Production of alkyl aromatic compounds

Abstract

The process for producing mono-alkylated benzenes comprises contacting benzene with di- and tri-alkylated benzenes in the presence of a transalkylation catalyst under transalkylation conditions to convert at least a portion of the di- and tri-alkylated benzenes to mono-alkylated benzenes, wherein the transalkylation catalyst composition comprises a treated zeolitic material having an increased mesoporous surface area compared to the precursor catalyst composition from which it is made.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 110,606, having a filing date of November 6, 2020, the disclosure of which is incorporated by reference in its entirety herein.

[0002] The present disclosure relates to processes for producing alkylaromatic compounds, particularly ethylbenzene and cumene. [Background technology]

[0003] Ethylbenzene and cumene are useful commodity chemicals used industrially for the production of styrene monomer and the co-production of phenol and acetone, respectively. Ethylbenzene and cumene are typically produced by alkylating benzene with a C2 or C3 alkylating agent, such as ethylene or propylene, in the presence of an acid catalyst, particularly a zeolite catalyst, under liquid phase or mixed gas-liquid phase conditions. In addition to the desired mono-alkylated product, the process inevitably produces di- and tri-alkylated analogs, as well as other heavy by-products. Therefore, to maximize the yield of ethylbenzene and cumene, it is customary to transalkylate the polyalkylated product with benzene to produce further mono-alkylated products. The product of the transalkylation reaction, together with the alkylation reaction effluent, is then fed to one or more benzene columns to recover unreacted benzene and then to one or more EB or cumene columns to recover the desired mono-alkylated product.

[0004] Current state-of-the-art transalkylation catalyst compositions use metallosilicate zeolites with channels defined by 12-membered rings of tetrahedrally coordinated atoms and / or surface pocket channels as active materials (see, for example, WO 2018 / 140149). These zeolites can convert polyalkylbenzene molecules to ethylbenzene and cumene with high selectivity and activity. However, these catalysts require high temperatures, low substrate feed flow rates, and large catalyst beds to achieve sufficient conversion, all of which increase process costs. Furthermore, the problem is exacerbated by the fact that trialkylated species are significantly less reactive than dialkylated species, making it difficult to find a processing window with existing catalysts that achieves effective conversion of the trialkylated species without adversely affecting the selectivity of the dialkylated species.

[0005] Therefore, there is great interest in providing transalkylation catalyst compositions that can be operated at lower temperatures without sacrificing conversion activity and monoalkylated benzene selectivity. Summary of the Invention

[0006] It has now been discovered that certain zeolitic materials, which have been treated to produce mesoporosity in addition to their inherent long-range crystallinity, are effective in catalyzing the transalkylation of benzene with di- and / or tri-alkylated benzenes, particularly diisopropylbenzene and / or triisopropylbenzene, at relatively low temperatures with high conversion efficiency and high selectivity to the desired mono-alkylated species, particularly cumene.

[0007] Accordingly, a first aspect of the present disclosure relates to a transalkylation process comprising the following steps: (I) a1m 2 / g; (II) treating the precursor catalyst composition to obtain a treated precursor catalyst composition, said treated precursor catalyst composition comprising a2m 2and a2>a1, preferably 10%≦(a2-a1) / a1×100%≦1000%, (III) forming a transalkylation catalyst composition from said treated precursor catalyst composition; (IV) feeding a transalkylation feed mixture comprising (i) benzene and (ii) di- and / or tri-alkylated benzenes to a transalkylation zone; and (V) contacting said transalkylation feed mixture with said transalkylation catalyst composition in a transalkylation zone under transalkylation conditions to produce a transalkylation effluent enriched in mono-alkylated benzenes relative to said transalkylation feed mixture.

[0008] A second aspect of the present disclosure relates to a process for producing mono-alkylated benzene, which may include one or more of the following steps: (a) contacting a feed stream comprising benzene with an alkylation reagent in the presence of an alkylation catalyst composition under alkylation conditions to effectively convert at least a portion of the benzene in the feed stream to the desired mono-alkylated benzene and produce an alkylation effluent comprising mono-, di-, and tri-alkylated benzenes; (b) separating the alkylation effluent into a first fraction comprising mono-alkylated benzene and a second fraction comprising di- and tri-alkylated benzenes; (c) contacting at least a portion of the second fraction with benzene in the presence of a transalkylation catalyst composition under transalkylation conditions comprising a temperature of 100 to 300° C. effective to convert at least a portion of the di- and tri-alkylated benzenes to mono-alkylated benzene and produce a transalkylation effluent, wherein the transalkylation catalyst composition is: (c1) a 1m 2 / g of a precursor catalyst composition; (c2) treating the precursor catalyst composition to obtain a treated precursor catalyst composition, the treated precursor catalyst composition comprising a2m 2 / g, and a2>a1, preferably 10%≦(a2−a1) / a1×100%≦1000%, and (c3) by forming a transalkylation catalyst composition from said treated precursor catalyst composition. [Brief description of the drawings]

[0009]

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[0010] Detailed Description Unless otherwise indicated, the terms "mesoporous" and "mesoporosity" are used in their art-recognized sense to refer to porous materials containing intermediate-sized pores, i.e., pores having at least one cross-sectional dimension anywhere in the range from about 20 to about 500 Å.

[0011] The terms "zeolite" and "zeolitic material" are used herein in the manner defined by the International Zeolite Society Convention (Section 1.3) to include both natural and synthetic zeolites, as well as molecular sieves and other porous materials having related properties and / or structures. The term "zeolite" also refers to a group of structured aluminosilicate minerals, or any member of the group, containing cations such as sodium and potassium, or less commonly barium, beryllium, lithium, potassium, magnesium and strontium, characterized by an (Al+Si):O ratio of approximately 1:2, an open tetrahedral framework structure capable of ion exchange, and loosely held water molecules capable of reversible dehydration. The term "zeolite" also refers to a group of structured aluminosilicate minerals, or any member of the group, containing cations such as sodium and potassium, or less commonly barium, beryllium, lithium, potassium, magnesium and strontium, characterized by an open tetrahedral framework structure capable of ion exchange, and loosely held water molecules capable of reversible dehydration. 4+ Or Al 3+ These include "zeolite-related materials" or "zeotypes" which are prepared by substituting other elements, as in the case of aminophosphates (e.g., MeAPO, SAPO, ElAPO, MeAPSO, and ElAPSO), gallophosphates, zinc phosphates, and titanium silicates.

[0012] Zeolites exhibit long-range crystallinity, meaning that they contain one or more phases with a repeating structure, called a unit cell, that repeats with a spacing of at least 10 nm. In one embodiment, the zeolites after the present invention modification and extrusion still exhibit long-range crystallinity and order (i.e., have peaks in XRD that can be attributed to the parent zeolite). The zeolitic materials employed in preparing the transalkylation catalyst compositions disclosed herein exhibit a microporous structure, i.e., contain pores with at least one cross-sectional diameter of less than 20 Å, e.g., less than 10 Å. Furthermore, the initial zeolitic materials used in preparing the transalkylation catalyst compositions disclosed herein may exhibit some mesoporosity, but are not required to do so. In some embodiments, the initial zeolitic materials may have a mesoporous to microporous surface area ratio of less than 0.8, e.g., less than 0.7, e.g., less than 0.6, prior to any treatment to enhance the mesoporosity of the material. Preferably, the initial zeolitic material has a framework structure selected from the group consisting of FAU, BEA, MOR, MWW and mixtures thereof, with FAU being particularly preferred.

[0013] I. The first aspect of the present disclosure Described herein is a transalkylation process and / or a process for producing mono-alkylated benzenes, such as ethylbenzene and cumene, comprising contacting benzene with a mixture comprising di- and / or tri-alkylated benzenes in the presence of a transalkylation catalyst composition under transalkylation conditions effective to convert at least a portion of the di- and tri-alkylated benzenes to mono-alkylated benzenes, wherein the transalkylation catalyst composition comprises a treated precursor catalyst composition (e.g., a treated zeolitic material) having mesoporosity (preferably in addition to long-range crystallinity), and wherein the treated precursor catalyst composition (e.g., the treated zeolitic material) exhibits a higher mesoporous surface area than the precursor catalyst composition prior to treatment. The treatment method may include treating the precursor catalyst composition having long-range crystallinity with at least a surfactant under conditions effective to create or increase mesoporosity in the precursor catalyst composition. A non-limiting example of a precursor catalyst is an initial zeolitic material.

[0014] The precursor catalyst composition can comprise, consist essentially of, or consist of a catalytically active component, such as an initial zeolitic material. Additionally or alternatively, the precursor catalyst composition can include a first auxiliary component, such as a cocatalyst, a second catalytically active component, or a catalytically inactive component.

[0015] A non-limiting example of the first auxiliary component is an additional molecular sieve that may be capable of, but is not required to, catalyze the reaction in the transalkylation zone. Such molecular sieves may include one or more zeolites. Non-limiting examples of useful molecular sieves for the first auxiliary component in the precursor catalyst composition may include large pore molecular sieves having a Constraint Index of less than 2, as well as mixtures and combinations thereof. Suitable large pore molecular sieves include zeolite beta, zeolite Y, ultrastable Y (USY), superhydrophobic Y (UHP-Y), dealuminated Y (Deal Y), mordenite, ZSM-3, ZSM-4, ZSM-14, ZSM-18, ZSM-20, and mixtures thereof. Zeolite beta is described in U.S. Pat. No. 3,308,069 and U.S. Reissue Pat. No. 28,341. Zeolite ZSM-3 is described in U.S. Patent No. 3,415,736. Zeolite ZSM-4 is described in U.S. Patent No. 4,021,947. Zeolite ZSM-14 is described in U.S. Patent No. 3,923,636. Zeolite ZSM-18 is described in U.S. Patent No. 3,950,496. Zeolite ZSM-20 is described in U.S. Patent No. 3,972,983. Low sodium ultrastable Y molecular sieve (USY) is described in U.S. Patent Nos. 3,293,192 and 3,449,070. Superhydrophobic Y (UHP-Y) is described in U.S. Patent No. 4,401,556. Dealuminized Y zeolite (Deal Y) can be prepared by the method found in U.S. Patent No. 3,442,795. Zeolite Y and mordenite are naturally occurring materials, but are also available in synthetic forms, such as TEA-mordenite (i.e., a synthetic mordenite prepared from a reaction mixture containing a tetramethylammonium derivatizing agent), which is disclosed in U.S. Patent Nos. 3,776,093 and 3,894,104.

[0016] Another class of molecular sieve materials that may be present in the precursor catalyst composition as a first auxiliary component is the group of mesoporous crystalline materials exemplified by MCM-41 and MCM-48 materials. These mesoporous crystalline materials are described in U.S. Patent Nos. 5,098,684, 5,102,643, and 5,198,203. MCM-41, described in U.S. Patent No. 5,098,684, is characterized by a microstructure with a uniform, hexagonal arrangement of pores with a diameter of at least about 1.3 nm, and after calcination, it exhibits an X-ray diffraction pattern with at least one d-spacing greater than about 1.8 nm and a hexagonal electron diffraction pattern that can be indexed with a d100 value greater than about 1.8 nm, which corresponds to the d-spacing of the peak in the X-ray diffraction pattern. The more preferred catalytic form of this material is an aluminosilicate, although other metallosilicates may also be utilized. MCM-48 has a cubic structure and can be prepared by a similar preparative method.

[0017] Yet another non-limiting example of the first auxiliary component in the precursor catalyst composition is a binder or matrix material. Non-limiting examples of binders include silica, alumina, zirconia, titanium oxide, thorium oxide, yttria, chromium oxide, manganese oxide, hafnia, lanthanum oxide, alkali metal oxides, alkaline earth metal oxides, and combinations, mixtures, and compounds thereof. Specific examples of binders include, but are not limited to, kaolin, bentonite, and mixtures and combinations thereof. The binder can be a naturally occurring material (with or without enhancing treatment) or a synthetic material. The binder can function to improve the mechanical properties of the precursor catalyst composition.

[0018] The precursor catalyst composition can consist essentially of or consist of the treated precursor catalyst and any additional molecular sieves, and can be substantially free or completely free of binders as described above.

[0019] The precursor catalyst composition may be formed in any desired shape and / or size in a non-limiting form such as powder, pellet, extrudate, etc.

[0020] The precursor catalyst composition has the following: (i) the molar ratio of r3 to r4 of silica (SiO2) to alumina (Al2O3) is such that r3 and r4 can independently be, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 as long as r3 < r4, (ii) s(t)3 to s(t)4 m 2 / g of the total surface area is such that s(t)3 and s(t)4 can independently be, for example, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1,000 as long as s(t)3 < s(t)4, (iii) s(mp)3 to s(mp)4 m 2 / g of the micropore surface area is such that s(mp)3 and s(mp)4 can independently be, for example, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, and the precursor catalyst composition can have one or more of these characteristics, although it is not required. In certain embodiments including but not limited to those where the precursor catalyst composition contains a zeolite-based material such as a faujasite, the precursor catalyst composition can have s(e)3 to s(e)4 m 2 / g of the mesopore surface area, and s(e)3 and s(e)4 can independently be, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 180, 200, 250, 300, 350, 400 as long as s(e)3 < s(e)4.

[0021] A method for treating the precursor catalyst composition can include the steps of: (a) treating the precursor catalyst composition with a surfactant; (b) treating the precursor catalyst composition with an acid before or after step (a); and (c) treating the precursor catalyst composition with a base after step (a) and / or step (b).

[0022] US Patent Application Publication No. 2013 / 0183231 discloses a process for introducing mesopores into zeolitic materials using a combination of acid treatment, surfactant treatment, and then alkaline solution treatment to increase the mesoporous surface area, the contents of which are incorporated herein by reference in their entirety. The various processes disclosed in US Patent Application Publication No. 2013 / 0183231 can be used to obtain transalkylation catalyst compositions from precursor catalyst compositions containing zeolites. Furthermore, US Patent Application Publication No. 2007 / 0244347, the contents of which are incorporated herein by reference, discloses a process for creating or increasing mesoporosity in zeolitic materials, which can be used to produce transalkylation catalyst compositions in the processes of the present disclosure.

[0023] In certain specific embodiments, in preparing the transalkylation catalyst composition for use in the present process, the initial zeolitic material can be first optionally combined with water to form an initial slurry. In one or more embodiments, the initial zeolitic material can be present in any initial slurry in an amount ranging from about 1 to about 50 weight percent, such as from about 5 to about 40 weight percent, such as from about 10 to about 30 weight percent, such as from about 15 to about 25 weight percent.

[0024] In certain specific embodiments, the initial zeolitic material (optionally as part of the initial slurry) is then contacted with a surfactant, typically a cationic surfactant. In one or more embodiments, the surfactant used can comprise one or more alkyltrimethylammonium salts and / or one or more dialkyldimethylammonium salts. Suitable salts include cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, and mixtures thereof. In other embodiments, the surfactant comprises a non-ionic surfactant. An example of a suitable commercially available non-ionic surfactant is Pluronic ammonium salt available from BASF Corporation. TM Surfactants (e.g., Pluronic P123 TM ), but is not limited to:

[0025] In certain specific embodiments, an acid can be combined with the initial zeolitic material before or after the addition of a surfactant to form a treatment mixture containing the acid, the surfactant, and the zeolitic material after the addition of the surfactant. The acid suitable for use herein can be any organic acid or inorganic (mineral) acid. In various embodiments, the acid used in this step of the treatment process can be a dealuminating acid. In further embodiments, the acid can also be a chelating agent. Specific examples of acids suitable for use include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, sulfonic acid, oxalic acid, citric acid, ethylenediaminetetraacetic acid, tartaric acid, malic acid, glutaric acid, succinic acid, and combinations of two or more thereof. In certain embodiments, the treatment mixture is prepared in the absence or substantial absence of hydrofluoric acid. As used herein, the term "substantial absence" refers to a concentration of less than 10 parts per million by weight ("ppmw").

[0026] In various embodiments, the amount of acid used in the treatment mixture can be in the range of about 1 to about 10 milliequivalents, such as about 2 to about 8 milliequivalents, or about 3 to about 6 milliequivalents per gram of the initial zeolitic material. Typically, the amount of acid used is such that the treatment mixture has a pH in the range of about 2 to about 6, or in the range of about 3 to about 4.

[0027] In certain specific embodiments, the resulting treatment mixture can then be stirred for a period ranging from about 1 minute to about 24 hours, such as from about 5 minutes to about 12 hours, such as from about 10 minutes to about 6 hours, or from about 30 minutes to about 2 hours. Further, the treatment mixture can be heated (with or without stirring) to a temperature of about 30 to about 100° C., such as from about 40 to about 80° C., for a period of time ranging from about 30 minutes to about 1 week, such as from about 1 hour to about 2 days.

[0028] In certain specific embodiments, following the above-described acid and surfactant treatment, at least a portion of the resulting surfactant-treated zeolitic material is recovered from the treatment mixture. Any known solid / liquid separation technique, such as filtration, can be used to achieve such recovery, and the recovered surfactant-treated zeolitic material can then be washed one or more times (e.g., with deionized water).

[0029] In certain specific embodiments, once the surfactant-treated zeolitic material is recovered from the treatment mixture, it may be contacted with a base. Suitable bases include NaOH, NH4OH, KOH, Na2CO3, TMAOH, and mixtures thereof. In certain embodiments, the base used may be in the form of an aqueous solution having a concentration in the range of 0.2 to 15% by weight. Further, the amount of base used may be such that the base is present in a ratio with respect to the initial amount of initial zeolitic material in the range of about 0.1 to about 20 mmol per gram of initial zeolitic material, such as about 0.1 to about 5 mmol per gram of initial zeolitic material, such as about 0.9 to about 4 mmol per gram of initial zeolitic material. The treatment of the surfactant-treated zeolitic material with a base may be carried out under high temperature conditions, including a temperature of about 30 to about 200° C., for example, about 50 to about 150° C., for about 1 minute to about 2 days, for example, about 30 minutes to about 1 day, for example, about 2 hours to about 20 hours, or about 16 hours to about 18 hours.

[0030] In certain specific embodiments, following treatment with base, at least a portion of the resulting mesoporous zeolitic material can be separated from the base-treated mixture. For example, the mesoporous zeolitic material can be filtered, washed, and / or dried. In one or more embodiments, the mesoporous zeolitic material can be filtered via suction filtration and washed with water. The recovered mesoporous zeolitic material can then be optionally filtered again and optionally dried.

[0031] The product of the above treatment method is a treated zeolitic material that has long range order or crystallinity (i.e., exhibits peaks in an X-ray diffraction pattern that can be attributed to the parent zeolite) and increased mesoporosity compared to the starting zeolitic material. The precursor catalyst composition prior to the treatment step is a 1m 2 / g of mesoporous surface area. 2The result is the mesoporous surface area of the precursor catalyst composition per g, where a2 > a1. Generally, a significant increase in the mesoporous surface area is desirable. In certain embodiments, x1% ≦ (a2 - a1) / a1 × 100% ≦ x2%, where x1 and x2 are independently, for example, as long as x1 < x2, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 150, 160, 180, 200, 220, 240, 250, 260, 280, 300, 320, 340, 350, 360, 380, 400, 420, 440, 450, 460, 480, 500, 600, 700, 800, 900, 1000. Preferably, x1 = 30 and x2 = 800. Preferably, x1 = 40 and x2 = 500. More preferably, x1 = 50 and x2 = 300. In some embodiments, the ratio of the mesoporous surface area to the microporous surface area of the treated zeolitic material is at least 10%, for example at least 20%, for example at least 30%, for example at least 40%, for example at least 50%, greater than that of the original zeolitic material. In certain embodiments, the treated zeolitic material has a ratio of mesoporous surface area to microporous surface area greater than 0.8, for example greater than 0.9, for example greater than 1.

[0032] After treatment of the precursor catalyst composition, a transalkylation catalyst composition can be formed from the treated precursor catalyst composition. In certain embodiments, this formation step can include (1) mixing the treated precursor catalyst composition with a second auxiliary component, and (2) obtaining a transalkylation catalyst composition from the mixed mixture from step (1). The second auxiliary component can include one or more of a cocatalyst, a second catalytically active component different from the catalytic components in the treated precursor catalyst composition, or a catalytically inert component.

[0033] A non-limiting example of the second auxiliary component is an additional molecular sieve capable of catalyzing the reaction in the transalkylation zone. The additional molecular sieve can be treated in a manner similar to the above treatment process to expand its mesoporous surface area, but is not required. Such molecular sieves can include one or more zeolites. Non-limiting examples of molecular sieves useful for the second auxiliary component can include large pore molecular sieves having a constraint index of less than 2, as well as mixtures and combinations thereof. Suitable large pore molecular sieves include zeolite beta, zeolite Y, ultrastable Y (USY), superhydrophobic Y (UHP-Y), dealuminated Y (Deal Y), mordenite, ZSM-3, ZSM-4, ZSM-14, ZSM-18, ZSM-20, and mixtures thereof. Zeolite beta is described in U.S. Pat. No. 3,308,069 and U.S. Pat. Re. No. 28,341. Zeolite ZSM-3 is described in U.S. Patent No. 3,415,736. Zeolite ZSM-4 is described in U.S. Patent No. 4,021,947. Zeolite ZSM-14 is described in U.S. Patent No. 3,923,636. Zeolite ZSM-18 is described in U.S. Patent No. 3,950,496. Zeolite ZSM-20 is described in U.S. Patent No. 3,972,983. Low sodium ultrastable Y molecular sieve (USY) is described in U.S. Patent Nos. 3,293,192 and 3,449,070. Superhydrophobic Y (UHP-Y) is described in U.S. Patent No. 4,401,556. Dealuminized Y zeolite (Deal Y) can be prepared by the method found in U.S. Patent No. 3,442,795. Zeolite Y and mordenite are naturally occurring materials, but are also available in synthetic forms, such as TEA-mordenite (i.e., a synthetic mordenite prepared from a reaction mixture containing a tetramethylammonium derivatizing agent), which is disclosed in U.S. Patent Nos. 3,776,093 and 3,894,104.

[0034] Other classes of molecular sieves that can be used as a second auxiliary component in the present transalkylation catalyst composition are the group of essentially mesoporous crystalline materials exemplified by MCM-41 and MCM-48 materials. These mesoporous crystalline materials are described in U.S. Patent Nos. 5,098,684, 5,102,643, and 5,198,203. MCM-41 described in U.S. Patent No. 5,098,684 is characterized by a microstructure having a uniform hexagonal array of pores with a diameter of at least about 1.3 nm: after calcination, it exhibits an X-ray diffraction pattern having at least one d-spacing greater than about 1.8 nm and a hexagonal electron diffraction pattern that can be indexed with a d100 value greater than about 1.8 nm corresponding to the d-spacing of the peaks in the X-ray diffraction pattern. The preferred catalytic form of this material is aluminosilicate, although other metallosilicates can also be utilized. MCM-48 has a cubic structure and can be produced by a similar preparation procedure. Other limiting examples of the second auxiliary component in the transalkylation catalyst composition useful in the process of the present disclosure are binder or matrix materials. Non-limiting examples of the binder include silica, alumina, zirconia, titanium oxide, thorium oxide, yttria, chromium oxide, manganese oxide, hafnia, lanthanum oxide, alkali metal oxides, alkaline earth metal oxides, and combinations, mixtures, and compounds thereof. Specific examples of the binder include, but are not limited to, kaolin, bentonite, and mixtures and combinations thereof. The binder can be a naturally occurring substance (with or without enhancement treatment) or a synthetic substance. The binder can function to improve the mechanical properties of the transalkylation catalyst composition. In certain embodiments, the binder can be present in an amount of c(b)1 to c(b)2 mass % based on the total mass of the transalkylation catalyst composition, where c(b)1 and c(b)2 are independently, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 as long as c(b)1 < c(b)2.

[0035] The transalkylation catalyst composition can consist essentially of or consist of the treated precursor catalyst and any additional molecular sieves, substantially free of or completely free of the binder as described above. A molecular sieve catalyst composition free of such a binder is sometimes referred to as a "self-bound catalyst".

[0036] In the forming step, the treated precursor catalyst composition, or a combined mixture of the treated precursor catalyst composition and the auxiliary component, can be formed into any desired shape and / or size in a non-limiting form such as powder, pellet, extrudate, etc. Optionally, a drying and / or calcination step can be performed on the formed composite mixture to produce the transalkylation catalyst composition.

[0037] In certain embodiments, the transalkylation catalyst composition useful in the process of the present disclosure has the following characteristics: (i) s(t)1 to s(t)2 m 2 / g of the total surface area, where s(t)1 and s(t)2 can independently be, for example, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800 as long as s(t)1 < s(t)2, (ii) s(mp)1 to s(mp)2 m 2 / g of the micropore surface area, where s(mp)1 and s(mp)2 can independently be, for example, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, and (iii) s(e)1 to s(e)2 m 2 / g of the mesoporous surface area, where s(e)1 and s(e)2 can independently be, for example, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 120, 140, 150, 160, 180, 200, 220, 240, 250, 260, 280, 300, 350, 400, 450, 500, 550, 600, 650 as long as s(e)1 < s(e)2, and can have one or more of them.

[0038] In the transalkylation step, the transalkylation catalyst composition can be present in a transalkylation zone in a fixed bed, moving bed, slurry, etc. suitable for the exchange reaction under transalkylation conditions. In certain embodiments, the transalkylation conditions are as follows: (i) a temperature in the range of T1 to T2 °C, where T1 and T2 can independently be, for example, 100, 120, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 300, 350 as long as T1 < T2; (ii) an absolute pressure in the range of p1 to p2 kilopascals, where p1 and p2 can independently be, for example, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1500, 2000, 3000, 4000, 5000 as long as p1 < p2; (iii) a hydrogen molecule (H2) concentration in the hydrocarbon feed in the range of c(H2)1 to c(H2)2 mass ppm based on the total mass of the hydrocarbon feed, where c(H2)1 and c(H2)2 can independently be, for example, 0, 1, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500 as long as c(H2)1 < c(H2)2, and can include at least one of these. Preferably, c(H2)2 = 200. Preferably, c(H2)2 = 100. Preferably, c(H2)2 = 50. Preferably, c(H2)2 = 10. Preferably, H2 is not supplied to the transalkylation zone, and (iv) w1 to w2 hr -1The WHSV of hydrocarbon feed in the range can be 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 as long as w1 and w2 are independently, for example, w1 < w2. In the transalkylation zone, the aromatic hydrocarbons can be present in the gas phase and / or the liquid phase. Advantageously, = 25%, or = 30%, or = 40%, or = 50%, or = 60%, or = 70%, or = 80%, or = 90%, or = 95%, or = 98%, or even substantially all of the aromatic hydrocarbons are present in the liquid phase in the transalkylation zone. In certain specific embodiments, (i) a hydrocarbon feed containing polyethylbenzene and benzene and (ii) a hydrocarbon feed containing polyisopropylbenzene and benzene are subjected to transalkylation conditions suitable for carrying out in the presence of the transalkylation catalyst composition described herein at a temperature of 100 °C to 300 °C, a pressure of 696 kPa-a to 5100 kPa-a, a weight hourly space velocity based on the mass of the polyalkylated aromatic compound of 0.5 to 200 h -1 -1, and a benzene / polyalkylated benzene mass ratio of 0.5:1 to 20:1. Preferred conditions are a temperature of 150 °C to 250 °C, a pressure of 696 kPa-a to 4137 kPa-a, a weight hourly space velocity based on the mass of the polyalkylated aromatic compound of 0.5 to 100 h -1 -1, and a benzene / polyalkylated benzene mass ratio of 1:1 to 10:1. As one preferred embodiment, the transalkylation feed contains diisopropylbenzene and triisopropylbenzene, and the desired monoalkylated product contains cumene, and the transalkylation conditions include a temperature in the range of 150 °C to 200 °C. Typically, the transalkylation conditions can be controlled such that the polyalkylated aromatic compound and the benzene are at least partially or mostly present in the liquid phase.

[0039] A transalkylation catalyst composition produced by treating a precursor catalyst composition and then forming any catalyst composition as described above exhibits increased performance in terms of selectivity to a desired compound (e.g., a monoalkylaromatic hydrocarbon such as ethylbenzene or cumene) in at least the transalkylation step, compared to a comparative catalyst composition formed from the precursor catalyst composition, under the same transalkylation conversion conditions. Thus, in a transalkylation step that includes contacting a hydrocarbon feed with the transalkylation catalyst composition under a series of transalkylation conditions to produce a conversion product, a selectivity of sel(pX)2 mass % to a desired compound (e.g., a monoalkylaromatic hydrocarbon such as ethylbenzene or cumene) can be obtained. In contrast, in the following reference step (S-ref), a selectivity of sel(pX)1 to the same desired compound, where sel(pX)1 < sel(pX)2, is obtained: (S-ref) contacting a hydrocarbon feed with a comparative catalyst composition in a conversion zone under the same series of transalkylation conditions to produce a reference conversion product. Desirably, and advantageously, is TIFF0007665746000001.tif13150, and y1 and y2 can independently be, for example, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 150, 160, 180, 200, 220, 240, 250, 260, 280, 300, 320, 340, 350, 360, 380, 400, 420, 440, 450, 460, 480, 500, 600, 700, 800, 900, 1000 as long as, for example, y1 < y2. Without intending to be bound by any particular theory, an increase in the mesoporous surface area in the transalkylation catalyst composition is thought to improve the catalytic activity compared to the comparative catalyst composition.

[0040] In certain specific embodiments, depending on the composition of the hydrocarbon feed and the transalkylation conditions used, the transalkylation catalyst composition used herein can be effective to convert at least 50 wt.%, preferably at least 75 wt.%, of the dialkylated benzene in the feed to an equivalent monoalkylated benzene product, and at a conversion of 50 wt.% of the dialkylated benzene, to at least 25 wt.%, preferably at least 50 wt.% of the trialkylated benzene in the feed. Typically, the weight ratio of the conversion of the trialkylated benzene to the conversion of the dialkylated benzene is at least 0.2, such as 0.2 to 2, such as 0.2 to 1.2.

[0041] While any mixture of di- and tri-alkylated benzenes can be used in the present transalkylation process, in most practical embodiments, the polyalkylated benzene feedstock used herein comprises some or all of the heavy fraction remaining after separation of the desired mono-alkylated products, particularly ethylbenzene or cumene, from the reaction effluent of the alkylation of benzene with an alkylating agent, particularly a C2 or C3 alkylating agent. In such cases, the polyalkylated benzene feedstock typically comprises 40% to 85% by weight of di- and tri-alkylated benzenes, and 5% to 60% or 15% to 60% by weight of tri-alkylated benzenes.

[0042] II. The second aspect of the present disclosure Thus, in a second aspect, the disclosure relates to a process for producing mono-alkylated benzene, wherein a feedstream comprising benzene is first contacted with an alkylating agent in the presence of an alkylation catalyst composition under alkylation conditions effective to convert at least a portion of the benzene in the feedstream to the desired mono-alkylated benzene and to produce an alkylation effluent comprising mono-, di-, and tri-alkylated benzenes. The alkylation effluent is then separated into a first fraction comprising the mono-alkylated benzene and a second fraction comprising the di- and tri-alkylated benzenes. At least a portion of the second fraction is then contacted with additional benzene in the presence of a transalkylation catalyst composition as described above in connection with the first aspect of the disclosure to convert at least a portion of the di- and tri-alkylated benzenes to mono-alkylated benzene and to produce a transalkylation effluent from which the mono-alkylated benzene can be recovered.

[0043] The above process may find utility with a wide range of alkylating agents, but is particularly advantageous with C2 and C3 alkylating agents. Suitable alkylating agents are olefins and alcohols, which may be linear, branched, or cyclic. In some embodiments, the alkylating agent is a C2 alkylating agent, such as ethylene, or a C3 alkylating agent, such as propylene and / or isopropanol. Preferably, the alkylating agent comprises propylene and / or isopropanol, and the desired mono-alkylated benzene product comprises cumene.

[0044] Suitable alkylation catalyst compositions include any or all of the molecular sieves described above in connection with transalkylation catalysts, including zeolitic materials that have been treated to enhance mesoporosity. Additionally, the alkylation catalyst may include at least one medium pore molecular sieve having a constraint index (as defined in U.S. Pat. No. 4,016,218) of 2 to 12. Suitable medium pore molecular sieves include ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48. ZSM-5 is described in detail in U.S. Pat. No. 3,702,886 and U.S. Reissue Pat. No. 29.948. ZSM-11 is described in detail in U.S. Pat. No. 3,709,979. ZSM-12 is described in detail in U.S. Pat. No. 3,832,449. ZSM-22 is described in U.S. Pat. No. 4,556,477. ZSM-23 is described in U.S. Patent No. 4,076,842. ZSM-35 is described in U.S. Patent No. 4,016,245. ZSM-48 is described in more detail in U.S. Patent No. 4,234,231.

[0045] Other suitable molecular sieves for use as the alkylation catalyst in the present process include those of the MCM-22 family. As used herein, the term "molecular sieve of the MCM-22 family" (or "material of the MCM-22 family" or "MCM-22 family material" or "MCM-22 family zeolite") includes one or more of the following: · A molecular sieve made from a common primary crystal building block unit cell, the unit cell having the MWW framework topology. (A unit cell is a spatial arrangement of atoms that, when arranged in three-dimensional space, represents a crystal structure. Such crystal structures are described in "Atlas of Zeolite framework Types", 5th Edition, 2001, the entire contents of which are incorporated by reference); · Molecular sieves made from common secondary building blocks are two-dimensional tilings of such MWW framework topology unit cells, forming one unit cell thickness, preferably one c unit cell thickness; Molecular sieves made from common secondary building blocks are layers one or more unit cell thick, and the layers one or more unit cell thick are made by stacking, packing, or bonding at least two monolayers one unit cell thick. The stacking of such secondary building blocks can be in a regular, irregular, or random manner, or any combination thereof; and ·Molecular sieves made by any regular or random two- or three-dimensional combination of unit cells with the MWW framework topology.

[0046] The MCM-22 family of molecular sieves includes molecular sieves having X-ray diffraction patterns that include d-spacing maxima at 12.4±0.25, 6.9±0.15, 3.57±0.07, and 3.42±0.07 Å. The X-ray diffraction data used to characterize the materials are obtained by standard techniques using a copper Kα doublet as the incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system.

[0047] The MCM-22 family of materials includes MCM-22 (described in U.S. Pat. No. 4,954,325), PSH-3 (described in U.S. Pat. No. 4,439,409), SSZ-25 (described in U.S. Pat. No. 4,826,667), ERB-1 (described in European Patent No. 0293032), ITQ-1 (described in U.S. Pat. No. 6,077,498), ITQ-2 (described in WO 97 / 17290), MCM-36 (described in U.S. Pat. No. 5,250,277), MCM-49 (described in U.S. Pat. No. 5,236,575), MCM-56 (described in U.S. Pat. No. 5,362,697), UZM-87 (described in U.S. Pat. No. 6,756,030), UZM-8HS (described in U.S. Pat. No. 7,713,513), and combinations thereof.

[0048] Preferred alkylation catalysts include zeolite beta or zeolites of the MCM-42 family. The above molecular sieves can be used as alkylation catalysts without a binder or matrix, or can be combined with any of the binder materials described above as suitable for use in transalkylation catalysts.

[0049] The reaction conditions used to carry out the alkylation step will depend on the particular alkylating agent used, but suitable conditions are well within the purview of one skilled in the art. For example, the alkylation of ethylene with benzene to produce ethylbenzene is typically carried out at a temperature of about 120°C to 300°C, preferably about 150°C to 260°C, and at a pressure of 500 to 8300 kPa-a, preferably 1500 to 4500 kPa-a, such that at least a portion of the reaction mixture is maintained in the liquid phase during the process. Generally, the molar ratio of benzene to ethylene is about 1 to about 100, preferably about 20 to about 80. For the alkylation of benzene with propylene to produce cumene, typical reaction conditions include a temperature of about 20° C. to about 350° C., e.g., about 50° C. to about 300° C., e.g., about 100° C. to 280° C., and a pressure of about 100 kPa to about 20,000 kPa, e.g., about 500 kPa to about 10,000 kPa, such that at least a portion of the reaction mixture is maintained in the liquid phase during the process. Generally, the molar ratio of benzene to propylene is maintained within the range of about 1:1 to about 30:1, typically 1.1:1 to 10:1.

[0050] In addition to the desired mono-alkylated aromatic product, the effluent from the main alkylation reaction may contain significant amounts of unreacted benzene and smaller amounts of polyalkylated species, such as diisopropylbenzene (DIPB) and some triisopropylbenzene (TIPB) in the cumene process, and diethylbenzene (DEB) and some triethylbenzene (TEB) in the ethylbenzene process. Thus, the effluent from the main alkylation reaction may be fed to a separation system to allow recovery of the mono-alkylated aromatic product and further processing of by-products and impurities.

[0051] The separation system may include one or more benzene distillation columns, where unreacted benzene may be removed from the effluent as an overhead or side stream for recycle to the alkylation reaction and / or transalkylation reactor (as described above). The bottoms from the benzene column may then be fed to one or more monoalkylation distillation columns to recover the desired monoalkylated aromatic product. The bottoms from the monoalkylation distillation column contain most of the by-products of the alkylation reaction that are heavier than the desired monoalkylated product. This bottoms stream may then be fed to one or more polyalkylation distillation columns to separate a polyalkylated aromatic product stream containing most of the dialkylated by-products and some of the trialkylated by-products, which may then be passed to the transalkylation reaction. The remainder of the trialkylated by-products and substantially all of the compounds heavier than the trialkylated by-products may be discharged as residue to the bottoms of the polyalkylate column.

[0052] In some embodiments, the benzene feed stream to the alkylation and / or transalkylation reaction contains impurities including, but not limited to, compounds having at least one of the following elements: nitrogen, halogens, oxygen, sulfur, arsenic, selenium, tellurium, phosphorus, and metals from groups 1 to 12. In such cases, the alkylation and / or transalkylation reaction step may further include contacting the benzene feed stream with an absorbent under conditions effective to remove at least a portion of the impurities. The absorbent may be catalytically active and may include a molecular sieve, such as any of the molecular sieves described above, and a small amount of an alkylation reagent may be co-fed to the absorbent and reacted with the benzene feed, and may thus act as a marker of the toxicity potential of the absorbent.

[0053] The invention will now be described in more detail with reference to the following non-limiting examples and the accompanying drawings. EXAMPLES

[0054] Examples 1 - 4 A commercially available high activity faujasite zeolite was used as the base zeolite (precursor catalyst composition) which was treated to produce three different batches of faujasite crystals (treated precursor catalyst compositions) with different mesoporous surface areas. The four different catalyst compositions were produced by (i) mixing the base zeolite and each of the three treated batches of zeolite with the same commercially available alumina binder in a zeolite / binder weight ratio of 65 / 35, (ii) extruding the mixture into 1 / 20" quadralobes, (iii) drying the extrudates at 900°F (482°C) in a nitrogen stream, and (iv) calcining the dried extrudates in air at 1000°F (538°C). The transalkylation catalyst compositions thus produced were then measured for surface area and pore volume, and recorded in Table 1 below. The comparative catalyst composition in Comparative Example 1 includes a base zeolite. As can be seen from Table 1, the transalkylation catalyst compositions in Examples 2, 3, and 4 exhibited increasingly higher mesopore surface areas than that of Example 1. U.S. Patent Application Publication No. 2013 / 0183231 teaches a method for varying the mesoporous surface area of ​​a zeolite.

[0055] Table 1 TIFF0007665746000002.tif41140

[0056] Examples 5 - 9 In Examples 5-8, a commercially available low activity faujasite zeolite was used as the base zeolite (precursor catalyst composition) and was treated to produce three different batches of treated faujasite crystals with different mesoporous surface areas. Four different transalkylation catalyst compositions were produced by (i) mixing the base zeolite and each of the three treated batches of zeolite with the same commercially available alumina binder in a zeolite / binder weight ratio of 65 / 35, (ii) extruding the mixture into 1 / 20" quadralobes, (iii) drying the extrudates at 900°F (482°C) in a nitrogen stream, and (iv) calcining the dried extrudates in air at 1000°F (538°C). In Example 9, a commercially available beta zeolite was used as the base zeolite and was treated to vary its surface area. The catalyst composition of Example 9 was produced from the treated zeolite and the alumina binder in the same manner as in Examples 6-8 above. The transalkylation catalyst compositions of Examples 5-9 thus produced were then measured for surface area and pore volume, which were recorded in Table 2 below. The comparative catalyst composition in Comparative Example 5 contained a low activity faujasite zeolite. As can be seen from Table 2, the transalkylation catalyst compositions in Examples 6, 7, and 8 containing treated zeolite exhibited increasingly higher mesopore surface area than the comparative catalyst composition in Comparative Example 5.

[0057] The properties of the comparative catalyst composition of Example 5 and the inventive transalkylation catalyst compositions of Examples 6-8 are summarized in Table 2. In addition, FIG. 1 displays a graph of differential pore volume versus pore diameter for the catalyst compositions of Examples 5-8. As can be seen, all four catalyst compositions exhibit similar sharp pores at ∼3.5 nm, which increase with increasing mesoporosity. The X-ray diffraction (XRD) patterns of the comparative catalyst composition of Comparative Example 1, the transalkylation catalyst composition of Inventive Example 4, the comparative catalyst composition of Comparative Example 5, and the transalkylation catalyst composition of Inventive Example 8 are shown in FIG. 2, and it can be seen that the transalkylation catalyst compositions of Examples 4 and 8 exhibit similar long-range order as evidenced by similar XRD peaks to those of Comparative Examples 1 and 5, respectively.

[0058] Table 2 TIFF0007665746000003.tif47161

[0059] Example 10 One gram of each of the transalkylation catalyst compositions of Examples 1-9 was sized using a mortar and pestle with No. 14 / 25 mesh and then mixed with 1 gram of quartz before being loaded into a 16-channel packed-bed flow reactor with independent temperature control for its four modules (4 channels / module). The reactor was then used to carry out transalkylation tests of a feed mixture of benzene, DIPB and TIPB having the composition shown in Table 3. The feed components were obtained from Aldrich, mixed and then filtered through three separate molecular sieves. The overall feed composition was determined by GC.

[0060] Table 3 TIFF0007665746000004.tif31142

[0061] In the transalkylation test, the temperature of each module was adjusted to achieve 50% conversion of DIPB, and this temperature was then used as the benchmark for activity. The reaction and products were in the liquid phase, and each reactor was maintained at a flow rate of 1.82 cc / min, corresponding to a weight hourly space velocity (WHSV) of 6, at a pressure of 300 psig (2710 kPa). The results of the test are summarized in Figures 3 and 4.

[0062] Figure 3 shows the relative selectivity to cumene of different transalkylation catalyst compositions at the temperature at which 50% conversion of DIPB occurs. As can be seen, the comparative catalyst compositions (Examples 1 and 5) show lower selectivity to cumene (with ethylbenzene and n-propylbenzene as common by-products) compared to samples with higher mesoporosity. In general, within a particular subset of materials, increased mesoporosity results in a more selective catalyst.

[0063] FIG. 4 displays the relative conversion efficiency of TIPB at temperatures at which 50% DIPB conversion was obtained (DIPB conversion is typically determined at standard operating conditions). As can be seen, the transalkylation catalyst compositions of Examples 6-9 exhibited step-out behavior compared to their non-mesoporous analogues. As the mesoporous surface area of ​​the catalyst composition gradually increased from Examples 5 to 6, 7, and 8, the conversion of TIPB to cumene increased. The increased mesoporous surface area catalyst compositions provide the opportunity to operate the transalkylation bed at extremely low temperatures or increased WHSV rates without the need for purge cycles to remove unreacted TIPB molecules.

[0064] Although the present disclosure has been described and illustrated with reference to specific embodiments, those skilled in the art will recognize that the present invention is amenable to variations not necessarily exemplified herein, and therefore, reference should now be made solely to the appended claims to determine the true scope of the present disclosure. Another aspect of the present invention may be as follows. 〔1〕(I) Supplying a precursor catalyst composition showing a first mesoporous surface area of a1 m 2 / g; (II) Treating the precursor catalyst composition to obtain a treated precursor catalyst composition showing a second mesoporous surface area of a2 m 2 / g, where a2 > a1; (III) Forming a transalkylation catalyst composition from the treated precursor catalyst composition; (IV) (i) Supplying a transalkylation feed mixture containing benzene and (ii) dialkylated benzene and / or trialkylated benzene to a transalkylation zone, and (V) Contacting the transalkylation feed mixture with the transalkylation catalyst composition in the transalkylation zone under transalkylation conditions to produce a transalkylation effluent rich in monoalkylated benzene with respect to the transalkylation feed mixture. A transalkylation process comprising these steps. 〔2〕The transalkylation process according to 〔1〕, wherein the precursor catalyst composition contains zeolite. 〔3〕The transalkylation process according to 〔2〕, wherein the zeolite is selected from the group consisting of FAU, BEA, MOR, and MWW framework zeolites, and their mixtures and combinations. 〔4〕The transalkylation process according to any one of 〔1〕 - 〔3〕, wherein the zeolite is an FAU framework zeolite. 〔5〕x1% ≦ (a2 - a1) / a1 × 100% ≦ x2%, where x1 and x2 are independently, for example, as long as x1 < x2, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 150, 160, 180, 200, 220, 240, 250, 260, 280, 300, 320, 340, 350, 360, 380, 400, 420, 440, 450, 460, 480, 500, 600, 700, 800, 900, 1000. The transalkylation process according to any one of 〔1〕 - 〔4〕. [6] The process according to any one of [1] to [5] above, wherein step (II) includes (IIa) treating the precursor catalyst composition with a surfactant. [7] The process according to [6], wherein the surfactant is selected from the group consisting of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, and mixtures thereof. [8] The process according to [6] or [7], wherein step (II) further comprises the step of (IIb) treating the precursor catalyst composition with an acid before or after step (IIa). [9] The process according to [8], wherein the acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, sulfonic acid, oxalic acid, citric acid, ethylenediaminetetraacetic acid, tartaric acid, malic acid, glutaric acid, succinic acid, and mixtures thereof.

[10] The process according to any one of [6] to [9] above, wherein step (II) further comprises a step of (IIc) treating the precursor catalyst composition with a base after step (IIa) and / or step (IIb).

[11] The base is preferably NaOH, NH 4 OH, KOH, Na 2 CO 3 , TMAOH, and mixtures thereof.

[12] The process according to any one of [1] to

[11] above, wherein the transalkylation conditions include a temperature in the range of about 100°C to about 300°C.

[13] The process according to any one of [1] to

[12] above, wherein the transalkylation conditions include a temperature in the range of about 150°C to about 220°C.

[14] The process according to any one of [1] to

[13] above, wherein the monoalkylated benzene comprises cumene.

[15] The process according to any one of [1] to

[14] above, wherein the transalkylation catalyst composition further comprises a binder. (a) contacting a feed stream comprising benzene with an alkylating agent in the presence of an alkylation catalyst composition under alkylation conditions effective to convert at least a portion of the benzene in the feed stream to the desired mono-alkylated benzenes, and to produce an alkylation effluent comprising mono-, di-, and tri-alkylated benzenes; (b) separating the alkylation effluent into a first fraction comprising mono-alkylated benzenes and a second fraction comprising di- and tri-alkylated benzenes; (c) Contact at least a portion of the second fraction with benzene under transalkylation conditions including a temperature of 100 °C to 300 °C effective to convert at least a portion of the dialkylated benzene and trialkylated benzene to monoalkylated benzene and to produce a transalkylation effluent, the transalkylation catalyst composition being: (c1) Supplying a precursor catalyst composition exhibiting a first mesoporous surface area of a1 m 2 / g; (c2) Treating the precursor catalyst composition to obtain a treated precursor catalyst composition exhibiting a second mesoporous surface area of a2 m 2 / g, where a2 > a1; (c3) Forming a transalkylation catalyst composition from the treated precursor catalyst composition; and (d) Recovering monoalkylated benzene from the transalkylation effluent. A process for producing monoalkylated benzene, comprising:

[17] The process according to

[16] , wherein x1% ≦ (a2 - a1) / a1 × 100% ≦ x2%, and x1 and x2 are independently, for example, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 150, 160, 180, 200, 220, 240, 250, 260, 280, 300, 320, 340, 350, 360, 380, 400, 420, 440, 450, 460, 480, 500, 600, 700, 800, 900, 1000 as long as x1 < x2.

[18] The process according to

[16] or

[17] , wherein the alkylation catalyst composition comprises one or more zeolites selected from the group consisting of BEA and MWW structure types.

[19] The process according to any one of

[16] to

[18] , wherein the alkylating agent comprises propylene and / or isopropanol, and the monoalkylated benzene comprises cumene.

[20] The process according to any one of

[16] to

[19] , wherein the transalkylation catalyst composition further comprises a binder.

[21] The alkylation effluent further comprises unreacted benzene, and the process is: (e) separating unreacted benzene from the alkylation effluent, and recycling at least a portion of the unreacted benzene to the contact (a) and / or the contact (c), The process according to any one of

[16] to

[20] .

[22] The transalkylation effluent further comprises unreacted benzene, and the process comprises: (f) separating unreacted benzene from the transalkylation effluent and recycling at least a portion of the unreacted benzene to the contact (a) and / or the contact (c), The process according to any one of

[16] to

[21] .

[23] The feed stream further comprises impurities, and the process further comprises: The process according to any one of

[16] to

[22] above, further comprising the step of: (g) contacting the feed stream with an absorbent under conditions effective to remove at least a portion of the impurities, the impurities including compounds having at least one of nitrogen, halogens, oxygen, sulfur, arsenic, selenium, tellurium, phosphorus, and Group 1 to Group 12 metals.

Claims

1. (I) a1m 2 providing a precursor catalyst composition exhibiting a first mesoporous surface area of ​​1 / g; (II) treating the precursor catalyst composition to obtain a2m where a2>a1; 2 obtaining a treated precursor catalyst composition exhibiting a second mesoporous surface area of ​​about 1 / g; (III) forming a transalkylation catalyst composition from the treated precursor catalyst composition, wherein the mesoporous surface area of ​​the transalkylation catalyst composition is in the range of 400 m 2 / g to 500 m 2 / g; (IV) feeding a transalkylation feed mixture comprising (i) benzene and (ii) di- and / or tri-alkylated benzenes to a transalkylation zone; and (V) contacting said transalkylation feed mixture with said transalkylation catalyst composition in a transalkylation zone under transalkylation conditions to produce a transalkylation effluent enriched in mono-alkylated benzene relative to the transalkylation feed mixture.

2. 10. The transalkylation process of claim 1, wherein the precursor catalyst composition comprises a zeolite.

3. 3. The transalkylation process of claim 2, wherein the zeolite is selected from the group consisting of FAU, BEA, MOR, and MWW framework zeolites, and mixtures and combinations thereof.

4. The transalkylation process of any one of claims 1 to 3, wherein the zeolite is a FAU framework zeolite.

5. The transalkylation process according to any one of claims 1 to 4, wherein 10%≦(a2−a1) / a1×100%≦1000%.

6. The transalkylation process of any one of claims 1 to 5, wherein step (II) comprises: (IIa) treating the precursor catalyst composition with a surfactant.

7. 7. The transalkylation process of claim 6, wherein the surfactant is selected from the group consisting of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, and mixtures thereof.

8. 8. The transalkylation process of claim 6 or 7, wherein step (II) further comprises the step of: (IIb) treating the precursor catalyst composition with an acid, before or after step (IIa).

9. 9. The transalkylation process of claim 8, wherein the acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, sulfonic acid, oxalic acid, citric acid, ethylenediaminetetraacetic acid, tartaric acid, malic acid, glutaric acid, succinic acid, and mixtures thereof.

10. 10. The transalkylation process of any one of claims 6 to 9, wherein step (II) further comprises the step of: (IIc) treating the precursor catalyst composition after step (IIa) and / or step (IIb) with a base.

11. The base may be NaOH, NH 4 OH, KOH, Na 2 CO 3 11. The transalkylation process of claim 10, wherein the alkyl group is selected from the group consisting of TMAOH, TMAOH, and mixtures thereof.

12. The transalkylation process of any one of claims 1 to 11, wherein the transalkylation conditions comprise a temperature in the range of from about 100°C to about 300°C.

13. The transalkylation process of any one of claims 1 to 12, wherein the transalkylation conditions comprise a temperature in the range of from about 150°C to about 220°C.

14. The transalkylation process of any one of claims 1 to 13, wherein the monoalkylated benzene comprises cumene.

15. The transalkylation process of any one of claims 1 to 14, wherein the transalkylation catalyst composition further comprises a binder.

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