TWI690509B - Transalkylation process and catalyst composition used therein - Google Patents

Abstract

The present disclosure relates to a process for producing a mono-alkylated aromatic compound, such as, for example, ethylbenzene or cumene, in which an alkylatable aromatic compound stream, such as, for example, benzene, and an alkylation agent stream, such as, for example, poly-ethylbenzene or poly-isopropylbenzene, are contacted in the presence of a transalkylation catalyst and under at least partial liquid phase transalkylation conditions. The transalkylation catalyst comprises a zeolite having a framework structure selected from the group consisting of FAU, BEA*, MOR, MWW and mixtures thereof. The zeolite has a silica-alumina molar ratio in a range of 10 to 15. The transalkylation catalyst composition has an external surface area/volume ratio in the range of 30 cm^-1 to 85 cm^-1.

Description

Transalkylation process and catalyst composition used therefor Cross-reference of related applications

This application claims the priority and rights of US Provisional Application No. 62/450,122 filed on January 25, 2017, which is incorporated by reference into the full text of its disclosure.

The present invention relates to a process for transalkylation of aromatics, in particular, a process for transalkylation of polyisopropylbenzene (PIPB) from benzene to cumene and polyethylbenzene (PEB) to produce ethylbenzene from benzene Transalkylation process.

Ethylbenzene is a valuable chemical commodity and is used to produce styrene monomer. Cumene (isopropylbenzene) is also a valuable chemical commodity and is used to produce phenol and acetone.

Ethylbenzene is currently produced by a liquid-phase alkylation process of benzene and ethylene in the presence of an alkylation catalyst. The liquid phase process is better than its vapor Operate at a lower temperature corresponding to the process. One advantage of liquid-phase alkylation is the low yield of undesirable by-products, polyalkylated aromatic compounds. The art knows and understands the alkylation process of aromatic hydrocarbon compounds using zeolite catalysts. US Patent No. 5,334,795 describes a liquid-phase alkylation process for producing ethylbenzene from benzene and ethylene in the presence of MCM-22; and US Patent No. 4,891,458 discloses liquid-phase alkylation and transalkylation using zeolite β Process.

Cumene is often produced by a liquid-phase alkylation process of benzene and propylene in the presence of an alkylation catalyst based on zeolite. US Patent No. 4,992,606 discloses a process for preparing cumene in liquid phase using MCM-22.

Commercial alkylation processes used to produce ethylbenzene and cumene usually produce specific polyalkylation by-products in addition to the desired ethylbenzene and cumene. Polyalkylated aromatic compounds can be transalkylated with benzene or other alkylatable aromatic compounds to produce additional ethylbenzene or cumene. This transalkylation reaction can be accomplished by feeding polyalkylated aromatic compounds through a transalkylation reactor operating under suitable conditions and in the presence of a transalkylation catalyst. U.S. Patent No. 5,557,024 discloses a process for preparing short-chain alkyl aromatic compounds using MCM-56 and zeolite catalysts (such as MCM-22, zeolite X, zeolite Y, and zeolite beta) for the conversion of polyalkylated aromatic compounds Uses for alkylation.

Despite the progress made in the liquid-phase aromatic alkylation process, the higher conversion of polyalkylated aromatic compounds has become the desired monoalkylated aromatic compound (such as ethylbenzene or cumene) improvement There is still demand for the transalkylation process.

Making the polyalkylated aromatic compound into the desired monoalkylated aromatic compound at a higher conversion rate in the transalkylation process can be achieved by using a higher active transalkylated catalyst composition. It has been found that a higher active transalkylation catalyst composition can be selected by increasing the external surface area/volume (SA/V) ratio of the transalkylation catalyst composition to a selected range of 30 cm ^-1 to 85 cm ^-1 It is produced in combination with a range of 10 to 15 in combination with a lower silica to alumina (Si/Al ₂ ) molar ratio of zeolite in the composition.

In one aspect, the invention is a process that includes one or more steps for producing ethylbenzene or cumene. In step (a), the transalkylation catalyst composition described below is provided to the reaction zone. In step (b), a stream comprising polyalkylated benzene and an alkylatable aromatic compound comprising benzene are provided to the reaction zone. The polyalkylated benzene stream contains diethylbenzene or diisopropylbenzene. In step (c), the polyalkylated benzene stream and the benzene stream are contacted in the presence of the aforementioned transalkylation catalyst composition under at least part of the liquid phase transalkylation conditions to produce a transalkylation effluent Logistics. These effluents contain ethylbenzene or cumene. Liquid-phase transalkylation conditions include a temperature of 100°C to 300°C and a pressure of 200kPa-a to 6000kPa-a.

In one or more implementation aspects of the process, when the catalysts are compared under equal transalkylation conditions, the transalkylation catalyst composition of the present invention (i.e., a lower molar ratio) The catalytic activity ratio of the silicon oxide) is lower than that of the low activity transalkylation catalyst composition containing the zeolite and having a silica-alumina molar ratio in the range of 25 to 37 (that is, a higher molar silica content) ) Has higher catalytic activity.

In one or more embodiments of the process, when the highly active transalkylation catalyst composition of the present invention (that is, a lower silica content) is used in a process for producing ethylbenzene or cumene, It demonstrates that the weighted space velocity per hour of the polyalkylated benzene stream is higher than the weighted space velocity per hour of the low activity transalkylation catalyst composition used in this process (i.e., higher molar silica content) , Where the catalysts are compared under equal transalkylation conditions. In another embodiment, a portion of the benzene-containing stream is contacted with the alkylating agent stream under alkylation conditions and in the presence of an alkylation catalyst to produce monoalkylated benzene and polyalkylene The alkylation effluent of alkylated benzene. The alkylation effluent is then separated to recover the polyalkylated benzene stream, and a portion of it is fed to step (b) of the process to produce ethylbenzene or cumene.

In yet another embodiment, the benzene stream is an impure stream, which additionally contains nitrogen-containing impurities. The impure stream is contacted with the processing material under processing conditions to remove at least a portion of nitrogen-containing impurities. The treatment material is selected from the group consisting of clay, resin, activated alumina, molecular sieve, and combinations thereof.

In another aspect, the present invention is a transalkylation catalyst comprising zeolite having a framework structure selected from the group consisting of FAU, BEA*, MOR, MWW, and mixtures thereof. The zeolite has a silica-alumina molar ratio in the range of 10 to 15. The transalkylation catalyst composition has an external surface area/volume ratio in the range of 30 cm ^-1 to 85 cm ^-1 .

In one embodiment, when the catalysts are compared under equal transalkylation conditions, the catalytic activity ratio of the transalkylation catalyst composition The transalkylation catalyst composition containing zeolite and having a silica-alumina molar ratio higher than the silica content in the range of 25 to 37 has a higher catalytic activity.

When the transalkylation catalyst composition of the present invention described herein is used by polyalkylated aromatic compounds and alkylatable aromatic compounds (preferably benzene) in the presence of this composition at least During the process of transalkylation under partial liquid phase transalkylation conditions to produce monoalkylated aromatic compounds (preferably ethylbenzene or cumene), this composition exhibits improved catalytic activity.

In order to achieve improved catalytic activity, the external surface area/volume ratio of the transalkylation catalyst composition was increased to a selected range of 30 cm ^-1 to 85 cm ^-1 , and the silica to alumina of zeolite (Si/Al ₂ ) The molar ratio is reduced to a selected range of 10 to 15. Zeolite has a framework structure selected from the group consisting of: FAU, BEA*, MOR, MWW, and mixtures thereof.

definition

The term "alkylatable aromatic compound" as used herein means an aromatic compound that can accept an alkyl group. One non-limiting example of an alkylatable aromatic compound is benzene.

The term "alkylating agent" as used herein means a compound that can give an alkyl group to an alkylatable aromatic compound. Non-limiting examples of alkylating agents are ethylene, propylene, and butene. Another non-limiting example is any polyalkylated aromatic compound capable of giving an alkyl group to an alkylatable aromatic compound Thing.

The term "aromatic" as used herein with respect to alkylatable aromatic compounds useful herein is understood in accordance with its technically recognized scope, which includes substituted and unsubstituted mono- and polynuclear compounds. Compounds with aromatic characteristics of heteroatoms (eg N or S) are also useful, provided that they do not act as catalyst poisons as defined below under the selected reaction conditions.

The term "at least part of the liquid phase" as used herein means a mixture having at least 1% by weight of liquid phase, optionally at least 5% by weight of liquid phase at the given temperature, pressure and composition.

The term "frame type" as used herein has the meaning described by Ch. Baerlocher, W. M. Meier and D. H. Olson in "Atlas of Zeolite Framework Types" (Elsevier, 5th edition, 2001).

As used herein, the term "MCM-22 family material" (or "MCM-22 family molecular sieve") may include: (i) a molecular sieve composed of common primary crystalline building blocks, "a unit crystal with a MWW framework topology" Cell". The unit cell is a spatial arrangement of atoms, which is laid out in three dimensions to illustrate the crystal, as described by Ch. Baerlocher, WMMeier, and DHOlson in "Atlas of Zeolite Framework Types" (Elsevier, 5th Edition, 2001) (Ii) Molecular sieves composed of common secondary building blocks, 2-dimensional arrangement of these unit cells of MWW framework type, forming "a single layer of unit cell thickness", preferably a c-unit crystal Cell thickness (iii) Molecular sieves composed of common secondary building blocks, "one or more layers per unit cell thickness", where layers exceeding one unit cell thickness are self-stacking, stacking or bonding at least two frames with MWW The topological unit cell consists of a single layer of unit cell thickness. The stacking of these secondary building blocks can be regular, irregular, random, or any combination thereof; or (iv) any regular or irregular 2-dimensional or Molecular sieve composed of 3-dimensional combination.

The MCM-22 family of materials are characterized by having X-ray diffraction patterns (calcined or as-synthesized) with a maximum d-spacing of 12.4±0.25, 3.57±0.07, and 3.42±0.07 Angstroms. The MCM-22 family of materials may also be characterized by X-ray diffraction patterns (calcined or as-synthesized) including lattice plane spacing maximum values of 12.4±0.25, 6.9±0.15, 3.57±0.07, and 3.42±0.07 Angstroms. The X-ray diffraction data used to characterize the molecular sieve was obtained by using copper K-α double lines as the standard technique for incident radiation and a diffractometer equipped with a scintillation counter and combined with a computer as a collection system.

Members of the MCM-22 family include but are not limited to MCM-22 (described in U.S. Patent No. 4,954,325), PSH-3 (illustrated in U.S. Patent No. 4,439,409), SSZ-25 (illustrated in U.S. Patent No. 4,826,667), ERB -1 (described in European Patent 0293032), ITQ-1 (illustrated in US Patent No. 6,077,498), ITQ-2 (illustrated in International Patent Publication No. WO97/17290), ITQ-30 (illustrated in International Patent Publication No. WO2005118476), MCM-36 (described in US Patent No. 5,250,277, MCM-49 (described in US Patent No. 5,236,575), MCM-56 (illustrated in US Patent No. 5,362,697), and EMM-10 family molecular sieves (illustrated or characterized in US Patent Nos. 7,959,899 and 8,110,176; and US Patent Application Publication No. 2008/0045768), such as EMM-10, EMM-10-P, EMM-12 and EMM-13.

The related zeolites included in the MCM-22 family are UZM-8 (described in US Patent No. 6,756,030) and UZM-8HS (illustrated in US Patent No. 7,713,513), UZM-37 (illustrated in US Patent No. 8,158,105), all It is also suitable as a molecular sieve of the MCM-22 family. Molecular sieves of the MCM-22 family are usually in the form of hydrogen and have hydrogen ions, for example, acidic.

Molecular sieves of the MCM-22 family are usually in the form of hydrogen and have hydrogen ions, for example, acidic. The entire contents of each of the aforementioned patents are incorporated herein by reference.

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 second butylbenzene.

The term "polyalkylated aromatic compound" as used herein means an aromatic compound having more than one alkyl substituent. Non-limiting examples of polyalkylated aromatic compounds are polyethylbenzene, such as diethylbenzene, triethylbenzene, and polyisopropylbenzene, such as diisopropylbenzene and triisopropylbenzene.

When the term "regeneration" is used in conjunction with an alkylation catalyst or a transalkylation catalyst, the term herein means that the oxygen content and temperature have been controlled At least partially deactivated catalyst that has been treated to remove at least a portion of the deposited coke or to remove at least a portion of the adsorbed catalyst poison and thereby increase the catalytic activity of these materials or catalyst under the conditions of the process.

When the term "fresh" is used in conjunction with molecular sieves, bed materials, alkylation catalysts or transalkylation catalysts, the term herein means molecular sieves or such catalysts that are not used in catalytic reactions after manufacture .

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

Process

In one aspect, the present invention is a process that includes one or more steps for producing a monoalkylated aromatic compound (preferably ethylbenzene or cumene). In step (a) of the process, the transalkylation catalyst composition described below is provided to the reaction zone. In step (b) of the process, a stream containing polyalkylated benzene and a stream of aromatic alkyl compound containing benzene are provided to the reaction zone. The polyalkylated benzene stream used to produce ethylbenzene contains diethylbenzene. The polyalkylated benzene stream used to produce cumene is diisopropylbenzene. In step (c) of the process, the polyalkylated benzene stream and the benzene stream are contacted in the presence of the aforementioned transalkylation catalyst composition under at least part of the liquid phase transalkylation conditions to produce Transalkylation effluent stream of benzene or cumene.

The products of the transalkylation reaction of the present invention include ethylbenzene from the transalkylation reaction of polyethylbenzene (such as diethylbenzene) with benzene, or from polyisopropylbenzene (such as diisopropylbenzene) ) Difference with benzene transalkylation Propylbenzene.

The transalkylation effluent is separated with a conventional separation system to recover the desired ethylbenzene stream or cumene stream. This conventional separation system includes, for example, a benzene column, an ethylbenzene or cumene column, and a polyalkylation column to recover a polyethylbenzene stream or a polyisopropylbenzene stream.

The polyalkylated benzene stream is generated from an alkylation process step specifically intended to produce monoalkylated aromatic compounds such as ethylbenzene and cumene in the alkylation step; however, the alkylation step is usually Some polyalkylated aromatic compounds are produced, such as polyethylbenzene or polyisopropylbenzene.

In the alkylation step, a portion of the stream containing benzene or a portion thereof is contacted with the stream containing the alkylating agent under alkylation conditions and in the presence of an alkylation catalyst to produce an alkylation effluent . This effluent stream contains monoalkylated benzene and polyalkylated benzene streams. The alkylating agent is preferably ethylene and is used to alkylate benzene to produce ethylbenzene, or preferably propylene and is used to alkylate benzene to produce cumene. In one embodiment, the monoalkylated benzene is ethylbenzene and the polyalkylated benzene is polyethylbenzene. In another embodiment, the monoalkylated benzene is cumene and the polyalkylated benzene is polyisopropylbenzene.

In one or more embodiments, the alkylation effluent is separated to recover the polyalkylated benzene stream. The recovered polyalkylated benzene stream can then be fed to step (b) of the process to produce ethylbenzene or cumene.

In one or more embodiments, the benzene-containing stream is an impure stream, which additionally contains nitrogen-containing impurities. The process of the present invention may additionally include the step of contacting the impure stream with the processing material under processing conditions to remove at least a portion of nitrogen-containing impurities. The treatment material is selected from the group consisting of Group: Clay, resin, activated alumina, Linde type X, Linde type A and combinations thereof.

When a treatment material is used to remove a portion of impurities, suitable treatment conditions include a temperature of about 30°C to 200°C (and preferably between about 60°C and 150°C), about 0.1 hours ^-1 to about 200 h ^-1 the weight hourly space velocity (WHSV) (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 Pressure between 3000kPa-a.

Transalkylation and alkylation conditions

Carry out the process of the present invention for producing mono-alkylated aromatic compounds (such as ethylbenzene or cumene) so that organic reactants, that is, alkylated aromatic compounds (such as benzene) and alkylating agents (That is, polyalkylated benzene or ethylene or propylene) contact with the alkylation catalyst or transalkylation catalyst. The contacting is carried out in a suitable reaction zone (such as a flow reactor containing a fixed bed of catalyst composition) under effective alkylation or transalkylation conditions. These conditions include at least part of the liquid phase transalkylation conditions or at least part of the liquid phase alkylation conditions.

In one or more embodiments, the reactant may be pure, that is, it is not intentionally blended or diluted with other materials, or the reactant may include a carrier gas or diluent, such as hydrogen or nitrogen.

The at least partial liquid phase conditions for transalkylation may include at least one of the following: a temperature of about 100°C to about 300°C or about 150°C to about 260°C, a temperature of about 200kPa to about 6000kPa or about 200kPa to about 500kPa Pressure, weight hourly space velocity (WHSV) based on total feed, from about 0.5 hours ^-1 to about 100 hours ^-1 , and aromatic/polyalkylated aromatic compound weight ratio of 1:1 to 6:1.

When the polyalkylated aromatic compound is polyethylbenzene and reacts with benzene to produce ethylbenzene, the transalkylation conditions include a temperature of about 220°C to about 260°C and a pressure of about 300 kPa to about 400 kPa, 2 The weight space velocity per hour based on the total feed to 6 and the benzene/PEB weight ratio of 2:1 to 6:1.

When the polyalkylated aromatic compound is polyisopropylbenzene (PIPB) and reacts with benzene to produce cumene, the transalkylation conditions include a temperature of about 100°C to about 200°C, and a temperature of about 300kPa to about 400kPa Pressure, 1 to 10 weight hourly space velocity based on total feed and benzene/PIPB weight ratio of 1:1 to 6:1.

The at least part of the liquid phase conditions for alkylation may include at least one of the following: a temperature of about 10°C to about 400°C, or about 10°C to about 200°C, or about 150°C to about 300°C; up to about 25000 kPa , Or at most about 20000kPa, or about 100kPa to about 7000kPa, or about 689kPa to about 4601kPa pressure; about 0.1:1 to about 50:1, preferably about 0.5:1 to 10:1 alkylatable aromatic The molar ratio of the compound to the alkylating agent, and the feed per hour between about 0.1 and about 100 hours ^-1 , or about 0.5 to 50 hours ^-1 , or about 10 hours ^-1 to about 100 hours ^-1 Weight space velocity (WHSV).

When benzene is alkylated with ethylene to produce ethylbenzene, then the alkylation reaction can be carried out under at least a portion of the liquid phase conditions used for alkylation. The conditions include between about 150°C and 300°C or between at a temperature of between about 260 ℃ 200 ℃; up to about 20,000 kPa, preferably a pressure of from about 200kPa to about 5600kPa; from about 0.1 ^hr-1 to about 50 ^hr-1, or about 1 hour to about 10 hours ^{-1 - 1} WHSV based on ethylene feed, and a molar ratio of benzene to ethylene in the alkylation reactor of 1:1 to 30:1, preferably the molar ratio of about 1:1 to 10:1.

When benzene is alkylated with propylene to produce cumene, the reaction can be carried out under at least part of the liquid phase conditions used for alkylation, the conditions including up to about 250°C, preferably from about 10°C to about 200°C Temperature; up to about 25000kPa, preferably about 100kPa to about 3000kPa pressure; and about 1 hour ^-1 to about 250 hours ^-1 , preferably 5 hours ^-1 to 50 hours ^-1 , preferably about 5 hours WHSV based on ethylene feed from ^-1 to about 10 hours ^-1 .

Alkylated aromatic compounds

The substituted alkylatable aromatic compounds that can be alkylated herein must have at least one hydrogen atom directly bonded to the aromatic core. The aromatic ring may be substituted with one or more alkyl groups, alkaryl groups, alkoxy groups, aryloxy groups, cycloalkyl groups, halides, and/or other groups that do not interfere with the alkylation reaction.

Suitable alkylatable aromatic hydrocarbons in any of the embodiments of the present invention include benzene, naphthalene, anthracene, fused tetrabenzene, perylene, cobalt, and phenanthrene, with benzene being preferred.

Alkyl groups that may be present as substituents on aromatic compounds usually contain from 1 to about 22 carbon atoms, and often from about 1 to 8 carbon atoms, and most often from about 1 to 4 carbon atoms.

Alkyl-substituted aromatic compounds suitable for any of the embodiments of the present invention include toluene (also preferred), xylene, isopropylbenzene, n-propylbenzene, α-methyl Naphthalene, ethylbenzene, cumene, cumene, durene, p-isopropyltoluene, butylbenzene, pseudocumene, o-diethylbenzene, m-diphenyl Ethylbenzene, 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-butyl toluene, p-butyl toluene, 3,5-diethyl toluene, o -Ethyltoluene, p-ethyltoluene, m-propyltoluene, 4-ethyl m-xylene, dimethylnaphthalene, ethylnaphthalene, 2,3-dimethylanthracene, 9-ethylanthracene, 2-methylanthracene, o-methylanthracene, 9,10-dimethylphenanthrene and 3-methylphenanthrene. Higher molecular weight alkylated aromatic hydrocarbons can also be used as starting materials and include aromatic hydrocarbons, such as aromatic hydrocarbons produced by the alkylation of aromatic hydrocarbons and olefin oligomers. These products are often referred to as alkylates in this technology and include hexylbenzene, nonylbenzene, dodecylbenzene, pentadecylbenzene, hexyltoluene, nonyltoluene, dodecyltoluene, fifteen Alkyl toluene, etc. It is common to obtain alkylates in which the size of the alkyl group attached to the aromatic nucleus ranges from a high boiling point fraction ranging from about C ₆ to about C ₁₂ . When cumene or ethylbenzene is the desired product, the process of the present invention produces a small amount of acceptable by-products, such as xylene. The xylene produced by these examples can be less than about 500 ppm.

The recombinant product containing substantial amounts of benzene, toluene and/or xylene constitutes a useful feed for the process of the present invention.

Alkylating agent

Alkyl groups useful in one or more embodiments of the invention The agent generally includes any aliphatic or aromatic organic compound having one or more available alkylated olefin groups that can react with the alkylatable aromatic compound. The alkylating agent preferably contains an olefin group having 1 to 5 carbon atoms or a polyalkylated aromatic compound. The alkylating agent is more preferably polyethylbenzene and polyisopropylbenzene for transalkylation, and ethylene and propylene for alkylation. Examples of alkylating agents suitable for any of the embodiments of the present invention are olefins, preferably ethylene, propylene, butenes and pentenes, and mixtures thereof; alcohols (including monoalcohols, Alcohols, triols, etc.), such as methanol, ethanol, propanol, butanol, and pentanol; aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and n-valeraldehyde; and halogenated alkanes, such as Chloromethane, ethyl chloride, chloropropane, chlorobutane, chloropentane, etc.

The mixture of light olefins is especially used as an alkylating agent in the alkylation process of the present invention. Therefore, ethylene, propylene, butene as the main components of various refinery gas streams (such as fuel gas; gas plant waste gas containing ethylene, propylene, etc.; light oil cracker waste gas containing light olefins, refining FCC propane/propylene stream, etc.) And/or pentene mixtures are alkylating agents useful herein.

Polyalkylated aromatic compounds suitable for one or more embodiments of the present invention include, but are not limited to, diethylbenzene, triethylbenzene, and polyethylbenzene, as well as diisopropylbenzene (DIPB), tris Cumene (TIPB) and polyisopropylbenzene, or mixtures thereof.

Bed

The alkylatable aromatic compound stream for the process of the present invention The alkylating agent stream is usually an impure stream and contains some degree of reaction impurities (as defined above), such as nitrogen compounds, which are small enough to enter the catalyst (preferably alkylating catalyst and/or conversion) Alkylating catalyst) and thereby poisoning the catalyst. Moreover, it is normal that all the alkylatable aromatic compounds are supplied to the first alkylation and/or transalkylation reaction zone, but the alkylating agent is separated and supplied to the alkylation and/or transalkylation Between catalyst beds. Therefore, the catalyst in the first reaction zone is more likely to be poisoned by impurities. Therefore, in order to reduce the frequency with which the catalyst in the first reaction zone must be removed for replacement, regeneration or reactivation, the process of the present invention preferably uses a separate catalyst in the first alkylation and/or transalkylation reaction zone Bedding. Alternatively, the guard bed may be upstream of and separate from the first reaction zone. The effluent from the guard bed is a treated feed, such as a treated alkylatable aromatic compound and/or a treated alkylating agent, which is then fed into the process of the present invention.

In one or more embodiments, the process of the present invention further comprises contacting the alkylatable aromatic compound and/or the alkylating agent with a processing material to remove the alkylatable aromatic compound or the alkylene The step of removing at least a part of any impurities by the base agent. The treatment material can be selected from the group consisting of clay, resin, activated alumina, molecular sieve and combinations thereof. Molecular sieves can be selected from the group consisting of Linde X, Linde A, zeolite β, faujasite, zeolite Y, ultra-stable Y (USY), dealuminated Y (Deal Y), rare earth Y (REY) , Ultra-hydrophobic Y (UHP-Y), mordenite, TEA-mordenite, ZSM-3, ZSM-4, ZSM-14, ZSM-18, ZSM-20 and combinations thereof.

Transalkylation catalyst composition

In another aspect, the present invention is a transalkylation catalyst comprising zeolite having a framework structure selected from the group consisting of FAU, BEA*, MOR, MWW, and mixtures thereof. The zeolite has a silica-alumina molar ratio in the range of 10 to 15. The transalkylation catalyst composition has an external surface area/volume ratio in the range of 30 cm ^-1 to 85 cm ^-1 , or 40 cm ^-1 to 80 cm ^-1 , or 45 cm ^-1 or 75 cm ^-1 .

Zeolites with FAU framework type can be selected from the group consisting of: 13X, ultra stable Y (USY) and its low sodium modification, dealuminated Y (Deal Y), ultra-hydrophobic Y (UHP-Y), Rare earth exchange type Y (REY), rare earth exchange type USY (RE-USY) and mixtures thereof. The zeolite with FAU framework type is preferably USY.

Zeolites with MOR framework type can be selected from the group consisting of mordenite, EMM-34, TEA-mordenite and mixtures thereof. The zeolite with BEA* framework type is preferably EMM-34, which is disclosed and described in US Patent Publication 2016-0221832.

The zeolite having BEA* framework type is preferably zeolite β.

Zeolites with MWW framework type are MCM-22 family materials. This MCM-22 family material can be selected from the group consisting of: MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, ERB-1, EMM-10, EMM- 10-P, EMM-12, EMM-13, UZM-8, UZM-8HS, ITQ-1, ITQ-2, ITQ-30 and mixtures of two or more thereof. The MCM-22 group material having a zeolite of MWW framework type is preferably MCM-22 or MCM-49.

In one or more embodiments, the transalkylation catalyst composition is an acid catalyst in active form and has protons. The zeolite can be combined with an oxide binder (such as alumina or silica) in a conventional manner such that the final transalkylation contains between 1 and 100% by weight of zeolite based on the weight of the catalyst composition. Alternatively, the acidic transalkylation catalyst composition contains a binder greater than 0% by weight to at most 99% by weight based on the weight of the transalkylation catalyst composition. The zeolite constitutes 1% by weight to at most 100% by weight of the transalkylation catalyst composition, or 10% to 90% by weight, or 20% to 80% by weight. Zeolite preferably constitutes 65% to 80% by weight of the transalkylation catalyst composition.

The binder can be a metal or mixed metal oxide. The binder can be selected from the group consisting of alumina, silica, titania, zirconia, tungsten oxide, cerium oxide, niobium oxide, and combinations thereof.

In a preferred embodiment, the transalkylation catalyst composition of the present invention comprises a zeolite having a frame structure selected from the group consisting of: FAU, BEA*, MOR, MWW, and mixtures thereof, wherein The silica-alumina molar ratio of zeolite is in the range of 10 to 15, or in the range of 11 to 14, or in the range of 12 to 13: wherein the FAU framework structure is selected from the group consisting of Group: 13X, low sodium super stable type Y (USY), dealuminated type Y (Deal Y), super hydrophobic type Y (UHP-Y), rare earth exchange type Y (REY), rare earth exchange type Y (RE-USY) And mixtures thereof, wherein the zeolite having the BEA* framework structure is zeolite β, wherein the zeolite having the MOR framework structure is selected from the group consisting of mordenite, EMM-34, TEA-mordenite and mixtures thereof ; Where the zeolite with the MWW framework structure is a MCM-22 family material, the MCM-22 family molecular sieve is any of the following: MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, ERB-1, EMM-10, EMM-10-P, EMM-12, EMM-13, UZM-8, UZM-8HS, UZM-37, ITQ-1, ITQ-2, ITQ-30 or A combination of two or more thereof; wherein the transalkylation catalyst has an external surface area/volume ratio in the range of 30 cm ^-1 to 85 cm ^-1 ; and wherein the zeolite constitutes the transalkylation catalyst 65% to 80% by weight of the composition.

When the catalysts are compared under equal transalkylation conditions, the catalytic activity ratio of the transalkylation catalyst composition of the present invention includes the zeolite and has silica-alumina (Si/Al ₂ ) Molar ratio in the range of 25 to 37, or in the range of 27 to 35, or in the range of 29 to 33, low activity (ie, higher molar silica content) transalkylation catalyst composition The catalytic activity of the substance is higher. The high catalytic activity of the transalkylation catalyst of the present invention is achieved by reducing the amount of silica in the composition, which results in a lower silica-alumina molar ratio.

Therefore, when the high activity (ie, lower silica content) transalkylation catalyst composition of the present invention is used in the production process to produce ethylbenzene or cumene, the composition exhibits a higher ratio than that in this process. The weight per hour of the low activity (i.e. higher silica content) transalkylation catalyst composition used The per hour weight space velocity of the polyalkylated benzene stream with higher volumetric space velocity, where the catalysts are compared under equal transalkylation conditions, such as equal transalkylation temperatures.

Alternatively, when using the high activity (ie, lower silica content) transalkylation catalyst composition of the present invention to produce ethylbenzene or cumene in the process, the composition can be The low activity (ie, higher silica content) transalkylation catalyst composition used in this process operates at a lower transalkylation temperature, where the catalysts are at equal transalkylation Compared to conditions.

Without being bound by any theory, Xianxin's higher activity exhibited by the transalkylation catalyst composition of the present invention consists of the lower silica-alumina (Si/Al ₂ ) molar ratio of the zeolite and the composition. A high external surface area/volume (SA/V) ratio combination is provided. A lower Si/Al ₂ molar ratio provides a higher alumina content, which promotes the transalkylation reaction. A higher SA/V ratio provides increased surface area per unit volume for transalkylation of large volumes of reactants. This is especially true for reactions in the liquid phase.

Alkylation catalyst

In one or more embodiments, the alkylation catalyst includes aluminosilicate. The aluminosilicate is any one of the following: MCM-22 family molecular sieve, faujasite, mordenite, zeolite beta, or a combination of two or more thereof. The MCM-22 family molecular sieve is any of the following: MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, ERB-1, EMM-10, EMM-10-P, EMM-12, EMM-13, UZM-8, UZM- 8HS, UZM-37, ITQ-1, ITQ-2, ITQ-30, or a combination of two or more thereof.

In one or more embodiments, the alkylation catalyst is an acidic catalyst in active form and has protons. Zeolite can be combined with an oxide binder (such as alumina or silica) in a conventional manner such that the final alkylated catalyst composition contains between 1 and 100 weights based on the weight of the alkylated catalyst composition % Zeolite. Alternatively, the acidic alkylated catalyst composition contains a binder greater than 0% by weight to at most 99% by weight based on the weight of the alkylated catalyst composition. Zeolite constitutes 1% by weight to at most 100% by weight of the alkylation catalyst composition, or 10% to 90% by weight, or 20% to 80% by weight. Zeolite preferably constitutes 65% to 80% by weight of the alkylation catalyst composition.

The binder can be a metal or mixed metal oxide. The binder can be selected from the group consisting of alumina, silica, titania, zirconia, tungsten oxide, cerium oxide, niobium oxide, and combinations thereof.

In one or more embodiments, the alkylation or transalkylation catalyst composition may be fresh alkylation or transalkylation catalyst composition, at least partially deactivated alkylation or transalkylation Base catalyst or a combination thereof. In one or more embodiments, the at least partially deactivated alkylation or transalkylation catalyst is deactivated by coke deposition during its previous use in the alkylation or transalkylation process.

Catalyst regeneration

When performing the alkylation and/or transalkylation process of the present invention At this time, the alkylation and/or transalkylation catalyst composition gradually loses its alkylation activity, so that the reaction temperature required to achieve the given performance parameters (such as the conversion rate of the alkylating agent) increases. When the activity of the alkylation and/or transalkylation catalyst is reduced by some predetermined amount compared to the initial alkylation and/or transalkylation catalyst activity, it is usually 5% to 90%, and better 10% to 50%, the deactivated catalyst composition can be subjected to a regeneration procedure using any known method, such as the method disclosed in US Patent No. 6,380,119 issued to BASF, which is incorporated herein by reference .

Examples

The present invention will now be described more specifically with reference to the following examples.

Effect of Si/Al ₂ molar ratio of USY zeolite on transalkylation performance Examples 1 and 2: Catalyst preparation

In Example 1, the catalyst composition (catalyst A) contained 80% by weight of USY zeolite (Si/Al ₂ = 30 mol) and 20% by weight of amorphous Al ₂ O ₃ (alumina), which was Acid form.

In Example 2, the catalyst composition (catalyst B) contains 80% by weight of USY zeolite (Si/Al ₂ = 12 mol) and 20% by weight of amorphous Al ₂ O ₃ (alumina), which is Acid form.

Evaluation of catalyst transalkylation performance of Examples 1 and 2

After the catalyst preparation, the transalkylation of polyethylbenzene (PEB) and benzene is carried out with catalyst A and catalyst B in a fixed bed reactor. The PEB stream includes diethylbenzene (DEB). The test procedure consists of the following: the dry catalyst is loaded in a batch reactor together with benzene. The reactor was then heated to 266°F (130°C), and then PEB was added under an inert gas pressure of 300 psig (2068.43 kPa). Regarding catalyst A, a benzene/PEB ratio of 2:1 by weight and a weight hourly space velocity (WHSV) of 1.1 hours ^{-1 were set} , and the reaction temperature was gradually increased to 190°C to achieve the target DEB conversion of 65%. Regarding catalyst B, a benzene/PEB ratio of 2:1 by weight and a weight hourly space velocity (WHSV) of 1.1 hours to ¹ hour were set, and the reaction temperature was gradually reduced to 177°C to achieve the target DEB conversion of 65%. Samples were periodically removed during the test and analyzed by gas chromatography to determine DEB conversion.

Table 1 shows the performance data of Catalyst A and Catalyst B used in the transalkylation of polyethylbenzene (PEB) and benzene:

As can be seen in Table 1, lower temperature operation is achieved with constant DEB conversion and constant PEB output. Alternatively, a higher PEB output can be achieved with a constant temperature and a constant DEB conversion rate.

Effect of particle size and shape of USY zeolite catalyst on transalkylation catalyst activity Examples 3 to 6: Catalyst preparation

In Example 3, the catalyst composition (Catalyst C) contains 80% by weight of USY zeolite (Si/Al ₂ = 12 mol) and 20% by weight of amorphous Al ₂ O ₃ (alumina), which is It is in acid form and has a particle size and shape of 1/16 inch cylindrical extrudate.

In Example 4, the catalyst composition (catalyst D) contains 80% by weight of USY zeolite (Si/Al ₂ = 12 mol) and 20% by weight of amorphous Al ₂ O ₃ (alumina), which is It is in acid form and has a particle size and shape of 1/20 inch quad leaf extrudate.

In Example 5, the catalyst composition (catalyst C) contains 80% by weight of USY zeolite (Si/Al ₂ = 12 mol) and 20% by weight of amorphous Al ₂ O ₃ (alumina), which is Type I is in acid form and has a particle size and shape of 1/16 inch cylindrical extrudate.

In Example 6, the catalyst composition (catalyst D) contains 80% by weight of USY zeolite (Si/Al ₂ = 12 mol) and 20% by weight of amorphous Al ₂ O ₃ (alumina), which is It is in acid form and has a particle size and shape of 1/20 inch quad leaf extrudate.

Although the calculation of cylindrical geometry is well known, the calculation of quadrilateral geometry is more complicated. The formula below details calculations that determine the area/volume (SA/V) of the four-lobed material.

The surface area/volume ratio of the four-lobed and cylindrical extrudates is calculated from particles approximately cylindrical with a diameter of 0.25 mm and a length of 0.25 mm. The following table lists the SA/V ratio of the tested particle sizes.

Evaluation of catalyst activity in Examples 3 to 6

After the catalyst preparation, the transalkylation of polyethylbenzene (PEB) and benzene was carried out with catalyst C and catalyst D and as catalyst E and catalyst F in a fixed bed reactor. Use the same test procedure as described above. The transalkylation activity is based on the DEB conversion rate. The transalkylation activity of catalyst D is standardized relative to the transalkylation activity of catalyst C. The transalkylation activity of catalyst F is standardized relative to the transalkylation activity of catalyst W.

As can be seen, Table 2 shows that modification of catalyst extrudate particle size and shape can significantly affect transalkylation activity. Has a smaller diameter and The large surface area to volume ratio of the catalyst particles is better for liquid phase reactions where mass transport restrictions may persist.

Specific implementations and characteristics have been described using a set of upper numerical limits and a set of lower numerical limits. It should be understood that the range from any lower limit to any upper limit is considered unless otherwise indicated. The specific lower limit, upper limit and range appear within one or more of the following patent applications. All numerical values take into account experimental errors and variables that can be expected by those with ordinary knowledge in the technical field to which the invention belongs.

As used herein, the term "contains" (and its grammatical changes) is used in an inclusive sense of "having" or "including", rather than "only consisting of" or "consisting of". Use meaningfully. It should be understood that the terms "a" and "the" as used herein include both plural and singular.

Various terms have been defined above. In the case where the terms used in the scope of patent application are not defined above, the broadest definition given by the relevant technical person in accordance with the terms reflected in at least one printed publication and the issued patent shall be given. In addition, all patents, test procedures, and other documents cited in this application are not contradictory to this application by such disclosures and are fully incorporated by reference to the extent that all jurisdictions allow this merger.

This disclosure previously described examples and explained this description. In addition, this disclosure only shows and illustrates preferred implementations, but as described above, it should be understood that this disclosure can be used in various other combinations, modifications, and environments, and can be changed within the scope of the concepts expressed herein And repair The changes are commensurate with the skills or knowledge taught above and/or related technologies.

Claims (19)

A process for producing cumene, comprising the steps of: (a) providing a transalkylation catalyst composition to a reaction zone, the transalkylation catalyst comprising zeolite having a frame structure selected from the group consisting of : FAU, BEA*, MOR, MWW, and mixtures thereof, wherein the silica-alumina molar ratio of the zeolite is in the range of 10 to 15, and the transalkylation catalyst composition has an external surface area/ In the form of an extrudate with a volume ratio in the range of 30 cm ^-1 to 85 cm ^-1 ; (b) providing a stream comprising polyalkylated benzene and a portion of the alkylatable aromatic compound stream to the reaction zone, wherein The polyalkylated benzene stream contains diisopropylbenzene, and the alkylatable aromatic compound stream contains benzene; (c) The polyalkylated benzene stream and the alkylatable aromatic compound stream Contacting in the presence of a transalkylation catalyst composition under at least part of the liquid phase transalkylation conditions to alkylate the alkylatable aromatic compound and produce a transalkylation effluent stream comprising cumene , Where the catalytic activity of the transalkylation catalyst composition is higher than that of the zeolite and the transalkylation catalyst composition having a silica-alumina molar ratio in the range of 25 to 37 with a higher silica content The catalytic activity is higher, and the catalyst compositions are compared under equal transalkylation conditions; (d) providing a stream containing an alkylating agent and another part of the alkylatable aromatic compound stream to Another reaction zone; (e) contacting the other portion of the alkylatable aromatic compound stream with the stream containing an alkylating agent under alkylation conditions in the presence of an alkylation catalyst, so that the The alkylable aromatic compound can be alkylated and produce an alkylation effluent comprising monoalkylated benzene and the polyalkylated benzene; (f) separating the alkylation effluent to recover the polyalkylated benzene Stream; and (g) feeding at least a portion of the polyalkylated benzene stream to step (b), wherein the alkylation conditions include 0.1:1 to 50:1 alkylatable aromatic compound for alkylation Morbi. According to the process of item 1 of the patent application scope, the alkylatable aromatic compound stream containing benzene is an impure stream, which additionally contains nitrogen-containing impurities. The process according to item 2 of the patent application scope additionally includes the step of contacting the impure stream with the processing material under processing conditions to remove at least a portion of the nitrogen-containing impurities, wherein the processing conditions include 30°C to 200°C Temperature, weight hourly space velocity (WHSV) from 0.1 hour ^-1 to 200 hour ^-1 and pressure between ambient pressure and 3000 kPa-a, and the treatment material is selected from the group consisting of: clay , Resin, activated alumina, molecular sieve and combinations thereof. According to the process of item 3 of the patent application scope, it additionally includes steps: (h) separating the transalkylation effluent stream to recover the cumene stream. According to the process of item 4 of the patent application scope, it additionally includes steps: (i) separating the alkylation effluent stream to recover the cumene stream. According to the process of item 5 in the patent application scope, wherein the monoalkylated benzene is cumene, the polyalkylated benzene is polyisopropylbenzene, and the alkylating agent is propylene. The process according to item 1 of the patent application scope, wherein the weighted space velocity per hour of the polyalkylated benzene stream in the presence of the transalkylated catalyst composition is higher than that of the transalkylated silicon oxide content The hourly weight space velocity is higher in the presence of catalyst compositions, and the catalyst compositions are compared under equal transalkylation conditions. According to the process in item 7 of the patent application scope, the transalkylation temperatures are equal. According to the process of claim 8 of the patent application scope, the at least partial liquid phase transalkylation conditions include a temperature of 100°C to 200°C and a pressure of 200 kPa-a to 600 kPa-a. The process according to item 9 of the patent application scope, wherein the alkylation conditions are at least part of the liquid phase conditions and include a temperature of 150° C. to 300° C. and a pressure of at most 20,000 kPa, and 0.1 hours ^-1 to 30 hours ^-1 based on the WHSV by weight of alkylating agent. According to the process of item 10 of the patent application scope, the conversion rate of diisopropylbenzene is in the range of 25% to 95% by weight. According to the process of claim 11 of the patent application scope, the zeolite with the FAU framework structure is selected from the group consisting of: 13X, low sodium super stable type Y (USY), dealuminated type Y (Deal Y), Super-hydrophobic Y (UHP-Y), rare earth exchange Y (REY), rare earth exchange USY (RE-USY) and mixtures thereof. According to the process of item 12 of the patent application scope, the zeolite having the BEA* framework structure is zeolite β. According to the process of claim 13 of the patent application scope, the zeolite having the MOR framework structure is selected from the group consisting of mordenite, EMM-34, TEA-mordenite and mixtures thereof. According to the process of item 14 of the patent application scope, the zeolite with the MWW framework structure is a MCM-22 family molecular sieve and a combination thereof. According to the process of item 15 of the patent application scope, the MCM-22 family molecular sieve is any of the following: MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, ERB- 1. EMM-10, EMM-10-P, EMM-12, EMM-13, UZM-8, UZM-8HS, UZM-37, ITQ-1, ITQ-2, ITQ-30 or two or more of them Of the combination. According to the process of claim 16 of the patent application scope, the alkylation catalyst Contains aluminosilicate. According to the process of claim 17 of the patent application scope, the aluminosilicate is any one of the following: MCM-22 family molecular sieve, faujasite, mordenite, zeolite beta, or a combination of two or more thereof. According to the process of claim 3, the molecular sieve is selected from the group consisting of Linde X, Linde A, zeolite β, faujasite, zeolite Y, ultra stable Y (USY), and dealuminized Y (Deal Y), rare earth Y (REY), super-hydrophobic Y (UHP-Y), mordenite, TEA-mordenite, ZSM-3, ZSM-4, ZSM-14, ZSM-18, ZSM-20 And combinations.