TW201136869A - Alkylated aromatics production - Google Patents

Abstract

Disclosed is a process for the production of alkylated aromatics by contacting a feed stream comprising an alkylatable aromatic, an alkylating agent and trace amounts of water and impurities in the presence of first and second alkylation catalysts wherein the water and impurities are removed in order to improve the cycle length of such alkylation catalysts. Water and a portion of impurities are removed in a dehydration zone. A first alkylation zone having a first alkylation catalyst which, in some embodiments is a large pore molecular sieve, acts to remove a larger portion of impurities, such as nitrogenous and other species, and to alkylate a smaller portion of the alkylatable aromatic compound. A second alkylation zone, which in some embodiments is a medium pore molecular sieve, acts to remove a smaller portion of impurities, and to alkylate a larger portion of the alkylatable aromatic compound.

Description

201136869 VI. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for producing an alkylated aromatic compound from a feed stream comprising an alkylating agent, an alkylatable aromatic material, and traces of water and impurities. [Prior Art] Alkylated aromatic compounds (such as cumene·ethylbenzene and secondary butylbenzene) are usually alkylated aromatic materials (such as benzene) and alkylating agents (such as olefins such as ethylene and propylene). The liquid phase alkylation reaction with butene) is carried out in the presence of an acidic molecular sieve catalyst such as zeolite. Compared to earlier vapor phase technologies, liquid phase aromatics alkylation processes typically result in reduced operating costs and the production of less undesirable by-products such as xylene. The acidic molecular sieve catalyst which can be used for the alkylation reaction of the liquid phase aromatic substance includes zeolite/3, zeolite Y, zeolite ω, ZSM-5·. ZSM-12, MCM-22, MCM-36, MCM-49, MCM- 56, MCM-58, MCM-68, UZM-8, faujasite, mordenite, porous crystalline magnesium niobate and tungstate modified oxidation pins (such as Zr (W04) 2 ) Known by technology. The liquid phase aromatics gasification reaction, particularly for relatively low temperature operation, results in a higher catalyst sensitivity (e.g., "catalytic agent") for trace impurities in the alkylateable aromatic or alkylating agent feed stream. This impurity typically results in more frequent catalyst regeneration requirements and reduced end life before being replaced. Catalyst replacement typically includes downtime, lost capacity, and significant cost. A variety of methods have been developed for pretreatment of the parent material and/or the chemical feed stream to remove the catalyst poison. These methods include distillation, adsorption, and extraction. 201136869 U.S. Patent No. 6,3, 3, 3, 62 (Green) proposes an aromatics alkylation process in which an alkylation product is contacted with a macroporous molecular sieve catalyst (such as MCM-22) in a liquid phase step. The impurities are removed prior to the phase alkylation process. The impurities removed are said to include olefins, dienes, styrene, oxygen-containing organic compounds, sulfur-containing compounds, nitrogen-containing compounds, and oligomeric compounds. U.S. Patent No. 4,3,8,3,62 (Smith) teaches a method for enhancing the catalytic activity of a zeolite catalyst by contacting a feed stream containing impurities which are unfavorable for catalysis with a zeolite absorbent. This discloses the use of an absorbent having a Si/Al ratio greater than 12 to 0.12 member rings and a constraining index between 1 and 12, preferably ZSM-1 1. U.S. Patent No. 5,030,075 (Shamshoum) teaches a process for the production of ethylbenzene wherein the catalyst life is increased by reducing the concentration of water in the feed to the reactor. U.S. Patent No. 5,744,686 (Gajda) teaches a method of removing nitrogen compounds from an aromatic hydrocarbon stream by contacting the aromatic hydrocarbon stream with a selective adsorbent having an average pore size of less than about 5.5 angstroms. The selective adsorbent is a non-acid molecular sieve' which is selected from the group consisting of pore-sealed zeolite 4A, zeolite 4A, zeolite 5A, smectite, F-phthalmic rock, ZSM-5, and mixtures thereof. One method of preparing alkylated benzene is disclosed in U.S. Patent No. 6,297,417 (Samson). The method comprises reacting a benzene feedstock with a solid acid (e.g., an acidic clay or an acidic zeolite) in the pretreatment zone at between about 130 ° C and about 300 °. (: Temperature contact between to improve the life of alkylation and transalkylation catalysts. US Patent No. 6, 3 5 5, 8 5 1 (Wu) discloses zeolite-catalyzed iso-201136869 propylbenzene synthesis, in which benzene is used. Contact with a "hot" clay bed, and then the benzene feedstock is distilled to separate the benzene from the higher molecular weight species formed by the olefinic agent during the hot clay treatment and then subjected to "cold" clay treatment wherein the benzene distillate is contacted with normal temperature clay. The propylene feedstock is pretreated by contact with alumina to remove traces of sodium compounds and moisture, contact with molecular sieves to remove water, and contact with the two modified aluminas to remove other catalyst poisons. The pretreated propylene and benzene starting materials are then reacted in the presence of a zeolite catalyst to form cumene without a rapid decrease in catalyst activity. The PCT published application W00214240 (Venkat) discloses the removal of aromatic materials. A method of polar contaminants by using a molecular sieve having a pore size greater than 5.6 angstroms at a temperature below 13 (TC contact). U.S. Patent No. 6,894,20 (Schmidt) discloses use. A conventional adsorption bed for adsorbing an alkaline organic nitrogen compound and a thermal adsorption bed of an acidic molecular sieve adsorbing a weakly basic nitrogen compound (such as nitrite) remove a nitrogen compound from a domesticated substrate such as benzene before the alkylation reaction. Schmidt pointed out that water contributes to the adsorption of weakly basic nitrogen compounds and the alkylation of the substrate stream to increase the temperature and the appropriate water concentration from the fractionation tube to the thermal adsorption bed. US Patent No. 7, 1 99, 27 5 (Smith) a hydrocarbon conversion process in which a partially dehydrated hydrocarbon feedstock and at least two different molecular sieve materials (including a first molecular sieve having a Si/Al molar ratio of less than about 5 and a Si/Al molar ratio of greater than about 5) In addition, in the method proposed by Smith, the material is contacted with a first molecular sieve having a pore of at least about 6 angstroms and a second molecular sieve having a pore of less than about 6 angstroms. These prior references do not provide a feed stream by means of a feed stream. The alkylation reaction with the alkylation catalyst is carried out in 201136869, wherein the feed stream contains a chemical agent and traces of water and impurities and a portion of the water is simultaneously removed. The water and medium present in the feed stream are alkylated. Catalysis in the law The nature and length of the cycle are therefore required to make the alkylation of the feed stream with the first and then with a different portion of the water and impurities and the alkylation of the aralkyl to mitigate water and impurities. A negative impact on this alkylation touch. This disclosure is consistent with this and other aspects. [Disclosure] This disclosure describes a process for producing a portion of an alkylated aromatic and selective impurity from a feed stream comprising an alkylating agent, traces of water, and impurities. In the dehydration zone bed, the dehydration stream and the alkylating agent are contacted with a second alkylation catalyst of the first alkylation, wherein any residue is removed simultaneously. Alternatively, in the non-reactive first catalyst contact, Wherein any residual impurities are removed from contact with the alkylation catalyst and alkylated with an alkylating agent - in some embodiments, the first alkylation zone is a pore molecular sieve. In some embodiments, the second alkane medium is a mesoporous molecular sieve or a M C Μ - 2 2 family material. Without wishing to be bound by any theory, it is believed that this dehydration selectively reduces the alkylation of the aromatic material in the alkylate-containing aromatic material feed, and the impurity of the alkylation impurity in the feed stream is negatively impacted by the alkylation of the contact group. The improved method is based on the activity of the medium and the length of the cycle by the dialkylation catalyst contact. A method of alkylating aromatic substances and group compounds. The water was removed. The reactive protective agent is contacted, and then the impurities are left in the flow through the alkane guard bed, the dehydrated stream and the mass, and then the second in the first alkylation catalyst system of the ruthenium The alkylation step reduces the water concentration and selects the impurity content. Part of the impurity -8 - 201136869 is removed simultaneously with a part of the water. This facilitates the removal of a portion (preferably a majority) of residual impurities (such as nitrogen or other species) contained in the feed of the alkylateable aromatic material by the first alkylation step, and the alkylation of the aromatics A portion of the family compound is alkylated. Preferably, at least 80%, at least 70%, or at least 60% by weight of residual impurities are removed. This second alkylation step is also used to remove a portion of the residual impurities and to alkylate most of the alkylateable aromatic species. Preferably, at least 80%, at least 70% or at least 60% by weight of the alkylatable aromatic compound is alkylated with an alkylating agent. The alkylated aromatic compound produced mainly comprises a monoalkylated aromatic compound and a trace amount of the polyalkylated aromatic compound which is produced in the alkylation reaction zone. This polyalkylated aromatic compound can then be converted to an additional monoalkylated compound by contact with an additional alkylatable aromatic compound in the presence of a separate transalkylation catalyst in a transalkylation step. [Embodiment] Definitions The term "alkylatable aromatic compound" as used herein means an aromatic compound which is acceptable for an alkyl group. A non-limiting example of an alkylatable aromatic compound is benzene. The term "alkylating agent" as used herein refers to a compound which provides an alkyl group of an aromatic compound which can be alkylated. Non-limiting examples of alkylating agents are ethylene, propylene, and butene. Another non-limiting example is any polyalkylated aromatic compound capable of providing an alkyl group of an alkylate that can be alkylated. The term "aromatic material" as used herein refers to an alkylated aromatic compound useful herein according to the recognized range of the art, including substituted and unsubstituted mono- and polynuclear compounds. Aromatically characterized compounds having a hetero atom such as N or S are also useful 'as long as they do not act as a catalytic agent as defined below under the selected reaction conditions. By "at least a portion of the liquid phase" herein is meant a mixture having at least 1% by weight liquid phase, optionally at least 5% by weight liquid phase, at a selected temperature, pressure and composition. The term "catalytic agent" as used herein refers to an impurity defined herein to reduce the cycle time of a molecular sieve or a zeolite. The term "cycle length" as used herein refers to the total running time between regenerations, or the running time between new loading and regeneration. After the unused catalyst or regenerated catalyst is used for operation, the catalyst is passivated by coke deposition or poison. As the catalyst is passivated, the reaction zone must be operated at a higher temperature to maintain the same capacity or catalytic activity. Once the temperature of the reaction zone reaches a critical temperature (basically determined by the metallurgy of the reactor) or when there are economic factors, the catalyst must be regenerated. The "network type" herein has the meaning described in "Atlas of Zeolite Framework Types", Ch. Baerlocher, W. M. Meier and D. H. Olson (Elsevier, 5th Ed., 2001). The number of the periodic table family elements used here has Intetnational

The meaning described in the Periodic Table of the Elements published by Union of Pure and Applied Chemistry on June 22, 2007. The term "impurities" as used herein includes, but is not limited to, compounds having at least one of the following elements: nitrogen, halogen, oxygen, sulfur, arsenic, selenium, hoof, ortho and Group 1 to Group 12 metals. -10- 201136869 The amount of impurities used in this disclosure refers to the number of wppm of impurities based on the total weight of the aromatized aromatic compound and the bulking agent in the reaction zone. The so-called "MCM-22 family of materials," (or "MCM-22 family of materials" or "MCM-22 family of molecular sieves") include: (i) from a general primary crystal building block (building block) "with M WW A molecular sieve formed by a network of unit cells. The unit cell is a spatial arrangement of atoms that are tilted in a three-dimensional space describing the crystal, as described in "Atlas of Zeolite Framework Types,,, Ch.

Baerlocher, WMMeier and DHOlson (Elsevier, 5, h Ed., 2001); (Π) formed by a general secondary construction unit, 2-dimensionally inclined MWW network type unit cell 'with one unit cell thickness a single layer", preferably a c-unit unit cell thickness, formed molecular sieve; (iii) a molecular sieve formed by a general secondary construction unit, "one or more layers exceeding one unit cell thickness", wherein A layer having more than one unit cell thickness is formed by stacking, encapsulating, or combining a single layer of at least two unit cell thicknesses of a unit cell having a MWW network topology. The stack of secondary construction units may be in a regular manner, an irregular manner, a random manner, and any combination thereof; or (iv) by any rule or random 2-dimensional or unit cell having a MWW network topology The molecular sieve formed by the 3-dimensional combination. The MCM-22 family of materials is characterized by an X-ray diffraction pattern including d-spacing maximum enthalpy at 12.4 ± 0.25, 3.57 ± 0.07, and 3.42 ± 0.07 angstroms (calcined or synthesized). The MCM-22 family material is also -11 - 25, 201136869. The X-ray diffraction pattern includes the lattice face distance maximum 値 at 12.4 ± 0. 6.9 ± 0.15, 3.57 ± 0.07 and 3.42 ± 0 · 07 angstroms are characteristic (by calcination into a form). The X-ray diffraction data used as a feature of molecular sieves was measured using a copper κ-α double line as the incident ray and a diffractometer equipped with a scintillation meter and associated computer as a collection system. The term "monoalkylated aromatic compound" as used herein means an aromatic compound having only one substituent. Non-exemplified examples of monoalkylated aromatic compounds are ethylbenzene, cumene and secondary butylbenzene. By "running" herein is meant that the catalyst is under alkylation or transalkylation conditions for alkylation or transalkylation conditions including temperature, pressure, alkylatable aromatization, alkylating agent and WHSV, which are suitable for at least 1 weight. Preferably, at least a quantity of the alkylatable aromatic compound (based on the total amount of the alkylateable aromatics in the feed) is converted to the monoalkylated aromatic compound. The term "toxicity" as used herein refers to the absorption of Colin base (a catalyzed poison) mole number per gram of catalyst sample (which has been dried at 60 ° C for 60 minutes), which is used in a thermogravimetric analyzer (Model Q5000). Instruments, New Castle, manufactured by Delaware). Dry, the partial pressure of Colin base was 3 Torr, and the Colin base catalyzed poison was sprayed on the contact for 60 minutes. The poisoning power was calculated from the following formula: (the weight of the catalyst sample sprayed with Colin base - the weight of the dried catalyst sample) 〇6+ (the amount of the Co-X dry X catalyst sample). When the catalyst sample weight and the dry catalyst sample weight are expressed in grams, the molecular weight of the Colin base is gram per millimole. The term "polyalkylated aromatic compound" as used herein means having an excess or a combination of alkane limits. The compound 10 is combined with the milli-TA after the flow of the base after the base is dried 12 1.2 a -12-201136869 alkyl substituent aromatic compound. Non-limiting examples of polyalkylated aromatic compounds are polyalkylated benzenes such as diethylbenzene, triethylbenzene, diisopropylbenzene and triisopropylbenzene. The term "wppb" is defined herein as 'per billion parts by weight. The term "wppm" as used herein is defined as 'parts per million by weight. Starting Materials and Products Suitable unsubstituted aromatic compounds which may be disclosed herein include benzene, naphthalene 'anthracene, fused tetraphenyl, anthracene, anthracene and phenanthrene. Benzene is preferred. The substituted aromatic compound which can be used in the disclosure should have at least one hydrogen atom bonded directly to the aromatic nucleus. The aromatic ring may be substituted with one or more alkyl, aryl, alkaryl, alkoxy, aryloxy, cycloalkyl, halogen and/or other groups which do not interfere with the alkylation reaction. Typically, the alkyl group which may be present on the substituent on the aromatic compound contains from 1 to about 22 carbon atoms and is usually from about 1 to 8 carbon atoms, and most usually from about 1 to 4 carbon atoms. Suitable substituted aromatic compounds which may be used herein include, but are not limited to, toluene, xylene, cumene, n-propylbenzene, alpha-methylnaphthalene, ethylbenzene, 1,3,5-trimethylbenzene, anthracene. , isopropyl toluene, butylbenzene, 1,2,4-trimethylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, isoamylbenzene, isohexylbenzene, pentaethylbenzene, pentamethylbenzene ; 1,2,3,4-tetraethylbenzene; 1,2,3,5-tetramethylbenzene; 1,",4-triethylbenzene; 1,2,3-trimethylbenzene, m-butyl Toluene; p-butyltoluene; 3,5-diethyltoluene; o-ethyltoluene; p-ethyltoluene; m-propyltoluene; 4-ethyl-m-xylene; dimethylnaphthalene ; ethyl naphthalene; 2,3-dimethylhydrazine; 9-ethyl hydrazine; 2-methyl hydrazine; o-methyl hydrazine; 9,1 〇-dimethyl-13- 201136869 phenanthrene; Base-Philippines. Higher molecular weight alkyl aromatic hydrocarbons can also be used as starting materials and include aromatic hydrocarbons such as those produced by alkylation of aromatic hydrocarbons with olefin oligomers. This product is commonly referred to as a hospital base in the art and includes, but is not limited to, hexylbenzene, anthracene, laurylbenzene, pentadecylbenzene, hexyltoluene, decyltoluene, lauryltoluene, fifteen toluene, and the like. . It is very common to obtain an alkylate in the form of a high-boiling fraction, which has an alkyl size change from about C6 to about C16. A reformate stream which may contain substantial amounts of benzene, toluene and/or xylene is particularly suitable as an alkylateable aromatic material feed for use in the disclosed process. Although this method is particularly directed to the manufacture of ethylbenzene from polymer grades and dilute ethylene, it can also be used to make other C7-C2 alkylaromatic compounds (such as cumene) and C6+alkylaromatics (such as c8-). Cl6 straight chain and near linear alkyl benzene). Suitable alkylating agents which may be used herein include olefinic compounds, alcoholic compounds and/or alkylbenzenes, and mixtures thereof. Other suitable alkylating agents which may be used in the processes disclosed herein generally include, but are not limited to, any aliphatic or aromatic having one or more usable alkylating groups capable of reacting with an alkylatable aromatic compound. Organic compound. Examples of suitable alkylating agents are c2-c16 olefins, such as c2-c5 olefins, including ethylene, propylene, butene, and pentene; Ci-Cu-alcohols (including monools, diols, triols, etc.), Preferred are (^-0:5 alcohols such as methanol, ethanol, propanol, butanol and pentanol; c2-c2 oxime ethers, such as c2-c5 ethers, including dimethyl ether and diethyl ether: aldehydes such as formaldehyde, Acetaldehyde, propionaldehyde, butyraldehyde and n-pentanal; and alkyl halides such as methyl chloride, ethyl chloride, propyl chloride, butyl chloride, and pentyl chloride; polyalkylated aromatic compounds' a dialkylated benzene (such as diethylbenzene or diisopropylbenzene) and a trialkylated benzene (-14-201136869 such as triethylbenzene or triisopropylbenzene), etc. Therefore, the alkylating agent is preferably selected from the group consisting of C2-c5 olefin, CrC5 alcohol, diethylbenzene, diisopropylbenzene, triethylbenzene and/or triisopropylbenzene. Impurities In this disclosure, the feed stream comprising an alkylatable aromatic compound may comprise impurities. Optionally, the first alkylating agent stream and/or the second alkylating agent stream may comprise impurities. The impurities comprise a compound having at least one of the following elements: nitrogen, halogen, oxygen, sulfur 'arsenic, selenium, tellurium, phosphorus with Group 1 to Group 12. Metals include Colin base and N-methyl morphomorph. For the purposes of this disclosure, "impurities" do not include water, H20. - In some embodiments, The amount of impurities in the feed stream (or the first and/or second alkylating agent stream) is less than 20 wppm by weight of the feed stream 'less than 15 wppm > less than 10 wppm, less than 5 Wppm or less than 1 wppm In one or more embodiments, the feed stream may comprise water. Optionally, the first alkylating agent stream and/or the second alkylating agent stream may comprise water. The stream or alkylating agent stream can be dehydrated by, for example, distillation, adsorption, evaporation, extraction or flash evaporation in one or more dehydration zones. The dehydration zone can be a distillation column, a benzene column or a steaming column, a light component column ( 1 ights C ο 1 um η ) or extractor, absorber or quench drum 〇 In some implementations, the feed stream is saturated with water and temperature conditions -15- 201136869. Other implementations The amount of water in the feed stream is at least 500 wppm, at least 400 wppm, 3 wppm or at least 200 wppm by weight of the stream. It is determined by techniques such as GC, GC/MS, and other suitable techniques known to those skilled in the art. The methods disclosed in the reaction conditions include: (1) removing at least a portion of the water and selectivity in the dehydration zone under suitable dehydration conditions. (1) the first alkylation reaction zone has a first alkylation catalyst, and the first alkylation zone is first adapted to remove most of the residual impurities and to alkylate a portion of the alkylatetable compound Operating under the reaction conditions; (3 the alkylation reaction zone has a second alkylation zone different from the first alkylation catalyst; the second alkylation zone is suitable for removing a part of the residual impurities and the macroalkylated aromatic substance is The alkylation is carried out under the second reaction conditions to produce an additional amount of the monoalkylated compound. In the dehydration zone, suitable dehydration conditions are conventional dehydration conditions for separating water and impurities from the self-mass stream known in the art. In the first alkylation reaction zone and/or the second alkylation reaction zone, the first and second conditions when the aromatic compound and the alkylating agent are contacted under at least partial liquid phase conditions include a temperature of 100 to 2 8 respectively. 5 ° C, , the temperature is 150 to 260 ° C; the pressure is 689 to 4601 kPa-a, the pressure is 1 500 to 3 000 kPa-a; and for the total reactor, the alkylating agent and the alkane The aromatic-based WHSV is 103. The feed is less than 300 or the quality of the operation is one of the first aromatics. The second medium, when part of the aromatic aromatics can be alkylated, Preferably, the two are: 100 small -16 - 201136869 hours -1, preferably, 20 to 50 hours 1 . The total molar ratio of the alkylatable aromatic compound to the alkylating agent (such as benzene and ethylene, respectively) ranges from 1:1 to 10: 1, 2: 1 to 8: 1, 3: 1 to 7: 1 , or 1.5: 1 to 4.5: 1. In some embodiments, the first alkylation reaction zone can be operated in the form of a reactive guard bed in which at least a portion of the impurities in the feed stream are removed. In this embodiment, the total molar ratio of the alkylatable aromatic compound to the alkylating agent (such as benzene and ethylene, respectively) is much higher when used alone for alkylation purposes, ranging from 10: 1 to 200. : 1' or 15: 1 to 150: 1, or 20: 1 to 100: 1 or 25: 1 to 50: 1. In other embodiments, the first reactive alkylation zone is a first reaction zone operated in the form of a non-reactive guard bed that removes at least a portion of the impurities in the feed stream. In this embodiment, only the alkylatable aromatic compound is supplied to the first reaction zone. In some embodiments, the disclosed method includes a processing zone having a processing material, wherein the processing zone is operated under appropriate processing conditions. Remove a portion of the impurities. This treatment zone can be upstream or downstream of the dewatering zone. This treatment zone is upstream of the first and second alkylation zones. When a portion of the impurities is removed using the treatment material, suitable processing conditions include a temperature of from about 30 to 200 ° C, and preferably between about 60 and 150 ° C, and a weight space velocity per hour (WHSV) of about 0.1 hours. Up to about 200 hours ^, preferably from about 0.5 hours _1 to about 100 hours _1, and more preferably from about 1. 〇 hour _1 to about 50 hours _1; and the pressure is between about atmospheric pressure and 3 0 0 0 k P a - a between. In some embodiments, the disclosed method includes a transalkylation zone that operates under appropriate transalkylation conditions to produce additional from polyalkylated aromatic compounds and aromatic compounds that can be alkylated at -17-201136869 A quantity of a monoalkylated aromatic compound. In the transalkylation zone, when the polyalkylated aromatic compound (such as polyethylbenzene or polycumene) is contacted with the alkylatable aromatic compound under at least partial liquid phase conditions, suitable transalkylation conditions Including a temperature of from about 100 to about 300 ° C and a pressure of 696 to 4137 kPa-a (101 to 600 psia) based on the weight of the polyalkylated aromatic compound to the alkylation reaction zone. The WHSV is from about 0.5 hours η to about 100 hours μ and the molar ratio of benzene to the polyalkylated aromatic compound is from 1:1 to 3:1, preferably, from 1:1 to 1 0:1. Good place, 1: 1 to 5: 1. Catalyst The disclosed method includes: (1) a first alkylating catalyst: and (2) a second alkylating catalyst different from the first alkylating catalyst. The first hospitalized catalyst contains a large pore molecular sieve having a Constraint Index of less than 2 and a first poisoning power. The Constraint Index is a convenient indicator of the extent to which aluminosilicates or molecular sieves control the size of molecules of different sizes to their internal structure. For example, aluminophthalic acid, which is extremely difficult to access and does not readily exit from its internal structure, has a high confinement index, and such aluminosilicates typically have small pores, such as less than 5 angstroms. On the other hand, the aluminosilicate having a very close access to the internal aluminosilicate structure has a low confinement index and is usually macroporous. The method for determining the constraint index is fully described in U.S. Patent No. 4, 〇 16, 2 18 .

Suitable macroporous molecular sieves include zeolite/3, zeolite Y, Ultrastable Y (USY) 'Dealuminized Y (Deal Y) ' Ultrahydrophobic Y -18- 201136869 (UHP-Y) 'Rare Earth Exchanged Y (REY), mordenite, TEA - Mordenite, ZSM-3, ZSM-4, ZSM-14, ZSM-18, and ZSM-20. Zeolite ZSM-14 is described in U.S. Patent No. 3,923,63. The zeolite ZSM-20 is described in U.S. Patent No. 3,972,983. Zeolites are described in U.S. Patent Nos. 3, 3 08, 〇 69, and U.S. Reissue Patent No. 2 8, 3 4 1 . Low sodium Ultrastable Y molecular sieves (USY) are described in U.S. Patent Nos. 3,293,192 and 3,449,070. 〇63111111111126 (1丫 zeolite (〇631丫) can be prepared by the method of U.S. Patent No. 3,442,795. Ultrahydrophobic Y (UHP-Y) is described in U.S. Patent No. 4,401,556. Rare Earth exchanged Y (REY) U.S. Patent No. 3,524,820. Mordenite is a naturally occurring material, but can also be obtained in synthetic form, such as TE A-mordenite (i.e., synthetic mercerized from a reaction mixture comprising a tetraethylaluminum directing agent). Zeolites. TEA-mordenite is described in U.S. Patent Nos. 3,766,093 and 3,894,104.

The International Zeolite Association Structure Committee (IZA-SC) designates a MWW topological zeolitic material with a multilayer material having two pore systems derived from both 10 and 12 membered rings. The Atlas of Zeolite Framework Types currently classifies materials with this same topology into at least five different names including, but not limited to, MCM-22, ERB-1, ITQ-1, PSH-3, and SSZ-25. In some embodiments, the second alkylating catalyst comprising the MCM-22 family molecular sieve, preferably an acidic catalyst, has a second poisoning power. MCM-22 family molecular sieves have been found to be useful in a variety of hydrocarbon conversion processes. Examples of MCM-22 family molecular sieves are MCM-22, MCM-36, MCM-49, MCM-56, -19·201136869 ITQ-l, ITQ-2, ITQ-30, PSH-3, SSZ-25, ERB- 1 and UZM-8 o Materials belonging to the MCM-22 family include MCM-22 (described in U.S. Patent No. 4,954,325), PSH-3 (described in U.S. Patent No. 4,439,409), 352-25 (described in U.S. Patent Case No. 4,826,667), Ugly 118-1 (described in European Patent No. 0293032), ITQ-1 (described in U.S. Patent No. 6,077,498), ITQ-2 (described in International Patent Publication No. WO97/1 7290) ), IT Q - 3 0 (described in International Patent Publication No. WO2005 1 1 8476), MC Μ - 3 6 (described in US Patent No. 5,250,277), 14 €1^-49 (described in the US Patent No. 5, 236, 575), ^^1^-56 (described in U.S. Patent No. 5,362,697), and 1^1^-8 (described in U.S. Patent No. 6,756,030). It is understood that the aforementioned MCM-22 family molecular sieve differs from the conventional large pore zeolite alkylation catalyst (such as mordenite) discussed below in that the MC Μ - 2 2 material has a 12 - ring surface pocket which is not internal to the ruthenium ring of the molecular sieve. The pore system is in communication with a second alkylation catalyst, preferably an acidic catalyst, comprising a mesoporous molecular sieve having a Constraint Index of 2-12 (as defined in U.S. Patent No. 4,016,218), including ZSM-5, ZSM- 1 1. ZSM-1 2. ZSM-22, ZSM-2 3, ZSM-35 and ZSM-48. ZSM-5 is described in detail in U.S. Patent No. 3,702,886 and U.S. Patent No. 29,948. ZSM-11 is described in detail in U.S. Patent No. 3,709,979. ZSM-12 is described in U.S. Patent No. 3,8 3 2,449. ZSM-22 is described in U.S. Patent No. 4,5,567,77. 231^-23 is described in U.S. Patent No. 4, No. 76,842. 23^1-35 is described in the United States -20- 201136869 Patent No. 4,0 1 6,245. ZSM-48 is more specifically described in U.S. Patent No. 4,234,231. In one or more embodiments, the first poisoning power of the first alkylating catalyst is greater than the second poisoning power of the second alkylating catalyst, and the poisoning power is determined by Colin base force. In some embodiments, the disclosed methods include processing materials. This treatment material is selected from the group consisting of clay, resin, Linde type x, Linde type A, and combinations thereof. This treatment material can be acidic or non-acidic. In some embodiments, the disclosed methods include transalkylation catalysts. The transalkylation catalyst comprises a macroporous molecular sieve having a Constraint Index of less than 2. The transalkylation catalyst can be the same or different than the first alkylation catalyst. DETAILED DESCRIPTION OF THE PROCESS In an embodiment (e.g., a reactive guard bed), the method for producing an alkylated aromatic compound (e.g., a monoalkylated and polyalkylated aromatic compound) comprises the following steps : (a) supplying a feed stream to a dehydration zone comprising an alkylatable aromatic compound, water, and an impurity 'where the impurity comprises a compound having at least one of the following elements: nitrogen, halogen, oxygen , sulphur, monument, sun, sulphur, ortho to Group 1 Group 12 metal, (b) in the dewatering zone, removing at least a portion of the water from the feed stream to produce the alkylate An aromatic compound, any residual water, and a dehydrated stream of the impurity; (c) causing at least a portion of the dehydrated stream and the first alkylating agent stream to be associated with the first alkylating catalyst having a first poisoning power In the first alkylation reaction zone, in contact with at least a portion of the liquid phase first reaction conditions, at least a portion of the impurity is removed by shifting - 21,368,869, and a portion of the alkylatetable aromatic compound is An alkylating agent stream is alkylated to produce a first alkylation stream, This first alkylation stream comprises an alkylated aromatic compound (such as a monoalkylated and polyalkylated aromatic compound), an unreacted alkylatable aromatic compound, any residual water, and any residual Impurity, preferably wherein the residual impurity is reduced by at least 25% and (d) such that the first alkylation stream and the second alkylating agent stream are different from the impurity in the dehydrated stream Contacting a second alkylation catalyst of the first alkylation catalyst, the second alkylation catalyst having a second poisoning force in the second alkylation reaction zone and at least a portion of the liquid phase second reaction conditions, such that At least a portion of the unreacted alkylatable aromatic compound is alkylated with the second alkylating agent stream and produces a second alkylation stream comprising additional (etc.) alkylation. An aromatic compound, an unreacted alkylatable aromatic compound, any residual water, and any residual impurities in the reactive bed, poisoning the reactive impurities of the second alkylating catalyst (such as a catalytic agent) Part of the feed stream from the first alkylation reaction zone is shifted by the first alkylation catalyst The alkylatable aromatic compound is alkylated with an alkylating agent. In another embodiment (e.g., a non-reactive guard bed), the method for making an alkylated aromatic compound (e.g., a monoalkylated and polyalkylated aromatic compound) comprises the steps of: (a Providing a feed stream to a dehydration zone comprising an alkylatetable aromatic compound, water, and impurities, wherein the impurity comprises a compound having at least one of the following: nitrogen, halogen, oxygen, sulfur , arsenic, selenium, tellurium, phosphorus, and Group 1 to Group 12 metals; -22- 201136869 (b) in the dehydration zone, removing at least a portion of the water from the feed stream to produce the hexane a derivatized aromatic compound, any residual water, and a dehydrated stream of the impurity; (c) aligning at least a portion of the dehydrated stream with a first catalyst having a first poisoning force in the first reaction zone Contacting at least a portion of the liquid phase under the first reaction conditions to remove at least a portion of the impurity/and resulting in a reduction in the amount of impurities and comprising the alkylatable aromatic compound, any residual water, and any residual impurities Aromatic logistics, which is compared to Preferably, the impurity in the dehydration stream is reduced by at least 25%; and (d) the alkylate and alkylating agent stream of step (c) is different from the alkane different from the first catalyst Contacting the catalyst, the alkylation catalyst has a second poisoning power higher than the first poisoning force, and the contacting occurs in the alkylation reaction zone and at least a portion of the liquid phase second reaction conditions, so that the At least a portion of the reactable alkylatable aromatic compound is alkylated with the second alkylating agent stream and produces a second alkylation stream comprising an alkylated aromatic compound, unreacted An alkylateable aromatic compound, any residual water, and any residual impurities. In a non-reactive guard bed, the impurity is removed from the feed stream in the first reaction zone by the first catalyst under the alkylation reaction in the absence of an alkylating agent and without an alkylating aromatic compound. Preferably, at least 80%, or at least 70%, or at least 60%, or at least 50% by weight of the impurities are removed in step (c). Optionally, in step (b), at least a portion of the impurities in the feed stream are removed in the dewatering zone. Preferably, after step (b), the impurities in the dewatered stream are 1% lower than the impurities in the feed stream, -23-201136869 is 5% lower or 1% lower. More preferably, after removing at least a portion of the impurity in the dehydration zone, the dehydrated stream has an impurity of less than 1 000 wppb, less than 750 wppb, less than 500 wppb or less than 250 wppb. In the reactive guard bed, the first poisoning power of the first alkylating catalyst may be higher than the second poisoning power of the second alkylating catalyst. Preferably, the first poisoning power of the first alkylating catalyst is at least 5% higher than the second poisoning power of the second alkylating catalyst, at least 10%, at least 15%, at least 2 0 %, at least 2 5 %, at least 3 %, at least 3 5 %, at least 40 %, at least 4 5 % or at least 50 %. In the non-reactive guard bed, the first poisoning force of the first catalyst may be higher than the second poisoning power of the alkylating catalyst. Preferably, the second poisoning power is at least 5%, at least 1%, at least 1%, at least 20%, at least 25%, at least 30%, at least 35% higher than the second poisoning power of the alkylation catalyst. , at least 40%, at least 45% or at least 50%. In the reactive guard bed, the portion of the alkylated aromatic compound alkylated by the alkylating agent in step (e) is at least 1%, at least 2%, at least 5% of the alkylatable aromatic compound. , at least 7%, at least 1%, at least 1 3 % or at least 1 5 %. In the reactive guard bed, the flow rate of the second alkylating agent stream can be greater than the flow rate of the first alkylating agent stream. Preferably, the flow rate of the second alkylating agent stream is at least 5% higher than the flow rate of the first alkylating agent stream, at least 10%, at least 15%, at least 20%, at least 25%, at least 30 % 'at least 35%, at least 40%, at least 45% or at least 50%. In some embodiments, prior to step (c), the dehydrated stream is supplied to a treatment zone containing the treatment material, and then the dewatered stream is contacted with the treatment material in the treatment zone at -24,368,869 under appropriate processing conditions. And removing at least a portion of the residual impurity mass and forming the first alkylation stream. In these embodiments, after contact with the treated material, the amount of impurities is 1% lower, 5% lower, 10% lower, or 15% lower than the dehydrated stream. In other embodiments, prior to step (a), the feed stream is supplied to a treatment zone containing the treatment material, and then the feed stream and the treatment material in the treatment zone are adapted to remove at least a portion of the impurity. Contact under appropriate processing conditions. Preferably, the amount of impurities after treatment is 1% lower, 5% lower, 10% lower or 15% lower than the feed stream. In these embodiments, the treatment material is selected from the group consisting of clay, resin, activated oxidation, Linde type X, Linde type A, and combinations thereof. In a reactive guard bed, the first alkylating catalyst is a macroporous molecular sieve having a Constraint Index of less than 2. This macroporous molecule was screened from zeolite/3, faujasite, zeolite Y' Ultrastable Y (USY) 'Dealuminized Y (Deal Y) 'Rare Earth Y (REY), Ultrahydrophobic Y (UHP-Y), mordenite, TEA- Mordenite, ZSM-3, ZSM-4, ZSM-14, ZSM-18, ZSM-20, and combinations thereof <· In a non-reactive guard bed, the first catalyst is a macroporous molecular sieve having a Constraint Index of less than 2. This macroporous molecule was screened from zeolite A, faujasite, zeolite Y ' Ultrastable Y (USY)' Dealuminized Y (Deal Υ)' Rare Earth Υ (REY), Ultrahydrophobic Υ (UHP-Y), mordenite, TEA-silk Zeolite, ZSM-3 'ZSM-4, ZSM-14, ZSM-18, ZSM-20, and combinations thereof. a second alkylation catalyst (such as a reactive guard bed) or an alkylation catalyst (such as a non-trans-25-201136869 compliant bed) is a MCM-22 family material having a unit cell of the MWW network topology and The X-ray diffraction pattern is characterized by a lattice spacing of at most 値 at 12.4 ± 0.25, 3.57 ± 0.07, and 3.42 ± 〇 · 〇 7 angstroms. This MCM-22 family material is selected from ERB-1, ITQ-1, ITQ-2, ITQ-30, PSH-3, SSZ-25, MCM-22, MCM-36, MCM-49, MCM-56, UZM- 8. EMM-10, EMM-10P, EMM-12, EMM-13 and mixtures thereof. After removing at least a portion of the water in the dewatering zone, the water in the dewatered stream is less than 100 wppm, less than 50 wppm, less than 25 wppm ' less than 10 wppm, based on the dewatered stream. This water is removed, for example, by distillation, adsorption, evaporation, extraction or flash evaporation. The dehydration zone is a distillation column, a benzene column or a light component column. After removing additional impurities in the first alkylation zone or the first reaction zone, the amount of impurities in the first alkylation stream is 25% lower, 20% lower, and 15% lower than the weight of the feed stream. , 10% lower or 5% lower. Preferably, after the additional impurities are removed in the first alkylation zone, the amount of impurities in the first alkylation stream is less than 100 wppb, 75 wppb, 50 wppb or 25 wppb. The impurities in the second alkylation stream are 10% lower, 5% lower, or 1% lower than the impurities in the first alkylation stream. Preferably, the impurities in the second alkylation stream are less than 1 wppm, 5 wppm, less than 10 wppm 'less than 15 wppm, less than 20 wppm or less than 25 wppm. In some embodiments, the alkane The reaction zone is preferably in a single reactor tank. Alternatively, the first alkylation reaction zone can be located in a separate tank and can be operated by a reactive guard bed. The first reaction zone can be located in a separate tank and can be operated non-reactive -26-201136869. The catalyst in the reactive or non-reactive guard bed is more often regenerated and/or replaced than the second alkylation catalyst, and therefore, is basically equipped with a bypass tube so that the alkylation feed can be stopped while the guard bed is being operated Directly supplied to the reaction zone in series in the reactor. Preferably, the bypassable reactive guard bed is located upstream of the second alkylation zone. A bypassable non-reactive guard bed is located upstream of the alkylation zone. This guard can be operated in a cocurrent upstream or downstream mode. The reactive or non-reactive guard bed is maintained under appropriate at least partial liquid phase conditions. In the reactive guard bed, at least a portion of the alkylatable aromatic compound and at least a portion of the alkylating agent pass through the reactive guard bed prior to entering the second alkylation reaction zone. In a non-reactive guard bed, the alkylatable aromatic compound passes through a non-reactive guard bed before entering the alkylation reaction zone. The catalyst composition used in the reactive or non-reactive guard bed is different from the catalyst composition used in the second and subsequent alkylation reaction zones. The catalyst composition used in the reactive or non-reactive guard bed may have multiple catalyst compositions (e.g., a mixture of mordenite and zeolite Y, or a mixture of zeolite/3 and zeolite Y). The reactive guard bed and each of the general alkylation reaction zones are maintained under conditions effective to initiate alkylation of the alkylatable aromatic compound with the alkylating agent in the presence of an alkylation reaction. In other embodiments, the dewatered stream further comprises at least a portion of the overhead stream from the distillation zone. In another embodiment, the dewatered stream is cooled to condense at least a portion of the dewatered stream to remove at least one of any residual water and impurities -27-201136869. In another embodiment, the method further comprises the step of supplying the dehydrated stream to the distillation zone to remove at least a portion of any residual water prior to contacting step (C). In another embodiment, the method further Included prior to contacting step (C), the dehydrated stream is combined with the fluid from the distillation zone to remove at least a portion of any of the residual water, the distillation zone being a distillation column, a benzene column or a light component column. The method of claim 1, further comprising the step of supplying at least a portion of the dehydrated stream from the dewatering zone to the distillation column in reflux. In some embodiments, the alkylenable aromatic compound is benzene. The first alkylating agent stream or the second alkylating agent stream comprises an olefin. Optionally, the first or second alkylating agent stream comprises only alkylating agents and impurities, or only a domesticating agent and water, or an alkylating agent and a mixture of impurities and water. In some embodiments, The alkylated aromatic compound is a single-chambered aromatic compound. In this case, the alkylating agent is ethylene and the single-combined aromatic compound is ethylbenzene, or the alkylating agent is propylene and the single-combined aromatic compound is cumene or the alkylating agent. Butene and the single-institutional aromatic compound is a secondary butylbenzene. In some embodiments of the invention, the monoalkylated aromatic stream, and optionally the multi-combined compound stream, is separated from the second mesa stream. The olefinized compound is a multi-chambered aromatic compound, and the method further comprises the step (e) of ordering the polyalkylated aromatic compound and the transalkylation catalyst in trans-alkane, preferably from -28 to 201136869 The reaction zone is contacted under transalkylation conditions suitable for the manufacture of additional amounts of the monoalkylated aromatic compound. In another embodiment, the transalkylation catalyst is a macroporous molecular sieve having a Constraint Index of less than 2. In another embodiment, the macroporous molecule is selected from the group consisting of zeolite strontium, faujasite, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), Rare Earth Y (REY), mordenite, TEA-mordenite , ZSM-3, ZSM-4, ZSM-18, ZSM-20, and combinations thereof. The alkylation reactor used in the process of the present disclosure may be highly selective for the desired monoalkylated aromatic compound (e.g., ethylbenzene), but at least some polyalkylated species are produced at least. The effluent from the final alkylation reaction zone can be subjected to a separation step to recover the monoalkylated and polyalkylated aromatic compound. At least a portion of the polyalkylated aromatic compound can be supplied to a transalkylation reactor which can be separated from the alkylation reactor. In the transalkylation reactor, the polyalkylated aromatic compound is reacted with an alkylatable aromatic compound to produce an effluent containing additional monoalkylated aromatic compounds. At least a portion of these effluents can be separated to recover the alkylated aromatic compound (monoalkylated aromatic compound and/or polyalkylated aromatic compound). One or more embodiments of this disclosure are illustrated in Figures 1-8. Figure 1 shows a process 50 for producing an alkylated aromatic compound (e.g., a monoalkylated aromatic compound such as ethylbenzene) wherein feed stream 1 (containing an alkylatable aromatic compound, water) And impurities) are supplied to the processor 2 (having a treatment zone 2a and containing the treatment material 4), which is processed under the processing conditions (refer to the foregoing) suitable for removing the first part of the hybrid -29-201136869, and is produced and processed. The stream flows out of the stream 5. Optionally, the processor effluent stream 5 is heated or cooled in the heat exchanger 12a. The processor effluent stream 5 is then supplied to a dewatering zone 14 (e.g., a light component removal distillation column) where at least a portion of the water and a second portion of the impurity are selectively removed from the processor effluent stream 5. To produce a dehydrated stream 13 comprising the alkylatable aromatic compound, any residual amount of water, and the impurity. The dewatering stream 13 is supplied to the accumulation tank 16 of the distillation zone 18. The distillation zone 18 can be a benzene distillation column. In the accumulation tank 16, the dewatering stream 13 is combined with the overhead stream 15 from the distillation zone 18 (which is cooled by the heat exchanger l2c) to produce the cumulative tank effluent 17. A portion of the accumulated tank effluent 17 is supplied to the distillation zone 18 in the form of a reflux 19. Vapor 24 from accumulation tank 16 is supplied to dewatering zone 14 for further separation. The fluid 2 1 accumulates the residual portion of the tank effluent 17 , forms the alkylateable aromatic feed stream 41 to the alkylator 20, and the alkylatetable aromatic feed stream to the transalkylation unit 30. . Alternatively, fluid 2 1 can be heated or cooled in heat exchanger 12b. The heavy compound (e.g., polyalkylated aromatic compound) is removed as a bottoms stream 22 of distillation zone 18 and separated in a downstream separation apparatus (not shown) to produce a monoalkylated aromatic compound (e.g., ethylbenzene). And a polyalkylated aromatic compound (such as the polyalkylated feed stream 39a, discussed below). The oximation unit 20 has at least a first alkylation zone 20a (which contains a first alkylation catalyst 26) Located upstream of and in communication with at least a second alkylation zone 2〇b (which contains a second alkylation catalyst 28). In some embodiments, there are a plurality of alkylation zones connected in series. The first alkylating catalyst has a first poisoning power and the second alkylating catalyst has a second poisoning power of -30-201136869, wherein the first poisoning power is greater than the second poisoning power. In this embodiment, the first alkylation reaction zone reactive guard bed' is entirely within the alkylator 20. The first alkylation catalyst 26 comprises a macroporous molecular sieve having a Constraint Index of less than 2. In some embodiments, the second alkylation catalyst comprises a molecular sieve of the MCM-22 family, please refer to the foregoing. In other embodiments, the second alkylation catalyst comprises a mesoporous molecular sieve having a number of constraints of from 2 to 12. In the first alkylation zone 20a, the alkylateable aromatic feed stream 41 is passed to the alkylator and a portion of the first alkylating agent stream 43 and the first alkylation catalyst 26 are suitable in the first alkylation reaction zone. At least a portion of the liquid phase is contacted under the first reaction conditions. At least a portion of the impurity 'removed' and at least a portion of the processable aromatic compound is alkylated by weight of the first alkylating agent stream 4 3 to produce an alkylation-containing The first alkylation stream of the aromatic compound, the unreacted alkylateable aromatic compound, any residual water, and any residual impurities. The first alkylation stream and another portion of the alkylating agent 43 are at least partially suitable in the second alkylation reaction zone 20b in the presence of the second alkylation catalyst 28 (different from the first alkylation catalyst) The second reaction condition of the liquid phase is contacted. The unreacted alkylatable aromatic compound is alkylated by the second alkylating agent stream to produce a second alkylation comprising additional the alkylated aromatic compound, any residual water, and any residual impurities. flow. The first and second alkylation streams' and subsequent alkylation zones, if any, are combined to form an unreacted alkylatable aromatic compound, any residual water, and monoalkylated and The alkylated effluent of the polyalkylated aromatic compound is 4 5 . Different but possible, there are some residues -31 - 201136869 of alkylating agent present. The alkylateable aromatic feed stream to the alkylating unit 39 comprises an alkylatable aromatic compound and the polyalkylated feed stream 3 9 a (comprising from downstream separation equipment (not shown) The polyalkylated aromatic compound is supplied to the transalkylation zone 30a of the transalkylation unit 30. The transalkylation zone 30 has at least one transalkylation catalyst 34. In some embodiments, the transalkylation catalyst 34 is a macroporous molecular sieve having a Constraint Index of less than 2. In the transalkylation zone 30a, the polyalkylated aromatic compound in the polyalkylated feed stream 39a and the aromatic alkylation stream 39 which can be alkylated in the transalkylation unit are present in the transalkylation catalyst 34. Contacting under appropriate at least partial liquid phase alkylation conditions to produce additional monoalkylated aromatic compound alkylate effluent 45 in transalkylating effluent 47, optionally with The transalkylation effluent 47 is combined and supplied to the distillation zone 18 as a distillation feed stream 49 to separate the monoalkylated compound from the polyalkylated compound and the heavy compound. 2-4 illustrate an alternate embodiment of the dehydration stream 13 in the distillation zone 18 of the process 50 for making a monoalkylated aromatic compound of FIG. The device having the same number as in Figure 1 and the fluid block are the same. In the embodiment of Figure 2, it is supplied to the distillation zone 18 via a dehydration stream 13 and a reflux of 19. The overhead stream 15 is cooled in the heat exchanger 12c and then flows into the accumulation tank 16. Fluid 177 contains an alkylate stream of aromatic material which flows out of the accumulation tank 16. The portion of the fluid 17 is split and supplied to the distillation zone 18 as reflux 9. The reference is made to the foregoing. As shown in Figure 1, the fluid 2, the residual portion of the fluid 17 is formed into an aromatic feed stream 39 which can be alkylated by the transalkylation converter of the transalkylation unit 30, and to the alkylation unit 2 -32 - 201136869 Alkylated aromatic feed stream 4 1 . In the embodiment of Figure 3, the dewatering stream 13 is combined with the overhead stream 15 from the distillation zone 18 and then cooled in the heat exchanger 12c to form a fluid 23 which is then supplied to the accumulation tank 16. Fluid 25, comprising an alkylatable aromatic compound, exits from accumulation tank 16 and splits into reflux stream 27 and fluid 29. Fluid 29, a residual portion of fluid 25, an aromatic feed stream 39 that can be alkylated to a transalkylation unit of transalkylation unit 30, and an alkylateable aromatic feed stream 4 to alkylation unit 20 In the embodiment of Fig. 4, the overhead stream 15 of the distillation zone 18 flows into the accumulation tank 16 to form a fluid 17, which is as shown in Fig. 1. In this embodiment, the combined reflux stream 3 3 of the distillation zone 18 is formed by combining the dehydration stream 13 with the reflux stream 19 . The remainder of the fluid 35' fluid 17 forms an aromatic feed stream 39 that can be alkylated to the transalkylating unit of the transalkylation unit 30, and an alkylateable aromatic feed stream 4 to the alkylator 20 1. Alternatively, the fluid 35 can be heated or cooled in the heat exchanger 12b. Figure 5 shows a method 100 for producing a monoalkylated aromatic compound such as ethylbenzene, which is used in a separate tank. A guard bed and it operates in a reactive mode or a non-reactive mode. When the guard bed is operated in a non-reactive mode, no alkylating agent is supplied. When the guard bed is operated in a reactive mode, it receives a portion of the alkylating agent. The feed stream 101 comprises an alkylate-containing aromatic compound, water and impurities which are supplied to a dehydration zone 14' such as a light component removal distillation column. The devices and fluid blocks having the same number in Figure 1 are identical. In dewatering zone 4, at least a portion of the water and optionally a portion of the impurity are removed from the feed stream 1 - 33 - 201136869 to produce a dehydrated stream 109 comprising the alkylatable aromatic Group compound, any residual amount of this impurity and any residual water. The dewatering stream 1 09 is supplied to a treatment zone 102 containing a treatment material 10a, where it is treated under conditions suitable for removing additional impurities and producing an effluent stream 111. This impurity and treatment material 102a are the same as those described above. Alternatively, the effluent stream n丨 can be heated and cooled in a heat exchanger (not shown). The effluent stream 111 is supplied to the accumulation tank 16 of the distillation zone 18 where it is combined with the overhead stream 1 15 from the distillation zone 18 to produce a combined effluent 丨7. The distillation zone 18 can be a benzene distillation column. A portion of the combined effluent 117 is supplied to the distillation zone 18 in the form of a reflux 119. Steam 124 from the accumulation tank 16 is supplied to the dewatering zone 14 for further separation. Fluid 1 2 1, residual portion of the combined effluent 1 1 7 , available in heat exchanger 12 <1 heating or cooling. Similarly, fluid 1 2 1 forms an alkylateable aromatic feed stream 13 to the transalkylating unit 30 and a (reactive or non-reactive) guard bed 2 2 alkylateizable aromatic Stream 1 4 1. The heavy compound (e.g., polyalkylated aromatic compound) is removed as a bottoms stream 122 of distillation zone 18 and separated in a downstream separation apparatus (not shown) to produce an alkylated aromatic compound (e.g., ethylbenzene) and Polyalkylated aromatics (e.g., a polyalkylated feed stream 139 a, discussed below). The guard bed 22 is separated from the alkylator 20 and is located upstream of and in communication with the at least one second alkylation zone 20b. When the guard bed 22 is a reactive guard bed, it is a first alkylation zone and contains a first alkylation catalyst 26. When the guard bed 22 is a non-reactive guard bed, it is not an alkylation reaction zone because it is not supplied with an alkylating agent. The second alkylation zone 2〇b contains a second alkylation catalyst 28. The first alkylating catalyst has a first poisoning power which is the same as the second alkylating catalyst having the second poisoning power. The first poisoning power is greater than the second poisoning power. Preferably, the first alkylation catalyst 26 comprises a macroporous molecular sieve having a Constraint Index of less than 2. In some embodiments, the second alkylating catalyst comprises a molecular sieve of the MCM-22 family. Please refer to the foregoing. In other embodiments, the second alkylation catalyst comprises a mesoporous molecular sieve having a Constraint Index of 2-12. When the guard bed 22 is a reactive guard bed, the alkylateable aromatic feed stream 141 and a portion of the alkylating agent stream 143 are contacted in at least a portion of the liquid phase conditions in the presence of the first alkylating catalyst 26, To form a first alkylation stream comprising an alkylated aromatic compound, an unreacted alkylatable aromatic compound, any residual water, and any residual impurities. When the guard bed 22 is a non-reactive guard bed, it receives an alkylateable aromatic feed stream 141, and the feed stream is at least partially compatible with the first alkylation catalyst 26 (the absence of an alkylating agent) Contacting under liquid phase first reaction conditions to remove at least a portion of the impurities, by weight, and producing an alkylatable aromatic stream comprising the alkylatable aromatic compound, any residual water, and any residual impurities . The first alkylated stream or alkylatable aromatic stream is then supplied to the second alkylation zone 2 Ob and with additional alkylating agent stream 143 in the presence of the second alkylation catalyst 28, at least in appropriate The liquid phase is contacted under the second reaction conditions to produce a second alkylation stream comprising an additional amount of alkylated aromatic compound. The first and second alkylation streams, and subsequent alkylation zones, if any, are combined to form an alkylation-containing aromatic compound 'unreacted alkylatetable aromatic compound, any residue The alkylated effluent of water, and any residual impurities, 1 4 5 . The alkylate can be alkylated in an aromatic feed stream 1 3 9 (comprising an alkylatable aryl-35-201136869 compound) and a polyalkylated aromatic feed stream 1 3 9a (including polyalkylation) The aromatic compound) is supplied to the transalkylation zone 30 a. The transalkylation zone 30 has at least one transalkylation catalyst 3 4 » In some embodiments, the transalkylation catalyst 34 is a macroporous molecular sieve having a bundle index of less than 2. In the transalkylation zone 30a, the polyalkylated aromatic feed stream 139a and the aromatic alkylation stream 139 which can be alkylated by the transalkylation converter are suitably at least partially liquid phase in the presence of the transalkylation catalyst 34. Contacting under alkylation conditions produces additional monoalkylated aromatics in the transalkylator effluent 147. The alkylated effluent 1 45 is selectively combined with the transalkylation effluent 1 47 and supplied to the distillation zone 18 as a distillation feed stream 1 49 to be derived from the polyalkylated compound and The compound is isolated from the monoalkylated compound. The polyalkylated and heavy compounds are separated in a downstream separation unit (not shown). 6-8 illustrate an alternate embodiment of the use of an effluent stream 1 1 1 (which includes a dehydrated stream 1 09) in a distillation zone 18 of the process 1 for the manufacture of the monoalkylated aromatic compound of FIG. Aspect. The device having the same number as in Fig. 5 and the fluid block are the same. In the embodiment of Fig. 6, the effluent stream 1 Π and the reflux stream 1 19 are supplied to the distillation zone 18 » the overhead stream 1 15 of the distillation zone 18 flows into the accumulation tank 16. Fluid 117 contains an alkylate stream of aromatics which flows out of the accumulation tank 16. A portion of the fluid 117 is split and supplied to the distillation zone 18 as reflux 9. As shown in Figure 5, the fluid 1 2 1 , the residual portion of the fluid 1 1 7 forms a transalkylating agent feed stream 13 3 of the transalkylating unit 30 and the alkylate feed stream to the guard bed 22 1 4 1. Alternatively, fluid 1 2 1 can be heated or cooled in heat exchanger 12 2 d. In the embodiment of Figure 7, the effluent stream 1 1 1 is combined with the stream from the distillation zone 18 - 36 - 201136869 1 1 5 and then cooled in the heat exchanger 1 2 c to form β which is then supplied to the accumulation. Slot 1 6. The fluid 1 2 5 , containing the alkylate, flows out of the accumulation tank 16 . This fluid 16 splits into a reflux 194. The fluid 1 2 9, the residual portion of the fluid 1 2 5 is formed to the aromatic feed stream 1 3 9 ' to which the transalkylating agent can be alkylated and to the protected aromatic feed stream 141. Alternatively, fluid 129 can be heated or cooled in 12 2 d. In the embodiment of Fig. 8, the top flow raft 5 flows into the accumulation tank 1 17 and the return flow 1 1 9, which is as shown in Fig. 5. In this embodiment, the 'I fluid 1 1 9 (which is the split flow of the fluid 117) merges to form the incoming reflux stream 1 3 3 . Fluid 1 3 5, residual portion of fluid 1 1 7 alkylate 30 ° alkylate can be alkylated aromatic feed stream 1 3 9 22 alkylateable aromatic feed stream 1 . Optionally, the stream i switch 1 2 d is heated or cooled. This disclosure will be more specifically described with reference to the following examples. Example 1 Determination of Toxicity In Examples 1 - 6, the poisoning power of Colin was determined by supplying a gas phase of Colin base and recording its intake. An indicator of the total intake of nitrogen-containing compounds. The S fluid 1 2 3 , the aromatic compound ΐ 1 2 7 and the fluid transalkylation unit 30 of the bed 22 can form a fluid enthalpy stream 1 1 1 in the heat exchanger 16 and enter the distillation zone 18 to form a turn, and to protect Bed I 135 can be adsorbed in the thermogravimetric analyzer zeolite -37- 201136869 Table 1 Example Catalyst Zeolite Content (%) Approximate Toxicity (Millieq/g) 1 仳 Comparative Example) MWW iMCM-49) 80 80-130 2 β (non-MWW) 80 701 3 USY (non-MWW) 80 925 4 ZSM-12 (non-MWW) 65 531 5 mordenite (non-MWW) 65 385 6 solid phosphoric acid (non-MWW) 4τττ. None 501 as shown Table 1 shows that 'in terms of the poisoning power of Colin' is much lower for use with catalysts with MWW topologies than for catalysts with non-MWW topologies. Examples 7 and 8 In Examples 7 and 8, the ability of MWW and zeolite ruthenium to absorb Ν-methyl morpholine (NFM) impurities was determined. The two alkylation reactors are connected in series with a benzene feed containing NFM impurities to a first alkylation reactor (Rx 1 ) having a first alkylation catalyst. The effluent of Rx 1 is supplied to a second alkylation reactor (Rx 2) having a second alkylation catalyst. "Rx 1 and Rx 2 reactors have independent ethylene injection points and are constructed in series with multiple stages. The first two stages of the alkylation reactor are similar. For these experiments, the Rx 1 is a reactive guard bed and is the first reaction zone in the alkylation reactor. The passivation of Rx 2 is used to indicate that when Rx 1 has reached its maximum poisoning power and the catalyst poison is no longer completely retained by Rx 1, the NFM is fed at a concentration of 0.3 weight wppm based on the weight of the benzene-38-201136869 feed. The NFM absorption in the example was calculated from the run time and the passivation time observed in Rx 2. Table 2 Example Rx 1 zeolite (80% by weight of zeolite by weight of zeolite) Rx 2 zeolite (80% by weight of zeolite by weight of zeolite) NFM absorption (wppm by weight of zeolite) 7 (Comparative Example) MWW MWW 900-1000 8 β MWW 5950 As can be seen, Table 2 shows that the NFM absorption of zeolite yS as the first catalyst is better than when the first catalyst contains the MWW catalyst. All patents, patent applications, test procedures, priority documents, papers, bulletins, manuals, and other documents listed herein are inconsistent with this disclosure and are incorporated by reference. When the lower and upper limits are listed here, the range is from any lower limit to any upper limit. The exemplified embodiments of the present disclosure have been particularly described, and it is understood that various modifications of the invention are apparent to those skilled in the art and can be readily achieved without departing from the spirit and scope of the disclosure. Accordingly, the scope of the appended claims is not limited to the examples and descriptions set forth herein, but the claims are intended to cover all the novel features of the patents disclosed in the present disclosure. All features of its equivalent treatment are included -39-201136869 [Schematic Description of the Drawings] Figures 1-8 are flow diagrams of methods for making an alkylated aromatic compound in accordance with an embodiment of the present disclosure. [Main component symbol description] 1: Feed stream 2: Processor 2a: Processing area 4: Processing material 5: Processor outflow 12a: Heat exchanger 12b: Heat exchanger 12c: Heat exchanger 12d: Heat exchanger 1 3: Water stream 1 4 : Dewatering zone 1 5 : Tower top stream 16 : Accumulation tank 1 7 : Accumulation tank effluent 18 : Distillation zone 1 9 : Reflow 20 : Alkerator 20a : First alkylation reaction zone -40 - 201136869 2 0b : second alkylation reaction zone 2 1 : fluid 2 2 : bottoms stream 24 : vapor 26 : first alkylation catalyst 2 8 : second alkylation catalyst 3 0 : transalkylation converter 3 0 a : transalkylation Zone 3 3 : Fluid 3 4 : Transalkylation Catalyst 3 5 : Fluid 3 9 : Alkylated Aromatic Feed Stream 39a: Polyalkylated Feed Stream 4 1 : Alkylated Aromatic Feed Stream 43: first alkylating agent stream 4 5 : alkylating effluent 47 : transalkylating unit effluent 49 : distillation feed stream 5 0 : method 1 〇〇: method 1 〇 1 : feed stream 1 0 2 : treatment zone 1 0 2 a : treatment material 1 〇 9 : dehydrated stream -41 201136869 1 1 1 : effluent stream 1 1 5 : tower top stream 1 1 7 : combined effluent 1 1 9 : reflux stream 1 2 1 : Fluid 1 2 2 : bottom flow 123: fluid 124: steam 1 2 5 : flow Body 1 3 3 : Fluid 1 3 5 : Fluid 1 3 9 : Alkylated aromatic feed stream 1 3 9 a : Polyalkylated feed stream 1 4 1 : Alkylated aromatic feed stream 1 4 3 : alkylating agent stream 1 4 5 : alkylated effluent 1 4 7 : transalkylating effluent 149 : distillation feed stream - 42-

Claims (1)

201136869 VII. Patent application scope: 1. A method for producing an alkylated aromatic compound, the method comprising the steps of: (a) supplying a feed stream to a dehydration zone, the feed stream comprising an alkylatable aromatic compound , water, and impurities, wherein the impurity comprises a compound having at least one of the following elements: nitrogen, halogen, oxygen, sulfur, arsenic, selenium, tellurium, phosphorus, and Group 1 to Group 12 metals; (b) Removing at least a portion of the water from the feed stream in the dewatering zone operated under dehydration conditions to produce a dehydrated stream comprising the alkylatable aromatic compound, any residual water, and the impurities; Passing at least a portion of the dehydrated stream and the first alkylating agent stream with a first alkylating catalyst having a first poisoning power in a first alkylation reaction zone, under appropriate at least partial liquid phase first reaction conditions Contacting to remove at least a portion of the impurity, and subjecting at least a portion of the alkylatable aromatic compound to alkylation with the first alkylating agent stream to produce a first alkylation stream, the first alkylation Stream containing alkylated aromatic compounds An unreacted alkylatable aromatic compound, any residual water, and any residual impurities; and (d) a first alkylation stream and a second alkylating agent stream different from the first alkylation contact Contacting a second alkylation catalyst of the medium, the second alkylation catalyst having a second poisoning force in the second alkylation reaction zone and at least a portion of the liquid phase second reaction conditions, such that the unreacted alkane At least a portion of the aromatic compound is hospitalized with the second source of chemical agent and produces a second vaporized stream comprising additional (e.g.) alkylated aromatic compounds, The reaction of the alkylatable aromatic compound, any residual water, and any impurities remaining in -43-201136869. 2. The method of claim 1, wherein in the removing step (b), at least a portion of the impurities in the feed stream are removed in the dewatering zone. 3. The method of claim 1, wherein before the step (c), the dehydrated stream is sent to a treatment zone containing the treatment material, and then the dewatered stream and the treatment material are in the treatment zone. Contact is made under appropriate processing conditions to remove at least a portion of the impurities. 4. The method of claim 1, wherein before the step (a), the feed stream is sent to a treatment zone containing the treatment material, and then the feed stream and the treatment material are in the treatment zone. Contacting under appropriate processing conditions to remove at least a portion of the impurities. 5. The method of claim 1, wherein the first alkylation catalyst is a macroporous molecular sieve having a Constraint Index of less than 2. 6. The method of claim 5, wherein the macroporous molecule is selected from the group consisting of zeolite yS, faujasite, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), Rare Earth Y (RE Y), Ultrahydrophobic Y (UHP-Y), mordenite, TEA-mordenite, ZSM-3, ZSM-4, ZSM-14, ZSM-18, ZSM-20, and combinations thereof. 7. The method of claim 1, wherein the second alkylation catalyst is a MCM-22 family material having a unit cell of the MWW network topology and including a lattice spacing in an X-ray diffraction pattern. The (d-spacing) maximum 値 is characterized by 12.4±0·25' 3.57±0.07 and 3.42±0.07 angstroms. • 44 - 201136869 8. The method of claim 7, wherein the MC Μ - 2 2 family material is selected from the group consisting of ERB-1, ITQ-1, ITQ-2, ITQ-30, PSH-3, SSZ-25 , MCM-22, MCM-36, MCM-49, MCM-56, UZM-8, EMM-10, EMM-10P, EMM-12, EMM-13 and a mixture of them ο 9 · As claimed in the patent scope 1 The method of the present invention, wherein the (alternate) alkylated aromatic compound comprises a monoalkylated aromatic compound and a polyalkylated aromatic compound; and wherein the method further comprises the step of: (e) from the second Separating the monoalkylated aromatic stream t (f ) from the second alkylated stream via a alkylation stream to separate the polyalkylated compound stream; and (g) allowing the polyalkylated aromatic stream to Another portion of the feed stream is contacted with a transalkylation catalyst in a transalkylation reaction zone under suitable at least partial liquid phase alkylation conditions to transalkylate the polyalkylated aromatic stream. Additional monoalkylated aromatic compounds are obtained. 10. The method of claim 9, wherein the transalkylation catalyst is a macroporous molecular sieve having a constrained index of less than 2. 1 1. A method for producing an alkylated aromatic compound, the method comprising the steps of: (a) supplying a feed stream to a dehydration zone comprising an alkylatable aromatic compound, water, And impurities wherein the impurity comprises at least one of the following elements: nitrogen, halogen, oxygen, sulfur, arsenic, selenium, tellurium, phosphorus, and Group 1 to Group 12 metals; -45-201136869 (b) Removing at least a portion of the water from the feed stream in the dewatering zone operated under suitable dehydration conditions to produce a dehydrated stream comprising the alkylatable aromatic compound, any residual water, and the impurities; (c) contacting at least a portion of the dehydrated stream with a first catalyst having a first poisoning force in a first reaction zone, under suitable at least partial liquid phase first reaction conditions, to remove at least the impurity a portion, and producing an alkylenable aromatic stream comprising a reduced amount of impurities and comprising the alkylatable aromatic compound, any residual water, and any residual impurities; and (d) enabling the step (c) Alkylated aromatic and alkylating agent streams Contacting with the alkylating catalyst of the first catalyst, the alkylating catalyst has a second poisoning power higher than the first poisoning force, and the contacting occurs in the alkylation reaction zone and is suitable for at least part of the liquid phase Under two reaction conditions, at least a portion of the unreacted alkylatable aromatic compound is alkylated with the alkylating agent stream to produce an alkylation stream comprising an alkylated aromatic compound, Unreacted alkylateable aromatic compound, any residual water, and any residual impurities. 12. The method of claim 11, wherein in the removing step (b), at least a portion of the impurities in the feed stream are removed in the dewatering zone. The method of claim 11, wherein before the step (c), the dehydrated stream is sent to a treatment zone containing the treatment material 'and then' the dehydrated stream and the treated material are treated in the treatment The zone is contacted under appropriate processing conditions to remove at least a portion of the impurity. 1 4 · The method of claim 1 of the patent scope 'where the feed stream is sent to the treatment zone containing the treatment material before step (a) -46 - 201136869, and then the feed stream is treated with the treatment The material is contacted in the treatment zone under appropriate processing conditions to remove at least a portion of the impurities. The method of claim 3, 4, 3, or 4, wherein the treatment material is selected from the group consisting of clay, resin, activated alumina, Linde X, Linde A, and combinations thereof. . The method of claim 2, wherein the first catalyst is a macroporous molecular sieve having a constrained index of less than 2. 1 7 · The method of claim 16, wherein the macroporous molecule is selected from zeolite cold, faujasite, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), Rare Earth Y (REY) , Ultrahydrophobic Y (UHP-Y), mordenite, TEA-mordenite, ZSM-3 'ZSM-4' ZSM-14, ZSM-18, ZSM-20, and combinations thereof. 18. The method of claim 11, wherein the alkylation catalyst is a MCM_22 family material having a unit cell of the MWW network topology and including a lattice spacing maximum in an X-ray diffraction pattern. It is characterized by 12.4 ± 0.25, 3.57 ± 0.07 and 3.42 ± 0.07 angstroms. 1 9 · The method of claim 18, wherein the MC Μ - 2 2 family material is selected from the group consisting of ERB-1, ITQ-1, ITQ-2, ITQ-30, PSH-3, SSZ-25, MCM -22. MCM-36, MCM-49, MCM-56, UZM-8, EMM-10, ΕΜΜ-10Ρ, EMM-12, ΕΜΜ-13 and mixtures thereof. 20. The method of claim 11, wherein the pharmaceutically acceptable -47-201136869 aromatic compound is benzene. The method of claim 11, wherein the alkylating agent stream comprises an olefin and the impurity 'and wherein at least a portion of the impurity is removed in step (c). The method of claim 20, wherein the alkylating agent is ethylene and the monoalkylated aromatic compound is ethylbenzene, or the alkylating agent is propylene and the monoalkylated aromatic compound Is cumene, or the alkylating agent is butene and the monoalkylated aromatic compound is a secondary butylbenzene. 23. The method of claim 11, wherein the (alternate) alkylated aromatic compound comprises a monoalkylated aromatic compound and a polyalkylated aromatic compound; and wherein the method further comprises the steps of: e) separating the monoalkylated aromatic stream from the second alkylation stream » (f) separating the polyalkylated compound stream from the second alkylation stream; and (g) polyalkylating the mixture The aromatic stream and another portion of the dehydrated stream are contacted with a transalkylation catalyst in a transalkylation reaction zone under suitable at least partial liquid phase alkylation conditions to stream the polyalkylated aromatic compound It is transalkylated and an additional monoalkylated aromatic compound is obtained. 24. The method of claim 23, wherein the transalkylation catalyst is a macroporous molecular sieve having a Constraint Index of less than 2. 2 5 _ as in the method of claim 1 or 2, wherein the macroporous molecule is selected from zeolite/3, faujasite, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), Rare Earth Y (REY), -48- 201136869 Ultrahydrophobic Υ (UHP-Υ), mordenite, TEA-mordenite, ZSM-3, ZSM-4, ZSM-14, ZSM-18, ZSM-20, and combinations thereof . -49 ·