CONVERSION TO XYLENES

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Application Serial No. 16/720,918 filed on December 19, 2019, the entire disclosure of which is hereby incorporated by reference.

BACKGROUND

Technical Field

[0002] Embodiments of the present specification generally relate to zeolite composite catalysts, and specifically relate to zeolite composite catalysts and methods of using the same to convert heavy reformate to xylenes.

Technical Background

[0003] Aromatic hydrocarbon compounds derived from petrochemical sources, benzene

(OόEE), toluene (methylbenzene, C7H8), and xylenes (dimethylbenzenes, CxHio isomers) may be used as starting materials for a wide range of consumer products. The xylenes include three isomers of dimethylbenzene, namely: 1,2-dimethylbenzene (orthoxylene or o-xylene), 1,3-dimethylbenzene (meta-xylene or /«-xylene), and 1,4-dimethylbenzene (para-xylene or/-xylene). The three isomers of xylene may be used in the synthesis of a number of useful products. For example, upon oxidation, the //-xylene isomer yields terephthalic acid, which may be used in the manufacture of polyester plastics and synthetic textile fibers (such as Dacron®), films (such as Mylar®), and resins (such as polyethylene terephthalate, used in making plastic bottles). The «/-xylene isomer may be used in the manufacture of plasticizers, azo dyes, and wood preservers, for example. The o-xylene isomer may be used as a feedstock for phthalic anhydride production, which in turn may be used to make polyesters, alkyl resins, and PVC plasticizers. Therefore, the demand for xylenes remains strong as markets for polyester fibers and polyethylene terephthalate continue to demonstrate high growth rates.

[0004] Typically, heavy reformate contains 90 weight (wt.) % to 95 wt. % C9 and 5 wt. % to 10 wt. % C10 aromatic compounds. Among the C9 components, trimethylbenzenes (TMBs) (50 wt. % to 60 wt. %) and methylethylbenzenes (MEBs) (30 wt. % to 40 wt. %) are the major constituents. One of the economically viable options is to convert the heavy aromatics in the heavy reformate into valuable products, such as xylenes. Demand is growing faster for xylene derivatives than for benzene derivatives. Therefore, a higher yield of xylenes at the expense of benzene yield is a favorable objective.

[0005] Heavy reformate can be subjected to transalkylation either alone or with toluene

(C7) for the production of xylenes (Cx) and benzene (C6). Because many different compounds may be present in the heavy reformate, multiple parallel and consecutive reactions may take place. Transalkylation reactions for converting aromatic hydrocarbon compounds to compounds having a different number of carbon atoms may include the disproportionation reaction of toluene, which is two molecules of toluene reacting to form one molecule of benzene and one molecule of xylene (by transfer of a methyl group from one molecule of toluene to the other, a transalkylation reaction). Transalkylation reactions, however, are not limited to the disproportionation of toluene. Other methods of increasing xylene yields operate through inducing transalkylation by adding aromatic hydrocarbon compounds having nine or more carbon atoms into the starting materials, resulting in such reactions as the addition of one mole of toluene to one mole of a C9 aromatic hydrocarbon to produce two moles of xylene. These parallel and consecutive reaction methodologies may also be accompanied by multiple chemical equilibria, including isomerization of xylenes, TMBs (trimethylbeneze), and MEBs (methylethylbenzene). The transalkylation and disproportionation reactions are equilibrium constrained, while the dealkylation reactions are kinetically controlled.

[0006] Regardless, these conventional means to produce xylenes by fractionation of reformate results in a xylene yield that is insufficient to meet the demand, and conversion of other hydrocarbons is necessary to increase the yield of xylenes. Furthermore, xylene isomer streams from catalytic reforming or other sources do not meet the demand as chemical intermediates. Para-xylene in particular is a major chemical intermediate with rapidly growing demand, but equates to only 20% to 25% of a typical Cx aromatics stream.

SUMMARY

[0007] Accordingly, ongoing needs exist for catalysts suitable for converting heavy reformates to produce xylenes. Embodiments of the present disclosure are related to heretical zeolite catalysts, their preparation methods and performance, particularly to the synthesis of such catalysts having an ordered/disordered mesostructure and hydrothermal stability. The zeolite composite catalysts may convert a mixture of heavy aromatic compounds (such as those present in heavy reformate), particularly C9 aromatic hydrocarbons, to benzene, toluene, and xylenes, and particularly to commercially valuable xylenes. The conversion reactions include dealkylation, transalkylation, disproportionation, and isomerization. The zeolite composite catalysts have a high ethyl-dealkylation activity as well as high methyl-transalkylation activity to improve the yield of xylenes.

[0008] According to one embodiment, a method of producing a hierarchical zeolite composite catalyst is provided. The method comprises dissolving, in an alkaline solution and in the presence of a surfactant, a catalyst precursor comprising mesoporous zeolite while heating, stirring, or both to yield a dissolved zeolite solution, where the mesoporous zeolite comprises large pore ZSM-12 having a S1O2/AI2O3 ratio of 20 to 300 and medium pore ZSM-5 having a SiCk/AhCb ratio of 5 to 500, where a ratio of ZSM-12 to ZSM-5 is 1:1 to 5:1 by weight. The method further comprises condensing the dissolved zeolite solution to yield a solid zeolite composite from the dissolved zeolite solution, where condensing the dissolved zeolite solution comprises adjusting a pH of the dissolved zeolite solution and aging the pH adjusted dissolved zeolite solution. The method yet further comprises heating the solid zeolite composite to remove the surfactant; impregnating the solid zeolite composite with one or more active metals selected from the group consisting of platinum, rhenium, rhodium, molybdenum, nickel, tungsten, chromium, ruthenium, gold, and combinations thereof to yield impregnated solid zeolite composite; and calcining the impregnated solid zeolite composite to produce the hierarchical zeolite composite catalyst. The produced hierarchical zeolite composite catalyst has a mesostructure comprising at least one disordered mesophase and at least one ordered mesophase.

[0009] According to another embodiment, a method of converting C9+ alkyl aromatic hydrocarbons to a product stream comprising benzene, toluene, and xylene is provided. The method comprises reducing a hierarchical zeolite composite catalyst comprising a mesostructure comprising at least one disordered mesophase and at least one ordered mesophase with hydrogen gas at 400 to 500 °C. The hierarchical zeolite composite catalyst comprises large pore ZSM-12 having a SiCk/AkCb ratio of 20 to 300, medium pore ZSM-5 having a SiCk/AkCb ratio of 5 to 500, and one or more impregnated active metals. The method further comprises contacting a feed comprising C9+ alkylaromatic hydrocarbons with the reduced composite zeolite catalyst and hydrogen in a transalkylation zone of a reactor to produce a transalkylation product, stripping Ci- C5 and unreacted feed from the transalkylation product, and collecting at least the xylenes product from the transalkylation product. [0010] According to yet another embodiment, a hierarchical zeolite composite catalyst is provided. The hierarchical zeolite composite catalyst comprises a solid zeolite composite mixed with an alumina binder. The solid zeolite composite comprises a large pore ZSM-12 and a medium pore ZSM-5 in a 1:1 to 5:1 weight ratio. Further, the hierarchical zeolite composite catalyst has a mesostructure comprising at least one disordered mesophase and at least one ordered mesophase.

[0011] Additional features and advantages of the described embodiments will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the described embodiments, including the detailed description which follows, the claims, as well as the appended drawings.

BRIEF DESCRIPTION OF THE DRAWINGS [0012] FIG. 1 is a flow chart depicting the synthesis of a zeolite composite catalyst in accordance with one or more embodiments of the present disclosure.

[0013] FIG. 2 is a schematic illustration depicting the conversion of heavy reformate into xylenes in accordance with one or more embodiments of the present disclosure.

[0014] FIG. 3 is an X-Ray Diffraction (XRD) pattern of a zeolite catalyst, which was produced through the separate treatment of ZSM-12 and ZSM-5 with 0.2 N NaOH solution followed by still crystallization in the presence of CTAB.

[0015] FIG. 4 is an XRD pattern of a zeolite catalyst, which was produced through the synthesis of ZSM-12 according to a conventional procedure.

[0016] FIG. 5 is an XRD pattern of a zeolite catalyst, which was produced through the dissolution of ZSM-12 using 0.2M NaOH solution in the presence of CTAB.

[0017] FIG. 6 is an XRD pattern of a zeolite catalyst, which was produced by physically mixing untreated samples of ZSM-12 and ZSM-5.

DETAILED DESCRIPTION

[0018] Reference will now be made in detail to embodiments of a hierarchical zeolite composite catalyst comprising a mesostructure comprising at least one disordered mesophase and at least one ordered mesophase. In one embodiment, the ordered mesophase is a hexagonal mesophase, and the disordered mesophase comprises a hexagonal mesophase. Without being bound by theory, hierarchical zeolite composite catalyst with ordered and disordered mesophase formation provides improved transalkylation catalyst activity, which provides improved yield of xylenes. As defined, “ordered mesophase” means a crystalline zeolite uniform arrangement of mesopores, where “mesopores” have an average pore diameter between 2 and 50 nanometers. As defined, “disordered mesophase” means a non-uniform arrangement of pores, where mesopores have an average pore diameter between 2 and 50 nanometers. As defined, “ordered/disordered phase” means the surface has a combination of at least one ordered mesophase and at least one disordered mesophase. Induction of an ordered/disordered phase into the zeolite structure increases the probability of larger molecules in a feed having access to the active sites inside the hierarchical zeolite composite catalyst. Access to these active sites allows the feed to undergo chemical transformation and decreases the requisite residence time inside the framework of the hierarchical zeolite composite catalyst helping to avoid undesirable side reactions.

[0019] Moreover, the hierarchical zeolite composite catalyst may also comprise at least one additional mesoporous zeolite, for example, selected from the group of ZSM-11, ZSM-22, ZSM-23, MFI topology zeolite, NES topology zeolite, EU-1, MAPO-36, SAPO-5, SAPO-11, SAPO-34, and SAPO-41. The amount of this at least one additional mesoporous zeolite may range from 10 to 90 weight (wt.) % of the hierarchical zeolite composite catalyst in the final dried and calcined form. In further embodiments, the amount of this at least one additional mesoporous zeolite may range from 15 to 80 wt. %, 10 to 30 wt. %, 40 to 90 wt. %, or 10 to 20 wt. % of the hierarchical zeolite composite catalyst in the final dried and calcined form.

[0020] Moreover, the hierarchical zeolite composite catalyst may be impregnated with active metals for catalysis, for example, active metals selected from the group consisting of platinum, rhenium, rhodium, molybdenum, nickel, tungsten, chromium, ruthenium, gold, and combinations thereof. In one embodiment, the active metal is molybdenum. The active metal component exists within the final hierarchical zeolite composite catalyst as an elemental metal. The metal component may exist within the final hierarchical zeolite composite catalyst as a compound, such as a metal oxide, a metal sulfide, or a metal halide, in chemical combination with one or more of the other ingredients of the hierarchical zeolite composite catalyst, or as the active elemental metal. The metal oxide may be reduced under hydrogen pressure and an elevated temperature, for example 450 °C, to form the active elemental metal. The active metal component may be present in the final hierarchical zeolite composite catalyst in any amount that is catalytically effective, generally from 0.01 to 6.0 wt. %, or from 2 to 5 wt. % of the zeolite catalyst. [0021] As described in the synthesis discussion as follows, the hierarchical zeolite composite catalyst may comprise a large pore ZSM-12 and a medium pore ZSM-5 in a 3 : 1 weight ratio. In further embodiments, the hierarchical zeolite composite catalyst may comprise a large pore ZSM-12 and a medium pore ZSM-5 in a 2:1 weight ratio, a 4:1 weight ratio, a 5:1 weight ratio, or a 1:1 weight ratio. In further embodiments the large pore ZSM-12 or the medium pore ZSM-5 may be provided exclusively. For conciseness of the disclosure, further discussion includes both the large pore ZSM-12 and the medium pore ZSM-5 in combination with the understanding that the large pore ZSM-12 or the medium pore ZSM-5 could be provided individually.

[0022] ZSM-12 belongs to the MTW Topology with a pore size opening of 5.7-6.1 A.

ZSM-12 may be used as a transalkylation catalyst for converting C9+ molecules to Cx molecules. Without being bound by theory, a catalyst including ZSM-12 produces more benzene as compared to other transalkylation catalysts. ZSM-12 may be more efficient in dealkylation of ethylmethylbenzenes (EMBs) to produce toluene, which is utilized for transalkylation of trimethylbenezenes (TMBs) to produce xylenes.

[0023] Without being bound by theory, ZSM-5 helps in maximizing the dealkylation reactions to produce toluene in-situ and reduce the formation of heavy molecules, which are undesired precursors for the catalyst.

[0024] In various embodiments, the large pore ZSM-12 may have a SiCk/AkCb molar ratio of at least 20, of 20 to 300, of 40 to 200, of 60 to 100, or of 70 to 90. In various embodiments, the medium pore ZSM-5 may have a SiCk/AhCh ratio molar ratio of at least 5, of 5 to 500, of 10 to 100, of 20 to 75, of 30 to 50, of 35 to 45, or of 38 to 42.

[0025] In one embodiment, the molar ratio of silica to alumina in the hierarchical zeolite composite catalyst is from 20 to 500. In another embodiment, the molar ratio of silica to alumina in the hierarchical zeolite composite catalyst is at least 30. Moreover, the molar ratio of silica to alumina may be from 30 to 100, or from 40 to 80. The acidity is defined by the ratio of silica to alumina groups in the particular composite catalyst. In various embodiments, the hierarchical zeolite composite catalyst has an intermediate acidity. For purposes of this disclosure, a silica to alumina molar ratio less than 20 is considered high acidity, a silica to alumina molar ratio in the range of 20 to 100 is considered intermediate acidity, and a silica to alumina molar ratio of more than 100 is considered a low acidity. Without being bound by theory, lower alumina content in the zeolite framework negatively effects the Bronsted acidity of the zeolite. The Bronsted acidity of the hierarchical zeolite composite catalyst is a key parameter driving the catalytic properties for the dealkylation and transalkylation chemistry of the feed. Hence, any reduction of the Bronsted acidity directly effects the overall performance of the hierarchical zeolite composite catalyst. Accordingly, a zeolite composite catalyst with a silica to alumina molar ratio less than 20 (e.g., having relatively low alumina content) may not perform as well as a zeolite composite catalyst with a silica to alumina molar ratio of greater than 20.

[0026] From a property standpoint, the hierarchical zeolite composite catalyst may have a surface area defined by a Brunauer-Emmett-Teller (BET) analysis (also known as the Specific Surface Area) of at least 300 meters ² per gram (m ² /g), or a BET surface area of at least 500 m ² /g. The BET surface area represents the total surface area of a material per unit of mass. Further, the hierarchical zeolite composite catalyst may have an external surface area of at least 300 m ² /g, of at least 350 m ² /g, of at least 400 m ² /g, or 400 to 600 m ² /g.

[0027] In one or more embodiments, the hierarchical zeolite composite catalyst may have a total pore volume of 0.20 to 3.0 cubic centimeters per gram (cm ³ /g), or 0.30 to 1.0 cm ³ /g. Moreover, the hierarchical zeolite composite catalyst may have a total pore volume of at least 0.30 cm ³ /g, or of at least 0.40 cm ³ /g, or at least 0.50 cm ³ /g. In another embodiment, the hierarchical zeolite composite catalyst may have an average pore diameter of at least 30 angstroms (3 nanometers (nm)) or 3 nm to 3.5 nm.

[0028] Referring to FIG. 1, the method of producing the hierarchical zeolite composite catalyst may comprise the steps of providing a catalyst precursor 10 comprising a mesoporous zeolite and dissolving in an alkaline solution while heating, stirring, or both to yield a dissolved zeolite solution 20. The mesoporous zeolite may comprise a large pore ZSM-12 and a medium pore ZSM-5. In one embodiment, the catalyst precursor comprises the large pore ZSM-12 and the medium pore ZSM-5 as well as at least one additional mesoporous zeolite selected from the group consisting of ZSM-22, ZSM-11, and combinations thereof. Large pore zeolites are defined as zeolites with 12 membered rings forming the zeolite framework. Medium pore zeolites are defined as zeolites with 10 membered rings forming the zeolite framework. The combination of medium pore zeolite and large pore zeolite provide distinct reaction steps. Specifically, medium pore zeolite, such as ZSM-5, facilitates enhanced dealkylation of ethyltoluenes to produce toluene and large pore zeolites, such as ZSM-12, facilitates processing of toluene or trimethylbenezenes (TMBs) into xylenes. [0029] The dissolving step, also called desilication, may be conducted in the presence of a surfactant 30, where the surfactant is often called a templating agent for the zeolite catalyst. While the FIG. 1 embodiment shows templating surfactant, it is contemplated in other embodiments that surfactant is absent. For example and not by way of limitation, the surfactant is a cationic surfactant. The cationic surfactant may include a quaternary ammonium compound. For example and not by way of limitation, the quaternary ammonium cationic surfactant may be cetyltrimethyl ammonium bromide (CTAB). Various amounts of surfactant are contemplated for inclusion in the catalyst precursor. For example, the catalyst precursor may include 1 wt. % to 10 wt. % surfactant, for example CTAB, or 1 wt.% to 8 wt.% surfactant, or 2 wt. % to 8 wt. % surfactant, or 3 wt. % to 6 wt. % surfactant, or 4 wt. % to 5 wt. % surfactant.

[0030] During conventional desilication, the mesoporosity in the zeolite is generated by desilication using standard conditions. For example, desilication may be performed using 0.4 Molarity (M) NaOH with 30 minutes (min) of stirring at 100°C. By this process, one third of catalyst is lost due to desilication; however, the present method utilizes that desilicated source to generate mesoporosity using the surfactant template. During a desilication process, loss in the catalyst yield generally occurs due to zeolite dissolution such that approximately 15% of the expected catalyst yield is lost. However, the present methods include recrystallization of the dissolved silica species such that the wasted silica through desilication is effectively utilized and the final yield of hierarchical zeolite composite catalyst is maintained at or near 98%.

[0031] Further as shown in FIG. 1, the dissolution may occur slowly in the presence of a surfactant template by gradual heating for 24 hours (h). The filtrate is collected and mesopores are generated using a template mediated technique. In a template mediated technique, a partially dissolved zeolite is thermally recrystallized around a selected template which dictates the pore size of the regrown structure. In this way, the unutilized desilicated source is utilized to produce the mesophases. Various heating processes or elements are contemplated. For example, the heating may be hydrothermal heating. In one or more embodiments, the hydrothermal heating may occur at a temperature of 50 to 150°C, or a temperature of 90 to 110°C. Furthermore, the duration of hydrothermal heating may range from 30 minutes to 48 hours.

[0032] Various alkaline solutions are contemplated for the desilication. In one embodiment, the alkaline solution may comprise NaOH. In specific embodiments, the alkaline solution may comprise 0.01 to 0.5M NaOH, 0. 1 to 0.6M NaOH, 0.2 to 0.5M NaOH, 0.35 to 0.45M NaOH, or 0.4M NaOH. Without being bound by theory, it is surprisingly discovered that controlling the molarity of the NaOH is a parameter that impacts the ordered/disordered phase mesostructure of the hierarchical zeolite composite catalyst. It is believed the NaOH is responsible for breaking the chemical structure of the zeolites, thus a larger concentration of the NaOH leads to increased dissolution of the zeolite structure which is recrystallized in the presence of CTAB to form the mesostrucures of the hierarchical zeolite composite catalyst.

[0033] Referring again to FIG. 1, the method may comprise the step 40 of adjusting the pH of the dissolved zeolite solution. The adjustment of the pH is performed by an acidic solution. Various acids are contemplated. In one embodiment, the acidic solution comprises sulfuric acid. In one specific embodiment, the acid is 2 Normality (N) (equivalents/liter) dilute sulfuric acid. In specific embodiments, the pH is adjusted to 8 to 10, 8.5 to 9.5, or substantially 9.0.

[0034] Next, various additional steps 50 may be utilized, for example, hydrothermal aging, filtering, washing, drying, ion-exchanging, and calcining the pH adjusted dissolved zeolite solution. The hydrothermal aging may involve maintaining the pH adjusted dissolved zeolite solution at a temperature of 75 to 125°C for a duration of 12 to 48 hours. For example, the pH adjusted dissolved zeolite solution may be aged at 100°C for a duration of 24 hours. During hydrothermal aging, the soluble aluminosilicate species are hydrothermally condensed to form mesophases. The condensing of the dissolved zeolite solution may be performed under still conditions or agitated conditions. Specifically, under still conditions, the dissolved zeolite solution is not stirred or mixed where conversely under agitated conditions the dissolved zeolite solution is mixed or stirred. The solid products formed from condensing the dissolved zeolite solution may be filtered to form a solid zeolite composite, washed thoroughly using distilled water, and then dried. For example, the solid zeolite composite may be dried overnight at a temperature of 100°C. The ion exchange may occur in the presence of a nitrate solution, for example and not by way of limitation, a solution comprising NH4NO3. In one or more embodiments, the solid zeolite composite is ion exchanged three times with 0.05 M NH4NO3 solution at 80°C for 5 hours. The solid zeolite composite may be heated to remove the entrained surfactant. For example, the solid zeolite composite may be heated to 500 to 600°C for 5 to 8 hours, 570°C for 7 hours, or 550°C for 6 hours to vaporize and remove the surfactant template. By stage 60 the solid composite zeolite with ordered/disordered mesophase is formed.

[0035] Referring to FIG. 1, the process may also include the step 70 of extruding the solid zeolite composite in the presence of binder. A refractory binder or matrix is optionally utilized to facilitate fabrication of the catalyst, to provide strength, and to reduce fabrication costs. Suitable binders include inorganic oxides, such as one or more of alumina, magnesia, zirconia, chromia, titania, boric, phosphate, zinc oxide, and silica. In one embodiment, the binder is an alumina based binder. One commercial embodiment of the alumina binder is Cataloid AP-3, obtained from Catalysts & Chemicals Industries Co., Ltd (CCIC), Japan. The zeolites may be mixed in dry powdered form with the alumina binder in aqueous form to yield a homogeneous mixture, thus ensuring homogeneous composition of the extrudates formed. In one or more embodiments, the ratio by weight of solid zeolite composite to binder is 4 to 1 (80 wt. % solid zeolite composite and 20 wt. % binder), 3 to 1 (75 wt. % solid zeolite composite and 24 wt. % binder), or 2 to 1 (67 wt. % solid zeolite composite and 33 wt. % binder). The extrusion with binder step 70 may be conducted at a temperature of 100 to 150°C for a duration of 30 minutes to 2 hours.

[0036] Next, the process may comprise the step 80 of impregnating solid zeolite composite with one or more active metals prior to a calcining step. The one or more active metals are selected from the group consisting of platinum (Pt), rhenium (Re), rhodium (Rh), molybdenum (Mo), nickel (Ni), tungsten (W), chromium (Cr), ruthenium (Ru), gold (Au), and combinations thereof. In one or more embodiments, the active metals comprise 0.01 to 6.0 wt. % of the impregnated solid zeolite composite. In one embodiment, the active metal may comprise molybdenum at 2 to 6% by weight of the impregnated solid zeolite composite, including 4% by weight molybdenum. In one or more embodiments, the solid zeolite composite is impregnated with 4 wt. % of molybdenum in the form of ammonium molybdate tetrahydrate through wet impregnation. Optionally, the impregnated solid zeolite composite may be dried after wet impregnation. In one embodiment, the drying occurs for at least 2 hours at 100°C.

[0037] Referring again to FIG. 1, another calcining step 90 may be utilized to produce the hierarchical zeolite composite catalyst, which is effective as a transalkylation catalyst 100. The calcining step may occur for 4 to 8 hours at a temperature of 400 to 500°C, for 4 hours at a temperature of 400°C, for 5 hours at a temperature of 450°C.

[0038] Further as stated supra , the present hierarchical zeolite composite catalyst is a transalkylation catalyst suitable for converting C9+ alkyl aromatic hydrocarbons to a product stream comprising benzene, toluene, and xylene, particularly to commercially valuable xylenes. The feed stream to the conversion process generally comprises alkylaromatic hydrocarbons in the carbon number range C9 to C11+ that may include, for example, such hydrocarbons as propylbenzenes, ethylmethylbenzenes, tetramethylbenzenes, ethyldimethylbenzenes, diethylbenzenes, methylpropylbenzenes, and mixtures thereof. The heavy aromatics feed stream, characterized mainly by C9+ aromatics, permits effective transalkylation of light aromatics such as benzene and toluene with the heavier C9+ aromatics to yield additional Cx aromatics, such as xylenes. The heavy aromatics stream preferably comprises at least 90 wt. % C9 aromatics, and may be derived from the same or different known refinery and petrochemical processes, and may be recycled from the separation of the product from transalkylation.

[0039] Referring to the embodiment of FIG. 2, the method of using the hierarchical zeolite composite catalyst as a transalkylation catalyst may optionally include heating a feed stream 110 comprising C9+ alkylaromatic hydrocarbons from a feed source 105 with a heater unit 111. As shown, the heater unit 111 may be a heat exchanger which receives a heated stream 108, for example, a heated water stream to heat the feed stream 110 prior to delivery to a reactor 113. The heated stream 108 may also be the effluent of the reaction zone. Other methods of heating the feed are contemplated.

[0040] The reactor system may include a reactor 113 with hierarchical zeolite composite catalyst used in transalkylation catalyst zone 115 as shown in FIG. 2, or may include multiple reactors 113 or stages. The reactor 113 is depicted as a downflow 114 reactor but that is one of many possibilities. Similarly, in the embodiment of FIG. 2, the reactor 113 has a fixed cylindrical bed of catalyst; however, other reaction configurations utilizing moving beds of catalyst, radial- flow reactors, or fluidized beds may be employed. Prior to the feed being delivered, the hierarchical zeolite composite catalyst in transalkylation catalyst zone 115 may be reduced, for example, reduced with hydrogen gas 112. In one embodiment, the hierarchical zeolite composite catalyst is reduced by hydrogen gas 112 at a temperature of 350 to 450°C, or 400 °C.

[0041] Referring again to FIG. 2, the feed stream 110 contacts the reduced hierarchical composite zeolite catalyst and hydrogen 112 in the transalkylation catalyst zone 115 of the reactor 113. Specifically, the feed stream 110 is transalkylated in the vapor phase and in the presence of hydrogen 112. The hydrogen 112 may be delivered with the feed stream 110 in an amount from 0.1 to 10 moles of hydrogen per mole of alkylaromatics. This ratio of hydrogen to alkylaromatics is also referred to as the hydrogen-to-hydrocarbon ratio. The transalkylation results in the production of a transalkylation effluent stream 116 comprising product hydrocarbons, specifically, hydrocarbons having mixed xylene content, as well as unconverted feed, toluene, and benzene. Various conditions are contemplated for the reactor 113. Specifically, the transalkylation catalyst zone 115 may include a temperature between 50°C and 600°C, 200°C and 540°C, or 340°C and 450°C, for example, and moderately elevated pressures of 0.5 megapascal (MPa) to 15.0 MPa, 1.0 MPa to 5.0 MPa, or 1.5 MPa to 3.5 MPa, for example. The liquid hourly space velocity (LHSV) is in the range of 1.0 hr ^-1 to 3.0 hr ^-1 , or, 1.0 hr ^-1 to 5.0 hr ^-1 or 1.0 hr ^-1 to 15.0 hr ^-1 , for example.

[0042] The transalkylation effluent stream 116 may be cooled using a cooler 117. The cooler 117 may be a heat exchanger, condenser, or any other suitable cooling device. As shown, the cooler 117 is a heat exchanger which includes a cooling stream 118. Next, the transalkylation effluent stream 116 may be fed to a stripper column 120, where C1-C5 and lighter hydrocarbons 122 are separated from the transalkylation effluent stream 116.

[0043] Referring to FIG. 2, the product 124 of the stripper column 120, which may be discharged from the bottom of the stripper column 120, may include a light recovery stream 126 comprising benzene and toluene, a mixed Cx aromatics product 128, and a heavy recycle stream 130. These all may subsequently be separated in one or more reaction vessels 125, 127, 129. The mixed Cx aromatics product 128 can be sent for recovery of -xylene 132 and other valuable isomers 134. The light recovery stream 126 may undergo benzene and toluene recovery 136 with the remainder portion recycled as a light recycle stream 138 to the transalkylation zone or the feed source 105. The heavy recycle stream 130 may contain substantially all of the C9 and heavier aromatics and may be partially or totally recycled to the transalkylation reaction zone, or delivered to the feed source 105 for recycle, or removed from the process for disposal or other processing.

EXAMPLES

[0044] The described embodiments will be further clarified by the following examples and comparative examples.

[0045] For demonstration purposes, the preparation of composite catalysts is provided as follows. The synthesis of mesoporous hierarchical Catalyst A, which includes separate treatment of ZSM-12 and ZSM-5 with NaOH followed by still crystallization in CTAB and physical mixing of the separately treated ZSM-12 and ZSM-5 in a 3:1 ratio, respectively, is presented in Example 1

[0046] The performance of Catalyst A was compared with comparative examples representing an untreated constituent of catalyst A (untreated ZSM-12 synthesized according to a conventional procedure), an individually treated constituent of Catalyst A (treated ZSM-12 synthesized according to a conventional procedure), and a physical mixture of untreated constituents of Catalyst A (untreated ZSM-12 synthesized according to a conventional procedure and untreated commercial sample of ZSM-5 physically mixed). The performance of Catalyst A was compared with one of its constituents (untreated ZSM-12 synthesized according to a conventional procedure) in Comparative Example 2 (Catalyst B). The performance of Catalyst A was compared with one of its constituents (treated ZSM-12 synthesized according to a conventional procedure) in Comparative Example 3 (Catalyst C). The performance of Catalyst A was compared with a physical mix of untreated constituents (untreated ZSM-12 synthesized according to a conventional procedure and untreated commercial sample of ZSM-5) in Comparative Example 4 (Catalyst D).

[0047] The catalysts described in these examples are exemplary embodiments only, and are not intended to limit the general description of the composite catalyst covering this invention. In each example, the catalyst composition of Catalysts A and D comprise 48.24 wt. % ZSM-12, 16.08 wt. % ZSM-5, 31.68% binder, and 4 wt. % active metal. The catalyst composition of Catalysts B and C comprise 64.32 wt. % ZSM-12, 31.68 wt.% binder, and 4 wt. % active metal. The binder is an alumina binder (Cataloid, AP-3, obtained from Catalysts & Chemicals Industries Co., Ltd (CCIC), Japan) and the active metal is molybdenum in each example.

Table 1: Catalyst compositions [0048] Example 1: Separate treatment of ZSM-12 and ZSM-5 with 0.2 N NaOH Solution followed by still crystallization in the presence of CTAB.

[0049] In separate glass vessels, three grams of ZSM-12 (S1O2/AI2O3 molar ratio = 80, synthesized according to the procedure of Gopal et al., Synthesis of Al-rich ZSM-12 using TEAOH as template, Microporous and Mesoporous Materials, Volume 49, Issues 1-3, 15 November 2001, Pages 149-156, which describes the hydrothermal synthesis of ZSM-12 with tetraethyl ammonium hydroxide (TEAOH), hereinafter “Gopal et al ”) and one gram ZSM-5 (S1O2/AI2O3 molar ratio = 40, HSZ-840 NHA, Tosoh Chemicals, Japan), were respectively disintegrated using 0.2 M NaOH solution by gradual heating with stirring at 100°C for 24 hours (h). The heating was carried out in the presence of CTAB (4.45 wt. %). Each mixture was cooled down and then the pH was adjusted to 9.0 through the addition of dilute sulfuric acid (2 N). Each mixture was stirred for 24 h and then aged at 100°C for 24 h to form a solid zeolite composite of ZSM-12 and ZSM-5, respectively. The solid zeolite composites were individually filtered, washed thoroughly using distilled water, dried at 80°C overnight, then calcined at 570°C for 6 h to remove the surfactant (CTAB). Each solid zeolite composite (ZSM-12 and ZSM-5) thus obtained was ion-exchanged three times with 0.05 M NH4NO3 solution at 80°C for 5 h. The resulting me so- structured ZSM-12 and meso-structured ZSM-5 were physically mixed in a 3:1 weight ratio and made into extrudates by mixing 67 wt. % solid zeolite composite mixture (ZSM- 12 + ZSM-5 at 3:1 weight ratio) and 33 wt. % alumina binder (Cataloid AP-3) and then loaded with 4 wt.% of molybdenum in the form of ammonium molybdate tetrahydrate through wet impregnation. Then, the impregnated solid zeolite was calcined at 450°C for 5 h. The resulting zeolite ZSM-12/ZSM-5 composite is designated as Example 1 (Catalyst A). Table 2 includes selected properties of Example 1 (Catalyst A).

Table 2: Example 1 (Catalyst A) Data [0050] The separate dissolution of ZSM-12 and ZSM-5 using 0. 2M solution and still crystallization in the presence of CTAB leads to me so- structure formation with ordered and disordered mesophase as shown in the XRD pattern in FIG. 3.

[0051] Comparative Example 2: Synthesis of ZSM-12 according to a conventional procedure

[0052] ZSM-12 (S1O2/AI2O3 molar ratio = 80) was synthesized according to the procedure of Gopal et al. The resulting zeolite me so- structured ZSM-12 was made into extrudates by mixing 67 wt. % ZSM-12 and 33 wt. % alumina binder (Cataloid AP-3) and then loaded with 4 wt.% of molybdenum in the form of ammonium molybdate tetrahydrate through wet impregnation. Then, the impregnated solid zeolite was calcined at 450°C for 5 h. The resulting zeolite ZSM-12 composite is designated as Comparative Example 2 (Catalyst B). Table 3 includes selected properties of Comparative Example 2 (Catalyst B).

Table 3: Comparative Example 2 (Catalyst B) Data

[0053] The XRD pattern for Comparative Example 2 (Catalyst B) is provided in FIG. 4.

[0054] Comparative Example 3: Treatment of ZSM-12 with 0.2 M NaOH solution followed by still crystallization in the presence of CTAB

[0055] ZSM-12 (S1O2/AI2O3 molar ratio = 80, synthesized according to the procedure of

Gopal et al.) was disintegrated using 0.2 M NaOH solution by gradual heating and stirring at 100°C for 24 h. The heating was carried out in the presence of CTAB (4.45 wt. %). The mixture was cooled down and then the pH was adjusted to 9.0 through the addition of dilute sulfuric acid (2 N). The mixture was then stirred for 24 h and then aged at 100°C for 24 to form a solid zeolite composite. The solid zeolite composite was filtered, washed thoroughly using distilled water, dried at 80°C overnight, then calcined at 570°C for 7 h to remove the surfactant (CTAB). The resulting zeolite-mesostructured ZSM-12 was made into extrudates by mixing 67 wt. % ZSM-12 and 33 wt. % alumina binder (Cataloid AP-3) and then loaded with 4 wt.% of molybdenum in the form of ammonium molybdate tetrahydrate through wet impregnation. Then, the impregnated solid zeolite was calcined at 450°C for 5 h. The resulting zeolite ZSM-12 composite is designated as Comparative Example 3 (Catalyst C). Table 4 includes selected properties of Comparative Example 3 (Catalyst C).

Table 4: Comparative Example 3 (Catalyst C) Data

[0056] The XRD pattern for Comparative Example 3 (Catalyst C) is provided in FIG. 5.

[0057] Comparative Example 4: Untreated samples of ZSM-12 and ZSM-5 physically mixed

[0058] Untreated forms of ZSM-12 (SiCh/AhCb molar ratio = 80, synthesized according to the procedure of Gopal et al.) and ZSM-5 (SiCh/AhCb molar ratio = 40, HSZ-840 NHA, Tosoh Chemicals, Japan) in their ammoniated forms were physically mixed in a 3:1 weight ratio and made into extrudates by mixing 67 wt. % zeolite mixture (untreated ZSM-12 + untreated ZSM-5 in a 3:1 weight ratio) and 33 wt. % alumina binder (Cataloid AP-3) and then loaded with 4 wt.% of molybdenum in the form of ammonium molybdate tetrahydrate through wet impregnation. Then, the impregnated solid zeolite was calcined at 450°C for 5 h. The resulting zeolite ZSM- 12/ZSM-5 composite is designated as Comparative Example 4 (Catalyst D). Table 5 includes selected properties of Comparative Example 4 (Catalyst D).

Table 5: Comparative Example 4 (Catalyst D) Data [0059] The XRD pattern for Comparative Example 4 (Catalyst D) is provided in FIG. 6.

Table 6: Heavy reformate composition

[0060] Activity studies for Catalysts A, B, C, and D, represented in Table 1, were performed on a bench top reactor using industrial reformate feedstock (formulation provided infra in Table 6). The procedure used for determination of catalytic activity for each catalyst of Table 1 individually consisted of loading a vertical reactor with 2.0 grams of the catalyst in the isothermal zone of the reactor together with an inert silicon carbide in the lower and upper parts of the reactor. The total volume of the reactor was 100 ml. The catalyst was activated and reduced under 50 ml/min flow of pure hydrogen gas at 450°C and was kept at this temperature for 2 hours. Then, the pressure of the reactor was increased to 20 bar and the flow of the industrial reformate feedstock was started at 4.2 grams/h. The reaction was allowed to run at least one hour at 400°C before collecting the product sample. The reactor was allowed to further run for 300 hours without exhibiting loss of activity before termination.

[0061] The liquid product obtained from the reactor was analyzed using a gas chromatograph. The reaction product was directly injected into an on-line gas chromatograph equipped with one thermal conductivity detector (TCD) and two flame ionization detector. The gas chromatography uses a plurality of columns to conduct the analysis of the liquid product obtained from the reactor. A Hayesep N pre-column with a 0.5 meter (m) length, a Hayesep Q column with a 1.5 m length, a CP-Wax capillary column with a 5.0 m length and 0.32 mm inner diameter, and a 13C molecular sieve with a 1.2 m length were utilized. Each column was manufactured by Agilent Technologies (Santa Clara, California). The experimental results provided in Table 7 shows the comparison of the gas chromatograph liquid product analysis of Catalysts A, B, C, and D.

Table 7: Catalyst Experimental results

[0062] Table 7 allows for the determination of effect of the meso-structured ZSM-12 and

ZSM-5. Catalyst B (Comparative Example 2) represents ZSM-12 synthesized according a conventional procedure as described hereinabove. Catalyst B (Comparative Example 2) resulted in an average methylethylbenzenes (MEBs) conversion of 84.2 wt. % and an average trimethylbenzenes (TMBs) conversion of 40.9 wt. %. As a result of these conversions, Catalyst B (Comparative Example 2) resulted in a 27.9 wt. % xylenes yield, a 18.9 wt. % Cio+ yield, and a 0.6 wt.% ethylbenzene yield. While not being bound by theory heavy molecules (Cio+) are mostly aromatic in nature and potentially act as coke precursors, deactivate the catalyst performance, and significantly reduce the lifetime of the catalyst. Moreover, in industrial product plants, ethylbenzene, may act as an impurity in the fractionated xylenes because of the close boiling points of these components, which negatively contributes to the product quality and pricing of the xylenes.

[0063] In order to reduce the unwanted components like Cio+ molecules and ethylbenzene, the pore structure of ZSM-12 was modified through introduction of mesoporosity as described hereinabove to produce Catalyst C (Comparative Example 3). While not being bound by theory, the mesopores facilitate higher throughput and increase the active site accessibility. Catalyst C (Comparative Example 3) exhibited marginal improvement in methylethylbenzenes (MEBs) and trimethylbenzenes (TMBs) conversions as compared to Catalyst B (Comparative Example 2) with average conversions of 87.3 wt. % and 42 wt. %, respectively. The conversions of Catalyst C (Comparative Example 3) resulted in a xylene yield of 30.2 wt. %, which is a 2.3 wt. % increase as compared to Catalyst B (Comparative Example 2). The yields of Cio+ heavy molecules and ethylbenzene resulting from Catalyst C (Comparative Example 3) were marginally decreased to 17.5 wt. % and 0.5 wt .%, respectively, as compared to Catalyst B (Comparative Example 2).

[0064] Catalyst D (Comparative Example 4) represents a physical mix of untreated samples of ZSM-12 and ZSM-5 in a 3:1 ratio weight ratio as described hereinabove. Catalyst D (Comparative Example 4) exhibited an improved methylethylbenzenes conversion of 97.6 wt. % as compared to Catalyst C (Comparative Example 3). However, Catalyst D (Comparative Example 4) did not have an improved trimethylbenezene conversion as compared to Catalyst C (Comparative Example 3). Catalyst D (Comparative Example 4) resulted in a xylene yield of 32 wt. %, which is a 1.8 wt. % increase as compared to Catalyst C (Comparative Example 3). The yields of Cio+ heavy molecules and ethylbenzene resulting from CatalystD (Comparative Example 4) were 14.6 wt. % and 0.1 wt. %, respectively, which are further reductions as compared to Catalyst C (Comparative Example 3).

[0065] Catalyst A (Example 1) represents a 3:1 physical mix of separately treated ZSM-

12 and ZSM-5 with 0.2 N NaOH and recrystallized using CTAB as described hereinabove. Catalyst A (Example 1) had the largest methylethylbenzenes and trimethylbenzenes conversions of 99.5 wt. % and 47.4 wt.%, respectively, as compared to Catalyst B (Comparative Example 2), Catalyst C (Comparative Example 3), and Catalyst D (Comparative Example 4). The xylenes yield of Catalyst D was marginally improved to 32.8 wt. % as compared to Catalyst B (Comparative Example 2), Catalyst C (Comparative Example 3), and Catalyst D (Comparative Example 4). However, the Cio+ heavy molecules yield surprisingly decreased to 10.3 wt. % and the ethylbenzene yield decreased to almost negligible at 0.04 wt. %.

[0066] It should now be understood the various aspects of the hierarchical composite zeolite catalysts, the methods of producing a hierarchical zeolite composite, and the methods of converting C9+ alkyl aromatic hydrocarbons to a product stream comprising benzene, toluene, and xylene using the same are described and such aspects may be utilized in conjunction with various other aspects.

[0067] In a first aspect, the disclosure provides a method of producing a hierarchical zeolite composite catalyst. The method comprises dissolving, in an alkaline solution and in the presence of a surfactant, a catalyst precursor comprising mesoporous zeolite while heating, stirring, or both to yield a dissolved zeolite solution, where the mesoporous zeolite comprises large pore ZSM-12 having a S1O2/AI2O3 ratio of 20 to 300 and medium pore ZSM-5 having a SiCh/AhCb ratio of 5 to 500, where a ratio of ZSM-12 to ZSM-5 is 1:1 to 5:1 by weight. The method further comprises condensing the dissolved zeolite solution to yield a solid zeolite composite from the dissolved zeolite solution, where condensing the dissolved zeolite solution comprises adjusting a pH of the dissolved zeolite solution and aging the pH adjusted dissolved zeolite solution. The method yet further comprises heating the solid zeolite composite to remove the surfactant; impregnating the solid zeolite composite with one or more active metals selected from the group consisting of platinum, rhenium, rhodium, molybdenum, nickel, tungsten, chromium, ruthenium, gold, and combinations thereof to yield impregnated solid zeolite composite; and calcining the impregnated solid zeolite composite to produce the hierarchical zeolite composite catalyst. The produced hierarchical zeolite composite catalyst has a mesostructure comprising at least one disordered mesophase and at least one ordered mesophase.

[0068] In a second aspect, the disclosure provides the method of the first aspect, in which the method further comprises extruding the solid zeolite composite with binder.

[0069] In a third aspect, the disclosure provides the method of the second aspect, in which the binder is an alumina based binder.

[0070] In a fourth aspect, the disclosure provides the method of any of the first through third aspects, in which the ZSM-12 comprises pores formed from 12 membered rings forming a framework of the zeolite and the ZSM-5 comprises pores formed from 10 membered rings forming the framework of the zeolite.

[0071] In a fifth aspect, the disclosure provides the method of any of the first through fourth aspects, in which the ordered mesophase is a hexagonal mesophase.

[0072] In a sixth aspect, the disclosure provides the method of any of the first through fifth aspects, in which the aging involves maintaining the pH adjusted dissolved zeolite solution at a temperature of 75 to 125 °C for a duration of 12 to 48 hours.

[0073] In a seventh aspect, the disclosure provides the method of any of the first through sixth aspects, in which the ZSM-12 has a SiCk/AkCb ratio of 60 to 100 and the ZSM-5 has a SiCk/AhCb ratio of 20 to 75. [0074] In an eighth aspect, the disclosure provides the method of any of the first through seventh aspects, in which a ratio of ZSM-12 to ZSM-5 is 3 : 1 by weight.

[0075] In a ninth aspect, the disclosure provides the method of any of the first through eighth aspects, in which the method further comprises ion exchanging the solid zeolite composite.

[0076] In a tenth aspect, the disclosure provides the method of any of the first through ninth aspects, in which the surfactant is cetyltrimethyl ammonium bromide which comprises 1 to 8 wt. % of the dissolved zeolite solution.

[0077] In an eleventh aspect, the disclosure provides the method of any of the first through tenth aspects, in which the catalyst precursor further comprises at least one additional mesoporous zeolite selected from the group consisting of ZSM-22, ZSM-11, and combinations thereof.

[0078] In a twelfth aspect, the disclosure provides the method of any of the first through eleventh aspects, in which the adjusting of the pH is performed by an acidic solution to adjust the pH to less than 9.

[0079] In a thirteenth aspect, the disclosure provides the method of any of the first through twelfth aspects, in which the zeolite composite catalyst has a pore volume ranging from 0.2 to 3.0 cm ³ /g.

[0080] In a fourteenth aspect, the disclosure provides the method of any of the first through thirteenth aspects, in which a molar ratio of silica to alumina in the zeolite composite catalyst is from 20 to 500. a

[0081] In a fifteenth aspect, the disclosure provides the method of any of the first through fourteenth aspects, in which the active metals comprises 0.01 to 6.0 wt. % of the impregnated solid zeolite composite.

[0082] In a sixteenth aspect, the disclosure provides the method of any of the first through fifteenth aspects, in which the alkaline solution is a 0.1 to 0.6 M NaOH solution.

[0083] In a seventeenth aspect, the disclosure provides a method of converting C9+ alkyl aromatic hydrocarbons to a product stream comprising benzene, toluene, and xylene. The method comprises reducing a hierarchical zeolite composite catalyst comprising a mesostructure comprising at least one disordered mesophase and at least one ordered mesophase with hydrogen gas at 400 to 500 °C. The hierarchical zeolite composite catalyst comprises large pore ZSM-12 having a SiCk/AkCb ratio of 20 to 300, medium pore ZSM-5 having a SiCk/AkCb ratio of 5 to 500, and one or more impregnated active metals. The method further comprises contacting a feed comprising C9+ alkylaromatic hydrocarbons with the reduced composite zeolite catalyst and hydrogen in a transalkylation zone of a reactor to produce a transalkylation product, stripping Ci- C5 and unreacted feed from the transalkylation product, and collecting at least the xylenes product from the transalkylation product.

[0084] In an eighteenth aspect, the disclosure provides the method of the seventeenth aspect, in which the transalkylation zone is at a pressure between 1.0 to 3.0 MPa, a temperature of 200°C to 500°C, a space velocity of 1.0 to 5.0 h ¹ , and a hydrogen to hydrocarbon ratio of 1 to 4.

[0085] In a nineteenth aspect, the disclosure provides the method of the seventeenth or eighteenth aspects, in which the one or more active metals are selected from the group consisting of platinum, rhenium, rhodium, molybdenum, nickel, tungsten, chromium, ruthenium, gold, and combinations thereof.

[0086] In a twentieth aspect, the disclosure provides a hierarchical zeolite composite catalyst. The hierarchical zeolite composite catalyst comprises a solid zeolite composite mixed with an alumina binder. The solid zeolite composite comprises a large pore ZSM-12 and a medium pore ZSM-5 in a 1:1 to 5:1 weight ratio. Further, the hierarchical zeolite composite catalyst has a mesostructure comprising at least one disordered mesophase and at least one ordered mesophase.

[0087] It should be apparent to those skilled in the art that various modifications and variations can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the specification cover the modifications and variations of the various described embodiments provided such modification and variations come within the scope of the appended claims and their equivalents.

[0088] Throughout this disclosure ranges are provided. It is envisioned that each discrete value encompassed by the ranges are also included. Additionally, the ranges which may be formed by each discrete value encompassed by the explicitly disclosed ranges are equally envisioned.