JP5659247B2 - Production of alkylated aromatics - Google Patents

Description

  The present disclosure relates to a process for producing an alkylated aromatic compound from a feed stream comprising an alkylating agent, an alkylatable aromatic, and traces of water and impurities.

  Alkylating aromatics such as cumene, ethylbenzene and sec-butylbenzene are often alkylatable aromatics (eg, benzene) and alkylating agents (eg, benzene) in the presence of an acidic molecular sieve catalyst (eg, zeolite). It is produced by liquid phase alkylation reaction of olefins such as ethylene, propylene and butylene. Liquid phase aromatic alkylation processes often result in lower operating costs and less unwanted by-products (eg, xylene) than in earlier gas phase techniques.

Acidic molecular sieve catalysts that can 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 silicate and tungstate modified zirconia (eg, Zr (WO ₄ ) ₂ ), all of which are conventional Known in technology.

  Operation of a liquid phase aromatic alkylation reaction, particularly at relatively low temperatures, can make the catalyst sensitive to trace impurities (eg, “catalytic poisons”) in the feed stream of the alkylatable aromatic or alkylating agent. The result was great. Such impurities often resulted in a decrease in the ultimate life of the catalyst that required frequent catalyst regeneration before replacement of the catalyst was required. Catalyst replacement often results in process outages, lost production and significant costs. Various methods have been developed for pretreating aromatics and / or alkylating agent feed streams to remove catalyst poisons. These methods include distillation, adsorption and extraction.

  U.S. Pat. No. 6,313,362 (Green) teaches an aromatic alkylation process in which the molecular sieve catalyst in the liquid phase process has a large pore size molecular sieve catalyst such as MCM- 22 to remove impurities prior to the liquid phase alkylation reaction. Impurities taught to be removed include olefins, diolefins, styrene, oxygenated organic compounds, sulfur compounds, nitrogen compounds and oligomeric compounds.

  US Pat. No. 4,358,362 (Smith) teaches a method for enhancing the catalytic activity of a zeolite catalyst by contacting a feed stream containing impurities harmful to the catalyst with a zeolite adsorbent. . This disclosed technique uses an adsorbent, preferably ZSM-11, having a Si / Al ratio of greater than 12, a 10-12 membered ring and a Constrain Index of 1-12.

  US Pat. No. 5,030,786 (Shamshoum) teaches a process for producing ethylbenzene that increases catalyst life by reducing the concentration of water in the feed to the reactor.

  US Pat. No. 5,744,686 (Gajda) discloses nitrogen from a stream by contacting the aromatic hydrocarbon stream with a selective adsorbent having an average pore size of less than about 5.5 angstroms. Teaches how to remove compounds. The selective adsorbent is a non-acidic molecular sieve selected from the group consisting of pore-closed zeolite 4A, zeolite 4A, zeolite 5A, silicalite, F-silicalite, ZSM-5 and mixtures thereof.

  A method for preparing alkylated benzenes is taught in US Pat. No. 6,297,417 (Samson). The method comprises contacting the benzene feed with a solid acid, such as acidic clay or acidic zeolite in the pretreatment zone at a temperature of about 130 ° C. to about 300 ° C. to improve the lifetime of the alkylation and transalkylation catalyst. Including.

  US Pat. No. 6,355,851 (Wu) teaches a process for the synthesis of cumene catalyzed with zeolite, in which the benzene feed is contacted with a “hot” clay bed followed by The benzene feedstock is then distilled to separate benzene from the high molecular weight material produced during the hot clay treatment from the olefinic toxicant, and the benzene distillate is subsequently contacted with ambient temperature clay. “Cold” clay treatment. Propylene feedstock is contacted with alumina to remove traces of sodium compounds and moisture, contacted with molecular sieves to remove water, and contacted with two modified aluminas to remove other catalyst poisons. Preprocessed. The pretreated propylene feed and benzene feed are then reacted in the presence of a zeolite catalyst to produce cumene without causing rapid degradation of catalytic activity.

  PCT International Publication No. WO0214240 (Venkat) (Patent Document 7) describes a method for removing polar contaminants in an aromatic feedstock by contacting them with a molecular sieve having a pore size greater than 5.6 angstroms at a temperature below 130 ° C. Teach.

  US Pat. No. 6,894,201 (Schmidt) teaches a method of removing nitrogen compounds from alkylation reactants, such as benzene, prior to alkylation, the method comprising basic organic nitrogen compounds. A conventional adsorbent bed that adsorbs and a hot adsorbent bed of acidic molecular sieves that adsorb weakly basic nitrogen compounds, such as nitrite, are used. The patent has the advantage that water promotes the adsorption of weakly basic nitrogen compounds and that an alkylated reactant stream of elevated temperature and appropriate water concentration from a fractionation column is passed through a hot adsorbent bed. Teaching to get.

  US Pat. No. 7,199,275 (Smith) has a partially dehydrated hydrocarbon feedstock having at least two different molecular sieve materials, eg, Si / Al molar ratio less than about 5. A method of converting hydrocarbons contacted with a first molecular sieve and a second molecular sieve having a Si / Al molar ratio greater than about 5 is taught. The patent also teaches how such a feed is contacted with a first molecular sieve having at least about 6 angstroms of pores and a second molecular sieve having pores of less than about 6 angstroms.

US Pat. No. 6,313,362 U.S. Pat. No. 4,358,362 US Pat. No. 5,030,786 US Pat. No. 5,744,686 US Pat. No. 6,297,417 US Pat. No. 6,355,851 WO0214240 pamphlet US Pat. No. 6,894,201 US Pat. No. 7,199,275

  These prior art documents are methods for alkylating a feed stream by contact with an alkylation catalyst, the feed stream comprising an alkylatable aromatic compound, an alkylating agent and trace amounts of water and impurities, Nothing is taught about an alkylation process in which a portion of the water and impurities are removed at the same time that the feed stream is alkylated. The presence of water and impurities in the feed stream adversely affects the catalytic activity and cycle length of the alkylation catalyst in the alkylation process.

  Thus, such feed stream is contacted with a first and then a different second alkylation catalyst so that the negative impact on the activity and cycle length of such alkylation catalyst due to water and impurities is reduced. There is a need for an improved process for producing alkylated aromatics by removing a portion of water and impurities and alkylating a portion of the alkylatable aromatic. The disclosed invention satisfies this and other needs.

  This specification describes a process for producing alkylated aromatic compounds from a feed stream containing alkylating agents, alkylatable aromatics and traces of water and impurities. Water and optionally some of the impurities are removed in the dehydration zone. In the reaction guard bed, the dehydrated stream and the alkylating agent are contacted with the first alkylation catalyst and then with another second alkylation catalyst, at the same time as this stream is alkylated. The residual impurities that are obtained are removed. Alternatively, in a non-reacted guard bed, the dehydrated stream is contacted with the first catalyst, where possible residual impurities are removed, and this stream is then alkylated with an alkylating agent by contact with an alkylation catalyst. The

  The first alkylation catalyst in the first alkylation zone is a large pore molecular sieve in some embodiments. The second alkylation catalyst in the second alkylation zone is a medium pore size molecular sieve or MCM-22 family material in some embodiments.

  While not intending to be bound by any theory, it is believed that the dehydration process reduces the concentration of water and optionally reduces the level of impurities in the alkylatable aromatic feed. Some of the impurities are removed at the same time as some of the water is removed. This means that the first alkylation step removes some, preferably most, of the remaining impurities contained in the alkylatable aromatic feedstock, such as nitrogen-containing species and other species. And allowing a portion of the alkylatable aromatic compound to be alkylated. Preferably, at least 80%, at least 70% or at least 60% by weight of the remaining impurities are removed. The second alkylation step serves to remove a portion of the remaining impurities in the next order and to alkylate most of the alkylatable aromatic compound. 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 produced alkylated aromatic compound mainly comprises a monoalkylated aromatic compound, together with a trace amount of polyalkylated aromatic compound produced incidentally in the alkylation reaction zone. The polyalkylated aromatic compound is then converted to an additional monoalkylated aromatic compound in the transalkylation step by contacting the additional alkylatable aromatic compound in the presence of a separate transalkylation catalyst. be able to.

  1-8 are process flow diagrams of methods for producing alkylated aromatic compounds, respectively, according to embodiments of the present disclosure.

Definitions As used herein, the term "alkylatable aromatic compound" means an aromatic compound that can accept an alkyl group. One non-limiting example of an alkylatable aromatic compound is benzene.

  As used herein, the term “alkylating agent” means a compound capable of donating an alkyl group to an alkylatable aromatic compound. Non-limiting examples of alkylating agents are ethylene, propylene and butylene. Another non-limiting example is any polyalkylated aromatic compound capable of donating an alkyl group to the alkylatable aromatic compound.

  The term “aromatic” as used herein in connection with alkylatable aromatic compounds useful in the presently disclosed invention should be understood in accordance with the scope recognized in the aromatic art. Including substituted and unsubstituted mononuclear and polynuclear compounds. Compounds having heteroatoms (eg, N or S) and exhibiting aromatic properties are also useful as long as these compounds do not act as catalyst poisons as defined below under selected reaction conditions.

  As used herein, the phrase “at least partially liquid phase” refers to a mixture having at least 1 wt% liquid phase, optionally at least 5 wt% liquid phase at a given temperature, pressure and composition. means.

  As used herein, the term “catalyst poison” means an impurity as defined herein that acts to shorten the cycle length of molecular sieves or zeolites.

  As used herein, the term “cycle length” means the total oil passage time between regeneration and regeneration or the oil passage time between filling and regeneration of unused catalyst. After the unused or regenerated catalyst is placed under oil passage, it can be deactivated by coke deposits or poisons. When the catalyst is deactivated, the reaction zone must be operated at a higher temperature in order to maintain the same productivity or catalytic activity. The catalyst must be regenerated when the reaction zone temperature reaches a limit temperature, typically determined by metallurgical knowledge of the reactor or justified by economic factors.

  As used herein, the term “framework type” refers to “Atlas of Zeolite Framework Types” by Ch. Baerlocher, WM Meier and DH Olsen, 5th edition, published by Elsevier, 2001. Has the meaning described in.

  As used herein, the numbering of periodic table element groups has the meaning described in the periodic table of elements published on June 22, 2007 by the International Union of Applied Chemistry.

  As used herein, the term “impurity” is not limited to the following, but includes the following elements: nitrogen, halogen, oxygen, sulfur, arsenic, selenium, tellurium, phosphorus, and groups 1 to Includes compounds having at least one of the Group 12 metals.

  The impurity content used in this disclosure means wppm of impurities based on the total weight of the combined alkylatable aromatic compound and alkylating agent in the reaction zone.

As used herein, the term “MCM-22 family substance” (or “MCM-22 family substance” or “MCM-22 family molecular sieve”) includes:
(I) A molecular sieve made from a “unit cell having an MWW skeleton topology” which is a common primary crystal constituent unit. A unit cell is a spatial arrangement of atoms arranged in a three-dimensional space, written by Ch. Baerlocher, WM Meier and DH Olsen, “Atlas of Zeolite Framework Types”, 5th edition, Elsevier The crystal described in the publication, 2001 is described.
(Ii) a molecular sieve made from the above-mentioned “two-dimensional array of MWW skeleton type unit cell”, which is a common secondary constituent unit, and “a unit cell thickness, preferably 1 c-axis unit cell thickness” A single layer ".
(Iii) a molecular sieve made from a common secondary constituent unit "layer of unit cell thickness greater than or equal to 1", the layer of unit cell thickness greater than 1 having an MWW skeleton topology It is made by laminating, filling or bonding at least two monolayers of unit cell of 1 unit cell thickness. Such a stack of secondary building blocks can be in a regular manner, an irregular manner, a random manner and any combination thereof. Or (iv) molecular sieves made by any regular or random two-dimensional or three-dimensional combination of unit cells with MWW framework topology.

  The MCM-22 family materials have lattice spacing d peaks (after firing or as-synthesized) of 12.4 ± 0.25, 3.57 ± 0.07 and 3.42 ± 0.07 angstroms. Is characterized by having an X-ray diffraction pattern contained therein. The MCM-22 family material also has a peak in the lattice spacing d (after firing or as-synthesized) 12.4 ± 0.25, 6.9 ± 0.15, 3.57 ± 0.07. And by having an X-ray diffraction pattern comprising at 3.42 ± 0.07 angstroms. X-ray diffraction data used to characterize molecular sieves is obtained by a standard method using copper K-alpha double rays as incident radiation and a diffractometer equipped with a scintillation counter and an accompanying computer as a collection system. .

  The term “monoalkylated aromatic compound” means an aromatic compound having only one alkyl substituent. Non-limiting examples of monoalkylated aromatic compounds are ethylbenzene, isopropylbenzene (cumene) and sec-butylbenzene.

  As used herein, the term “under oil passage” should be understood as the catalyst being placed under alkylating or transalkylating conditions. Alkylation or transalkylation conditions include temperature, pressure, one or more alkylatable aromatics, one or more alkylating agents, and WHSV (all one or more alkyls in the feed). Suitable for converting at least 1% by weight, preferably at least 10% by weight of the one or more alkylatable aromatic compounds (based on the activatable aromatic compound) to one or more monoalkylated aromatic compounds.

As used herein, the term “catalytic poison capacity” refers to a catalyst dried under a stream of nitrogen at 200 ° C. for 60 minutes on a Thermogravimetric Analyzer (Model Q5000, New Castle, Delaware, USA). It means the number of millimoles of collidine (catalyst poison) absorbed per gram of sample. After drying, collidine catalyst poison is sprinkled over the catalyst sample for 60 minutes at a collidine partial pressure of 3 Torr. The catalyst poison capacity is calculated from the following formula:
(Catalyst sample weight after spraying collidine-catalyst weight after drying) × 10 ⁶ ÷ (molecular weight of collidine × catalyst sample weight after drying).
When the catalyst sample weight and after drying catalyst sample weight are measured in grams, the molecular weight of collidine is 121.2 grams / mmol.

  As used herein, the term “polyalkylated aromatic compound” means an aromatic compound having more than one alkyl substituent. Non-limiting examples of polyalkylated aromatic compounds are polyalkylated benzenes such as diethylbenzene, triethylbenzene, diisopropylbenzene and triisopropylbenzene.

  As used herein, the term “wppb” is defined as parts per billion by weight.

As used herein, the term “wppm” is defined as parts per million by weight.
Feedstock and products

  Suitable unsubstituted aromatic compounds that can be used in the disclosed invention include benzene, naphthalene, anthracene, naphthacene, perylene, coronene and phenanthrene, with benzene being preferred.

  Substituted aromatic compounds that can be used in the disclosed invention must have at least one hydrogen atom bonded directly to the aromatic nucleus. The aromatic ring can be substituted by one or more alkyl, aryl, alkaryl, alkoxy, aryloxy, cycloalkyl, halogen groups and / or other groups that do not interfere with the alkylation reaction. Generally, alkyl groups that can be present as substituents on aromatic compounds contain from 1 to about 22 carbon atoms, usually from about 1 to 8 carbon atoms, most usually from about 1 to 4 carbon atoms. .

  Suitable substituted aromatic compounds that can be used in the present disclosure are not limited to: toluene, xylene, isopropylbenzene, normal propylbenzene, alphamethylnaphthalene, ethylbenzene, mesitylene, durene, cymene, 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-diethyltoluene, o-ethyltoluene, p-ethyltoluene, m - Pyrtoluene, 4-ethyl-m-xylene, dimethylnaphthalene, ethylnaphthalene, 2,3-dimethylanthracene, 9-ethylanthracene, 2-methylanthracene, o-methylanthracene, 9,10-dimethylphenanthrene and 3-methylphenanthrene. Including.

High molecular weight alkyl aromatic hydrocarbons can also be used as starting materials, including aromatic hydrocarbons such as those produced by alkylating aromatic hydrocarbons with olefin oligomers. Such products are often referred to in the art as alkylates and are not limited to hexylbenzene, nonylbenzene, dodecylbenzene, pentadecylbenzene, hexyltoluene, nonyltoluene, dodecyltoluene, pentadecyltoluene. Etc. Very often alkylates are obtained as high boiling fractions in which the size of the alkyl group attached to the aromatic nucleus varies between about C ₆ and about C ₁₆ .

A reformate stream that may contain substantial amounts of benzene, toluene and / or xylene may be particularly suitable as an alkylatable aromatic feed for the process of the present disclosure. Although the process of the present invention is particularly directed to the production of ethylbenzene from polymer grade ethylene and dilute ethylene, the process is not limited to other C ₇ -C ₂₀ alkyl aromatics such as cumene and also C ₆₊ alkyl aromatics, For example, it is equally applicable to the production of C _{8 to} C ₁₆ linear and near linear alkylbenzenes.

Suitable one or more alkylating agents that can be used in the disclosed invention include one or more alkene compounds, one or more alcohol compounds and / or one or more alkylbenzenes and mixtures thereof. Other suitable alkylating agents that may be useful in the methods of the present disclosure are generally not limited to the one or more available for alkylation capable of reacting with alkylatable aromatic compounds. Any aliphatic or aromatic organic compound having the following aliphatic groups is included. Examples of suitable alkylating agents are C _{2 to} C ₁₆ olefins such as C _{2 to} C ₅ olefins such as ethylene, propylene, butene and pentene; C _{1 to} C ₁₂ alkanols (monoalcohols, dialcohols, trialcohols, etc. C ₁ -C ₅ alkanols such as methanol, ethanol, propanol, butanol and pentanol; C ₂ -C ₂₀ ethers such as C ₂ -C ₅ ethers such as dimethyl ether and diethyl ether; aldehydes, For example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and n-valeraldehyde; alkyl halides such as methyl chloride, ethyl chloride, propyl chloride, butyl chloride and pentyl chloride; one or more Polyalkylated aromatics such as bi-alkylated benzenes (eg, one or more bi-ethylbenzene or bi-isopropylbenzene) and one or more trialkylated benzenes (eg, tri-ethylbenzene or tri-isopropylbenzene) Etc. Thus, the alkylating agent is preferably _C 2 -C _{5 olefins,} C 1 -C ₅ alkanol, one or more bi - ethylbenzene, 1 or more bi - isopropylbenzene, 1 or more tri - ethylbenzene and 1 or more Of tri-isopropylbenzene.
impurities

In the presently disclosed invention, the feed stream containing the alkylatable aromatic compound may contain impurities. Optionally, the first alkylating agent stream and / or the second alkylating agent stream may also contain impurities. Impurities include compounds having at least one of the following elements: nitrogen, halogen, oxygen, sulfur, arsenic, selenium, tellurium, phosphorus, and Group 1-12 metals. Examples of such impurities include collidine and N-formylmorpholine. For the purposes of the present disclosure, the term “impurity” does not include water, ie, H ₂ O.

In some embodiments, the amount of the impurities in the feed stream (or first and / or second alkylating agent stream) is less than 20 wppm, less than 15 wppm, less than 10 wppm based on the weight of the feedstream. Less than 5 wppm or less than 1 wppm.
Water content

  In one or more embodiments, the feed stream may include water. Optionally, the first alkylating agent stream and / or the second alkylating agent stream may also include water. The feed stream or one or more alkylating agent streams can be dehydrated, for example, by distillation, adsorption, evaporation, extraction or vacuum flushing in one or more dehydration zones. The dehydration zone can be a distillation column, benzene column or flushing column, light fraction column or extraction tower, absorption tower or flash tank.

  In some embodiments, the feed stream is saturated with water at the feed temperature and pressure conditions. In other embodiments, the amount of water in the 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 the feedstream.

Impurity or water levels can be measured by conventional techniques such as GC, GC / MS or other suitable techniques known to those skilled in the art.
Reaction conditions

The method of the present disclosure
(1) a dehydration zone operated under suitable dehydration conditions to remove at least a portion of water and optionally a portion of 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 most of the remaining impurities; And a second alkylation reaction having a second alkylation catalyst different from the first alkylation catalyst, wherein the first alkylation reaction zone removes and alkylates a portion of the alkylatable aromatic compound. A zone where the second alkylation zone is operated under suitable second reaction conditions to remove some of the remaining impurities and alkylate most of the alkylatable aromatics to add A second alkylation reaction zone is included that produces a quantity of the monoalkylated aromatic compound.

  In the dewatering zone, suitable dewatering conditions are the conventional dewatering conditions known in the prior art for separating water and impurities from the aromatic stream.

When the alkylatable aromatic compound and the alkylating agent are contacted at least partially under liquid phase conditions in the first alkylation reaction zone and / or the second alkylation reaction zone, a suitable first And the second condition is a temperature of 100 to 285 ° C., preferably a temperature of 150 to 260 ° C., a pressure of 689 to 4601 kPa-a, preferably 1500 to 3000 kPa-a, and an alkyl for the whole reactor. 10～100Hr ^-1 based on the sum of the agent and the alkylatable aromatic compound, preferably a WHSV of 20~50hr ^-1. The total molar ratio of alkylatable aromatic compound to alkylating agent (eg, benzene and ethylene, respectively) is 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 as a reaction guard bed where at least a portion of the impurities in the feed stream are removed. In this embodiment, the total molar ratio of alkylatable aromatic compound and alkylating agent (eg, benzene and ethylene, respectively) is much higher than in the alkylation run alone, 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 alkylation reaction zone is the first reaction zone operated as a non-reacted guard bed, where at least a portion of the impurities in the feed stream is removed. In this embodiment, only the alkylatable aromatic compound is fed to the first reaction zone.

  In some embodiments, the disclosed method includes a treatment zone having a treatment material, the treatment zone being operated under treatment conditions suitable to remove a portion of impurities. The treatment zone may be upstream or downstream of the dewatering zone. The treatment zone is upstream of the first and second alkylation zones.

When the treatment material is used to remove a portion of the impurities, suitable treatment conditions are about 30-200 ° C, preferably about 60-150 ° C, about 0.1 hr ^-1 to about 200 hr ^-1 , preferably includes a pressure of from about 0.5 hr ^-1 ~ about 100 hr ^-1, more preferably a weight hourly space velocity of from about 1.0 hr ^-1 ~ about 50 hr ^-1 (WHSV) and approximately ambient pressure ~3000kPa-a.

  In some embodiments, the disclosed method of the invention comprises a transalkylation zone operated under suitable transalkylation conditions, and is added from a polyalkylated aromatic compound and an alkylatable aromatic compound. A quantity of monoalkylated aromatic compound is produced.

In the transalkylation zone, a polyalkylated aromatic compound (eg, one or more polyethylbenzenes or one or more polyisopropylbenzenes) is contacted with the alkylatable aromatic compound at least partially under liquid phase conditions. Suitable transalkylation conditions include a temperature of about 100 to about 300 ° C., a pressure of 696 to 4137 kPa-a (101 to 600 psia), and supply of one or more polyalkylated aromatics to the alkylation reaction zone. WHSV from about 0.5 hr ⁻¹ to about 100 hr ⁻¹ based on the weight of the raw material, and 1: 1 to 30: 1, preferably 1: 1 to 10: benzene and one or more polyalkylated aromatic compounds. 1, more preferably a molar ratio of 1: 1 to 5: 1.
catalyst

  The method of the present disclosure includes (1) a first alkylation catalyst and (2) a second alkylation catalyst 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 catalyst poison capacity.

  The restraining index is a convenient indicator of how well the aluminosilicate or molecular sieve allows controlled entry of various sized molecules into its internal structure. For example, aluminosilicates that are very limited in entering and exiting the internal structure of aluminosilicates have high values for the restraining index, and this type of aluminosilicate usually has a small pore size, eg less than 5 angstroms Has holes. On the other hand, aluminosilicate that allows relatively free entry into the interior of the aluminosilicate structure has a low value for the constraint index and usually has large pores. The method by which the restraining index can be measured is fully described in US Pat. No. 4,016,218.

  Suitable large pore molecular sieves are zeolite beta, zeolite Y, ultrastable Y (USY), dealuminated alumina Y (Deal Y), superhydrophobic Y (UHP-Y), rare earth exchange Y (REY), mordenite, TEA -Including mordenite, ZSM-3, ZSM-4, ZSM-14, ZSM-18 and ZSM-20. Zeolite ZSM-14 is described in US Pat. No. 3,923,636. Zeolite ZSM-20 is described in US Pat. No. 3,972,983. Zeolite beta is described in US Pat. No. 3,308,069 and US Reissue Patent 28,341. Low sodium ultrastable Y molecular sieve (USY) is described in US Pat. Nos. 3,293,192 and 3,449,070. Dealuminized Y zeolite (Deal Y) can be prepared by the method found in US Pat. No. 3,442,795. Superhydrophobic Y (UHP-Y) is described in US Pat. No. 4,401,556. Rare earth exchange Y (REY) is described in US Pat. No. 3,524,820. Mordenite is a naturally occurring substance, but is also available in synthetic form, for example, TEA-mordenite (ie, synthetic mordenite prepared from a reaction mixture containing tetraethylammonium directing agent). TEA-mordenite is described in US Pat. Nos. 3,766,093 and 3,894,104.

  The zeolitic material that has been identified as belonging to the MWW topology by the International Zeolite Association Structural Committee (IZA-SC) is a multi-layered material with two pore systems resulting from the presence of both 10 and 12 membered rings. The “Zeolite Framework Type Overview” currently categorizes at least 5 differently named materials as having this same topology, MCM-22, ERB-1, ITQ-1, PSH-3 and SSZ- 25, but is not limited thereto.

  In some embodiments, the second alkylation catalyst, preferably an acidic catalyst, comprises MCM-22 family molecular sieve having a second catalyst poison capacity. MCM-22 family molecular sieves have been found useful in a variety of hydrocarbon conversion processes. Examples of MCM-22 family molecular sieves are MCM-22, MCM-36, MCM-49, MCM-56, ITQ-1, ITQ-2, ITQ-30, PSH-3, SSZ-25, ERB-1 and UZM-8.

  Substances belonging to the MCM-22 family are MCM-22 (described in US Pat. No. 4,954,325) and PSH-3 (described in US Pat. No. 4,439,409). SSZ-25 (described in U.S. Pat. No. 4,826,667), ERB-1 (described in European Patent No. 093032), ITQ-1 (U.S. Pat. No. 6,077, 498), ITQ-2 (described in international application WO97 / 17290), and ITQ-30 international application WO2005118476. ), MCM-36 (described in US Pat. No. 5,250,277), MCM-49 (described in US Pat. No. 5,236,575), MCM-56 (US Pat. No. 5,362,697) and UZM-8 (described in US Pat. No. 6,756,030).

  The MCM-22 family molecular sieve described above has the conventional large pore size described below in that the MCM-22 material has a 12-membered outer surface pocket that is not in communication with the 10-membered internal pore system of the molecular sieve. It should be understood that it is distinguished from zeolite alkylation catalysts such as mordenite.

  Alternatively, the second alkylation catalyst, preferably an acidic catalyst, can comprise a medium pore size molecular sieve (defined in US Pat. No. 4,016,218) having a constraint index of 2-12. For example, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-48. ZSM-5 is described in detail in US Pat. No. 3,702,886 and US Reissue Patent 29,948. ZSM-11 is described in detail in US Pat. No. 3,709,979. ZSM-12 is described in US Pat. No. 3,832,449. ZSM-22 is described in US Pat. No. 4,556,477. ZSM-23 is described in U.S. Pat. No. 4,076,842. ZSM-35 is described in US Pat. No. 4,016,245. ZSM-48 is described in more detail in US Pat. No. 4,234,231.

  In one or more embodiments, the first catalyst poison capacity of the first alkylation catalyst is greater than the second catalyst poison capacity of the second alkylation catalyst, wherein the catalyst poison capacity is Measured by collidine capacity.

  In some embodiments, the methods of the present disclosure include a treatment material. The treatment material is selected from the group consisting of clay, resin, Linde-X type, Linde-A type and combinations thereof. The treatment material can be acidic or non-acidic.

In some embodiments, the methods of the present disclosure include 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.
Detailed description of the method of the invention

In the operation of one embodiment (eg, reaction guard bed) of a method for producing alkylated aromatic compounds, such as monoalkylated and polyalkylated aromatic compounds, such a method comprises:
(A) supplying a feed stream to a dehydration zone, the feed stream comprising an alkylatable aromatic compound, water and impurities, wherein the impurities are the following elements: nitrogen, halogen, oxygen, sulfur Including a compound having at least one of arsenic, selenium, tellurium, phosphorus and a Group 1 to Group 12 metal;
(B) removing at least a portion of the water from the feed stream in the dehydration zone to produce a dehydrated stream comprising the alkylatable aromatic compound, possible residual water and the impurities;
(C) in a suitable first alkylation reaction zone at least partially under liquid phase first reaction conditions, at least a portion of the dehydrated stream and a first alkylating agent stream are Contacting with a first alkylation catalyst having a catalytic poison capacity to remove at least a portion of the impurities and alkylate a portion of the alkylatable aromatic compound with the first alkylating agent stream; and 1 Or a first alkyl comprising a plurality of alkylated aromatics (eg, monoalkylated and polyalkylated aromatics), unreacted alkylatable aromatics, possible residual water and possible residual impurities Manufacturing a stream that is reduced by at least 25% compared to the impurities in the dehydrated stream. And (d) in a second alkylation reaction zone under suitable at least partly liquid phase second reaction conditions, said first alkylated stream and second alkylating agent stream Contacting with a second alkylation catalyst different from the first alkylation catalyst and having a second catalyst poison capacity, and at least the unreacted alkylatable aromatic compound in the second alkylating agent stream. A second alkylated stream comprising alkylating a portion and comprising the additional one or more alkylated aromatics, unreacted alkylatable aromatics, possible residual water and possible residual impurities The process of manufacturing is included.

  In the reaction guard bed, a portion of the reactive impurities (eg, catalyst poisons) that would otherwise poison the second alkylation catalyst are alkylated with an alkylating agent on the alkylatable aromatic compound. At the same time, the first alkylation catalyst removes it from the feed stream in the first alkylation reaction zone.

In the operation of another embodiment of the process for producing alkylated aromatic compounds, such as monoalkylated and polyalkylated aromatic compounds (e.g., non-reacted guard bed), such process comprises (a) dewatering the feed stream. Wherein the feed stream comprises an alkylatable aromatic compound, water and impurities, the impurities being the following elements: nitrogen, halogen, oxygen, sulfur, arsenic, selenium, tellurium, phosphorus and Including a compound having at least one of Group 1 to Group 12 metals;
(B) removing at least a portion of the water from the feed stream in the dehydration zone to produce a dehydrated stream comprising the alkylatable aromatic compound, possible residual water and the impurities;
(C) a first alkylation catalyst having a first catalyst poison capacity for at least a portion of the dehydrated stream in a first reaction zone under suitable at least partially liquid phase first reaction conditions; An alkylatable aromatic stream having a reduced amount of impurities, including at least a portion of the impurities and contacting with the alkylable aromatic compound, possible residual water and possible residual impurities Preferably wherein the residual impurities are reduced by at least 25% compared to the impurities in the dehydrated stream, and (d) a suitable at least partly liquid phase In the alkylation reaction zone under the second reaction conditions of the first catalyst, the alkylatable aromatic stream and the alkylating agent stream are different from the first catalyst and in a second contact. Contacting with an alkylation catalyst having a poisonous capacity, alkylating at least a portion of the unreacted alkylatable aromatic compound with the second alkylating agent stream, and one or more alkylated aromatics Producing a second alkylated stream comprising the compound, unreacted alkylatable aromatics, possible residual water and possible residual impurities.

  In the non-reacted guard bed, impurities are removed by the first catalyst from the feed stream in the absence of the alkylating agent in the first reaction zone and alkylation of the alkylatable aromatics does not occur.

  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 is removed in the dewatering zone. Preferably, the impurities in the dehydrated stream after step (b) are 10% by weight, 5% by weight or 1% by weight less than the impurities in the feed stream. More preferably, the impurities in the dehydrated stream after removing at least a portion of the impurities in the dehydration zone are less than 1000 wppb, less than 750 wppb, less than 500 wppb or less than 250 wppb.

  In the reaction guard bed, the first catalyst poison capacity of the first alkylation catalyst can be greater than the second catalyst poison capacity of the second alkylation catalyst. Preferably, the first catalyst poison capacity of the first alkylation catalyst is at least 5%, at least 10%, at least 15%, at least 20% greater than the second catalyst poison capacity of the second alkylation catalyst. At least 25%, at least 30%, at least 35%, at least 40%, at least 45% or at least 50% greater.

  In a non-reacted guard bed, the first catalyst poison capacity of the first catalyst can be greater than the second catalyst poison capacity of the alkylation catalyst. Preferably, the first catalyst poison capacity of the first catalyst is at least 5%, at least 10%, at least 15%, at least 20%, at least 25% greater than the second catalyst poison capacity of the alkylation catalyst. , At least 30%, at least 35%, at least 40%, at least 45% or at least 50% greater.

  In the reaction guard bed, the portion of the alkylated aromatic compound that is alkylated with the alkylating agent in step (c) is at least 1%, at least 2%, at least 5%, at least 7% of the alkylatable aromatic compound. %, At least 10%, at least 13% or at least 15%.

  In the reaction 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%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30% greater than the flow rate of the first alkylating agent stream. , At least 35%, at least 40%, at least 45% or at least 50% greater.

  In some embodiments, prior to step (c), the dehydrated stream is fed to a treatment zone containing a processing material, and then the dehydrated stream is treated under suitable processing conditions. The first alkylated stream is produced in contact with the treatment material in the zone to remove at least a portion of the remaining amount of the impurities. In these embodiments, the amount of impurities after contact with the treatment material is 1%, 5%, 10% or 15% by weight less than in the dehydrated stream.

  In other embodiments, prior to step (a), the feed stream is fed to a processing zone containing a processing substance, and then the feed stream is fed in the processing zone under suitable processing conditions. Contact with the treatment material removes at least a portion of the impurities. Preferably, the amount of impurities after treatment is 1%, 5%, 10% or 15% by weight less than in the feed stream. In these embodiments, the treatment material is selected from the group consisting of clay, resin, activated alumina, Linde-X type, Linde-A type, and combinations thereof.

  In the reaction guard bed, the first alkylation catalyst is a large pore molecular sieve having a constraint index of less than 2. Such large pore molecular sieves include zeolite beta, faujasite, zeolite Y, ultrastable Y (USY), dealuminated alumina Y (Deal Y), rare earth Y (REY), superhydrophobic Y (UHP-Y), mordenite, Selected from the group consisting of TEA-mordenite, ZSM-3, ZSM-4, ZSM-14, ZSM-18, ZSM-20 and combinations thereof.

  In a non-reacted guard bed, the first catalyst is a large pore molecular sieve having a constraint index of less than 2. Such large pore molecular sieves are zeolite beta, faujasite, zeolite Y, ultrastable Y (USY), dealuminated alumina (Deal Y), rare earth Y (REY), superhydrophobic Y (UHP-Y), mordenite, Selected from the group consisting of TEA-mordenite, ZSM-3, ZSM-4, ZSM-14, ZSM-18, ZSM-20 and combinations thereof.

  The second alkylation catalyst (eg, reaction guard bed) or alkylation catalyst (eg, non-reaction guard bed) has a unit cell of MWW skeleton topology and has a peak with a lattice spacing d of 12.4 ± 0. It is an MCM-22 family material characterized by an X-ray diffraction pattern including 25, 3.57 ± 0.07 and 3.42 ± 0.07 angstroms. Such MCM-22 family substances are 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 or less than 10 wppm on the dewatered stream basis.

  Water is removed, for example, by distillation, adsorption, evaporation, extraction or vacuum flushing. The dehydration zone is an evaporation column, benzene column or light fraction column.

  After further removal of impurities in the first alkylation zone or the first reaction zone, the amount of impurities in the first alkylated stream is 25% less based on the weight of the feed stream, 20% less, 15% less, 10% less or 5% less. Preferably, the amount of impurities in the first alkylated stream after further removal of impurities in the first alkylation zone is less than 100 wppb, less than 75 wppb, less than 50 wppb or less than 25 wppb.

  Impurities in the second alkylated stream are 10%, 5% or 1% less by weight than impurities in the first alkylated stream. Preferably, the impurities in the second alkylated stream are 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.

  In some embodiments, the one or more alkylation reaction zones are preferably placed in a single reaction vessel. Alternatively, the first alkylation reaction zone may be placed in a separate vessel and operated as a reaction guard bed. The first reaction zone may be placed in a separate vessel and may be operated as a non-reactive guard bed. The catalyst in the reacted or unreacted guard bed is subject to more frequent regeneration and / or replacement than the second alkylation catalyst. Thus, while the guard bed is not in operation, a bypass circuit is typically provided so that one or more alkylated feeds can be fed directly to the series connected reaction zones in the reactor.

  Preferably, a bypassable reaction guard bed is placed upstream of the second alkylation zone. A bypassable non-reactive guard bed is placed upstream of the alkylation zone. Such guard beds can be operated in cocurrent upflow or downflow operations. The reacted or unreacted guard bed is maintained under suitable at least partially liquid phase conditions.

  In the reaction guard bed, at least a portion of the alkylatable aromatic compound and at least a portion of the alkylating agent are passed through the reaction guard bed prior to entering the second alkylation reaction zone.

  In the non-reacted guard bed, the alkylatable aromatic compound is passed through the non-reacted guard bed before entering the alkylation reaction zone.

  The catalyst composition used in the reaction guard bed or the non-reaction guard bed is different from the catalyst composition used in the second and subsequent alkylation reaction zones. The catalyst composition used in the reaction guard bed or the non-reaction guard bed can have a plurality of catalyst compositions (eg, a mixture of mordenite and zeolite Y, or a mixture of zeolite beta and zeolite Y). The reaction guard bed and usually 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 the alkylation catalyst.

  In some other embodiments, the dehydrated stream further comprises at least a portion of the overhead stream from the distillation zone.

  In other embodiments, the dehydrated stream is cooled and at least a portion of the dehydrated stream is condensed to remove at least a portion of possible residual water and impurities.

  In other embodiments, the method feeds the dehydrated stream to a distillation zone to further remove at least a portion of possible residual water prior to contacting step (c).

  In another embodiment, the method comprises combining the dehydrated stream and the stream from the distillation zone to remove at least a portion of the possible residual water prior to contacting step (c). Further, wherein the distillation zone is a distillation column, benzene column or light fraction column.

  In other embodiments, the method further comprises supplying at least a portion of the dehydrated stream from the dehydration zone as reflux to a distillation column.

  In some embodiments, the alkylatable 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 the alkylating agent and impurities, or only the alkylating agent and water, or a mixture of alkylating agent, impurities and water.

  The alkylated aromatic compound is a monoalkylated aromatic compound in some embodiments. In such a case, 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 alkylated The agent is butylene and the monoalkylated aromatic compound is sec-butylbenzene.

  In some embodiments of the method, the monoalkylated aromatic compound stream, and optionally the polyalkylated compound stream, is separated from the second alkylated stream.

  In some embodiments, the alkylated aromatic compound is a polyalkylated aromatic compound, and the method comprises the polyalkylation of step (e) under suitable transalkylation conditions in a transalkylation reaction zone. The method further includes contacting the aromatic compound with a transalkylation catalyst to produce an additional amount of the monoalkylated aromatic compound.

  In other embodiments, the transalkylation catalyst is a large pore molecular sieve having a constraint index of less than 2.

  In other embodiments, the large pore molecular sieve is zeolite beta, faujasite, zeolite Y, ultrastable Y (USY), dealuminated 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 presently disclosed invention is very selective for the desired monoalkylated aromatic compound, such as ethylbenzene, but typically also produces at least a small amount of polyalkylation species. Can be. The effluent from the final alkylation reaction zone can be subjected to a separation step to recover the monoalkylated aromatic compound and the polyalkylated aromatic compound. At least a portion of the polyalkylated aromatic compound can be fed to a transalkylation reactor that may be separate from the alkylation reactor. In the transalkylation reactor, the polyalkylated aromatic compound is reacted with the alkylatable aromatic compound to produce an effluent containing additional monoalkylated aromatic compound. At least a portion of these effluents are separated to recover alkylated aromatics (monoalkylated aromatics and / or polyalkylated aromatics).

  One or more embodiments of the disclosed invention are illustrated in FIGS.

  FIG. 1 shows a process 50 for producing an alkylated aromatic compound, such as a monoalkylated aromatic compound, for example ethylbenzene, wherein a feed stream 1 comprising an alkylatable aromatic compound, water and impurities is treated with a treatment material 4. Supplyed to a treatment tank 2 having a built-in treatment zone 2a, where the feed stream 1 is treated under suitable treatment conditions to remove the first portion of the impurities and produce a treatment tank effluent stream 5. To do. Optionally, the treatment tank effluent stream 5 can be heated or cooled in the heat exchanger 12a.

  The treatment tank effluent stream 5 is then fed to a dehydration zone 14, such as a lighter distillation column where at least a portion of the water and optionally a second portion of the impurities are removed from the treatment tank effluent stream 5, A dehydrated stream 13 is produced containing the alkylatable aromatic compound, possible residual amount of water and the impurities.

  The dehydrated stream 13 is fed to a storage tank 16 in a distillation zone 18. The distillation zone 18 can be a benzene distillation column. In reservoir 16, dewatered stream 13 is combined with overhead stream 15 from distillation zone 18 (which is cooled by heat exchanger 12c) to produce reservoir effluent 17. A portion of the reservoir effluent 17 is fed to the distillation zone 18 as reflux 19. The steam component 24 from the storage tank 16 is supplied to the dehydration zone 14 and further divided. Stream 21, the remainder of reservoir effluent 17, forms an alkylatable aromatic feed stream 41 to alkylation reactor 20 and an alkylatable aromatic feed stream 39 to transalkylation reactor 30. To do. Optionally, stream 21 can be heated or cooled in heat exchanger 12b. Heavy compounds (eg, polyalkylated aromatics) are withdrawn as bottom stream 22 in distillation zone 18 and separated in a downstream separator (not shown) to produce monoalkylated aromatics such as ethylbenzene and poly An alkylated aromatic compound, such as the polyalkylated feed stream 39a described below, is produced.

  The alkylation reactor 20 has at least a first alkylation zone 20a containing a first alkylation catalyst 26 and at least a second alkylation zone 20b containing a second alkylation catalyst 28, The first alkylation zone 20a is located upstream of and in fluid communication with the second alkylation zone 20b. In some embodiments, there are multiple serially connected alkylation zones. The first alkylation catalyst has a first catalyst poison capacity, the second alkylation catalyst has a second catalyst poison capacity, and the first catalyst poison capacity is the second catalyst poison capacity. Bigger than. In this embodiment, the first alkylation reaction zone is a reaction guard bed integrated within the alkylation reactor 20.

  The first alkylation catalyst 26 includes a large pore molecular sieve having a constraint index of less than 2. In some embodiments, the second alkylation catalyst comprises the MCM-22 family molecular sieve described above. In other embodiments, the second alkylation catalyst comprises a medium pore size molecular sieve having a constraint index of 2-12.

  In the first alkylation reaction zone 20a, an alkylatable aromatic feed stream 41 to the alkylation reactor and a portion of the first alkylating agent stream 43 are suitable in the first alkylation reaction zone. Contacted with the first alkylation catalyst 26 under at least partially liquid phase first reaction conditions. At least a portion is removed based on the weight of the impurity and at least a portion is alkylated with the alkylating agent stream 43 based on the weight of the alkylatable aromatic compound to produce one or more first alkylated aromatics. A first alkylated stream is produced comprising the compound, unreacted alkylatable aromatic compound, possible residual water and possible residual impurities.

  The first alkylated stream is subjected to a second alkyl (different from the first alkylation catalyst) under suitable at least partially liquid phase second reaction conditions in the second alkylation reaction zone 20b. In contact with other parts of the alkylating agent 43 in the presence of the activating catalyst 28. The unreacted alkylatable aromatic compound is alkylated with the second alkylating agent stream to provide additional one or more alkylated aromatic compounds, possible residual water and possible residual impurities. A second alkylated stream containing is produced. The first and second alkylated streams and those from subsequent alkylation zones, if any, are combined to yield unreacted alkylatable aromatics, possible residual water and monoalkylated aromatics An alkylated effluent 45 is formed comprising the compound and the polyalkylated aromatic compound. Although not likely, there are also some residual alkylating agents.

  Alkylatable aromatics to a transalkylation reactor comprising an alkylatable aromatic compound and a polyalkylated feed stream 39a (containing a polyalkylated aromatic compound from a downstream separator (not shown)) Feed stream 39 is fed to transalkylation zone 30 a of transalkylation reactor 30. Transalkylation zone 30 a has at least one transalkylation catalyst 34. In some embodiments, the transalkylation catalyst 34 is a large pore molecular sieve having a constraint index of less than 2.

  In the transalkylation zone 30a, the polyalkylated aromatics in the polyalkylated feed stream 39a are translocated in the presence of the transalkylation catalyst 34 under suitable at least partially liquid phase transalkylation conditions. The alkylation reactor is contacted with an alkylatable aromatic feed stream 39 to produce additional such monoalkylated aromatics in the transalkylation reactor effluent 47.

  The alkylated effluent 45 is optionally combined with the transalkylation reactor effluent 47 and fed to the distillation zone 18 as a distillation feed stream 49 where the polyalkylated compound and heavy compound From the monoalkylated compound.

  2-4 illustrate another embodiment using a dehydrated stream 13 in the distillation zone 18 of the process 50 to produce the monoalkylated aromatic compound of FIG. Equipment equipment and streams having the same numbers as in FIG. 1 are the same. In the embodiment of FIG. 2, the dehydrated stream 13 is fed to the distillation zone 18 along with reflux 19. The tower top stream 15 is cooled by the heat exchanger 12 c and then flows into the storage tank 16. Stream 17 contains an alkylatable aromatic stream and exits from reservoir 16. A portion of stream 17 is divided and fed to distillation zone 18 as reflux 19 described above. As in FIG. 1, the remaining portion of stream 17, stream 21, is transalkylation reactor alkylable aromatic feed stream 39 to transalkylation reactor 30 and alkylation reactor 20. To form an alkylatable aromatic feed stream 41.

  In the embodiment of FIG. 3, dewatered stream 13 is combined with overhead stream 15 from distillation zone 18 and then cooled in heat exchanger 12c to form stream 23, which is then fed to reservoir 16. The A stream 25 containing alkylatable aromatics exits the reservoir 16 and is divided into a reflux 27 and a stream 29. The remaining portion of stream 25, stream 29, is transalkylation reactor alkylatable aromatic feed stream 39 to transalkylation reactor 30 and alkylatable aromatic feed stream to alkylation reactor 20. 41 is formed.

  In the embodiment of FIG. 4, the overhead stream 15 of the distillation zone 18 flows into the reservoir 16 to form a stream 17 as in FIG. In this embodiment, the dehydrated stream 13 is combined with the reflux 19 to form a combined reflux 33 to the distillation zone 18. Stream 35, the remainder of stream 17, is transalkylation reactor alkylatable aromatic feed stream 39 to transalkylation reactor 30 and alkylatable aromatic feed stream to alkylation reactor 20. 41 is formed. Optionally, stream 35 can be heated or cooled in heat exchanger 12b.

  FIG. 5 shows a process 100 for producing a monoalkylated aromatic compound 100, such as ethylbenzene, using a guard bed that is in a separate vessel and operated in a reactive or non-reactive manner. When the guard bed is operated in a non-reactive manner, no alkylating agent is supplied. When the guard bed is operated in a reaction mode, the guard bed is supplied with a portion of the alkylating agent.

  A feed stream 101 comprising an alkylatable aromatic compound, water and impurities is fed to a dehydration zone 14, such as a delighted fraction distillation column. Equipment equipment and streams having the same numbers as in FIG. 1 are the same. In the dehydration zone 14, at least a portion of the water and optionally a portion of the impurities are removed from the feed stream 101 to remove the alkylatable aromatics, possible residual amounts of the impurities and possible residual water. A dehydrated stream 109 containing is produced. The dehydrated stream 109 is fed to a processing zone 102 containing a processing substance 102a where it is processed under suitable processing conditions to remove additional such impurities and produce an effluent stream 111. The impurities and the processing substance 102a are the same as described above. Optionally, the effluent stream 111 can be heated or cooled in a heat exchanger (not shown).

  The effluent stream 111 is fed to the reservoir 16 of the distillation zone 18 where it is combined with the overhead stream 115 from the distillation zone 18 to produce a combined effluent 117. The distillation zone 18 can be a benzene distillation column. A portion of the combined effluent 117 is fed to distillation zone 18 as reflux 119. The vapor component 124 from the storage tank 16 is supplied to the dehydration zone 14 for further separation. Stream 121, the remaining portion of the combined effluent 117, can be heated or cooled in heat exchanger 12d. Stream 121 also forms an alkylatable aromatic feed stream 139 to transalkylation reactor 30 and an alkylatable aromatic feed stream 141 to guard bed 22 (reacted or non-reacted). Heavy compounds (eg, polyalkylated aromatics) are withdrawn as bottom stream 122 in distillation zone 18 and separated by downstream separators (not shown) to produce alkylated aromatics such as ethylbenzene and polyalkyls. Aromatic compounds, such as the polyalkylated feed stream 139a described below, are produced.

  The guard bed 22 is separate from the alkylation reactor 20, and is located at least upstream of and in fluid communication with the second alkylation zone 20b. When the guard bed 22 is a reaction guard bed, it is the first alkylation zone and contains the first alkylation catalyst 26. When the guard bed 22 is a non-reactive guard bed, it is not an alkylation zone because no alkylating agent is supplied.

  The second alkylation zone 20 b contains a second alkylation catalyst 28. The first alkylation catalyst has a first catalyst poison capacity and is different from a second alkylation catalyst having a second catalyst poison capacity. The first catalyst poison capacity is greater than the second catalyst poison capacity. Preferably, the first alkylation catalyst 26 comprises a large pore molecular sieve having a constraint index of less than 2.

  In some embodiments, the second alkylation catalyst comprises the MCM-22 family molecular sieve described above. In some other embodiments, the second alkylation catalyst comprises a medium pore size molecular sieve having a constraint index of 2-12.

  When the guard bed 22 is a reaction guard bed, the alkylatable aromatic feed stream 141 and a portion of the alkylating agent stream 143 are formed of the first alkylation catalyst 26 at least partially under liquid phase conditions. Contacted in the presence of a first alkylated stream comprising one or more alkylated aromatics, unreacted alkylatable aromatics, possible residual water and possible residual impurities Form.

  When the guard bed 22 is a non-reactive guard bed, the guard bed 22 receives an alkylatable aromatic feed stream 141 that is suitable at least partially in a liquid phase. The alkylatable aromatic compound can be contacted with the first alkylation catalyst 26 under one reaction condition (in the absence of an alkylating agent) and at least partially removed based on the weight of the impurities. An alkylatable aromatic stream is produced comprising residual water and possible residual impurities.

  The first alkylated stream or the alkylatable aromatic stream is then fed to the second alkylation zone 20b, and the second alkylated under suitable at least partially liquid phase second reaction conditions. Contacted with an additional alkylating agent stream 143 in the presence of the oxidization catalyst 28 to produce a second alkylated stream comprising an additional amount of an alkylated aromatic compound.

  The first and second alkylated streams and those from subsequent alkylation zones, if any, are combined to yield an alkylated aromatic, unreacted alkylatable aromatic, possible residual water And forms an alkylated effluent 145 containing possible residual impurities.

  Transalkylation reactor containing alkylatable aromatic compound Alkylatable aromatic feed stream 139 and polyalkylated aromatic feed stream 139a containing polyalkylated aromatic compound are fed to transalkylation zone 30a. The Transalkylation zone 30 a has at least one transalkylation catalyst 34. In some embodiments, the transalkylation catalyst 34 is a large pore molecular sieve having a constraint index of less than 2.

  In the transalkylation zone 30a, the polyalkylated aromatic feed stream 139a is passed through a transalkylation reactor alkyl in the presence of a transalkylation catalyst 34 under suitable at least partially liquid phase transalkylation conditions. Is contacted with a convertible aromatic feed stream 139 to produce additional such monoalkylated aromatics in the transalkylation reactor effluent 147.

  The alkylated effluent 145 is optionally combined with the transalkylation reactor effluent 147 and fed to the distillation zone 18 as a distillation feed stream 149, from which the polyalkylated compound and the heavy compound are mixed. Separate the alkylated compound. The polyalkylated compound and the heavy compound are separated by a downstream separation device (not shown).

  6-8 illustrate another embodiment using an effluent stream 111 (including dehydrated stream 109) in distillation zone 18 of process 100 to produce the monoalkylated aromatic compound of FIG. Equipment equipment and streams having the same numbers as in FIG. 5 are the same. In the embodiment of FIG. 6, effluent stream 111 is fed to distillation zone 18 along with reflux 119. The overhead stream 115 in the distillation zone 18 flows into the storage tank 16. A stream 117 containing an alkylatable aromatic stream exits the reservoir 16. A portion of stream 117 is split and fed to distillation zone 18 as reflux 119. Stream 121, the remaining portion of stream 117, is the same as in FIG. 5, transalkylation reactor feed stream 139 to transalkylation reactor 30 and alkylation reactor feed to guard bed 22. A stream 141 is formed. Optionally, stream 121 can be heated or cooled in heat exchanger 12d.

  In the embodiment of FIG. 7, effluent stream 111 is combined with overhead stream 115 from distillation zone 18 and then cooled in heat exchanger 12c to form stream 123, which is then fed to reservoir 16. . A stream 125 containing alkylated aromatics exits the reservoir 16. This stream 125 is divided into reflux 127 and stream 129. Stream 129, the remainder of stream 125, converts transalkylation reactor alkylatable aromatic feed stream 139 to transalkylation reactor 30 and alkylatable aromatic feed stream 141 to guard bed 22. Form. Optionally, stream 129 can be heated or cooled in heat exchanger 12d.

  In the embodiment of FIG. 8, the overhead stream 115 flows into the reservoir 16 as in FIG. 5 to form a stream 117 and a reflux 119. In this embodiment, effluent stream 111 is combined with stream 119, which is a split stream of stream 117, to form reflux 133 to distillation zone 18. Stream 135, the remaining portion of stream 117, converts transalkylation reactor alkylatable aromatic feed stream 139 to transalkylation reactor 30 and alkylatable aromatic feed stream 141 to guard bed 22. Form. Optionally, stream 135 can be heated or cooled in heat exchanger 12d.

The presently disclosed invention will now be described in more detail with reference to the following examples.
[Examples 1 to 6]
Measurement of catalyst poison capacity

In Examples 1-6, the catalytic poison capacity for collidine was measured by feeding collidine in the gas phase, and the amount absorbed was recorded by a thermogravimetric analyzer. Total absorption is a measure of the zeolite's capacity to absorb nitrogenous compounds.

As shown in Table 1, the catalyst poison capacity with collidine for catalysts with MWW topology was much smaller than for catalysts with non-MWW topology.
[Examples 7 and 8]

  In Examples 7 and 8, the capacity of MWW catalyst and zeolite beta catalyst to absorb N-formylmorpholine (NFM) impurities was measured. Two alkylation reactors were placed in series and the first alkylation reactor (Rx1) with the first alkylation catalyst was fed with the NFM impurity containing benzene feed. The Rx1 effluent was the feed to the second alkylation reactor (Rx2) with the second alkylation catalyst. Each of the Rx1 and Rx2 reactors has a separate ethylene injection point, and this arrangement is similar to the first two stages of a multistage serially connected alkylation reactor. For these experiments, Rx1 was the reaction guard bed and was the first reaction zone in the alkylation reactor. Inactivation of Rx2 was used as an indicator of when Rx1 reached its maximum catalyst poison capacity and the catalyst poison could no longer be fully retained by Rx1. NFM was supplied at a concentration of 0.3 wppm based on the weight of the benzene feed.

The NFM absorption capacity in the examples is calculated from the oil passage start time and the time at which inactivation is observed at Rx2.

  As shown in Table 2, the zeolite beta has an NFM absorption capacity that is superior to the first catalyst containing MWW as the first catalyst.

  All patents, patent applications, test methods, priority documents, papers, publications, manuals and other references cited herein are to the extent that such disclosures are not inconsistent with the disclosure herein. And for all jurisdictions where such incorporation is permitted, it is fully incorporated by reference.

  When numerical lower limits and numerical upper limits are given in this specification, ranges from possible lower limits to possible upper limits are contemplated.

  Although exemplary embodiments of the disclosed invention have been described in detail, various other modifications will be apparent to those skilled in the art and can be readily made by those skilled in the art without departing from the spirit and scope of the disclosed invention. It will be understood that can be made. Accordingly, it is not intended that the claims appended hereto be limited to the examples and the description provided herein, which claims receive the patents present in the disclosed invention It is intended that all features of novelty that can be interpreted as encompassing all features that would be treated as equivalents of the disclosed invention by those skilled in the art to which the disclosed invention pertains. Is done.

Claims (9)

In a method for producing an alkylated aromatic compound, the method comprises:
(A) supplying a feed stream to a dehydration zone, the feed stream comprising an alkylatable aromatic compound, water and impurities, wherein the impurities are the following elements: nitrogen, halogen, oxygen, sulfur Including a compound having at least one of arsenic, selenium, tellurium, phosphorus and a Group 1 to Group 12 metal;
(B) removing at least a portion of the water from the feed stream in the dehydration zone operated under suitable dehydration conditions, and dehydrating the alkylatable aromatic compound, possible residual water and the impurities; Manufacturing a stream
(C) in a suitable first alkylation reaction zone at least partially under liquid phase first reaction conditions, at least a portion of the dehydrated stream and a first alkylating agent stream are Contacting with a first alkylation catalyst having a catalyst poison capacity to remove at least a portion of the impurities and alkylating at least a portion of the alkylatable aromatic compound with the first alkylating agent stream; and Producing a first alkylated stream comprising one or more alkylated aromatics, unreacted alkylatable aromatics, possible residual water and possible residual impurities, The first alkylation catalyst is a large pore molecular sieve having a constraint index of less than 2, and (d) a suitable at least partially liquid phase second reaction strip. In the second, second alkylation reaction zone, the first alkylated stream and the second alkylating agent stream are separated from the first alkylation catalyst and have a second catalyst capacity. In contact with a second alkylation catalyst to alkylate at least a portion of the unreacted alkylatable aromatic compound with the second alkylating agent stream, and additional one or more alkylated aromatic compounds; Producing a second alkylated stream comprising unreacted alkylatable aromatics, possible residual water and possible residual impurities, wherein the second alkylation catalyst comprises an MWW framework topology X-ray diffraction pattern having a unit cell size of 1 and a lattice spacing d of 12.4 ± 0.25, 3.57 ± 0.07 and 3.42 ± 0.07 angstroms Including characteristics with are MCM-22 family material is a step by the above method. The one or more alkylated aromatic compounds comprise a monoalkylated aromatic compound and a polyalkylated aromatic compound, and the method comprises (e) a monoalkylated aromatic compound from the second alkylated stream Separating the process,
(F) separating the polyalkylated aromatic compound from the second alkylated stream, and (g) under suitable at least partially liquid phase transalkylation conditions in the transalkylation reaction zone. Contacting the polyalkylated aromatic compound stream and another portion of the feedstock stream with a transalkylation catalyst to transalkylate the polyalkylated aromatic compound stream to provide additional monoalkylated aromatic compound The method of claim 1, further comprising the step of: In a method for producing an alkylated aromatic compound, the method comprises:
(A) supplying a feed stream to a dehydration zone, the feed stream comprising an alkylatable aromatic compound, water and impurities, wherein the impurities are the following elements: nitrogen, halogen, oxygen, sulfur Including a compound having at least one of arsenic, selenium, tellurium, phosphorus and a Group 1 to Group 12 metal;
(B) in the dehydration zone operated under suitable dehydration conditions, excluding at least a portion of the water from the feed stream and including the alkylatable aromatic compound, possible residual water and the impurities. Producing a stream of
(C) at least a portion of the dehydrated stream in a first reaction zone under suitable at least partially liquid phase first reaction conditions with a large pore molecular sieve having a restraining index less than 2; In contact with a first catalyst having a first and a first catalyst poison capacity to remove at least a portion of the impurities and comprising the alkylatable aromatic compound, possible residual water and possible residual impurities; Producing an alkylatable aromatic stream having a reduced amount of impurities, and (d) in an alkylation reaction zone suitable under at least partially liquid phase second reaction conditions, step (c) The alkylatable aromatic stream and the alkylating agent stream of the catalyst having a second catalyst poison capacity that is different from the first catalyst and greater than the first catalyst poison capacity. Comprising contacting with Le catalyst to alkylate at least a portion of in the alkylating agent flow skilled 該A alkylation can aromatics, and 1 or more alkylated aromatic compounds, possible alkylation of unreacted Producing an alkylated stream comprising aromatics, possible residual water and possible residual impurities, wherein the alkylation catalyst has a unit cell of MWW skeleton topology and has a lattice spacing d Comprising the above steps of a MCM-22 family material characterized by an X-ray diffraction pattern comprising peaks at 12.4 ± 0.25, 3.57 ± 0.07 and 3.42 ± 0.07 angstroms Method.   4. A method according to claim 1 or 3, wherein in removal step (b), at least a portion of the impurities in the feed stream is removed in the dehydration zone.   Prior to step (c), the dehydrated stream is fed to a treatment zone containing a treatment substance, and the dehydrated stream contacts the treatment substance in the treatment zone under suitable treatment conditions. Wherein at least a portion of the impurities are removed and the treatment material is selected from the group consisting of clay, resin, activated alumina, Linde-X, Linde-A, and combinations thereof. 3. The method according to 3.   Prior to step (a), the feed stream is fed to a treatment zone containing a treatment substance, and the feed stream is contacted with the treatment substance in the treatment zone under suitable treatment conditions. Wherein at least a portion of the impurities are removed and the treatment material is selected from the group consisting of clay, resin, activated alumina, Linde-X type, Linde-A type, and combinations thereof. The method described.   The large pore molecular sieve is zeolite beta, faujasite, zeolite Y, ultrastable Y (USY), dealuminated alumina (Deal Y), rare earth Y (REY), superhydrophobic Y (UHP-Y), mordenite. The method of claim 1 or 3, selected from the group consisting of: TEA-mordenite, ZSM-3, ZSM-4, ZSM-14, ZSM-18, ZSM-20 and combinations thereof. The alkylated aromatic compound is a monoalkylated aromatic compound, the alkylating agent is ethylene and the monoalkylated aromatic compound is ethylbenzene, or the alkylating agent is propylene and the monoalkylated aromatic compound The group 1 compound is cumene, or the alkylating agent is butylene, the monoalkylated aromatic compound is sec-butylbenzene, and the alkylatable aromatic compound is benzene. The method described. The one or more alkylated aromatic compounds comprise a monoalkylated aromatic compound and a polyalkylated aromatic compound, the method comprising:
(E) separating the monoalkylated aromatic compound from the alkylated stream from the alkylation reaction zone under the second reaction conditions ;
(F) separating the polyalkylated aromatic compound from the alkylated stream from the alkylation reaction zone under the second reaction conditions ; and (g) a suitable at least partially liquid phase transalkyl. In the transalkylation reaction zone under oxidization conditions, the polyalkylated aromatic compound stream and other portions of the dehydrated stream are contacted with a transalkylation catalyst to transduce the polyalkylated aromatic compound stream. 4. The method of claim 3, further comprising the steps of alkylating and producing the additional monoalkylated aromatic compound and wherein the transalkylation catalyst is a large pore molecular sieve having a constraint index of less than 2. .

Images