesis using suitable sources of Si and Al, and structure-directing agents such as alkali metals, alkaline earth metals, amines, or organic ammonium cations. The structure-directing agent is present within the pores of the zeolite and is greatly involved in the specific structure that is ultimately formed. These species balance the skeletal charge associated with aluminum and can also function as space fillers. Zeolites are characterized by having pore openings of uniform dimensions, having significant ion-exchange capacity, and being able to reversibly desorb an adsorbed phase that is dispersed throughout the internal voids of the crystal without significantly displacing any of the atoms that make up the permanent zeolite crystal structure. Zeolites can be used as catalysts for hydrocarbon conversion reactions, which can occur on the outer surface of the pores as well as on the internal surface within the pores.

[0003] A specific zeolite, referred to as TNU-9, was first disclosed by Hong et al. in 2004 (J.Am.Chem.Soc.2004,126,5817-26) and subsequently disclosed in Korean Patent No. 480229, granted in 2005. This report and patent were followed in 2007 by a complete synthesis report (J.Am.Chem.Soc.2007,129,10870-85). These papers describe the synthesis of TNU-9 from the flexible dicationic structure-directing agent, 1,4-bis(N-methylpyrrolidinium)butanedibromide, in the presence of sodium. After the structure of TNU-9 was elucidated (Nature, 2006, 444, 79-81), the International Zeolite Association Structure Commission assigned the code TUN to this zeolite structure type. See the Atlas of Zeolite Framework Types, managed by the International Zeolite Association Structure Commission (http: / / www.iza-structure.org / databases / ). The TUN structure type was found to contain three sets of mutually orthogonal channels, each defined by a 10-membered ring of a tetrahedral coordinating atom. In addition, two 10-membered ring channels of different sizes are present within the structure.

[0004] Another specific zeolite, IM-5, was first disclosed in 1996 by Benazzi et al. (French Patent Publication No. 96 / 12873, International Publication No. 98 / 17581), which describes the synthesis of IM-5 from the flexible dicationic structure-directing agent, 1,5-bis(N-methylpyrrolidinium)pentanedibromide or 1,6-bis(N-methylpyrrolidinium)hexanedibromide, in the presence of sodium. After the structure of IM-5 was elucidated by Baerlocher et al. (Science, 2007, 315, 113-6), the International Zeolite Structure Commission assigned an IMF code to this zeolite structure type (see Atlas of Zeolite Framework Types). The IMF structure was also found to contain three mutually orthogonal sets of channels, each channel defined by a 10-membered ring of a tetrahedral coordinating atom; however, connectivity in three dimensions is interrupted every 2.5 nm, and therefore diffusion is somewhat limited. In addition, multiple 10-membered ring channels of different sizes are present within the structure.

[0005] The applicant previously developed a new family of materials referred to as UZM-39. The topology of these materials is similar to that observed in TNU-9 and IM-5. These materials can be used in various hydrocarbon conversion processes, as described in U.S. Patents 8,642,823, 8,940,952, 8,946,497, and 8,846,998.

[0006] Xylene isomers are produced in large quantities from petroleum as raw materials for various important industrial chemicals. The most important of these isomers is paraxylene, the main raw material for polyesters, which continues to enjoy high growth rates due to high base demand. Orthoxylene is used to produce phthalic anhydride, which has a large but mature market. Metaxylene is used in products such as plasticizers, azo dyes, and wood preservatives, and is growing in volume, albeit on a smaller scale.

[0007] Among aromatic hydrocarbons, the overall importance of xylene is comparable to that of benzene as a raw material for industrial chemicals. Neither xylene nor benzene can be produced from petroleum in sufficient quantities to meet demand through naphtha reforming. Therefore, the conversion of other hydrocarbons is necessary to increase the production of xylene and benzene. Often, toluene is selectively disproportionated to obtain benzene and C8 aromatic compounds, from which individual xylene isomers are recovered.

[0008] Para-selective toluene disproportionation is a process commercialized in the 1980s for the purpose of converting toluene to benzene and xylene, typically with a high molar ratio of para-xylene to total xylene (pX / X molar ratio) of over 0.85. This technique is particularly desirable when there is a demand for polyesters and other chemicals derived from para-xylene, but the demand for other xylenes is limited. High pX / X ratios were initially achieved by "selectively" selecting the catalyst with carbon and / or coke to narrow the MFI pore size and coat the acidic moieties on the outer surface of the MFI crystal. Subsequently, it was found that similar results could be achieved by depositing silica on the catalyst.

[0009] U.S. Patent No. 4,016,219(B1) (Kaeding) discloses a process for toluene disproportionation using a catalyst comprising a zeolite modified by the addition of at least 0.5 mass% of phosphorus. The zeolite crystals are brought into contact with a phosphorus compound to react with the phosphorus compound. The modified zeolite can then be incorporated into the indicated matrix material.

[0010] U.S. Patent No. 4,097,543(B1) (Haag et al.) teaches toluene disproportionation for the selective production of paraxylene using zeolite with controlled pre-coking. Zeolites can be ion-exchanged with various elements from groups IB to VIII and compounded 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. The combination involves selective hydrogenation of the toluene feedstock, followed by contact with a zeolite catalyst in which oil droplets are dropped onto an aluminum phosphate binder to achieve a high yield of paraxylene.

[0012] U.S. Patent No. 6,429,347(B1) (Boldingh) teaches a toluene disproportionation reaction for the selective production of paraxylene using a catalyst containing an MFI zeolite bonded to alumina phosphate, after selectively pre-coking the catalyst by contacting it with a coke-forming feed under pre-coking conditions.

[0013] In these processes, the selected zeolite was ZSM-5 with an MFI framework. Using these catalysts, the molar ratio of paraxylene to xylene (pX / X) can be increased from an equilibrium level of 0.24–0.90 or higher by depositing a sufficient amount of coke or silica. This increases the molar ratio of pX / X, which is always accompanied by an increase in the molar ratio of benzene to xylene (Bz / X) that significantly exceeds the theoretical value of 1. The higher the pX / X molar ratio, the higher the Bz / X molar ratio.

[0014] While we do not wish to be bound by theory, it is clear that an increase in the Bz / X molar ratio is caused by a loss of total xylene yield. Generally, as the p-xylene yield increases beyond a certain level, the total xylene yield typically decreases. This is considered unavoidable, and much research has been done to optimize the use of coke and silica to minimize the Bz / X molar ratio. Using the best silica deposition techniques to increase the pX / X molar ratio above 0.90, it is quite common to see Bz / X molar ratio values ​​up to 1.4 under disproportionation conditions of 30% toluene conversion rate, H2 / HC=2, WHSV=4, and a pressure of 400 psig.

[0015] Therefore, there is a need for an improved toluene disproportionation process with a high pX / X molar ratio (e.g., 0.70 or higher) and a Bz / X molar ratio of less than 1.2. [Brief explanation of the drawing]

[0016] [Figure 1] This is a diagram illustrating one embodiment of the toluene disproportionation process. [Figure 2] This graph shows the Bz / X molar ratio as a function of the pX / X molar ratio for various catalysts with a 30% conversion rate. [Figure 3] This graph shows the selectivity for toluene as a function of the pX / X molar ratio for various catalysts at a 30% conversion rate. [Figure 4] This graph shows the selectivity for various catalysts at a 30% conversion rate for light fractions (C1-C6) as a function of the pX / X molar ratio. [Figure 5] This graph shows the temperature required to achieve a 30% conversion rate for various catalysts, plotted against the achieved pX / X molar ratio. [Modes for carrying out the invention]

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

[0018] This invention relates to the catalytic use of an aluminosilicate zeolite called UZM-39. UZM-39 is a zeolite whose topological structure is related to TUN, as described in the Atlas of Zeolite Framework Types managed by the International Zeolite Association Structure Commission (http: / / www.iza-structure.org / databases / ), and its member is called TNU-9. However, UZM-39 differs from TNU-9 in several of its properties, including its X-ray diffraction pattern (XRD). UZM-39 is also related to IMF, as described in the Atlas of Zeolite Framework Types, and its member is called IM-5. As described in U.S. Patents 8,642,823, 8,940,952, 8,946,497, and 8,846,998, each incorporated herein in whole, UZM-39 differs from TNU-9 and IM-5 in several of its properties, including its X-ray diffraction pattern. Surprisingly, UZM-39, after being strengthened under disproportionation conditions until its pX / X molar ratio exceeded 0.75, was found to possess a unique combination of a high pX / X molar ratio and high total xylene selectivity without generating excess benzene.

[0019] The UZM-39 is Na , (k4)+ , (k3)+ , (k2)+ , m4 , m3 , M m k+ T t Al 1-x E x Si y O z having an experimental composition on an anhydrous basis as synthesized, represented by the empirical formula wherein, "n" is the molar ratio of Na to (Al + E), having a value of 0.05 to 0.5, M represents one or more metals 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), having a value of 0 to 0.5, "k" is the average charge of the metal(s) M, T is an organic structure-directing agent(s) derived from reactants R and Q, R is an Α,Ω-dihalogen-substituted alkane having 3 to 6 carbon atoms, Q is at least one neutral monoamine having 6 or fewer carbon atoms, "t" is the molar ratio of N to (Al + E) from the organic structure-directing agent(s), having a value of 0.5 to 1.5, E is an element selected from the group consisting of gallium, iron, boron, and combinations thereof, "x" is the mole fraction of E, having a value from 0 to 1.0, "y" is the molar ratio of Si to (Al + E), varying from greater than 9 to 25, "z" is the molar ratio of O to (Al + E), and the equation: z = (n + k·m + 3 + 4·y) / 2 having a value determined by wherein, M is only one metal, and then the weighted average valence is the valence of one metal, i.e., +1 or +2. However, when two or more M metals are present, M m k+ = M m1 (k1)+ + M m2 (k2)+ + M m3 (k3)+ + M m4 (k4)+ +... the total amount of and the weighted average valence "k" is given by the following equation.

[0020]

number

[0021] UZM-39 can be synthesized by hydrothermal crystallization of a reaction mixture prepared by combining a reactive sodium source, an organic structure directing agent T(or more), aluminum, silicon, a layered material seed L, and optionally E, M, or both. Sources of aluminum include, but are not limited to, aluminum alkoxides, precipitated alumina, metal aluminum, aluminum hydroxide, sodium aluminate, aluminum salts, and alumina sols. Specific examples of aluminum alkoxides include, but are not limited to, aluminum sec-butoxide and aluminum orthoisopropoxide. Sources of silica include, but are not limited to, tetraethyl orthosilicate, colloidal silica, precipitated silica, and alkali silicates. Sources of sodium include, but are not limited to, sodium hydroxide, sodium bromide, sodium aluminate, and sodium silicate.

[0022] T is an organic structure-directing agent(s) derived from reactants R and Q, where R is an α,Ω-dihalogen-substituted alkane having 3 to 6 carbon atoms, and Q comprises at least one neutral monoamine having 6 or fewer carbon atoms. R can be an α,Ω-dihalogen-substituted alkane having 3 to 6 carbon atoms, selected from the group consisting of 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,3-diiodopropane, 1,4-diiodobutane, 1,5-diiodopentane, 1,6-diiodohexane, and combinations thereof. Q includes at least one neutral monoamine having six or fewer carbon atoms, such as 1-ethylpyrrolidine, 1-methylpyrrolidine, 1-ethylazetidine, 1-methylazetidine, triethylamine, diethylmethylamine, dimethylethylamine, trimethylamine, dimethylbutylamine, dimethylpropylamine, dimethylisopropylamine, methylethylpropylamine, methylethylisopropylamine, dipropylamine, diisopropylamine, cyclopentylamine, methylcyclopentylamine, and hexamethyleneimine. Q may include a combination of multiple neutral monoamines having six or fewer carbon atoms.

[0023] L contains at least one seed of layered zeolite. A preferred seed zeolite is a layered material that is a microporous zeolite having a crystal thickness of at least one dimension between less than 30 and 50 nm. The microporous material has a pore diameter of less than 2 nm. The seed layered zeolite is of a different zeotype from the UZM-39 coherent grown composite during synthesis. Examples of preferred layered materials include UZM-4M (US Patent No. 6,776,975), UZM-5 (US Patent No. 6,613,302), UZM-8 (US Patent No. 6,756,030), UZM-8HS (US Patent No. 7,713,513), UZM-26 (US Patent Publication No. 2010 / 0152023(A1)), UZM-27 (US Patent No. 7,575,737), BPH, FAU / EMT material, *Examples include, but are not limited to, BEA or zeolite beta, MCM-22P and MCM-22, MCM-36, MCM-49, MCM-56, ITQ-1, ITQ-2, ITQ-30, ERB-1, EMM-10P and EMM-10, SSZ-25, and SSZ-70, as well as smaller microporous materials such as PREFER (preferrielite) and NU-6.

[0024] M represents at least one exchangeable cation from Group 1 (IUPAC1), Group 2 (IUPAC2), Group 3 (IUPAC3) of the periodic table, or the lanthanide series, and / or zinc. Specific examples of M include, but are not limited to, lithium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, yttrium, lanthanum, gadolinium, and mixtures thereof. Sources of reactive M include, but are not limited to, halides, nitrates, sulfates, hydroxides, or acetates. E is an element selected from the group consisting of gallium, iron, boron, and combinations thereof, and preferred sources of reactive E include, but are not limited to, boric acid, gallium oxyhydroxide, gallium nitrate, gallium sulfate, ferric nitrate, ferric sulfate, ferric chloride, and mixtures thereof.

[0025] A reaction mixture containing a source of the desired reactive components is given by formula: ab Na2O:bM n / 2 O:cRO:dQ:1-eAl2O3:eE2O3:fSiO2:gH2O The molar ratio of oxides may be described accordingly. In the formula, "a" has a value of 10 to 30, "b" has a value of 0 to 30, "c" has a value of 1 to 10, "d" has a value of 2 to 30, "e" has a value of 0 to 1.0, "f" has a value of 30 to 100, and "g" has a value of 100 to 4000. In addition, the reaction mixture contains 1 to 10% by weight of seed zeolite L, based on the amount of SiO2 in the reactants. For example, if 100 g of SiO2 is present in the reactant mixture, 1 to 10 g of seed zeolite L is added. The examples show several specific addition sequences for the reaction mixture leading to UZM-39. However, since there are at least six starting materials, many addition sequences are possible. For example, seed crystal L may be added to the reaction mixture as the last component. They can be added to the reactive Si source or at other suitable time points. Furthermore, if alkoxides are used, it is preferable to include a distillation or evaporation step to remove alcohol hydrolysis products. While the organic structure directing agents R and Q can be added separately or together to the reaction mixture at many time points during the process, it is preferable to mix R and Q together at room temperature and add the mixed mixture to a cooled mixture of reactive Si, Al, and Na sources maintained at 0-10°C. Alternatively, the mixture of R and Q can be mixed at room temperature, cooled, and then the reactive Si, Al, and Na sources can be added to the organic structure directing agent mixture while maintaining a temperature of 0-10°C. In alternative embodiments, reagents R and Q can be added separately or together to the reaction mixture at room temperature.

[0026] Next, the reaction mixture is reacted in a sealed reaction vessel, stirred under spontaneous pressure at a temperature of 150°C to 200°C, 155°C to 190°C, or 160°C to 180°C, for a period of 1 day to 3 weeks, preferably 3 to 12 days. After crystallization is complete, the solid product is isolated from the heterogeneous mixture by means of filtration or centrifugation, then washed with deionized water and dried in air at an ambient temperature of up to 100°C.

[0027] UZM-39, a coherent growth composite of as-synthesized TUN and IMF zeotypes, is characterized by an X-ray diffraction pattern having at least the d-layer spacing and relative intensity described in Tables A1-A3 below. The diffraction patterns herein are for copper K α The diffraction peaks were obtained using a typical experimental powder diffractometer with the CuKα line. The characteristic interplanar distance d of the sample was determined from the position of the diffraction peaks represented by the angle 2-theta (2θ). hkl This can be calculated using Bragg's equation.

[0028] The intensity is calculated based on a relative intensity scale, where 100 is the value of the line representing the strongest peak on the X-ray diffraction pattern, then very weak (vw) means less than 5, weak (w) means less than 15, moderate (m) means in the range of 15 to 50, strong (s) means in the range of 50 to 80, and very strong (vs) means greater than 80. Intensity can also be expressed as encompassing the above ranges. The X-ray diffraction pattern from which the data (interplanar spacing and intensity) is obtained is characterized by numerous reflections, some of which are broad peaks(s) forming shoulders to higher intensity peaks. Some or all of the shoulders may not be resolved. This may be the case with low crystallinity samples of certain coherent grown composite structures, or samples with crystals small enough to cause significant X-ray broadening. This may also be the case if the equipment or operating conditions used to generate the diffraction pattern are significantly different from those used in this case. As will be understood by those skilled in the art, the determination of the parameter 2θ is susceptible to both human and mechanical errors, which together can impose an uncertainty of ±0.4° on each reported value of 2θ. This uncertainty also naturally manifests itself in the reported values ​​of the d-layer spacing calculated from the 2θ values. This inaccuracy is common throughout the art and is not sufficient to distinguish the crystalline materials from each other and from compositions of the prior art.

[0029] The X-ray diffraction pattern of UZM-39 contains numerous peaks. The characteristics of these peaks for UZM-39 are shown in Tables A1-A3 for various coherent grown composite structures. Additional peaks, particularly very weak intensity peaks, may also be present. All medium- or higher intensity peaks present in the UZM-39 family of coherent grown composite structures are shown in Table A3 at a minimum.

[0030] Table A1 contains selected d-layer spacings and relative intensities for the X-ray diffraction patterns of UZM-39. The relative intensities are shown as a range covering UZM-39 material with various relative amounts of TUN and IMF zeotypes.

[0031] [Table 1] * A composite peak consisting of multiple overlapping reflections.

[0032] Zeolites can be further characterized by X-ray diffraction patterns having at least the d-interlacing and intensity described in Table A2, where the d-interlacing and intensity are provided for different relative concentrations of the components of the coherent grown composite structure.

[0033] [Table 2]

[0034] Zeolites can also be further characterized by X-ray diffraction patterns having at least the d-interlacing and intensity described in Table A3, where the d-interlacing and intensity are provided by different relative concentrations of the components of the coherent grown composite structure.

[0035] [Table 3]

[0036] In Tables A2 and A3, the term "high" refers to 60-95% by mass of the specified component, the term "medium" refers to 25-70% by mass of the specified component, and the term "low" refers to 5-40% by mass of the specified component. Some peaks may be shoulders on stronger peaks, and some peaks may be composite peaks consisting of multiple overlapping reflections.

[0037] The UZM-39 material is thermally stable up to a temperature of at least 600°C, or at least 700°C, or at least 800°C. The UZM-39 material may have a micropore volume as a percentage of the total pore volume exceeding 60%.

[0038] Characterization of UZM-39 products using high-resolution scanning electron microscopy reveals that UZM-39 is formed in a lathe-like manner, often in starburst cluster arrangements, where it aggregates into rectangular rod-shaped particles.

[0039] UZM-39 is a coherent growth composite structure of the TUN and IMF zeotypes. A coherent growth composite structure means that both structures are present in the major part of the crystal in a given sample. This coherent growth composite structure is possible when the two zeotype structures have nearly identical spatial arrangements of atoms, at least along the planar protrusions of their crystal structures, and have similar pore topology. Each vertex is a tetrahedral site (or T site), and at the center of each stick is a corner-shared oxygen atom. Along these protrusions, both the TUN and IMF zeotypes contain nearly identical protrusions of 6-rings and 10-rings linked to 5-ring chains, forming channels running perpendicular to the plane.

[0040] Both TUN and IMF zeolites are three-dimensional 10-ring zeolites with nearly identical protrusions on a single plane; therefore, the two structures can coherently grow from crystals of the other structure that have an interface on an interchangeable plane, forming coherent grown composite structures.

[0041] Coherent growth composite structures are not physical mixtures of two molecular sieves. Electron diffraction, transmission electron microscopy, and X-ray diffraction analysis are used to demonstrate that a material is a coherent growth composite structure rather than a physical mixture. Typically, a combination of electron diffraction and TEM imaging is the most reliable method for determining whether one has produced a coherent growth composite structure, as it provides direct evidence of the presence of both structures within a single crystal.

[0042] It should be understood that coherent grown composite zeolites can possess varying amounts of two structural types, and therefore, the relative intensity and linewidth of some diffraction lines will change depending on the amount of each structure present in the coherent grown composite structure. While the degree of change in the X-ray powder diffraction pattern can be theoretically predicted for certain structures, the more likely modes of coherent grown composite structures are inherently random and therefore difficult to predict without using a large hypothetical model as the basis for calculations.

[0043] Unlike a physical mixture of TNU-9 and IM-5, optical diffractograms obtained by transmission electron microscopy (TEM) analysis and calculations using high-resolution imaging show that UZM-39 consists of a coherent growth composite structure of TUN and IMF zeotypes.

[0044] In addition, UZM-39 zeolite can be characterized by Rietveld analysis of its XRD pattern. Rietveld analysis is a least-squares method developed by Rietveld (Journal of Applied Crystallography 1969, 2:65-71) and is a preferred method for deriving structural information from samples such as UZM-39 containing strongly overlapping reflectances, by refining the theoretical XRD profile until it closely matches the measured XRD pattern. It is often used to quantify the amounts of two different phases in an XRD diffractogram. The accuracy of the Rietveld method is determined by parameters such as crystallite size (peak broadening), peak shape function, lattice unit cell constant, and background fit. The applicant determined that under the conditions used, the error of the reported values ​​could be ±5%. The applicant also determined that the Rietveld model used could not quantify the amounts of minority composite structural phase components by values ​​of less than 10%. However, the amounts of minority components can be visually observed at levels exceeding 5% by comparison with the model pattern. The results of Rietveld modifications to various UZM-39 samples indicate that UZM-39 contains more than 0% and less than 100% by weight of IMF zeotype, and less than 100% by weight and more than 0% by weight of TUN zeotype. In another embodiment, UZM-39 contains more than 5% and less than 95% by weight of IMF zeotype, and less than 95% by weight and more than 5% by weight of TUN zeotype, and in yet another embodiment, UZM-39 contains more than 10% and less than 90% by weight of IMF zeotype, and less than 90% by weight and more than 10% by weight of TUN zeotype. By changing the synthesis conditions, a wide range of coherent grown composite structures are possible.

[0045] As-synthesized UZM-39 material contains some exchangeable or charge-equilibrium cations within its pores. These exchangeable cations may be exchangeable with other cations, or, in the case of organic cations, may be removed by heating under controlled conditions. It is also possible to directly remove some organic cations from UZM-39 zeolite by ion exchange. UZM-39 zeolite can be modified by many means to suit specific applications. Modifications include calcination, ion exchange, steam treatment, various acid extractions, ammonium hexafluorosilicate treatment, or any combination thereof, as outlined in the case of UZM-4M in U.S. Patent No. 6,776,975 (B1), which is incorporated in whole by reference. Conditions may be more severe than those shown in U.S. Patent No. 6,776,975. Properties to be modified include porosity, adsorption, Si / Al ratio, acidity, and thermal stability.

[0046] After calcination, ion exchange, and calcination, and on an anhydrous basis, the modified microporous crystalline zeolite UZM-39 (UZM-39M) has a three-dimensional framework of at least AlO2 and SiO2 tetrahedral units, and M1 a N+ Al (l-x) E x Si y’ O z” Having an experimental composition of hydrogen form represented by the empirical formula, In the formula, M1 is at least one exchangeable cation selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, 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 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, varying from 0 to 1.0, y' is the molar ratio of Si to (Al+E), varying from greater than 9 to substantially pure silica, and z'' is the molar ratio of O to (Al+E), and the equation is: z”=(a·N+3+4·y') / 2 It has a value determined by [the specified method / function].

[0047] In the hydrogen form, after calcination, ion exchange, and calcination to remove NH3, UZM-39 exhibits the XRD patterns shown in Tables B1-B3. The peak characteristics of UZM-39 are shown in Tables B1-B3 for various coherent grown composite structures. Additional peaks, particularly very weak intensity peaks, may also be present. All medium- or higher intensity peaks present in the UZM-39 family of coherent grown composite structures are shown in Table B3 at a minimum.

[0048] Table B1 contains selected d-layer spacings and relative intensities for hydrogen forms of the X-ray diffraction patterns of UZM-39. The relative intensities are shown as a range covering UZM-39 material with various relative amounts of TUN and IMF zeotypes.

[0049] [Table 4] * A composite peak consisting of multiple overlapping reflections.

[0050] Zeolites can be further characterized by X-ray diffraction patterns having at least d-interlacing and intensity as shown in Table B2, where d-interlacing and intensity are provided for different relative concentrations of the components of the coherent grown composite structure.

[0051] [Table 5]

[0052] Zeolites can also be further characterized by X-ray diffraction patterns having at least d-interlacing and intensity as described in Table B3, where d-interlacing and intensity are provided for different relative concentrations of the components of the coherent grown composite structure.

[0053] [Table 6]

[0054] In Tables B2 and B3, the term "high" refers to 60-95% by mass of the specified component, the term "medium" refers to 25-70% by mass of the specified component, and the term "low" refers to 5-40% by mass of the specified component. Some peaks may be shoulders on stronger peaks, and some peaks may be composite peaks consisting of multiple overlapping reflections.

[0055] Where specified herein, when specifying the proportion of zeolite starting materials or the adsorption properties of zeolite products, the zeolite is intended to be in an anhydrous state unless otherwise stated. The term "anhydrous state" is used herein to refer to a zeolite that is substantially free of both physically and chemically adsorbed water.

[0056] UZM-39 or UZM-39M may be fortified to increase the pX / X ratio achieved during toluene disproportionation. Fortification means a process that increases the pX / X molar ratio to a significantly higher equilibrium value of 0.24 during toluene disproportionation. Three known examples are carbon deposition, silica treatment, and steam treatment after carbon and / or silica deposition.

[0057] Surprisingly, catalysts containing UZM-39 that underwent a strengthening process until the pX / X molar ratio achieved during disproportionation exceeded 0.6 were found to possess a unique combination of a high pX / X molar ratio and high total xylene selectivity without generating excess benzene.

[0058] The catalyst may further include a refractory binder or matrix intended to facilitate the fabrication of the disproportionation catalyst, provide strength, reduce fabrication costs, or a combination thereof. The binder may be homogeneous in the composition and relatively refractory to the conditions used in the process. Suitable binders may include inorganic oxides such as one or more of alumina, magnesia, zirconia, chromia, titania, boria, tria, zinc oxide, and silica. Alumina and / or silica are preferred binders. The amount of zeolite present in the bound catalyst can vary considerably, but is typically present in an amount of 30 to 90 mass percent, preferably 50 to 80 mass percent, of the catalyst.

[0059] An exemplary strengthening process for silica deposition involves exposing the zeolite to a silicon reagent such as tetraethyl orthosilicate (TEOS), followed by a calcination process. Exemplary strengthening by silica treatment incorporates silica into the zeolite. Strengthening by silica deposition can be achieved by treatment of the zeolite, on the zeolite before bonding with refractory oxides, or on a bonding catalyst.

[0060] In one embodiment, UZM-39 may be extruded together with a metal oxide binder before strengthening. The ion-exchanged zeolite powder may be extruded as a cylinder or trilobe, and the refractory metal oxide may include SiO2, TiO2, ZrO2, Al2O3, or a mixture thereof. In one embodiment, the refractory metal oxide may be SiO2. The relative proportions of zeolite and refractory metal oxide may vary. The zeolite content in the catalyst extruder may be more than 50% by weight, or more than 55% by weight, or more than 60% by weight, or more than 65% by weight, or less than 95% by weight, or less than 90% by weight, or less than 80% by weight. The size and shape of the extruder may vary within known technical ranges, with cylinders and 1.6 mm trilobes being preferred. The width of the extruder may be 0.75 mm to 4 mm, or 1.0 mm to 3 mm.

[0061] The dry extruded material may be calcined in air for 5 minutes to 6 hours at a temperature in the range of 350°C to 600°C. 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 water:ammonium nitrate:extruded material in a weight ratio of 10:1:1. After ion exchange, the extruded material is rinsed multiple times with deionized H2O. If used, ion exchange may be repeated as needed. The final dry extruded material may then be calcined as described above.

[0062] Silica strengthening can be carried out by placing the sample in a container and adding an organic solvent. In one embodiment, the amount of organic solvent to be 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. Then, a silicon reagent may be added to the container. In one embodiment, the silicon reagent may be a silicon alkoxide, but is not limited to these. 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 alkoxide or silicon siloxane. A suitable source may be one of the products in the Dynaslan® Silbond® family available from Evonik. The silicon reagent may be a chlorosilane. The concentration of the silicon reagent used can range from 5% to 25% by weight, based on the weight of the sample.

[0063] Upon addition of the silicon reagent, the contents of the container may react under reflux for 5 minutes to 8 hours, or 30 minutes to 4 hours. After reflux, the solvent may be removed from the sample. Preferred solvent removal methods may involve decantation, distillation, or vacuum distillation. The sample may then be subjected to a heat treatment process at a temperature of at least 175°C to a maximum of 600°C to form a strengthened catalyst. This strengthening treatment may be repeated as many times as necessary to achieve the desired pX / X selectivity.

[0064] Enhancement by carbon deposition can be brought about by conditions for subsequent disproportionation processes that include one or more of the following: higher temperature, lower pressure, higher space velocity, or a higher hydrogen-to-hydrocarbon ratio. Such carbon deposition conditions include absolute pressures of 100 kPa to 4 MPa and a duration of 0.2 to 10 hours. -1 The liquid space-time velocity may include the following. The conditions may include one or more of the following: an inlet temperature at least 50°C higher than the reaction temperature, a pressure at least 100 kPa lower than the reaction pressure, or preferably a pressure of no more than half the pressure used in the subsequent disproportionation step. Preferably, the molar ratio of free hydrogen to feedstock coke-forming hydrocarbons is no more than half of that used in the subsequent disproportionation step. Lower pressures and / or lower hydrogen / hydrocarbon ratios reduce the rate of exothermic aromatic saturation reactions and thus limit the temperature rise, resulting in a relatively flat temperature profile. Thus, a typical temperature range is 300°C to 700°C, and a typical hydrogen to coke-forming feed range is 0.01 to 5. Enhancement by carbon deposition can result in a catalytic carbon content of 5 to 40% by mass of carbon, preferably 10 to 30% by mass of carbon. The coke-forming feed for carbon deposition may include the feedstocks to the disproportionation step described below. In one embodiment, toluene, or other specific hydrocarbons or mixtures known in the art, preferably including aromatic compounds, may be used as coke-forming feed.

[0065] UZM-39 may be strengthened one or more times with carbon and / or silica. Strengthening may involve incorporating carbon or silica into a catalyst containing zeolite. "Inside" means inside or on the surface, and means that carbon or silica strengthening may deposit material on the outer surface of the zeolite crystal, and / or on the outer surface and / or within the pore structure of any refractory oxide present. While we do not wish to be bound by theory, "inside" does not describe the deposition of material into the micropores of the zeolite. In one embodiment, strengthening may be carried out on the zeolite, or on the zeolite before bonding with the refractory oxide, or on a bonding catalyst containing UZM-39 or UZM-39M. Individual strengthening steps may be repeated until the desired selectivity is achieved under disproportionation conditions. In one embodiment, the strengthening steps may be carried out until pX / X is greater than 0.6, or greater than 0.7, or greater than 0.8, or greater than 0.85, or greater than 0.9.

[0066] Following strengthening by carbon or silica deposition, strengthened UZM-39 can optionally undergo steam treatment. Steam treatment after strengthening may increase the pX / X achieved during disproportionation. However, steam treatment may also reduce the activity of the zeolite or catalyst. In one embodiment, steam treatment conditions may utilize temperatures of 100°C to 750°C, or 200°C to 700°C, or 450°C to 650°C, partial pressure of water of 0.1 to 0.5, or 0.15 to 0.35, and durations of 10 minutes to 26 hours, or 30 minutes to 6 hours. In one embodiment, a high pX / X ratio during disproportionation can be achieved by strengthening steps or by a combination of strengthening steps and steam treatment steps. The steam treatment and strengthening steps may be performed in any order found to achieve a high pX / X.

[0067] The reinforced UZM-39 zeolite of the present invention can be used as a catalyst or catalyst support in a toluene disproportionation process.

[0068] The toluene disproportionation process involves contacting a toluene-containing supply logistics with a zeolite-containing catalyst under disproportionation conditions to obtain an effluent logistics containing benzene and xylene. In selective disproportionation processes such as those of the present invention, the catalyst can be enhanced by one or more processing steps to increase the molar ratio of paraxylene to xylene (pX / X) from an equilibrium level of 0.24 to 0.60 or higher by depositing a sufficient amount of coke or silica. This enhancement increases the pX / X molar ratio, which previously resulted in an increase in the molar ratio of benzene to xylene (Bz / X) significantly exceeding the theoretical value of 1. Using the optimal silica deposition technique to increase the pX / X molar ratio to 0.90 or higher, a toluene conversion rate of 30%, H2 / HC=2, WHSV=4hr is obtained. -1 Under disproportionation conditions that may include such conditions, it was common to observe a maximum Bz / X molar ratio value of 1.4 at a pressure of 2.8 MPa(g).

[0069] Ideally, the toluene disproportionation process operates at the highest possible toluene conversion rate while maximizing the xylene yield from the reaction. In one embodiment, the toluene conversion rate may be greater than 20% by weight, or 25% or more by weight, or greater than 28% or more by weight, or greater than 30% or more by weight, or greater than 32% or more by weight, or greater than 35% or less by weight, or less than 50% or less than 40% or less than 35% by weight.

[0070] The feed for the disproportionation reaction may include toluene and optionally a combination of C9 aromatic compounds, and may be preferably derived from one or various sources. The feed material may be produced synthetically, for example, from naphtha by catalytic modification or hydrogenation following thermal decomposition to obtain a product rich in aromatic compounds. The feed material may be derived from such a product to a suitable purity by extraction of aromatic hydrocarbons from a mixture of aromatic and non-aromatic hydrocarbons, and fractionation of the extract. For example, aromatic compounds may be recovered from the modified product. The feed material may contain at least 80% by mass of toluene, or more than 85% of toluene, or more than 90% of toluene, or more than 95% of toluene, or even more than 98.5% of toluene. The feed material may contain more than 90% by 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 material may contain 10% by mass or less of non-aromatic compounds. In one embodiment, the feed may contain 10% by mass or less of benzene. In one embodiment, the feed may contain 10% by mass or less of xylene. In one embodiment, the feed may contain 10% by mass or less of A9 aromatic compounds. Preferably, the non-aromatic compounds, benzene, xylene, and A9 aromatic compounds are close to 0% by mass. In one embodiment, all or any combination of the conditions listed in this section may be applied to the characterization of the feed.

[0071] The disproportionation reaction conditions can range from 200°C to 600°C, or 300°C to 450°C, or 350°C to 425°C. The pressure can range from 1.0 MPa to 7.0 MPa, or 1.4 MPa(g) to 4.5 MPa(g), or 2.0 MPa(g) to 3.5 MPa(g). The disproportionation reaction can occur over a wide range of space velocities, with higher space velocities resulting in a higher ratio of paraxylene at the expense of conversion. The weight-time-space velocity (WHSV) is 0.5 to 10 hr. -1 , or 1.0-7 hours -1 , or 1.0-5 hours -1The hydrogen-to-hydrocarbon ratio can be in the range of 0.25 to 10, or 0.5 to 5.

[0072] The molar ratio (pX / X) of para-xylene to xylene in the effluent is a critical factor in the selective toluene disproportionation process. Since the equilibrium pX / X is 0.24 under toluene disproportionation conditions, the para-selective toluene disproportionation process produces effluent containing pX / X greater than 0.25 or greater than 0.30. Effluent from the toluene disproportionation process may have pX / X molar ratios 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 may be less than 0.98, less than 0.96, or less than 0.94.

[0073] Ideally, the toluene disproportionation process operates with a molar ratio (Bz / X) of benzene to xylene in the effluent of 1.00. A Bz / X of 1.00 indicates that for every mole of benzene produced, a mole of xylene is produced. A Bz / X ratio close to 1.00 is preferred, and in one embodiment, 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, and greater than 1.00, or greater than 0.99, or greater than 0.98. For example, in some embodiments, the Bz / X ratio is in the range of 0.98 to 1.20 over a pX / X molar ratio in the range of 0.25 to 0.95. In some embodiments, the Bz / X ratio is in the range of 0.98 to 1.16 over pX / X molar ratios of 0.25 to 0.95. In some embodiments, the Bz / X ratio is in the range of 0.98 to 1.12 over pX / X molar ratios of 0.25 to 0.95. In some embodiments, the Bz / X ratio is in the range of 0.98 to 1.08 over pX / X molar ratios of 0.25 to 0.95. In some embodiments, the Bz / X ratio is in the range of 0.98 to 1.06 over pX / X molar ratios of 0.25 to 0.90. In some embodiments, the Bz / X ratio is in the range of 0.98 to 1.05 over pX / X molar ratios of 0.25 to 0.85. In some embodiments, the Bz / X ratio is in the range of 0.98 to 1.02 over pX / X molar ratios of 0.25 to 0.85. In some embodiments, the Bz / X ratio is in the range of 0.98 to 1.01 over pX / X molar ratios 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 pX / X molar ratios in the range of 0.80 to 0.95. In some embodiments, the Bz / X ratio is in the range of 1.00 to 1.16 over pX / X molar ratios in the range of 0.80 to 0.95. In some embodiments, the Bz / X ratio is in the range of 1.00 to 1.12 over pX / X molar ratios 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 pX / X molar ratios 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 of 0.80 to 0.90.

[0074] If the feedstock contains benzene or xylene, the amount of benzene, xylene, or paraxylene in the feedstock is subtracted from the amount in the product to determine the Bz / X ratio and pX / X ratio. In other words, Bz / X molar ratio = (Bz 生成物 -Bz 供給物 ) / (X 生成物 -X 供給物 ).

[0075] In addition, the molar ratio of paraxylene to total xylene is pX / X molar ratio = (pX 生成物 -pright 供給物 ) / (X 生成物 -X 供給物 ) = This can be determined by PXX.

[0076] A relationship exists between the molar ratio of benzene to xylene (Bz / X) and the molar ratio of paraxylene to xylene (pX / X), where pX / X increases as Bz / X increases. Surprisingly, catalysts containing UZM-39 exhibit this problem significantly less than conventionally known catalysts. Therefore, when pX / X is in the range of 0.60 to 1.0, Bz / X is in the range of 1.00 to 0.375. * PXX can be in the range of +0.825, where PXX is the molar ratio of paraxylene to xylene. Although not bound by theory, this equality allows a person skilled in the art to calculate that for a pX / X of 0.60, Bz / X can be in the range of 1.00 to 1.05. For a pX / X of 0.80, Bz / X can be in the range of 1.00 to 1.13. For a pX / X of 0.90, Bz / X can be in the range of 1.00 to 1.16.

[0077] Very high selectivity for xylene at all pX / X ratios can be achieved using an enhanced catalyst prepared with UZM-39, even at pX / X molar ratios greater than 0.8. Selectivity for xylene can exceed 52% at pX / X molar ratios in the range of 0.3 to 0.9 or higher, or exceed 53% at pX / X molar ratios in the range of 0.3 to 0.85 or higher, or exceed 54% at pX / X molar ratios in the range of 0.3 to 0.85 or higher, or exceed 55% at pX / X molar ratios in the range of 0.3 to 0.8 or higher. In one embodiment, a mixture of all or any of the conditions enumerated in this section may be applied at pX / X molar ratios in the range of 0.6 to 0.95, or at pX / X molar ratios in the range of 0.8 to 0.95.

[0078] Very low selectivity for light fractions (e.g., C1-C6 hydrocarbons) can be achieved using an enhanced catalyst prepared with UZM-39 at all pX / X molar ratios, and even more so at pX / X molar ratios greater than 0.8. Selectivity for light fractions may be less than 3.5% by weight at pX / X molar ratios in the range of 0.3 to 0.9 or higher, or less than 3% by weight at pX / X molar ratios in the range of 0.3 to 0.9 or higher, or less than 2% by weight at pX / X molar ratios in the range of 0.3 to 0.85 or higher, or less than 1.5% by weight at pX / X molar ratios in the range of 0.3 to 0.8 or higher, or even less than 1% by weight at pX / X molar ratios in the range of 0.3 to 0.8 or higher. In one embodiment, a mixture of all or any of the conditions enumerated in this section may be applied at pX / X molar ratios in the range of 0.6 to 0.95, or pX / X molar ratios in the range of 0.8 to 0.95.

[0079] The strengthened catalyst of the present invention may have low ring loss. Ring loss can be calculated by subtracting the number of moles of monocyclic aromatic compounds in the feed from the number of moles of monocyclic aromatic compounds in the product, dividing by the number of moles of monocyclic aromatic compounds in the feed, and multiplying by 100. Therefore, ring loss = (Ar 生成物 -Ar 供給物 ) / (Ar 供給物 ) *The value is 100. Monocyclic aromatic compounds may include benzene, toluene, xylene, 9-carbon aromatic compound molecules, 10-carbon aromatic compound molecules, etc. Monocyclic aromatic compounds do not include naphthalene. Although not bound by theory, selectivity for light fractions and ring loss may be proportional to cracking. That is, catalysts with high selectivity for light fractions may also have high ring loss. Light fractions represent non-aromatic hydrocarbons having 1 to 6 carbon atoms. In one embodiment, methane, ethane, propane, butane, pentane, hexane, and cyclohexane may include light fractions. In one embodiment, ring loss 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%.

[0080] In one embodiment, the industry desires the retention of methyl groups during disproportionation. For example, benzene has zero moles of methyl groups per mole of benzene, toluene has one mole of methyl groups per mole of toluene, xylene has two moles, and so on. The ratio of methyl to phenyl in the flow can be calculated by dividing the number of moles of methyl groups in the flow by the number of moles of monocyclic aromatic compounds in the flow. In one embodiment, the ratio of methyl to phenyl in the product may be the same as the ratio of methyl to phenyl in the feed. The MPP is calculated by dividing the ratio of methyl to phenyl in the product flow by that of the feed flow. The MPP may be greater than 0.96, or 0.97, or 0.98, or 0.99, and less than 1.0.

[0081] Reinforced UZM-39 zeolite can be used in toluene disproportionation processes, such as those illustrated in Figure 1. The toluene disproportionation process may comprise multiple modules. In one embodiment, a toluene-containing supply flow 100 is combined with a second flow 304 to form a mixed supply flow 102 that is sent to a reaction zone 200. Within the disproportionation process, the supply flow or mixed supply flow may first be heated by indirect heat exchange with respect to the effluent of the reaction zone, and then further heated in a combustion heater. The resulting vapor flow may then pass through a reaction zone that may comprise one or more individual reactors. The supply preferably contains less than 10% by mass of benzene, less than 10% by mass of xylene, less than 10% by mass of A9 aromatic compounds, and less than 10% by mass of non-aromatic compounds. Benzene, xylene, A9 aromatic compounds, and non-aromatic compounds may be less than 5% by mass in the mixed supply flow 102. Preferably, all of these are close to 0% by mass.

[0082] The reaction zone 200 may include one or more reactors. One or more reactors may be fixed-bed reactors in which a fixed bed(s) of catalyst containing UZM-39 is located. It is preferable to use a single reaction vessel with a fixed cylindrical catalyst bed, but other reaction configurations utilizing a moving bed or radial flow reactor of catalyst may be used as needed. The reaction conditions in reaction zone 200 may include the disproportionation reaction conditions described above.

[0083] The passage of the mixed flow 102 into the reaction zone results in the generation of a vapor effluent 204 containing hydrogen, product hydrocarbons, and unconverted feed hydrocarbons. The effluent 204 is generated from the reaction zone 200, where it has a higher concentration of pX than that present in the mixed feed flow 102. In one embodiment, pXX 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 can be sent to a separation zone 300 to separate unreacted toluene from the product benzene and xylene. This effluent can typically be cooled by indirect heat exchange with respect to the flow entering the reaction zone, and then further cooled through the use of air or cooling water. The temperature of the effluent flow can be reduced by sufficient heat exchange to result in substantially all concentration of feed and product hydrocarbons having six or more carbon atoms per molecule. The resulting mixed phase flow can be sent to a gas-liquid separator, where the two phases are separated, and from there, hydrogen-rich vapor is recirculated in a first recirculation flow to the reaction zone.

[0084] The separation zone 300 may include one or more distillation columns. The concentrate from the separator may be sent to a stripping column, where substantially all C5 and light hydrocarbons present in the effluent are concentrated into an overhead flow and removed from the process. An aromatic compound-rich flow, referred to as the disproportionation effluent flow, may be recovered as the net stripper bottom. In one embodiment, benzene and toluene columns may be present. The disproportionation effluent flow may be fed to the benzene and toluene columns in the separation zone. The first flow 302 containing benzene may be separated and utilized for other reaction operations in the aromatic compound complex, or sent to a tank for sale. In one embodiment, the first flow 302 may be an overhead flow from the benzene column. A second flow 304 containing toluene may be separated. In one embodiment, all or part of the second flow 304 may be recycled to the reaction zone as part of the mixed feed flow 102. In one embodiment, the second flow 304 contains less than 10% by mass of benzene, or less than 5% by mass of benzene, or less than 3% by mass of benzene, or less than 1% by mass of benzene. In one embodiment, the second flow 304 is essentially benzene-free. "Essentially benzene-free" means less than 0.1% by mass. In one embodiment, the second flow 304 contains less than 10% by mass of xylene, or less than 5% by mass of xylene, or less than 3% by mass of xylene, or less than 1% by mass of xylene. In one embodiment, the second flow 304 is essentially xylene-free. In one embodiment, the second flow 304 may be an overhead flow of a toluene column. In one embodiment, a bottom flow from a benzene column may be supplied to the toluene column. A third flow 306 containing xylene may be separated.

[0085] The third stream 306 may be used as is or sent to the pX purification section 400, depending on the desired paraxylene purity. In one embodiment, the separation zone or pX purification section may also include a catalytic alkyl aromatic compound zone for ethylbenzene conversion and dealkylation. The purification section 400 may include one or more pX purification devices. Many pX purification devices are known, including, but are not limited to, crystallization 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 waste stream 402 containing metaxylene (mX) and orthoxylene (oX). The waste stream 402 may also contain ethylbenzene (EB). The waste stream may be purged from the process. An exemplary use of the waste stream may be as a feedstock to a xylene isomerization process such as the Isomar® process available from UOP. The xylene isomerization product can be recycled to the purification section 400.

[0086] One aspect of the present invention is a toluene disproportionation process. In one embodiment, the process involves contacting a feed containing toluene with a catalyst containing microporous crystalline zeolite under disproportionation conditions to produce an effluent containing paraxylene and benzene, wherein the molar ratio of benzene to xylene in the effluent is in the range of 1.00 to 1.14, the molar ratio of paraxylene to xylene in the effluent is in the range of 0.80 to 1.0, and the toluene conversion rate is 20% to 40%.

[0087] In some embodiments, the molar ratio of benzene to xylene is in the range of 1.00 to 1.08.

[0088] In some embodiments, the microporous crystalline zeolite, after calcination, ion exchange, and calcination, and on an anhydrous basis, has a three-dimensional framework of at least AlO2 and SiO2 tetrahedral units, and M1 aN+ Al (l-x) E x Si y’ O z” The TUN and IMF zeotype coherent growth composite comprises an experimental composition of hydrogen in a form represented by the empirical formula, In the formula, M1 is at least one exchangeable cation selected from the group consisting of alkali metals, 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 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, varying from 0 to 1.0, y' is the molar ratio of Si to (Al+E), varying from greater than 9 to substantially pure silica, and z'' is the molar ratio of O to (Al+E), and the equation is: z”=(a·N+3+4·y') / 2 It has a value determined by, The zeolite is characterized by having an X-ray diffraction pattern having at least the d-layer spacing and intensity described in Table B1.

[0089] [Table 7] * A composite peak consisting of multiple overlapping reflections.

[0090] In some embodiments, the catalyst is strengthened by at least one strengthening process.

[0091] In some embodiments, at least one strengthening process includes at least one process for incorporating silica.

[0092] In some embodiments, the catalyst is steam-treated after at least one enhancement treatment step.

[0093] In some embodiments, the molar ratio of benzene to xylene is in the range of 1.00 to 1.08, and the molar ratio of paraxylene to xylene is in the range of 0.80 to 0.95.

[0094] In some embodiments, when the molar ratio of paraxylene to xylene is in the range of 0.80 to 0.90, the selectivity for xylene exceeds 52%.

[0095] In some embodiments, when the molar ratio of paraxylene to xylene is in the range of 0.80 to 0.90, the selectivity for the light fraction is less than 3.5%.

[0096] 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 a duration of 0.1 to 10 hours. -1 It includes one or more of the following: gravitational time-space velocities in the range of 0.25:1 to 10:1, or a hydrogen-to-hydrocarbon ratio in the range of 0.25:1 to 10:1.

[0097] In some embodiments, the ring loss is less than 1.5%.

[0098] Another aspect of the present invention is a toluene disproportionation process. In one embodiment, the process comprises contacting a feed containing toluene with a catalyst containing microporous crystalline zeolite under disproportionation conditions to produce an effluent containing paraxylene and benzene, wherein the molar ratio of benzene to xylene in the effluent is in the range of 1.00 to 1.20, and the molar ratio of paraxylene to xylene in the effluent is in the range of 0.60 to 1.0, and the zeolite, after calcination, ion exchange and post-calcination, and on an anhydrous basis, has a three-dimensional framework of at least AlO2 and SiO2 tetrahedral units, and M1 a N+ Al (l-x) E xSi y’ O z” The TUN and IMF zeotype coherent growth composite comprises an experimental composition of hydrogen in a form represented by the empirical formula, In the formula, M1 is at least one exchangeable cation selected from the group consisting of alkali metals, 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 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, varying from 0 to 1.0, y' is the molar ratio of Si to (Al+E), varying from greater than 9 to substantially pure silica, and z'' is the molar ratio of O to (Al+E), and the equation is: z”=(a·N+3+4·y') / 2 It has a value determined by, The zeolite is characterized by having an X-ray diffraction pattern having at least the d-layer spacing and intensity described in Table B1.

[0099] [Table 8] * A composite peak consisting of multiple overlapping reflections.

[0100] In some embodiments, the toluene conversion rate is 20% to 40%.

[0101] In some embodiments, the zeolite is strengthened by at least one enhancement selected from treatments for carbon deposition, treatments for silica deposition, or both.

[0102] In some embodiments, the catalyst is steam-treated after at least one enhancement treatment step.

[0103] In some embodiments, the molar ratio of benzene to xylene is in the range of 1.00 to 1.08, and the molar ratio of paraxylene to xylene is in the range of 0.80 to 0.95.

[0104] In some embodiments, when the molar ratio of paraxylene to xylene is in the range of 0.80 to 0.90, the selectivity for xylene exceeds 52%.

[0105] In some embodiments, when the molar ratio of paraxylene to xylene is in the range of 0.80 to 0.90, the selectivity for the light fraction is less than 3.5%.

[0106] 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 a duration of 0.1 to 10 hours. -1 It includes one or more of the following: a gravitational time-space velocity in the range of 0.25 to 10, or a hydrogen-to-hydrocarbon ratio in the range of 0.25 to 10.

[0107] Another aspect of the present invention is a toluene disproportionation process. In one embodiment, the process comprises contacting a feed containing toluene with a catalyst containing microporous crystalline zeolite under disproportionation conditions to produce an effluent containing paraxylene and benzene, where PXX is the molar ratio of paraxylene to xylene in the effluent and BX is the molar ratio of benzene to xylene in the effluent, where if PXX is in the range of 0.60 to 1.0, BX is in the range of 1.00 to 0.375. * It is within the range of PXX+0.825.

[0108] In certain cases, the purity of a synthesized product can be evaluated by referring to its X-ray powder diffraction pattern. Therefore, for example, when a sample is described as pure, it is intended only that the X-ray pattern of this sample does not contain lines due to crystalline impurities, and not that amorphous materials are absent.

[0109] To better illustrate the present invention, the following examples are provided. It should be understood that these examples are for illustrative purposes only and are not intended to be an excessive limitation on the broad scope of the invention as described in the appended claims. [Examples]

[0110] UZM-39 zeolite material was prepared at an SiO2 / Al2O3 ratio of 28 according to the procedures described in U.S. Patents Nos. 8,642,823, 8,940,952, 8,946,497, and 8,846,998. UZM-39 types A, B, and C are as described above and have high, medium, and low relative concentrations of TUN in the material, respectively. MFI#1 is an MFI zeolite with an SiO2 / Al2O3 ratio of 38 available from UOP. MFI#2 is an MFI zeolite with an SiO2 / Al2O3 ratio of 23 available from Zeolyst.

[0111] Standard catalytic extrusion Zeolites were typically extruded before reinforcement. Unless otherwise specified, ion-exchanged zeolite powder was extruded as a 1 / 16-inch cylinder or trilobe containing 35% by weight of SiO2 and dried overnight. The dried extruded material was calcined in air at 550°C for 2–4 hours. If necessary, the extruded material was ion-exchanged at 75°C for 1 hour using a water:ammonium nitrate:extruded material mixture in a 10:1:1 weight ratio. If ion-exchanged, the sample was rinsed multiple times with deionized H2O. After repeating ion exchange three times, the final dried extruded material was calcined in air at 450–500°C for 4 hours.

[0112] General enhancement procedure: The sample to be strengthened was placed in a glass round-bottom flask, and an appropriate amount of the organic solvent listed in Table 1 was added. A Dean-Stark trap and condenser were attached to the round-bottom flask, filled with additional solvent, and insulated with tin foil. The flask was heated under reflux on a heating mantle for 1 hour, after which the Dean-Stark trap was drained and removed from the flask. Unless otherwise specified, tetraethyl orthosilicate or another silicon reagent was added to the flask at 14% by weight, based on the sample weight. The condenser was reattached, and the contents of the flask were reacted under reflux for 2 hours. The solvent was then removed from the sample by decantation, distillation, or vacuum distillation. The sample was then subjected to a heat treatment step of at least 175°C to form a strengthening catalyst. The strengthening treatment was repeated as many times as needed to achieve the desired pX / X selectivity.

[0113] [Table 9]

[0114] Example 1. Type C UZM-39 was used in a standard preparation using five processing cycles.

[0115] Example 2. Type C UZM-39 was used in a standard preparation using six processing cycles.

[0116] Example 3. Type C UZM-39 was used in a standard preparation using seven processing cycles.

[0117] Example 4. Type C UZM-39 was used in a standard preparation using three processing cycles.

[0118] Example 5. Type C UZM-39 was used in a standard preparation using five processing cycles.

[0119] Example 6. Type C UZM-39 was used in a standard preparation using five processing cycles.

[0120] Example 7. Type C UZM-39 was used in a standard preparation using seven processing cycles.

[0121] Example 8. Type C UZM-39 was extruded as a trilobe and used in a standard preparation using three processing cycles.

[0122] Example 9. Type C UZM-39 was extruded as a trilobe and used in a standard preparation using five processing cycles.

[0123] Example 10. Type C UZM-39 was extruded as a trilobe and used in a standard preparation using six processing cycles.

[0124] Example 11. Type C UZM-39 was extruded as a trilobe and used in a standard preparation using 7 processing cycles.

[0125] Example 12. Type C UZM-39 was extruded as a trilobe and used in a standard preparation using mesitylene as the solvent and three processing cycles. Decantation was used as the solvent removal method.

[0126] Example 13. Type C UZM-39 was extruded as a trilobe and used in a standard preparation using mesitylene as the solvent and four processing cycles. Decantation was used as the solvent removal method.

[0127] Example 14. Type C UZM-39 was extruded as a trilobe and used in a standard preparation using mesitylene as the solvent and five processing cycles. Decantation was used as the solvent removal method.

[0128] Example 15. Type C UZM-39 was extruded as a trilobe and used in a standard preparation using mesitylene as the solvent and 6 processing cycles, with decantation being used as the solvent removal method.

[0129] Example 16. Type C UZM-39 was prepared using mesitylene as the solvent and a standard preparation method involving four treatment cycles. Decantation was used as the solvent removal method.

[0130] Example 17. Type C UZM-39 was used in a standard preparation using mesitylene as the solvent and five processing cycles, with decantation being used as the solvent removal method.

[0131] Example 18. Type C UZM-39 was prepared using mesitylene and 28% TEOS as solvents in a three-cycle treatment. Decantation was used as the solvent removal method.

[0132] Example 19. Type B UZM-39 was used in a standard preparation using three processing cycles.

[0133] Example 20. Type B UZM-39 was used in a standard preparation using four processing cycles.

[0134] Example 21. Type B UZM-39 was used in a standard preparation using five processing cycles.

[0135] Example 22. Composites of type B extruded UZM-39 material were prepared with an average of 4 strengthening cycles using standard TEOS in the toluene process performed earlier in toluene disproportionation, resulting in a C content of 3% from contact with the previous feed.

[0136] Example 23. Type B UZM-39 was used in a preparation using toluene as the solvent and TEOS as the silicon source, with a solvent-to-catalyst ratio of 1.9, and rotary evaporation as the solvent removal method. Three strengthening steps were performed.

[0137] Example 24. The material from Example 23 was treated once in a preparation using 10% TEOS in toluene with a solvent:catalyst ratio of 1.9, and rotary evaporation was used as the solvent removal method.

[0138] Example 25. Type B UZM-39 was used in a standard preparation using two processing cycles, where rotary evaporation was the solvent removal method.

[0139] Example 26. Type B UZM-39 was used in a standard preparation using three processing cycles, where rotary evaporation was the solvent removal method.

[0140] Example 27. Type A UZM-39 was used in a standard preparation using mesitylene as the solvent and two processing cycles, with decantation being used as the solvent removal method.

[0141] Example 28. The catalyst from Example 2, after toluene disproportionation, was calcined and then further strengthened by steam treatment at 650°C and an H2O partial pressure of 0.2 for 20 minutes.

[0142] Example 29. The catalyst from Example 3, after toluene disproportionation, was calcined and then further strengthened by steam treatment at 650°C and an H2O partial pressure of 0.2 for 20 minutes.

[0143] Comparative Examples 30-56 and Examples 30-49 were fabricated using MFI#1. Examples 50-56 were fabricated using MFI#2.

[0144] Comparative Example 30. MFI#1 was used in a preparation process involving three treatment cycles using hexane as the solvent.

[0145] Comparative Example 31. MFI#1 was used in a standard preparation using three processing cycles.

[0146] Comparative Example 32. MFI#1 was used in a standard preparation using three processing cycles.

[0147] Comparative Example 33. MFI#1 was used in a standard preparation using four processing cycles.

[0148] Comparative Example 34. MFI#1 was used in a standard preparation using three processing cycles.

[0149] Comparative Example 35. MFI#1 was used in a standard preparation using four processing cycles.

[0150] Comparative Example 36. MFI#1 was used in a standard preparation using three processing cycles.

[0151] Comparative Example 37. MFI#1 was used in a standard preparation using four processing cycles.

[0152] Comparative Example 38. MFI#1 was used in a standard preparation using three processing cycles, where the solvent was removed by distillation.

[0153] Comparative Example 39. MFI#1 was extruded using TiO2 with a 70% zeolite content and processed four times using a standard processing cycle.

[0154] Comparative Example 40. MFI#1 was used in a standard preparation using three processing cycles.

[0155] Comparative Example 41. MFI#1 was used in a standard preparation using two processing cycles.

[0156] Comparative Example 42. MFI#1 was used in a standard preparation before three treatment cycles using 20% ​​TEOS in hexane.

[0157] Comparative Example 43. MFI#1 was used in a standard preparation procedure consisting of three processing cycles using hexane as the solvent, followed by a heating step at 190°C.

[0158] Comparative Example 44. MFI#1 was used in a standard preparation involving three processing cycles using hexane as the solvent, and distillation as the solvent removal method.

[0159] Comparative Example 45. MFI#1 was used in a standard preparation method consisting of two processing cycles using n-octane as the solvent, and decantation as the solvent removal method.

[0160] Comparative Example 46. MFI#1 was used in a standard preparation method involving three processing cycles using n-decane as the solvent, and decantation as the solvent removal method.

[0161] Comparative Example 47. MFI#1 was prepared using a standard preparation method involving three treatment cycles with 10.2% TMOS in cyclohexane.

[0162] Comparative Example 48. MFI#1 was prepared using a standard method involving two treatment cycles with 14% TBOS in toluene, and rotary evaporation as the solvent removal method.

[0163] Comparative Example 49. MFI#1 was prepared using a standard preparation method involving four treatment cycles of Dynaslan Silbond, a TEOS derivative product available from Evonik.

[0164] Comparative Example 50. MFI#2 was used in a standard preparation using three processing cycles.

[0165] Comparative Example 51. MFI#2 was used in a standard preparation using three processing cycles.

[0166] Comparative Example 52. MFI#2 was prepared in a spherical form using ZrO2 with a 70% zeolite content by the method described in U.S. Patent No. 4,629,717. Subsequently, the 70 / 30 MFI / ZrO2 spheres were strengthened in three treatment cycles.

[0167] Comparative Example 53. MFI#2 was used in a standard preparation with one processing cycle and rotary evaporation as the solvent removal method.

[0168] Comparative Example 54. MFI#2 was used in a standard preparation with two processing cycles and rotary evaporation as the solvent removal method.

[0169] Comparative Example 55. MFI#2 was used in a standard preparation with three processing cycles and rotary evaporation as the solvent removal method.

[0170] Comparative Example 56. MFI#2 was used in the standard preparation, where one cycle of 14% TEOS in mesitylene was used as the solvent, and decantation was used as the solvent removal method.

[0171] Catalyst testing procedure: The catalyst was tested in a disproportionation reaction using a nominal 100% by weight toluene supply. The disproportionation reaction conditions were 4 hours. -1 The parameters were WHSV, a hydrogen-to-supply molar ratio of 2, a pressure of 2.8 MPa(g)(400 psig), and a temperature of 350°C to 460°C. The results achieved are shown in Table 2 and compared with a target overall toluene conversion rate of 30% by weight.

[0172] Figure 2 shows the results from Table 2, plotted as the molar ratio of benzene to xylene in the product (Bz / X) versus the achieved molar ratio of paraxylene (pX / X). Catalysts prepared using MFI#1 are shown as black circles with dark black trend lines, catalysts prepared using MFI#2 as white circles with gray trend lines, and the catalyst of the present invention prepared using UZM-39 as a white square with a dashed trend line. For all pX / X ratios, the enhanced catalyst prepared using UZM-39 exhibits a very low Bz / X ratio, even when pX / X exceeds 0.8. Catalysts prepared using MFI zeolite have a Bz / X ratio exceeding 1.17 at pX / X above 0.85.

[0173] Figure 3 shows the results from Table 2, plotted as xylene selectivity in the product versus the achieved para-xylene molar ratio (pX / X). Catalysts prepared using MFI#1 are shown as black circles with dark black trend lines, catalysts prepared using MFI#2 as white circles with gray trend lines, and the catalyst of the present invention prepared using UZM-39 as a white square with a dashed trend line. At all pX / X ratios, the enhanced catalyst prepared using UZM-39 exhibits very high selectivity for xylene, even when pX / X exceeds 0.8. Catalysts prepared using UZM-39 may have xylene selectivity exceeding 52%, 53%, or 54% at pX / X ratios greater than 0.8, 0.85, or 0.9.

[0174] Figure 4 shows the results from 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). Catalysts prepared using MFI#1 are shown as black circles with dark black trend lines, catalysts prepared using MFI#2 as white circles with gray trend lines, and the catalyst of the present invention prepared using UZM-39 as a white square with a dashed trend line. At all pX / X ratios, the reinforced catalyst prepared using UZM-39 exhibits very low selectivity for light fractions, even when pX / X is greater than 0.8. Catalysts prepared using UZM-39 may have selectivity for light fractions 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% at pX / X values ​​greater than 0.8, greater than 0.85, or greater than 0.9.

[0175] Figure 5 shows the results from Table 2, plotted as the temperature required to reach a toluene conversion rate of 30% versus the achieved paraxylene molar ratio (pX / X). Catalysts prepared using MFI#1 are shown as black circles with dark black trend lines, catalysts prepared using MFI#2 as white circles with gray trend lines, and the catalyst of the present invention prepared using UZM-39 as a white square with a dashed trend line.

[0176] The enhanced UZM-39 catalyst is entirely unique. In addition to its remarkably low Bz / X molar ratio, it exhibits higher total xylene yield, lower ring loss, lower light fraction (e.g., C1-C6 hydrocarbons), and better methyl / phenyl retention than any other catalyst with a similar pX / X molar ratio.

[0177] [Table 10-1]

[0178] [Table 10-2]

[0179] Specific Embodiments The following will be described in conjunction with specific embodiments, but it should be understood that this specification is intended to illustrate, and not limit, the scope of the foregoing description and the appended claims.

[0180] A first embodiment of the present invention is a process comprising contacting a feed containing toluene with a catalyst containing microporous crystalline zeolite under disproportionation conditions to produce an effluent containing paraxylene and benzene, wherein the molar ratio of benzene to xylene in the effluent is in the range of 1.00 to 1.14, the molar ratio of paraxylene to xylene in the effluent 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 one or all of the preceding embodiments to the first embodiment of this section, 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 a microporous crystalline zeolite having a three-dimensional framework of at least AlO2 and SiO2 tetrahedral units, after calcination, ion exchange and post-calcination, and on an anhydrous basis, and M1 a N+ Al (l-x) E x Si y’ O z” One, any, or all of the preceding embodiments to the first embodiment in this section, comprising an experimental composition of hydrogen form represented by the empirical formula, constituting a coherent growth composite of TUN and IMF zeotype, In the formula, M1 is at least one exchangeable cation selected from the group consisting of an alkali metal, an alkaline earth metal, a rare earth metal, zinc, an ammonium ion, a hydrogen ion, and combinations thereof; "a" is the molar ratio of M1 to (Al + E), which varies from 0.05 to 50; "N" is the weighted average valence of M1, which 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, which varies from 0 to 1.0; y' is the molar ratio of Si to (Al + E), which varies from more than 9 to substantially pure silica; z" is the molar ratio of O to (Al + E), and the equation: z”=(a·N + 3 + 4·y’) / 2 has a value determined by The zeolite is characterized in that it has an X-ray diffraction pattern having at least the d-spacing and intensity described in Table B1.

[0181]

Table 11

[0182] One embodiment of the present invention is one or all of the preceding embodiments to the first embodiment in this section, wherein the catalyst is strengthened in at least one strengthening process. One embodiment of the present invention is one or all of the preceding embodiments to the first embodiment in this section, wherein at least one strengthening process includes at least one process for incorporating silica. One embodiment of the present invention is one or all of the preceding embodiments to the first embodiment in this section, wherein the catalyst is steam-treated after at least one strengthening process. One embodiment of the present invention is one or all of the preceding embodiments to the first embodiment in this section, wherein the molar ratio of benzene to xylene is in the range of 1.00 to 1.08 and the molar ratio of paraxylene to xylene is in the range of 0.80 to 0.95. One embodiment of the present invention is one or all of the preceding embodiments to the first embodiment described in this section, wherein the selectivity for xylene exceeds 52% when the molar ratio of paraxylene to xylene is in the range of 0.80 to 0.90. Another embodiment of the present invention is one or all of the preceding embodiments to the first embodiment described in this section, wherein the selectivity for the light fraction is less than 3.5% when the molar ratio of paraxylene to xylene is in the range of 0.80 to 0.90. Another embodiment of the present invention is a disproportionation condition in which the temperature is in the range of 200°C to 600°C, the pressure is in the range of 1.4 to 4.5 MPa(g), and the aging period is 0.1 to 10 hours. -1 One or all of the preceding embodiments to the first embodiment in this section, including one or more of the gravimetric time-space velocity in the range of 0.251 to 101, or the hydrogen-to-hydrocarbon ratio in the range of 0.251 to 101. One embodiment of the present invention is one or all of the preceding embodiments to the first embodiment in this section, having a ring loss of less than 1.5%.

[0183] A second embodiment of the present invention is a process comprising contacting a feed containing toluene with a catalyst containing microporous crystalline zeolite under disproportionation conditions to produce an effluent containing paraxylene and benzene, wherein the molar ratio of benzene to xylene in the effluent is in the range of 1.00 to 1.20, and the molar ratio of paraxylene to xylene in the effluent is in the range of 0.60 to 1.0, and the zeolite, after calcination, ion exchange and post-calcination, and on an anhydrous basis, has a three-dimensional framework of at least AlO2 and SiO2 tetrahedral units, and M1 a N+ Al (l-x) E x Si y’ O z” The TUN and IMF zeotype coherent growth composite comprises an experimental composition of hydrogen in a form represented by the empirical formula, In the formula, M1 is at least one exchangeable cation selected from the group consisting of alkali metals, 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 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, varying from 0 to 1.0, y' is the molar ratio of Si to (Al+E), varying from greater than 9 to substantially pure silica, and z'' is the molar ratio of O to (Al+E), and the equation is: z”=(a·N+3+4·y') / 2 It has a value determined by, The zeolite is characterized by having an X-ray diffraction pattern having at least the d-layer spacing and intensity described in Table B1.

[0184] [Table 12] * A composite peak consisting of multiple overlapping reflections.

[0185] One embodiment of the present invention is one, any, or all of the preceding embodiments to the second embodiments described in this section, wherein the toluene conversion rate is 20% to 40%. One embodiment of the present invention is one, any, or all of the preceding embodiments to the second embodiments described in this section, wherein the zeolite is strengthened by at least one strengthening selected from a treatment for carbon deposition, a treatment for silica deposition, or both. One embodiment of the present invention is one, any, or all of the preceding embodiments to the second embodiments described in this section, wherein the catalyst is steam-treated after at least one strengthening treatment step. One embodiment of the present invention is one, any, or all of the preceding embodiments to the second embodiments described in this section, wherein the molar ratio of benzene to xylene is in the range of 1.00 to 1.08 and the molar ratio of paraxylene to xylene is in the range of 0.80 to 0.95. One embodiment of the present invention is one or all of the preceding embodiments to the second embodiment of this section, wherein the selectivity for xylene exceeds 52% when the molar ratio of paraxylene to xylene is in the range of 0.80 to 0.90. Another embodiment of the present invention is one or all of the preceding embodiments to the second embodiment of this section, wherein the selectivity for the light fraction is less than 3.5% when the molar ratio of paraxylene to xylene is in the range of 0.80 to 0.90. Another embodiment of the present invention is a disproportionation condition in which the temperature is in the range of 200°C to 600°C, the pressure is in the range of 1.4 to 4.5 MPa(g), and the aging period is 0.1 to 10 hours. -1 One or all of the preceding embodiments to the second embodiment in this section, including one or more of the gravitational time-space velocity in the range of 0.25 to 10, or the hydrogen-to-hydrocarbon ratio in the range of 0.25 to 10.

[0186] A third embodiment of the present invention is a process comprising contacting a feed containing toluene with a catalyst containing microporous crystalline zeolite under disproportionation conditions to produce an effluent containing paraxylene and benzene, where PXX is the molar ratio of paraxylene to xylene in the effluent, and BX is the molar ratio of benzene to xylene in the effluent, where if PXX is in the range of 0.60 to 1.0, BX is in the range of 1.00 to 0.375. * It is within the range of PXX+0.825.

[0187] Without further detail, it is expected that those skilled in the art will be able to utilize the invention to the fullest extent without departing from the spirit and scope of the invention, readily identify its essential characteristics, and make various changes and modifications to the invention to suit various uses and conditions. Accordingly, the prior preferred specific embodiments should be construed as merely illustrative and not to limit the remainder of this disclosure in any way, but are intended to cover various modifications and equivalent configurations that fall within the scope of the appended claims.

[0188] In the above, all temperatures are given in degrees Celsius, and all parts and percentages are based on weight unless otherwise specified.

Claims

1. A toluene disproportionation process comprising contacting a feed containing toluene with a catalyst containing microporous crystalline zeolite under disproportionation conditions to generate an effluent containing paraxylene and benzene, The molar ratio of benzene to xylene in the aforementioned effluent is in the range of 1.00 to 1.

14. The molar ratio of paraxylene to xylene in the aforementioned spilled logistics is in the range of 0.80 to 1.

0. The conversion rate of toluene is 20% to 40%. The microporous crystalline zeolite comprises a coherent growth composite of TUN and IMF zeotypes. The zeolite is strengthened by at least one strengthening process selected from a treatment for carbon deposition, a treatment for silica deposition, and both. process.

2. The aforementioned microporous crystalline zeolite, after calcination, ion exchange, and calcination, and on an anhydrous basis, contains at least AlO ２ and SiO ２ A three-dimensional skeleton based on tetrahedrons, and M1 ａ Ｎ＋ Al （ｌ－ｘ） E ｘ Si ｙ’ O ｚ” The TUN and IMF zeotype coherent growth composite comprises an experimental composition of hydrogen form represented by the empirical formula, In the formula, M1 is at least one exchangeable cation selected from the group consisting of alkali metals, 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 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, varying from 0 to 1.0, y' is the molar ratio of Si to (Al + E), varying from greater than 9 to substantially pure silica, and z'' is the molar ratio of O to (Al + E), and the equation is: z"=(a・N+3+4・y') / 2 It has a value determined by, The process according to claim 1, characterized in that the zeolite has an X-ray diffraction pattern having at least the d-layer spacing and intensity described in Table B1. Table 1

Images