WO2011112189A1 - Alkylated aromatics production - Google Patents
Alkylated aromatics production Download PDFInfo
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- WO2011112189A1 WO2011112189A1 PCT/US2010/026844 US2010026844W WO2011112189A1 WO 2011112189 A1 WO2011112189 A1 WO 2011112189A1 US 2010026844 W US2010026844 W US 2010026844W WO 2011112189 A1 WO2011112189 A1 WO 2011112189A1
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/067—C8H10 hydrocarbons
- C07C15/073—Ethylbenzene
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/085—Isopropylbenzene
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present disclosure relates to a process for the production of alkylated aromatic compounds from a feed stream comprising an alkylating agent, an alkylatable aromatic and trace amounts of water and impurities.
- Alkylated aromatic compounds such as cumene, ethylbenzene and sec-butyl benzene
- alkylatable aromatics e.g., benzene
- alkylating agents e.g., olefins such as ethylene, propylene and butylene
- acidic molecular sieve catalysts e.g., zeolites
- Acidic molecular sieve catalysts that may be used for such liquid phase aromatic alkylation reactions include zeolite beta, zeolite Y, zeolite omega, ZSM-5, ZSM-12, MCM- 22, MCM-36, MCM-49, MCM-56, MCM-58, MCM-68, UZM-8, faujasite, Mordenite, porous crystalline magnesium silicates, and Tungstate-modified zirconia (e.g., Zr(W0 4 ) 2 , all of which are known in the art.
- U.S. Patent No. 6,313,362 (Green) teaches an aromatic alkylation process in which the alkylation product is contacted with a large pore molecular sieve catalyst such as MCM-22 in a liquid phase step to remove impurities prior to liquid phase alkylation. Impurities taught as being removed include olefins, diolefins, styrene, oxygenated organic compounds, sulfur-containing compounds, nitrogen-containing compounds, and oligomeric compounds.
- a large pore molecular sieve catalyst such as MCM-22
- Impurities taught as being removed include olefins, diolefins, styrene, oxygenated organic compounds, sulfur-containing compounds, nitrogen-containing compounds, and oligomeric compounds.
- 4,358,362 (Smith) teaches a method for enhancing catalytic activity of a zeolite catalyst by contacting a feed stream which contains a catalytically deleterious impurity with a zeolitic sorbent.
- This disclosure uses a sorbent with a Si/Al ratio greater than 12, 10-12-membered rings, and a Constraint Index between 1 and 12, preferably ZSM-11.
- U.S. Patent No. 5,030,786 (Shamshoum) teaches a process for production of ethylbenzene in which the catalyst lifetime is increased by reducing the concentration of water in the feed to the reactor.
- U.S. Patent No. 5,744,686 (Gajda) teaches a process for the removal of nitrogen compounds from an aromatic hydrocarbon stream by contacting the stream with a selective adsorbent having an average pore size less than about 5.5 Angstroms.
- the selective adsorbent is a non-acidic molecular sieve selected from the group consisting of pore closed zeolite 4 A, zeolite 4 A, zeolite 5 A, silicalite, F-silicalite, ZSM-5, and mixtures thereof.
- a process for preparing alkylated benzenes is taught in U.S. Patent No. 6,297,417 (Samson).
- the process includes contacting a benzene feedstock with a solid acid, such as acidic clay or acidic zeolite, in a pretreatment zone at a temperature between about 130°C and about 300°C to improve the lifetime of the alkylation and transalkylation catalyst.
- a solid acid such as acidic clay or acidic zeolite
- U.S. Patent No. 6,355,851 teaches a zeolite-catalyzed cumene synthesis process in which benzene feedstock is contacted with a "hot" clay bed, followed by distillation of the benzene feedstock to separate the benzene from the higher molecular weight materials formed from olefmic poisons during the hot clay treatment, followed by a "cold” clay treatment wherein the benzene distillate is contacted with an ambient-temperature clay.
- the propylene feedstock is pretreated by contact with an alumina to remove trace sodium compounds and moisture, a molecular sieve to remove water, and two modified aluminas to remove other catalyst poisons.
- the pretreated propylene and benzene feedstocks are then reacted in the presence of a zeolite catalyst to form cumene without causing rapid degradation of the catalyst's activity.
- PCT published application WO0214240 (Venkat) teaches removal of polar contaminants in an aromatic feedstock by contacting it with molecular sieves with pore size greater than 5.6 Angstroms at temperatures below 130°C.
- U.S. Patent No. 6,894,201 (Schmidt) teaches removing nitrogen compounds from an alkylation substrate such as benzene prior to alkylation using a conventional adsorbent bed which adsorbs basic organic nitrogen compounds and a hot adsorbent bed of acidic molecular sieve which adsorbs weakly basic nitrogen compounds such as nitrites. Schmidt teaches that water facilitates the adsorption of the weakly basic nitrogen compounds and that running an alkylation substrate stream from a fractionation column of elevated temperature and suitable water concentration to the hot adsorbent bed may be advantageous.
- U.S. Patent No. 7,199,275 teaches a process for hydrocarbon conversion in which a partially dehydrated hydrocarbon feedstock is contacted with 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 second molecular sieve having a Si/Al molar ratio of greater than about 5. Also, Smith teaches processes in which such feedstocks are contacted with a first molecular sieve having pores of at least about 6 Angstroms and a second molecular sieve having pores of less than about 6 Angstroms.
- the present disclosure describes a process for the production of alkylated aromatic compounds from a feed stream comprising an alkylating agent, an alkylatable aromatic and trace amounts of water and impurities. Water, and optionally a portion of impurities, is removed in a dehydration zone. In a reactive guard bed, the dehydrated stream and an alkylating agent are contacted with a first alkylation catalyst, and then a different second alkylation catalyst, wherein any remaining impurities are removed at the same time as this stream is alkylated.
- the dehydrated stream is contacted with a first catalyst wherein any remaining impurities are removed, and then this stream is alkylated with an alkylating agent by contact with an alkylation catalyst.
- the first alkylation catalyst in the first alkylation zone in some embodiments is a large pore molecular sieve.
- the second alkylation catalyst in the second alkylation zone in some embodiments is a medium pore molecular sieve or a MCM-22 family material.
- the dehydration step reduces the concentration of water and optionally reduces the level of impurities in the alkylatable aromatic feed.
- a portion of the impurities are removed at the same time as a portion of the water.
- the first alkylation step to remove a portion, preferably a major portion, of the remaining impurities, such as nitrogenous and other species, contained in the alkylatable aromatic feed, and to alkylate a portion of the alkylatable aromatic compound.
- the second alkylation step in turn acts to remove a portion of the remaining impurities, and to alkylate a major portion of the alkylatable aromatic compound.
- the alkylated aromatic compounds produced comprise primarily mono-alkylated aromatic compounds with trace amounts of poly-alkylated aromatic compounds produced concomitantly in the alkylation reaction zones.
- the poly-alkylated aromatic compounds may then be converted to additional mono-alkylated compounds by contact with additional alkylatable aromatic compounds in the presence of a separate transalkylation catalyst in a transalkylation step.
- Figs. 1-8 are each process flow diagrams of a process for producing alkylated aromatic compounds in accordance with an embodiment of the present disclosure.
- alkylatable aromatic compound as used herein means an aromatic compound that may receive an alkyl group.
- alkylatable aromatic compound is benzene.
- alkylating agent means a compound which may donate an alkyl group to an alkylatable aromatic compound.
- alkylating agent are ethylene, propylene, and butylene.
- Another non-limiting example is any poly- alkylated aromatic compound that is capable of donating an alkyl group to an alkylatable aromatic compound.
- aromatic as used herein in reference to the alkylatable aromatic compounds which are useful herein is to be understood in accordance with its art-recognized scope which includes substituted and unsubstituted mono- and polynuclear compounds.
- Compounds of an aromatic character which possess a heteroatom e.g., N or S
- At least partially liquid phase means a mixture having at least 1 wt. % liquid phase, optionally at least 5 wt. % liquid phase, at a given temperature, pressure, and composition.
- catalyst poison means an impurity, defined herein, which acts to reduce the cycle-length of a molecular sieve or zeolite.
- cycle length means the total on-oil time between regenerations, or the on-oil time period between fresh load and regeneration.
- the catalyst may be deactivated due to coke deposition or poison.
- the reaction zone has to be operated at higher temperatures to maintain the same productivity or catalytic activity.
- the catalyst has to be regenerated once the reaction zone temperature reaches a threshold temperature, typically determined by metallurgy of the reactor or when economic factors warrant.
- framework type is used herein has the meaning described in the "Atlas of Zeolite Framework Types," by Ch. Baerlocher, W.M. Meier and D.H. Olson (Elsevier, 5th Ed., 2001.)
- impurities includes, but is not limited to, compounds having at least one of the following elements: nitrogen, halogens, oxygen, sulfur, arsenic, selenium, tellurium, phosphorus, and Group 1 through Group 12 metals.
- the impurities content as used in this disclosure means the wppm of impurities based on the total weight of the combined alkylatable aromatic compound and alkylating agent in the reaction zone.
- MCM-22 family material (or “material of the MCM-22 family” or “molecular sieve of the MCM-22 family”), as used herein, includes: (i) molecular sieves made from a common first degree crystalline building block "unit cell having the MWW framework topology.”
- a unit cell is a spatial arrangement of atoms which is tiled in three-dimensional space to describe the crystal as described in the "Atlas of Zeolite Framework Types," by Ch. Baerlocher, W.M. Meier and D.H. Olson (Elsevier, 5th Ed., 2001.);
- molecular sieves made from common second degree building blocks, "layers of one or more than one unit cell thickness", wherein the layer of more than one unit cell thickness is made from stacking, packing, or binding at least two monolayers of one unit cell thick of unit cells having the MWW framework topology.
- the stacking of such second degree building blocks can be in a regular fashion, an irregular fashion, a random fashion, and any combination thereof; or
- the MCM-22 family materials are characterized by having an X-ray diffraction pattern including d-spacing maxima at 12.4 ⁇ 0.25, 3.57 ⁇ 0.07 and 3.42 ⁇ 0.07 Angstroms (either calcined or as-synthesized).
- the MCM-22 family materials may also be characterized by having an X-ray diffraction pattern including d-spacing maxima at 12.4 ⁇ 0.25, 6.9 ⁇ 0.15, 3.57 ⁇ 0.07 and 3.42 ⁇ 0.07 Angstroms (either calcined or as-synthesized).
- the X-ray diffraction data used to characterize the molecular sieve are obtained by standard techniques using the K-alpha doublet of copper as the incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system.
- mono-alkylated aromatic compound means an aromatic compound that has only one alkyl substituent.
- mono-alkylated aromatic compounds are ethylbenzene, iso-propylbenzene (cumene) and sec-butylbenzene.
- on-oil as used herein is to be understood as the catalyst being brought under alkylation or transalkylation conditions.
- the alkylation or transalkylation conditions include temperature, pressure, alkylatable aromatic compound(s), alkylating agent(s), and WHSV, which are suitable to covert at least 1 wt. %, preferably at least 10 wt. % of the alkylatable aromatic compound(s) (based on the total alkylatable aromatic compound(s) in the feed) to the mono-alkylated aromatic compound(s).
- the term "poison capacity" as used herein means the millimoles of collidine (a catalyst poison) absorbed per gram of a catalyst sample that is dried under nitrogen flow at 200°C for 60 minutes on a Thermogravametric Analyzer (Model Q5000, manufactured by TA Instruments, New Castle, Delaware). After drying, the collidine catalyst poison is sparged over the catalyst sample for 60 minutes at a collidine partial pressure of 3 torr.
- the poison capacity is calculated from the following formula: (Catalyst Sample Weight after Sparging with collidine - Dried Catalyst Sample Weight) X 10 6 ⁇ (Molecular Weight of Collidine X Dried Catalyst Sample Weight). When the Catalyst Sample Weight and the Dried Catalyst Sample Weight is measured in grams, the molecular weight of collidine is 121.2 grams per millimole.
- poly-alkylated aromatic compound as used herein means an aromatic compound that has more than one alkyl substituent.
- a non-limiting example of a poly- alkylated aromatic compound is poly-alkylated benzene, e.g., di-ethylbenzene, tri- ethylbenzene, di-isopropylbenzene, and tri-isopropylbenzene.
- wppb as used herein is defined as parts per billion by weight.
- wppm as used herein is defined as parts per million by weight.
- Suitable unsubstituted aromatic compounds that may be used for this disclosure include benzene, naphthalene, anthracene, naphthacene, perylene, coronene, and phenanthrene, with benzene being preferred.
- Substituted aromatic compounds which may be used for the disclosure should possess at least one hydrogen atom directly bonded to the aromatic nucleus.
- the aromatic rings may be substituted with one or more alkyl, aryl, alkaryl, alkoxy, aryloxy, cycloalkyl, halide, and/or other groups which do not interfere with the alkylation reaction.
- the alkyl groups which can be present as substituents on the aromatic compound contain from 1 to about 22 carbon atoms and usually from about 1 to 8 carbon atoms, and most usually from about 1 to 4 carbon atoms.
- Suitable substituted aromatic compounds include, but are not limited to, toluene, xylene, isopropylbenzene, normal propylbenzene, alpha-methylnaphthalene, ethylbenzene, mesitylene, durene, cymenes, butylbenzene, pseudocumene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, isoamylbenzene, isohexylbenzene, pentaethylbenzene, pentamethylbenzene; 1,2,3,4-tetraethylbenzene; 1,2,3,5- tetramethylbenzene; 1,2,4-triethylbenzene; 1,2,3-trimethylbenzene, m-butyltoluene; p- butyltoluene; 3,5-diethylto
- alkylaromatic hydrocarbons may also be used as starting materials and include aromatic hydrocarbons such as are produced by the alkylation of aromatic hydrocarbons with olefin oligomers.
- aromatic hydrocarbons such as are produced by the alkylation of aromatic hydrocarbons with olefin oligomers.
- Such products are frequently referred to in the art as alkylate and include, but are not limited to, hexylbenzene, nonylbenzene, dodecylbenzene, pentadecylbenzene, hexyltoluene, nonyltoluene, dodecyltoluene, pentadecytoluene, and the like.
- alkylate is obtained as a high boiling fraction in which the alkyl group attached to the aromatic nucleus varies in size from about C 6 to about
- Reformate streams that may contain substantial quantities of benzene, toluene and/or xylene may be particularly suitable as an alkylatable aromatic feed for the process of this disclosure.
- the process is particularly directed to the production of ethylbenzene from polymer grade and dilute ethylene, it is equally applicable to the production of other C7-C20 alkylaromatic compounds, such as cumene, as well as C 6+ alkylaromatics, such as Cs-Ci6 linear and near linear alkylbenzenes.
- Suitable alkylating agent(s) that may be used in this disclosure comprise alkene compound(s), alcohol compound(s), and/or alkylbenzene(s), and mixtures thereof.
- Other suitable alkylating agents that may be useful in the process of this disclosure generally include, but are not limited to, any aliphatic or aromatic organic compound having one or more available alkylating aliphatic groups capable of reaction with the alkylatable aromatic compound.
- alkylating agents are C2-C16 olefins, such as C2-C5 olefins, including ethylene, propylene, the butenes, and the pentenes; C1-C12 alkanols (inclusive of monoalcohols, dialcohols, trialcohols, etc.), preferably C1-C5 alkanols, such as methanol, ethanol, the propanols, the butanols, and the pentanols; C 2 -C 2 o ethers, e.g., C 2 -C 5 ethers including dimethylether and diethylether; aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and n-valeraldehyde; and alkyl halides such as methyl chloride, ethyl chloride, the propyl chlorides, the butyl chlorides, and
- the alkylating agent may preferably be selected from the group consisting of C 2 -C 5 olefins, C 1 -C 5 alkanols, bi-ethylbenzene(s), bi- isopropylbenzene(s), tri-ethylbenzene(s) and/or tri-isopropylbenzene(s).
- the feed stream comprising the alkylatable aromatic compound may comprise impurities.
- 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, halogens, oxygen, sulfur, arsenic, selenium, tellurium, phosphorus, and Group 1 through Group 12 metals. Examples of such impurities include collidine and N-formyl morpholine.
- the term "impurities" does not include water, H 2 0.
- the amount of said impurities in said feed stream (or the first and/or the second alkylating agent stream) is less than 20 wppm, less than 15 wppm, less than 10 wppm, less than 5 wppm or less than 1 wppm based on the weight of said feed stream.
- the feed stream may comprise water.
- the first alkylating agent stream and/or the second alkylating agent stream may comprise water.
- the feed stream or the alkylating agent stream(s) may be dehydrated by distillation, adsorption, evaporation, extraction or flashing, for example, in one or more dehydration zones.
- the dehydration zone may be a distillation column, a benzene column or a flashing column, lights column or an extractor, absorber or flash drum.
- the feed stream is saturated with water at the temperature and pressure conditions of the feed stream.
- the amount of water in said feed stream is at least 500 wppm, at least 400 wppm, at least 300 wppm or at least 200 wppm based on the weight of said feed stream.
- the level of impurities or water may be measured by conventional techniques, such as, GC, GC/MS, or other suitable techniques known to one skilled in the art.
- the disclosed process includes: (1) a dehydration zone operated under suitable dehydration conditions to remove at least a portion of water and optionally, a portion of the impurities; (2) a first alkylation reaction zone having a first alkylation catalyst, wherein the first alkylation zone is operated under suitable first reaction conditions to remove a major portion of remaining impurities and to alkylate a portion of the alkylatable aromatic compound; (3) a second alkylation reaction zone having a second alkylation catalyst which is different from the first alkylation catalyst, wherein the second alkylation zone is operated under suitable second reaction conditions to remove a portion of remaining impurities and alkylate a major portion of the alkylatable aromatic to produce an additional amount of mono-alkylated aromatic compounds.
- the suitable dehydration conditions are conventional dehydration conditions known in the art to separate water and impurities from an aromatic stream.
- suitable first and second conditions include a temperature of 100 to 285°C, preferably, a temperature from 150 to 260°C; a pressure of 689 to 4601 kPa-a, preferably, a pressure of 1500 to 3000 kPa-a; and a WHSV based on both alkylating agent and alkylatable aromatics for the overall reactor of 10 to 100 hr -1 , preferably, 20 to 50 hr "1 .
- the overall molar ratio of the alkylatable aromatic compound to the alkylating agent 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.
- the first alkylation reaction zone may be operated as a reactive guard bed in which at least a portion of impurities in the feed stream are removed.
- the overall molar ratio of the alkylatable aromatic compound to the alkylating agent e.g., benzene and ethylene, respectfully
- the alkylating agent is much higher than in alkylation service alone, in the range from 10: 1 to 200: 1, or 15: 1 to 150: 1, or 20: 1 to 100: 1 or 25: 1 to 50: 1.
- the first reaction alkylation zone is a first reaction zone operated as a non-reactive guard bed in which at least a portion of impurities in the feed stream are removed. In this embodiment, only the alkylatable aromatic compound is fed to the first reaction zone.
- the disclosed process includes a treatment zone having a treatment material, wherein the treatment zone is operated under suitable treatment conditions to remove a portion of impurities.
- the treatment zone may be upstream or downstream of the dehydration zone.
- the treatment zone is upstream of the first and second alkylation zones.
- suitable treatment conditions include a temperature from about 30 to 200°C, and preferably between about 60 to 150°C, a weight hourly space velocity (WHSV) of from about 0.1 hr “1 and about 200 hr “1 , preferably from about 0.5 hr “1 to about 100 hr “1 , and more preferably from about 1.0 hr “1 to about 50 hr “1 ; and a pressure between about ambient and 3000 kPa-a.
- WHSV weight hourly space velocity
- the disclosed process includes a transalkylation zone operated under suitable transalkylation conditions to produce additional amounts of mono- alkylated aromatic compounds from poly-alkylated aromatic compounds and the alkylatable aromatic compound.
- suitable transalkylation conditions may include a temperature of from about 100 to about 300°C, a pressure of 696 to 4137 kPa-a (101 to 600 psia), a WHSV based on the weight of the polyalkylated aromatic compound(s) feed to the alkylation reaction zone of from about 0.5 hr "1 to about 100 hr "1 and a molar ratio of benzene to polyalkylated aromatic compound(s) of from 1 : 1 to 30: 1, preferably, 1 : 1 to 10: 1, more preferably, 1 : 1 to 5: 1.
- the disclosed process includes: (1) a first alkylation catalyst; and (2) a second alkylation catalyst that is different from the first alkylation catalyst.
- the first alkylation catalyst comprises a large pore molecular sieve having a Constraint Index of less than 2 and a first poison capacity.
- the Constraint Index is a convenient measure of the extent to which an aluminosilicate or molecular sieve provides controlled access to molecules of varying sizes to its internal structure.
- aluminosilicates which provide a highly restricted access to and egress from its internal structure have a high value for the Constraint Index, and aluminosilicates of this kind usually have pores of small size, e.g. less than 5 Angstroms.
- aluminosilicates which provide relatively free access to the internal aluminosilicate structure have a low value for the constraint index, and usually pores of large size.
- the method by which Constraint Index may be determined is described fully in U.S. Patent No. 4,016,218.
- Suitable large pore molecular sieves include zeolite beta, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), Ultrahydrophobic Y (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. 3,923,636.
- Zeolite ZSM-20 is described in U.S. Patent No. 3,972,983.
- Zeolite beta is described in U.S. Patent No. 3,308,069, and U.S. Reissue Patent 28,341.
- Ultrastable Y molecular sieve USY
- U.S. Patent Nos. 3,293,192 and 3,449,070 Dealuminized Y zeolite (Deal Y) may be prepared by the method found in U.S. Patent No. 3,442,795.
- Ultrahydrophobic Y UHP-Y
- Rare earth exchanged Y REY
- Mordenite is a naturally occurring material but is also available in synthetic forms, such as TEA-mordenite (i.e., synthetic mordenite prepared from a reaction mixture comprising a tetraethylammonium directing agent).
- TEA-mordenite is disclosed in U.S. Patent Nos. 3,766,093 and 3,894,104.
- the zeolitic materials designated by the International Zeolite Association Structure Committee (IZA-SC) as being of the MWW topology are multi-layered materials which have two pore systems arising from the presence of both 10 and 12 membered rings.
- the Atlas of Zeolite Framework Types currently classes at least five differently named materials as having this same topology include, but are not limited to MCM-22, ERB-1, ITQ- 1, PSH-3, and SSZ-25.
- the second alkylation catalyst preferably an acidic catalyst, comprises a MCM-22 family molecular sieve having a second poison capacity.
- the MCM-22 family molecular sieves have been found to be useful in a variety of hydrocarbon conversion processes. Examples of MCM-22 family molecular sieve are MCM-22, MCM- 36, MCM-49, MCM-56, ITQ-1, ITQ-2, ITQ-30, PSH-3, SSZ-25, ERB-1 and UZM-8.
- Materials which belong 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), SSZ-25 (described in U.S. Patent No. 4,826,667), ERB-1 (described in European Patent 0293032), ITQ-1 (described in U.S. Patent No. 6,077,498), ITQ-2 (described in International Patent Publication No. WO97/17290), ITQ-30 (described in International Patent Publication No. WO2005118476), MCM-36 (described in U.S. Patent No. 5,250,277), MCM-49 (described in U.S. Patent No. 5,236,575), MCM-56 (described in U.S. Patent No. 5,362,697), and UZM-8 (described in U.S. Patent No. 6,756,030).
- the MCM-22 family molecular sieves described above are distinguished from conventional large pore zeolite alkylation catalysts, discussed below, such as mordenite, in that the MCM-22 materials have 12-ring surface pockets which do not communicate with the 10-ring internal pore system of the molecular sieve.
- the second alkylation catalyst preferably an acidic catalyst, may comprise a medium pore molecular sieve having a Constraint Index of 2-12 (as defined in U.S. Pat. No. 4,016,218), including ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48.
- ZSM-5 is described in detail in U.S. Patent No.
- ZSM-11 is described in detail in U.S. Patent No. 3,709,979.
- ZSM-12 is described in U.S. Patent No. 3,832,449.
- ZSM-22 is described in U.S. Patent 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 more particularly described in U.S. Patent No. 4,234,231.
- said first poison capacity of said first alkylation catalyst is greater than said second poison capacity of said second alkylation catalyst, said poison capacity measured by collidine capacity.
- the disclosed process includes a treatment material.
- the treatment material is selected from the group consisting of clay, resin, Linde type X, Linde type A, and combinations thereof.
- the treatment material may be acidic or non-acidic.
- the disclosed process includes a transalkylation catalyst.
- the transalkylation catalyst comprises a large pore molecular sieve having a Constraint Index of less than 2.
- the transalkylation catalyst may be the same as or different from the first alkylation catalyst.
- the process for producing alkylated aromatic compounds comprises the steps of: (a) supplying a feed stream to a dehydration zone, said feed stream comprising an alkylatable aromatic compound, water, and impurities, wherein said impurities comprise a compound having at least one of the following elements: nitrogen, halogens, oxygen, sulfur, arsenic, selenium, tellurium, phosphorus, and Group 1 through Group 12 metals; (b) removing at least a portion of said water from said feed stream in said dehydration zone to produce a dehydrated stream comprising said alkylatable aromatic compound, any remaining water, and said impurities; (c) contacting at least a portion of said dehydrated stream and a first alkylating agent stream with a first alkylation catalyst having a first poison capacity in a first alkylation reaction zone under suitable at least partially liquid phase first reaction
- a portion of the reactive impurities e.g., catalyst poisons
- the reactive impurities which could otherwise poison the second alkylation catalyst are removed from the feed stream in the first alkylation reaction zone by the first alkylation catalyst at the same time as the alkylatable aromatic compound is alkylated with alkylating agent.
- the process for producing alkylated aromatic compounds comprises the steps of: (a) supplying a feed stream to a dehydration zone, said feed stream comprising an alkylatable aromatic compound, water, and impurities, wherein said impurities comprise a compound having at least one of the following elements: nitrogen, halogens, oxygen, sulfur, arsenic, selenium, tellurium, phosphorus, and Group 1 through Group 12 metals; (b) removing at least a portion of said water from said feed stream in said dehydration zone to produce a dehydrated stream comprising said alkylatable aromatic compound, any remaining water, and said impurities; (c) contacting at least a portion of said dehydrated stream with a first catalyst having a first poison capacity in a first reaction zone under suitable at least partially liquid phase first reaction conditions to remove at least a portion of said impurities
- the impurities are removed from the feed stream in the first reaction zone by the first catalyst in the absence of the alkylating agent and there is no alkylation of the alkylatable aromatic compound.
- step (c) Preferably at least 80%, or at least 70%, or at least 60%, or at least 50%, by weight, of said impurities are removed in step (c).
- step (b) At least a portion of said impurities in said feed stream are removed in said dehydration zone.
- the impurities in said dehydrated stream after step (b) is 10%) less, 5% less or 1% less by weight than the impurities in said feed stream. More preferably, the impurities in said dehydrated stream after removing at least a portion of impurities in the dehydration zone is less than 1000 wppb, less than 750 wppb, less than 500 wppb or less than 250 wppb.
- the first poison capacity of said first alkylation catalyst may be greater than said second poison capacity of said second alkylation catalyst.
- the first poison capacity of said first alkylation catalyst is at least 5%, 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% greater than said second poison capacity of said second alkylation catalyst.
- the first poison capacity of said first catalyst may be greater than said second poison capacity of said alkylation catalyst.
- the first poison capacity of said first catalyst is at least 5%, 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% greater than said second poison capacity of said alkylation catalyst.
- the portion of said alkylated aromatic compound that is alkylated with alkylating agent in step (c) is at least 1%, at least 2%, at least 5%, at least 7%, at least 10%, at least 13% or at least 15% of said alkylatable aromatic compound.
- the flow rate of said second alkylating agent stream may be greater than the flow rate of said first alkylating agent stream.
- the flow rate of said second alkylating agent stream is at least 5%, 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% greater than the flow rate of said first alkylating agent stream.
- step (c) said dehydrated stream is fed to a treatment zone containing a treatment material, and then said dehydrated stream is contacted with said treatment material in said treatment zone under suitable treatment conditions to remove at least a portion of said remaining amount of impurities and to produce said first alkylated stream.
- the amount of impurities after contact with said treatment material is 1% less, 5% less, 10%> less or 15% less by weight than is said dehydrated stream.
- step (a) said feed stream is fed to a treatment zone containing a treatment material, and then said feed stream is contacted with said treatment material in said treatment zone under suitable treatment conditions to remove at least a portion of said impurities.
- the amount of impurities after treatment is 1% less, 5% less, 10%) less or 15% less by weight than is said feed stream.
- the treatment material is selected from the group consisting of clay, resin, activated alumina, Linde type X, Linde type A, and combinations thereof.
- said first alkylation catalyst is a large pore molecular sieve having a Constraint Index of less than 2.
- Such large pore molecular sieve is selected from the group of consisting of zeolite beta, faujasite, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), Rare Earth Y (KEY), Ultrahydrophobic Y (UHP-Y), mordenite, TEA-mordenite, ZSM-3, ZSM-4, ZSM-14, ZSM-18, ZSM-20, and combinations thereof.
- said first catalyst is a large pore molecular sieve having a Constraint Index of less than 2.
- Such large pore molecular sieve is selected from the group of consisting of zeolite beta, 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.
- the second alkylation catalyst e.g., reactive guard bed
- the alkylation catalyst e.g., non-reactive guard bed
- MCM-22 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 mixtures thereof.
- the water in said dehydrated stream is less than 100 wppm, less than 50 wppm, less than 25 wppm or less than 10 wppm based on said dehydrated stream.
- the water is removed, for example, via distillation, adsorption, evaporation, extraction or flashing.
- the dehydration zone is a distillation column, a benzene column or a lights column.
- the amount of impurities in said first alkylated stream is 25% less, 20% less, 15%) less, 10%o less or 5% less based on the weight of said feed stream.
- the amount of impurities in said first alkylated stream after removing additional impurities in said first alkylation zone is less than 100 wppb, 75 wppb, 50 wppb or 25 wppb.
- the impurities in said second alkylated stream is 10%> less, 5% less or 1% less by weight than the impurities in said first alkylated stream.
- the impurities in said second alkylated stream is less than 1 wppm, less than 5 wppm, less than 10 wppm, less than 15 wppm, less than 20 wppm or less than 25 wppm.
- the alkylation reaction zone(s) are preferably located in a single reactor vessel.
- said first alkylation reaction zone may be located in a separate vessel and may operate as a reactive guard bed.
- Said first reaction zone may be located in a separate vessel and may operate as a non-reactive guard bed.
- the catalyst in the reactive or non-reactive guard bed is subject to more frequent regeneration and/or replacement than the second alkylation catalyst, and hence it is typically provided with a bypass circuit so that the alkylation feed(s) may be fed directly to the series connected reaction zones in the reactor while the guard bed is out of service.
- the by-passable reactive guard bed is located upstream from the second alkylation zone.
- the by-passable non-reactive guard bed is located upstream from the alkylation zone.
- Such guard beds may be operated in co-current upflow or downflow operation.
- the reactive or non-reactive guard bed is maintained under suitable at least partial liquid phase conditions.
- the reactive guard bed At least a portion of the alkylatable aromatic compound and at least a portion of the alkylating agent are passed through the reactive guard bed prior to entry into the second alkylation reaction zone.
- the alkylatable aromatic compound is passed through the non-reactive guard bed prior to entry into the alkylation reaction zone.
- the catalyst composition used in the reactive guard bed or the non-reactive guard bed is different from the catalyst composition used in the second and subsequent alkylation reaction zone(s).
- the catalyst composition used in the reactive guard bed or the non-reactive guard bed may have multiple catalyst compositions (e.g., a mixture of mordenite and zeolite Y, or a mixture of zeolite beta and zeolite Y).
- the reactive guard bed and normally each alkylation reaction zone is maintained under conditions effective to cause alkylation of the alkylatable aromatic compound with the alkylating agent in the presence of an alkylation.
- said dehydrated stream further comprises at least a portion of an overhead stream from a distillation zone.
- said dehydrated stream is cooled to condense at least a portion of said dehydrated stream to remove at least a portion of any remaining water and impurities.
- the process further comprises the step of supplying said dehydrated stream to a distillation zone to remove said at least a portion of any remaining water before contacting step (c).
- the process further comprises the step of combining said dehydrated stream with a stream from a distillation zone to remove at least a portion of any said remaining water before contacting step (c), said distillation zone is a distillation column, a benzene column or a lights column.
- said alkylatable aromatic compound is benzene.
- Said first alkylating agent stream or said second alkylating agent stream comprises an olefin.
- said first or second alkylating agent stream comprises only alkylating agent and impurities, or only alkylating agent and water, or a mixture of alkylating agent and impurities and water.
- Said alkylated aromatic compound is a mono-alkylated aromatic compound in some embodiments.
- said alkylating agent is ethylene and said mono-alkylated aromatic compound is ethylbenzene, or said alkylating agent is propylene and said mono- alkylated aromatic compound is cumene, or said alkylating agent is butylene, and said mono- alkylated aromatic compound is sec-butyl benzene.
- a mono-alkylated aromatic compound stream, and optionally said poly-alkylated compound stream is separated from said second alkylated stream.
- Said alkylated aromatic compound is a poly-alkylated aromatic compound, wherein the process further comprises the step of contacting said poly-alkylated aromatic compound of step (e) with a transalkylation catalyst in a transalkylation reaction zone under suitable transalkylation conditions to produce an additional amount of said mono-alkylated aromatic compound.
- said transalkylation catalyst is a large pore molecular sieve having a Constraint Index of less than 2.
- said large pore molecular sieve is selected from the group of consisting of zeolite beta, faujasite, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), Rare Earth Y, 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 to the desired mono-alkylated aromatic compound, such as ethylbenzene, but typically produces at least some poly-alkylated species.
- the effluent from the final alkylation reaction zone may be subjected to a separation step to recover mono-alkylated and polyalkylated aromatic compounds.
- At least a portion of the poly-alkylated aromatic compound may be supplied to a transalkylation reactor which may be separate from the alkylation reactor.
- the poly-alkylated aromatic compound is reacted with the alkylatable aromatic compound to produce an effluent which contains additional mono-alkylated aromatic compound. At least a portion of these effluents may be separated to recover the alkylated aromatic compound (mono-alkylated aromatic compound and/or poly-alkylated aromatic compound).
- Fig. 1 shows a process 50 for producing an alkylated aromatic compound, for example, a mono-alkylated aromatic compound, such as ethylbenzene, in which a feed stream 1, comprising an alkylatable aromatic compound, water and impurities, is fed to treaters 2 having a treatment zone 2a containing a treatment material 4 where it is treated under suitable treatment conditions to remove a first portion of said impurities, referenced above, and to produce a treater effluent stream 5.
- the treater effluent stream 5 may be heated or cooled in heat exchanger 12a.
- the treater effluent stream 5 is then fed to a dehydration zone 14, such as a lights removal distillation column, where at least a portion of said water, and optionally a second portion of said impurities are removed from treater effluent stream 5 to produce a dehydrated stream 13 comprising said alkylatable aromatic compound, any remaining amount of water and said impurities.
- a dehydration zone 14 such as a lights removal distillation column
- the dehydrated stream 13 is fed to accumulator 16 of distillation zone 18.
- Distillation zone 18 may be a benzene distillation column.
- dehydrated stream 13 is combined with the overhead stream 15 from distillation zone 18 (which is cooled by a heat exchanger 12c) to produce an accumulator effluent 17.
- a portion of accumulator effluent 17 is fed as reflux 19 to distillation zone 18.
- Vapors 24 from accumulator 16 are fed to dehydration zone 14 for further separation.
- Stream 21 the remaining portion of accumulator effluent 17, forms an alkylatable aromatic feed stream 41 to alkylator 20, and a alkylatable aromatic feed stream 39 to transalkylator 30.
- stream 21 may be heated or cooled in heat exchanger 12b.
- Heavier compounds e.g., poly-alkylated aromatic compounds
- stream 21 may be heated or cooled in heat exchanger 12b.
- Heavier compounds e.g., poly-alkylated aromatic compounds
- stream 22 of distillation zone 18 is separated in downstream separation equipment (not shown) to produce a mono-alkylated aromatic compound, such as ethylbenzene, and polyalkylated aromatic compounds, such as polyalkylated feed stream 39a, discussed below.
- Alkylator 20 has at least a first alkylation zone 20a which contains a first alkylation catalyst 26 located upstream of and in fluid communication with at least a second alkylation zone 20b which contains a second alkylation catalyst 28.
- the first alkylation catalyst has a first poison capacity and the second alkylation catalyst has a second poison capacity, wherein the first poison capacity is greater than the second poison capacity.
- the first alkylation reaction zone is a reactive guard bed that is integral within alkylator 20.
- the first alkylation catalyst 26 comprises a large pore molecular sieve having a Constraint Index of less than 2.
- the second alkylation catalyst comprises a MCM-22 family molecular sieve, referenced above.
- the second alkylation catalyst comprises a medium pore molecular sieve having a Constraint Index of 2-12.
- the alkylatable aromatic feed stream 41 to the alkylator and a portion of first alkylating agent stream 43 are contacted with the first alkylation catalyst 26 in the first alkylation reaction zone under suitable at least partially liquid phase first reaction conditions. At least a portion, by weight, of said impurities are removed, and at least a portion, by weight, of said alkylatable aromatic compound is alkylated with said first alkylating agent stream 43, to produce a first alkylated stream comprising alkylated aromatic compound(s), unreacted alkylatable aromatic compound, any remaining water , and any remaining impurities.
- the first alkylated stream is contacted with another portion of said alkylating agent 43 in the presence of a second alkylation catalyst 28 (different from said first alkylation catalyst) in a second alkylation reaction zone 20b under suitable at least partially liquid phase second reaction conditions.
- Said unreacted alkylatable aromatic compound is alkylated with said second alkylating agent stream, to produce a second alkylated stream comprising additional said alkylated aromatic compound(s), any remaining water, and any remaining impurities.
- the alkylatable aromatic feed stream 39 to the transalkylator comprising the alkylatable aromatic compound, and the polyalkylated feed stream 39a (comprising the polyalkylated aromatic compound from the downstream separation equipment (not shown)), are fed to transalkylation zone 30a of transalkylator 30.
- Transalkylation zone 30a has at least one transalkylation catalyst 34.
- the transalkylation catalyst 34 is a large pore molecular sieve having a Constraint Index of less than 2.
- transalkylation zone 30a the poly-alkylated aromatic compound in the polyalkylated feed stream 39a is contacted with the transalkylator alkylatable aromatic feed stream 39 in the presence of transalkylation catalyst 34 under suitable at least partially liquid phase transalkylation conditions, to produce additional said mono-alkylated aromatic compound in transalkylator effluent 47.
- the alkylated effluent 45 optionally combined with transalkylator effluent 47, are fed as distillation feed stream 49 to distillation zone 18, to separate the mono-alkylated compounds from said poly-alkylated compounds and heavier compounds.
- Figs. 2-4 show alternative embodiments of the use of dehydrated stream 13 in the distillation zone 18 of process 50 for producing a mono-alkylated aromatic compound of Fig. 1.
- the pieces of equipment and streams with the same numerals as in Fig. 1 are the same.
- the dehydrated stream 13, along with reflux 19, are fed to the distillation zone 18.
- Overhead stream 15 is cooled in heat exchanger 12c and then flows into accumulator 16.
- Stream 17, which comprises the alkylatable aromatic stream flows from accumulator 16.
- a portion of stream 17 is split off and feed as the reflux 19, referenced above, to distillation zone 18.
- stream 21 the remaining portion of stream 17, forms the transalkyator alkylatable aromatic feed stream 39 to transalkylator 30, and the alkylatable aromatic feed stream 41 to alkylator 20.
- the dehydrated stream 13 is combined with the overhead stream 15 from distillation zone 18 and then cooled in heat exchanger 12c to form stream 23 which is then fed to accumulator 16.
- Stream 25 comprising the alkylatable aromatic compound, flows from accumulator 16 and is split into reflux stream 27 and stream 29.
- the overhead stream 15 of distillation zone 18 flows into accumulator 16 to form stream 17 as in Fig. 1.
- the dehydrated stream 13 is combined with reflux stream 19 to form combined reflux stream 33 to distillation zone 18.
- Stream 35, the remaining portion of stream 17, forms the transalkyator alkylatable aromatic feed stream 39 to transalkylator 30, and the alkylatable aromatic feed stream 41 to alkylator 20.
- stream 35 may be heated or cooled in a heat exchanger 12b.
- Fig. 5 shows a process 100 for producing a mono-alkylated aromatic compound 100, such as ethylbenzene, using a guard bed in a separate vessel, and which is operated in a reactive mode or a non-reactive mode.
- a guard bed When the guard bed is operated in non-reactive mode, no alkylating agent is fed.
- the guard bed When the guard bed is operated in reactive mode, it receives a portion of an alkylation agent.
- Feed stream 101 comprising an alkylatable aromatic compound, water and impurities are fed to dehydration zone 14, such as a lights removal distillation column.
- dehydration zone 14 At least a portion of said water, and optionally a portion of said impurities are removed from the feed stream 101 to produce a dehydrated stream 109 comprising said alkylatable aromatic compound, any remaining amount of said impurities and any remaining water.
- the dehydrated stream 109 is fed to a treatment zone 102 containing a treatment material 102a where it is treated under suitable treatment conditions to remove additional said impurities and to produce effluent stream 111.
- the impurities and treatment material 102a are the same as those described above.
- the effluent stream 111 may be heated or cooled in a heat exchanger (not shown).
- Effluent stream 1 11 is fed to accumulator 16 of distillation zone 18, where it is combined with the overhead stream 115 from distillation zone 18 to produce a combined effluent 117.
- Distillation zone 18 may be a benzene distillation column.
- a portion of combined effluent 117 is fed as reflux 119 to distillation zone 18.
- Vapors 124 from accumulator 16 are fed to dehydration zone 14 for further separation.
- Stream 121, the remaining portion of combined effluent 117, may be heated or cooled in a heat exchanger 12d.
- stream 121 forms an alkylatable aromatic feed stream 139 to transalkylator 30, and an alkylatable aromatic feed stream 141 to (reactive or non-reactive) guard bed 22.
- Heavier compounds e.g., poly-alkylated aromatic compounds
- a bottoms stream 122 of distillation zone 18 is separated in downstream separation equipment (not shown) to produce an alkylated aromatic compound, such as ethylbenzene, and polyalkylated aromatic compounds, such as polyalkylated feed stream 139a, discussed below.
- alkylated aromatic compound such as ethylbenzene
- polyalkylated aromatic compounds such as polyalkylated feed stream 139a, discussed below.
- Guard bed 22 is separate from alkylator 20 and located upstream of and is in fluid communication with at least a second alkylation zone 20b. When guard bed 22 is a reactive guard bed, it is the first alkylation zone and contains a first alkylation catalyst 26. When guard bed 22 is a non-reactive guard bed, is not an alkylation zone because no alkylating agent is fed.
- Second alkylation zone 20b contains a second alkylation catalyst 28.
- the first alkylation catalyst has a first poison capacity and is different from the second alkylation catalyst which has a second poison capacity.
- the first poison capacity is greater than the second poison capacity.
- the first alkylation catalyst 26 comprises a large pore molecular sieve having a Constraint Index of less than 2.
- the second alkylation catalyst comprises a MCM-22 family molecular sieve, referenced above. In other embodiments, the second alkylation catalyst comprises a medium pore molecular sieve having a Constraint Index of 2-12.
- guard bed 22 is a reactive guard bed
- the alkylatable aromatic feed stream 141 and a portion of alkylating agent stream 143 are contacted in the presence of the first alkylation catalyst 26, under at least partial liquid phase condition, to form the first alkylated stream which comprises comprising alkylated aromatic compound(s), unreacted alkylatable aromatic compound, any remaining water, and any remaining impurities.
- guard bed 22 When guard bed 22 is a non-reactive guard bed, it receives the alkylatable aromatic feed stream 141 which is contacted with the first alkylation catalyst 26 (in the absence of alkylating agent) under suitable at least partially liquid phase first reaction conditions to remove at least a portion, by weight, of said impurities, and produce an alkylatable aromatic stream comprising said alkylatable aromatic compound, any remaining water, and any remaining impurities.
- the first alkylated stream or the alkylatable aromatic stream is then fed to second alkylation zone 20b and contacted with additional alkylating agent stream 143 in the presence of second alkylation catalyst 28, under suitable at least partially liquid phase second reaction conditions, to produce a second alkylated stream which comprises additional amounts of alkylated aromatic compounds.
- transalkylator alkylatable aromatic feed stream 139 comprising the alkylatable aromatic compound
- polyalkylated aromatic feed stream 139a comprising the poly-alkylated aromatic compound
- Transalkylation zone 30a has at least one transalkylation catalyst 34.
- transalkylation catalyst 34 is a large pore molecular sieve having a Constraint Index of less than 2.
- transalkylation zone 30a the poly-alkylated aromatic feed stream 139a is contacted with transakylator alkylatable aromatic feed stream 139 in the presence of transalkylation catalyst 34 under suitable at least partially liquid phase transalkylation conditions to produce additional said mono-alkylated aromatic compound in transalkylator effluent 147.
- the alkylated effluent 145 optionally combined with transalkylator effluent 147, are fed as distillation feed stream 149 to distillation zone 18, to separate the mono-alkylated compounds from said poly-alkylated compounds and heavier compounds.
- the polyalkylated and heavier compounds are separated in downstream separation equipment (not shown).
- Figs. 6-8 show alternative embodiments of the use of effluent stream 111 (which comprises dehydrated stream 109) in distillation zone 18 of process 100 for producing a mono-alkylated aromatic compound of Fig. 5.
- the pieces of equipment and streams with the same numerals as in Fig. 5 are the same.
- the effluent stream 111 along with reflux stream 119 is fed to the distillation zone 18.
- Overhead stream 115 of distillation zone 18 flows into accumulator 16.
- Stream 117 which comprises the alkylatable aromatic stream, flows from accumulator 16. A portion of stream 117 is split off and fed as reflux 19 to distillation zone 18.
- stream 121 the remaining portion of stream 117, forms the transalkylator feed stream 139 to transalkylator 30, and the alkylator feed stream 141 to guard bed 22, as in Fig. 5.
- stream 121 may be heated or cooled in heat exchanger 12d.
- stream 129 comprising the alkylated aromatic compound, flows from accumulator 16. This stream 16 is split into reflux stream 127 and stream 129. Stream 129, the remaining portion of stream 125, forms the transalkylator alkylatable aromatic feed stream 139 to transalkylator 30, and the alkylatable aromatic feed stream 141 to guard bed 22.
- stream 129 may be heated or cooled in a heat exchanger 12d.
- the overhead stream 115 flows into accumulator 16 to form stream 117 and reflux stream 119 as in Fig. 5.
- the effluent stream 111 is combined with stream 119 that is split off of stream 17 to form reflux stream 133 to distillation zone 18.
- stream 135 may be heated or cooled in a heat exchanger 12d.
- the poison capacity for collidine was determined by feeding collidine in the gas phase in which its uptake was recorded via thermogravimetric analyzer.
- the total uptake is one measure of a zeolite's capacity for adsorbing nitrogen-containing compounds. Table 1
- Table 1 shows that the poison capacity using collidine for a catalyst having MWW topology is much less than that for catalyst having non-MWW topology.
- Rx 2 Deactivation of Rx 2 was used to indicate when Rx 1 has achieved its maximum poison capacity and catalyst poisons were no longer completely retained by Rx 1.
- NFM was fed at a concentration of 0.3 wt wppm based on the weight of the benzene feed.
- the NFM absorption capacities in the Examples are calculated from the time on stream and the time at which deactivation is observed in Rx 2.
- Table 2 shows that the NFM absorption capacity for zeolite beta as the first catalyst is superior to a first catalyst comprising an MWW catalyst.
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EP10847601.1A EP2545018A4 (en) | 2010-03-10 | 2010-03-10 | Alkylated aromatics production |
BR112012022691A BR112012022691A2 (en) | 2010-03-10 | 2010-03-10 | production of alkylated aromatics |
KR1020127023242A KR101533875B1 (en) | 2010-03-10 | 2010-03-10 | Alkylated aromatics production |
SG2012060281A SG183322A1 (en) | 2010-03-10 | 2010-03-10 | Alkylated aromatics production |
RU2012141942/04A RU2528825C2 (en) | 2010-03-10 | 2010-03-10 | Production of alkylated aromatic compounds |
CN201080065284.2A CN102906054B (en) | 2010-03-10 | 2010-03-10 | Alkylating aromatic substance is produced |
JP2012557019A JP5659247B2 (en) | 2010-03-10 | 2010-03-10 | Production of alkylated aromatics |
PCT/US2010/026844 WO2011112189A1 (en) | 2010-03-10 | 2010-03-10 | Alkylated aromatics production |
TW099144498A TWI523831B (en) | 2010-03-10 | 2010-12-17 | Alkylated aromatics production |
US14/075,218 US8877996B2 (en) | 2010-03-10 | 2013-11-08 | Alkylated aromatics production |
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PCT/US2010/026844 WO2011112189A1 (en) | 2010-03-10 | 2010-03-10 | Alkylated aromatics production |
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US12/721,326 Continuation US8629311B2 (en) | 2010-03-10 | 2010-03-10 | Alkylated aromatics production |
Publications (2)
Publication Number | Publication Date |
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WO2011112189A1 true WO2011112189A1 (en) | 2011-09-15 |
WO2011112189A8 WO2011112189A8 (en) | 2012-03-08 |
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PCT/US2010/026844 WO2011112189A1 (en) | 2010-03-10 | 2010-03-10 | Alkylated aromatics production |
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EP (1) | EP2545018A4 (en) |
JP (1) | JP5659247B2 (en) |
KR (1) | KR101533875B1 (en) |
CN (1) | CN102906054B (en) |
BR (1) | BR112012022691A2 (en) |
RU (1) | RU2528825C2 (en) |
SG (1) | SG183322A1 (en) |
WO (1) | WO2011112189A1 (en) |
Cited By (5)
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WO2013175490A1 (en) * | 2012-04-03 | 2013-11-28 | Reliance Industries Limited | An oxygenates-free c8-c12 aromatic hydrocarbon stream and a process for preparing the same |
WO2016073543A2 (en) | 2014-11-07 | 2016-05-12 | Uop Llc | Highly selective alkylation process with low zeolite catalyst composition |
WO2018160327A1 (en) * | 2017-02-28 | 2018-09-07 | Exxonmobil Chemical Patents Inc. | Catalyst compositions and their use in aromatic alkylation processes |
CN113333014A (en) * | 2021-06-02 | 2021-09-03 | 辽宁师范大学 | Solid catalyst for preparing diethylbenzene by ethyl benzene ethanol/ethylene alkylation and preparation method thereof |
RU2769447C2 (en) * | 2017-02-28 | 2022-03-31 | Эксонмобил Кемикэл Пейтентс Инк. | Catalytic compositions and application thereof in methods for alkylation of aromatic compounds |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US9249067B2 (en) | 2010-05-20 | 2016-02-02 | Exxonmobil Chemical Patents Inc. | Alkylation process |
RU2640595C2 (en) * | 2013-05-08 | 2018-01-10 | БЭДЖЕР ЛАЙСЕНСИНГ ЭлЭлСи | Method for alkylation of aromatic compounds |
KR102343528B1 (en) * | 2017-03-29 | 2021-12-29 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | Catalyst compositions and their use in aromatic alkylation processes |
CN111574318B (en) * | 2020-06-04 | 2022-09-30 | 常州瑞华化工工程技术股份有限公司 | Energy-saving reaction process for producing ethylbenzene from pure ethylene |
RU2756954C1 (en) * | 2020-12-09 | 2021-10-07 | Акционерное общество "Газпромнефть - Омский НПЗ" (АО "Газпромнефть-ОНПЗ") | Method for obtaining alkyl derivatives of arenes |
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JP2000516248A (en) * | 1996-08-20 | 2000-12-05 | ザ ダウ ケミカル カンパニー | Method for producing alkylated benzene |
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US7645913B2 (en) * | 2007-01-19 | 2010-01-12 | Exxonmobil Chemical Patents Inc. | Liquid phase alkylation with multiple catalysts |
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2010
- 2010-03-10 SG SG2012060281A patent/SG183322A1/en unknown
- 2010-03-10 WO PCT/US2010/026844 patent/WO2011112189A1/en active Application Filing
- 2010-03-10 JP JP2012557019A patent/JP5659247B2/en active Active
- 2010-03-10 BR BR112012022691A patent/BR112012022691A2/en not_active IP Right Cessation
- 2010-03-10 KR KR1020127023242A patent/KR101533875B1/en active IP Right Grant
- 2010-03-10 CN CN201080065284.2A patent/CN102906054B/en active Active
- 2010-03-10 RU RU2012141942/04A patent/RU2528825C2/en active IP Right Revival
- 2010-03-10 EP EP10847601.1A patent/EP2545018A4/en not_active Withdrawn
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US6995295B2 (en) * | 2002-09-23 | 2006-02-07 | Exxonmobil Chemical Patents Inc. | Alkylaromatics production |
US20080287720A1 (en) * | 2006-01-31 | 2008-11-20 | Clark Michael C | Alkylaromatics Production |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2013175490A1 (en) * | 2012-04-03 | 2013-11-28 | Reliance Industries Limited | An oxygenates-free c8-c12 aromatic hydrocarbon stream and a process for preparing the same |
US9725383B2 (en) | 2012-04-03 | 2017-08-08 | Reliance Industries Limited | Oxygenates-free C8-C12 aromatic hydrocarbon stream and a process for preparing the same |
WO2016073543A2 (en) | 2014-11-07 | 2016-05-12 | Uop Llc | Highly selective alkylation process with low zeolite catalyst composition |
EP3215477A4 (en) * | 2014-11-07 | 2018-03-07 | Uop Llc | Highly selective alkylation process with low zeolite catalyst composition |
WO2018160327A1 (en) * | 2017-02-28 | 2018-09-07 | Exxonmobil Chemical Patents Inc. | Catalyst compositions and their use in aromatic alkylation processes |
RU2769447C2 (en) * | 2017-02-28 | 2022-03-31 | Эксонмобил Кемикэл Пейтентс Инк. | Catalytic compositions and application thereof in methods for alkylation of aromatic compounds |
US11654423B2 (en) | 2017-02-28 | 2023-05-23 | Exxonmobil Chemical Patents Inc. | Catalyst compositions and their use in aromatic alkylation processes |
US20230249167A1 (en) * | 2017-02-28 | 2023-08-10 | ExxonMobil Technology and Engineering Company | Catalyst Compositions and Their Use in Aromatic Alkylation Processes |
US11986807B2 (en) | 2017-02-28 | 2024-05-21 | ExxonMobil Engineering & Technology Company | Catalyst compositions and their use in aromatic alkylation processes |
CN113333014A (en) * | 2021-06-02 | 2021-09-03 | 辽宁师范大学 | Solid catalyst for preparing diethylbenzene by ethyl benzene ethanol/ethylene alkylation and preparation method thereof |
Also Published As
Publication number | Publication date |
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BR112012022691A2 (en) | 2016-08-23 |
RU2528825C2 (en) | 2014-09-20 |
CN102906054B (en) | 2015-11-25 |
RU2012141942A (en) | 2014-04-10 |
WO2011112189A8 (en) | 2012-03-08 |
SG183322A1 (en) | 2012-09-27 |
CN102906054A (en) | 2013-01-30 |
KR20120136357A (en) | 2012-12-18 |
JP5659247B2 (en) | 2015-01-28 |
EP2545018A4 (en) | 2014-10-08 |
JP2013521336A (en) | 2013-06-10 |
EP2545018A1 (en) | 2013-01-16 |
KR101533875B1 (en) | 2015-07-03 |
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