KR102176960B1 - Method for producing mono-alkylated aromatic compounds - Google Patents

Abstract

The present disclosure relates to a method for producing mono-alkylated aromatic compounds using the treated catalyst prepared by the method of the present invention. The method includes heating the untreated catalyst in the presence of a gas stream having a dew point temperature of less than about 5° C. to form a treated catalyst. This treatment is effective in improving the activity and selectivity of the catalyst.

Description

Method for producing mono-alkylated aromatic compounds

preference

The present invention claims the benefit and priority of U.S. patent application 62/347,667 filed on June 9, 2016 and European patent application 16181311.8 filed on June 26, 2016, both of which are incorporated herein by reference in their entirety. Included.

Invention field

The present invention relates to a method for treating a catalyst, preferably an alkylation or transalkylation catalyst, and a method for producing a mono-alkylated aromatic compound using the treated catalyst.

Mono-alkylated aromatic compounds such as ethylbenzene and cumene are valuable raw material chemicals used industrially for the production of styrene monomers and phenols, respectively. Ethylbenzene can be produced by a number of different chemical processes, but one process that has achieved significant commercial success is the liquid phase process for producing ethylbenzene from benzene and ethylene, because the liquid phase process is lower than the vapor phase process. Because it is operated at temperature, the yield of by-products tends to be lower. For example, U.S. Patent 4,891,458 discloses a liquid phase synthesis of ethylbenzene using zeolite beta, while U.S. Patent 5,334,795 discloses the use of MCM-22 in the liquid phase synthesis of ethylbenzene. Examples of such ethylbenzene production processes are disclosed in U.S. Patents 3,751,504 (Keown), 4,547,605 (Kresge), and 4,016,218 (Haag).

For a long time, cumene has been commercially produced by liquid phase alkylation of benzene with propylene in zeolite catalyst systems that are more active and selective to cumene than Friedel-Craft catalysts such as phosphoric acid or aluminum chloride. For example, US Pat. No. 4,992,606 discloses the use of MCM-22 in the liquid phase alkylation of benzene with propylene.

Other molecular sieves known for use as liquid-phase alkylation and transalkylation catalysts include MCM-36 (see US Pat. No. 5,258,565), MCM-49 (see US Pat. No. 5,371,310) and MCM-56 (see US Pat. No. 5,453,554).

In the commercial operation of this process, polyalkylated benzene containing both di-ethylbenzene and di-isopropylbenzene, which is essentially co-produced with ethylbenzene and cumene in the alkylation reactor, is recycled to the alkylation reactor or to a separate transalkylation reactor. By feeding it is transalkylated with benzene to give additional ethylbenzene or cumene. Cumene and ethylbenzene catalysts are conventionally calcined in air and have a wide range of moisture content (as measured by the air's dew point and relative humidity).

Summary of the invention

It has been found that when the moisture content in the final calcined air is high, this negatively affects the monoselectivity and catalytic activity of the catalyst. According to the present invention, careful control of the dew point of a gas stream such as air used for the final calcination of a catalyst with a zeolite component improves the monoselectivity for the desired mono-alkylated aromatic compounds and catalytic activity in the aromatic alkylation process. Was found to improve.

In one aspect, the present invention is a method of treating a catalyst comprising a molecular sieve, preferably an alkylation or transalkylation catalyst, wherein the catalyst is heated in the presence of a gas stream having a dew point temperature of 5° C. or less to And forming. Preferably, the dew point of the gas stream is in the range of about -40°C to about 5°C or less. Preferably, the molecular sieve is an aluminosilicate.

In another aspect, the present invention is a catalyst treated by any of the methods of the present invention.

In another aspect, the present invention is a process for preparing a mono-alkylated aromatic compound. The process includes contacting an alkylatable aromatic compound and an alkylating agent with a catalyst under alkylation conditions or transalkylation conditions to produce an effluent comprising the mono-alkylated aromatic compound. Such catalysts are treated catalysts of the present invention, or catalysts treated by either method of the present invention.

In one or more embodiments, the product further comprises a poly-alkylated aromatic compound which may be transalkylated with an additional alkylatable aromatic compound to produce an additional mono-alkylated aromatic compound.

In one or more embodiments, the process further comprises contacting the alkylatable aromatic compound or the alkylating agent with a treatment material to remove at least a portion of any impurities from the alkylatable aromatic compound and/or the alkylating agent.

Detailed description of the invention

The present invention is a mono-alkylated aromatic compound, for example by at least partial liquid phase alkylation of an alkylatable aromatic compound using an alkylating agent in the presence of a treated catalyst comprising a molecular sieve such as aluminosilicate (e.g., an alkylation or transalkylation catalyst). It relates to a method of treating a compound, in particular a catalyst used in the process for the production of ethylbenzene or cumene. More particularly, the present catalyst treatment method includes heating the catalyst in the presence of a gas stream having a dew point temperature of about 5° C. or less to form a treated catalyst. It is believed that the treatment method of the present disclosure is effective in improving the catalyst selectivity for the desired mono-alkylated aromatic compounds while increasing the activity of the catalytic activity.

Justice

The term "alkylatable aromatic compound", as used herein, refers to an aromatic compound capable of accepting an alkyl group. One non-limiting example of an alkylatable aromatic compound is benzene.

The term “alkylating agent”, as used herein, refers to 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 poly-alkylated aromatic compound capable of donating an alkyl group to the alkylatable aromatic compound.

The term “aromatic”, as used herein in connection with the alkylatable aromatic compounds useful herein, is to be understood to include substituted and unsubstituted mononuclear and polynuclear compounds according to the art-recognized scope. Compounds of aromatic nature having heteroatoms (eg, N or S) are also useful as long as they do not act as catalyst poisons as defined below under selected reaction conditions.

The term “at least partially liquid” as used herein means a mixture having at least 1% by weight liquid, optionally at least 5% by weight liquid at a given temperature, pressure and composition.

The term “skeletal type”, as used herein, is described in Ch. Baerlocher, W.M. Meier and D.H. Olson's "Atlas of Zeolite Framework Types" (Elsevier, 5th edition, 2001)].

The term "MCM-22 class material" (or "MCM-22 class molecular sieve"), as used herein, may include:

(i) Molecular sieves prepared from conventional first-class crystal building blocks "unit cells with MWW skeleton topology". The unit cell is described in Ch. Baerlocher, W.M. Meier and D.H. It is a spatial arrangement of atoms tiled in three-dimensional space to represent crystals as disclosed in Olson's "Atlas of Zeolite Framework Types" (Elsevier, 5th ed., 2001);

(ii) a "monolayer of one unit cell thickness", preferably a conventional second class building block, forming a c-unit cell thickness, a molecular sieve made from two-dimensional tiling of such MWW skeletal unit cells ;

(iii) a molecular sieve made from a conventional class 2 building block, "a layer of one or more unit cell thickness," wherein the layer of one or more unit cell thicknesses is of the thickness of one unit cell of the unit cells having the MWW skeleton topology. It is obtained by laminating, packing or combining two or more single layers. The stacking of these class 2 building blocks can be regular, irregular, random and any combination thereof; or

(iv) Molecular sieves prepared by any regular or random two-dimensional or three-dimensional combination of unit cells having an MWW skeleton topology.

MCM-22 class materials are characterized by having an X-ray diffraction pattern comprising a maximum d-spacing at 12.4±0.25, 3.57±0.07 and 3.42±0.07 angstroms (in the calcined or synthesized state). MCM-22 class materials are also characterized as having an X-ray diffraction pattern comprising a maximum d-spacing at 12.4±0.25, 6.9±0.15, 3.57±0.07 and 3.42±0.07 angstroms (in the calcined or synthesized state). I can. X-ray diffraction data used for characterization of molecular sieves are obtained by standard techniques using a diffractometer equipped with a scintillation counter and associated computer as a collection device and a K-alpha doublet of copper as the incident line.

Members of the MCM-22 class are MCM-22 (disclosed in U.S. Patent 4,954,325), PSH-3 (disclosed in U.S. Patent 4,439,409), SSZ-25 (disclosed in U.S. Patent 4,826,667), ERB-1 (European Patent 0293032 No.), ITQ-1 (disclosed in U.S. Patent No. 6,077,498), ITQ-2 (disclosed in International Patent Publication No. WO97/17290), ITQ-30 (disclosed in International Patent Publication No. WO2005118476), MCM-36 (United States Patent No. 5,250,277), MCM-49 (disclosed in U.S. Patent No. 5,236,575), MCM-56 (disclosed in U.S. Patent No. 5,362,697), UZM-8 (disclosed in U.S. Patent No. 6,756,030), and UZM-8HS (United States Patent 7,713,513); And EMM-10 molecular sieves such as EMM-10, EMM-10-P, EMM-12 and EMM-13 (U.S. Patent Nos. 7,959,899 and 8,110,176; and U.S. Patent Application Publication No. 2008/0045768 characterized and disclosed) Including, but not limited to.

The term "mono-alkylated aromatic compound" means an aromatic compound having only one alkyl substituent. Non-limiting examples of mono-alkylated aromatic compounds are ethylbenzene, iso-propylbenzene (cumene) and sec-butylbenzene.

The term “poly-alkylated aromatic compound”, as used herein, refers to an aromatic compound having more than one alkyl substituent. Non-limiting examples of poly-alkylated aromatic compounds are poly-alkylated benzenes such as di-ethylbenzene, tri-ethylbenzene, di-isopropylbenzene, and tri-isopropylbenzene.

The term "regeneration", as used herein in connection with an alkylation catalyst or transalkylation catalyst, is treated under controlled oxygen content and temperature conditions to remove at least a portion of the deposited coke or by removing at least a portion of the adsorbed catalyst poison. It means an at least partially deactivated catalyst which has increased the catalytic activity of such a substance or catalyst.

The term "new", when used herein in connection with a molecular sieve, guard bed material, alkylation catalyst, or transalkylation catalyst, means that the molecular sieve or the catalyst has not been used in the catalytic reaction after it has been prepared. do.

The term “impurity”, as used herein, includes, but is limited to, compounds having one or more of the following elements: nitrogen, halogen, oxygen, sulfur, arsenic, selenium, tellurium, phosphorus, and Group 1-12 metals It doesn't work.

Catalyst treatment method

If the moisture content of the air used during the final calcination is not tightly controlled, the high relative humidity and dew point of the calcination air, together with the high temperature, cause the problem of partial steaming of the zeolite components and cause the dealumination of the zeolite. This dealumination of the zeolite component results in a catalyst with lower selectivity (monoselectivity) to the desired mono-alkylated aromatic compound in the aromatic alkylation process and lower catalytic activity. The catalyst treatment method of the present invention solves this problem.

Unexpectedly, during the final calcination of the catalyst, the catalysts are, for example, di-isopropyl benzene (DIPB) and tri-isopropylbenzene (as measured by a decrease in the dew point temperature) in the moisture content of the gas stream, such as air, It has been found that it exhibits reduced formation of unwanted poly-alkylated aromatic compounds such as TIPB) and increased catalytic activity in the production process of mono-alkylated aromatic compounds.

Without being bound by any theory, the reduction in the formation of undesired poly-alkylated aromatic compounds in the process for the production of mono-alkylated aromatic compounds can be attributed to the zeolite component forming the Bronsted acid site outside the aluminosilicate (such as an alumina binder). It is believed to be due to the formation of external acid moieties resulting from the reaction of the binder or dealumination of the molecular sieve or aluminosilicate (e.g., by loss of the Bronsted acid moiety inside the micropores of the aluminosilicate or molecular sieve) do.

In one aspect, the present invention is a method of treating a catalyst comprising molecular sieve, preferably an alkylation or transalkylation catalyst. The method includes heating the catalyst in the presence of a gas stream having a dew point temperature of 5° C. or less to form a treated catalyst. The dew point of the gas stream ranges from about -40°C to about 5°C or less, or from about -30°C to about 0°C or less, or from about -20°C to about 0°C or less. Preferably, the molecular sieve is an aluminosilicate.

The gas stream may comprise air in any embodiment of the present invention. The gas stream may also comprise oxygen in the range of about 1 v/v% to about 21 v/v% in one or more embodiments.

The gas stream may further comprise one or more diluents. The diluent may be selected from the group consisting of nitrogen, helium and mixtures thereof.

In one or more embodiments, the flow rate of the gas stream is at least 1 vol./vol. Catalyst/min.

The catalyst is heated to a temperature of about 600° C. or higher to a temperature of 300° C. or higher, preferably 325° C. or higher and maintained at that temperature for a period of time. The catalyst must not be heated to temperatures exceeding 800°C. In one or more embodiments, the catalyst is heated for a time of at least 1 hour and up to about 48 hours or more.

Moisture can be removed from the air in several ways. One of them is, for example, the absorption of water in a desiccant layer containing molecular sieves. Another method is to compress the gas stream, such as air, prior to absorption by the desiccant. Thereafter, the drying agent can be regenerated while changing the pressure or temperature. Another method is to use refrigeration to knock out moisture from an incoming gas stream, such as air, and use this for the final calcination of the catalyst.

Alkylation catalyst and/or transalkylation catalyst

In another aspect, the present invention is a catalyst treated with any one of the inventive methods. Preferably, the catalyst is an alkylation or transalkylation catalyst and comprises an aluminosilicate. Such aluminosilicates may be selected from MCM-22 molecular sieves, sporesite, mordenite, zeolite beta, or combinations thereof.

In another embodiment, the alkylation catalyst and/or the transalkylation catalyst has a skeletal type selected from the group consisting of FAU (e.g., sporesite), MOR (e.g. mordenite), *BEA (e.g., zeolite beta), and mixtures thereof. It includes a molecular sieve having.

Sporesite molecular sieve is 13X, super-stable Y (USY) and its low sodium modified, dealuminated Y (Deal Y), superhydrophobic Y (UHP-Y), rare earth exchange Y (REY), rare earth exchange USY (RE -USY) and mixtures thereof. The mordenite molecular sieve may be selected from the group consisting of mordenite, TEA-mordenite and mixtures thereof. MCM-22 molecular sieves are 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 may be selected from the group consisting of mixtures thereof.

In one or more embodiments, the catalyst is an acidic catalyst in active form and has a proton. The molecular sieve can be combined in a conventional manner with an oxide binder such as alumina or silica such that the final alkylation catalyst and/or transalkylation catalyst contains 1 to 100% by weight of molecular sieve, based on the weight of the catalyst. Alternatively, the acidic catalyst comprises from greater than 0% to 99% by weight of a binder, based on the weight of the catalyst. The binder can be a metal or mixed metal oxide. The binder may be selected from the group consisting of alumina, silica, titania, zirconia, tungsten oxide, ceria, niobia, and combinations thereof.

The effect of the dew point of the final calcined gas stream on the catalyst is independent of the catalyst geometry. Any shape, such as cylindrical or tetralobed, is expected to reveal the unexpected discovery of increased activity and increased monoselectivity of the treated catalyst.

In one or more embodiments, the alkylation or transalkylation catalyst may be a fresh alkylation or transalkylation catalyst, an at least partially deactivated alkylation or transalkylation catalyst, or a combination thereof. In one or more embodiments, the at least partially deactivated alkylation or transalkylation catalyst is one that has been deactivated due to coke deposition during previous use in the alkylation or transalkylation process.

Catalyst regeneration

As the alkylation and/or transalkylation process of the present invention proceeds, the alkylation and/or transalkylation catalyst gradually loses its alkylation activity, such that the reaction temperature required to achieve certain performance parameters, such as conversion of the alkylating agent, It will increase. When the alkylation and/or transalkylation catalytic activity is reduced by a certain amount, generally 5% to 90%, more preferably 10% to 50%, compared to the initial alkylation and/or transalkylation catalytic activity, the denatured catalyst May be subjected to a regeneration procedure using any known method, such as the method disclosed in US Pat. No. 6,380,119 to BASF, which is incorporated herein by reference.

In some embodiments, the catalyst that can be treated by the process of the invention is a fresh catalyst, or a catalyst that is at least partially deactivated, such as a catalyst deactivated in a previous alkylation and/or transalkylation reaction, or a regenerated catalyst. Can be

fair

In another aspect, the present invention is a method of preparing a mono-alkylated aromatic compound. The method includes contacting an alkylatable aromatic compound and an alkylating agent with a catalyst under at least partially liquid alkylation conditions or at least partially liquid transalkylation conditions to produce an effluent comprising the mono-alkylated aromatic compound. Such catalysts are the treated catalysts of the present invention, or catalysts treated by any one of the present methods.

The reaction products obtainable from the process of the present invention are ethylbenzene from the reaction of benzene and ethylene, cumene from the reaction of benzene and propylene, ethyltoluene from the reaction of toluene and ethylene, cementene from the reaction of toluene and propylene, and And sec-butylbenzene from the reaction of benzene with n-butene.

The alkylation process of the present invention is particularly aimed at producing mono-alkylated aromatic compounds such as ethylbenzene and cumene in the alkylation step, but the alkylation step usually produces some poly-alkylated aromatic compounds. In one or more embodiments, the product further comprises poly-alkylated aromatic compound(s). Thus, the process preferably comprises the steps of separating the poly-alkylated aromatic compound from the effluent and then contacting it with a further alkylatable aromatic compound in the presence of a suitable transalkylation catalyst in at least partial transalkylation conditions in the transalkylation step. Include more. The transalkylation catalyst is preferably a molecular sieve selective for the production of the desired mono-alkylated aromatic compound, e.g., a molecular sieve identical or different from the alkylation catalyst, preferably an MCM-22 class molecular sieve (as defined herein) , And sporesite, mordenite, or zeolite-beta, and combinations thereof.

Alkylatable aromatic compounds

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

Suitable alkylatable aromatic hydrocarbons for any one embodiment of the present invention include benzene, naphthalene, anthracene, naphthacene, perylene, coronene, and phenanthrene, with benzene being preferred.

In general, the alkyl groups that may be present as substituents in the aromatic compound contain 1 to about 22 carbon atoms, typically about 1 to 8 carbon atoms, and most typically about 1 to 4 carbon atoms.

Alkyl substituted aromatic compounds suitable for any of the embodiments of the present invention are toluene (which is also preferred), xylene, isopropylbenzene, normal propylbenzene, alpha-methylnaphthalene, ethylbenzene, cumene, methiylene, durene, p- 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-propyltoluene; 4-ethyl-m-xylene; Dimethylnaphthalene; Ethylnaphthalene; 2,3-dimethylanthracene; 9-ethylanthracene; 2-methylanthracene; o-methylanthracene; 9,10-dimethylphenanthrene; And 3-methyl-phenanthrene. Alkylated aromatic hydrocarbons of higher molecular weight can also be used as starting materials, and include aromatic hydrocarbons such as those produced by alkylation of aromatic hydrocarbons with olefin oligomers. Such products are frequently referred to as alkylates in the industry and include hexylbenzene, nonylbenzene, dodecylbenzene, pentadecylbenzene, hexyltoluene, nonyltoluene, dodecyltoluene, pentadecyltoluene, and the like. Very often, alkylates are obtained as high boiling fractions in which the alkyl groups attached to the aromatic nucleus vary in size from about C ₆ to about C ₁₂ . When cumene or ethylbenzene is the desired product, the process of the present invention produces acceptablely less byproducts such as xylene. In such a case, the xylene produced may be less than about 500 ppm.

Reformates containing substantial amounts of benzene, toluene and/or xylene constitute a useful feed in the process of the present invention.

Alkylating agent

Alkylating agents useful in one or more embodiments of the present invention generally include any aliphatic or aromatic organic compound having one or more available alkylated olefin groups capable of reacting with the alkylatable aromatic compound. Preferably, the alkylating agent comprises an olefin group having 1 to 5 carbon atoms, or a poly-alkylated aromatic compound(s). Examples of alkylating agents suitable for any one of the embodiments of the present invention include olefins, preferably ethylene, propylene, butene, and pentene, and mixtures thereof; Alcohols such as methanol, ethanol, propanol, butanol and pentanol (including monoalcohol, dialcohol, trialcohol, etc.); Aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and n-valeraldehyde; And alkyl halides such as methyl chloride, ethyl chloride, propyl chloride, butyl chloride, and pentyl chloride.

Mixtures of light olefins are particularly useful as alkylating agents in the inventive alkylation process. Thus, mixtures of ethylene, propylene, butene, and/or pentene, which are the main constituents of the various refining streams, such as fuel gas, gas plant offgas containing ethylene, propylene, etc., naphtha cracker offgas containing light olefins, Refined FCC propane/propylene streams and the like are useful alkylating agents herein.

Poly-alkylated aromatic compounds suitable for one or more embodiments of the present invention are di-ethylbenzene, tri-ethylbenzene and polyethylbenzene(s), and di-isopropylbenzene (DIPB), tri-isopropylbenzene (TIPB) And polyisopropylbenzene(s) or mixtures thereof.

For example, a typical FCC light olefin stream has a composition as shown in Table I below:

Alkylation and/or transalkylation conditions

The process for the production of mono-alkylated aromatic compounds of the present invention, under effective conditions, for example in a suitable reaction zone such as a flow reactor comprising a fixed bed of the catalyst composition, the organic reactants, i.e., the alkylatable aromatic compound and the alkylating agent, are catalysts, preferably Is implemented to contact an alkylation catalyst and/or a transalkylation catalyst. Such conditions include at least partially liquid phase alkylation conditions or at least partially liquid phase transalkylation conditions.

The at least partial liquid phase alkylation conditions may include at least one of the following: about 10°C to about 400°C, or about 10°C to about 200°C, or about 150°C to about 300°C, about 25000 kPa or less, or Pressure of about 20000 kPa or less, or about 100 kPa to about 7000 kPa, or about 689 kPa to about 4601 kPa, about 0.1:1 to about 50:1, preferably about 0.5:1 to 10:1 alkylatable aromatic The molar ratio of compound to alkylating agent, and an hourly weight space velocity (WHSV) of the feed of about 0.1 to about 100 hr ^-1 , or about 0.5 to 50 hr ^-1 , or about 10 hr ^-1 to about 100 hr ^-1 .

In one or more embodiments, the reactants may be in the absence of addition, i.e., no dilution or intentional mixing with other substances, or may include a diluent or carrier gas such as, for example, hydrogen or nitrogen.

When benzene is alkylated with ethylene to produce ethylbenzene, the alkylation reaction is at a temperature of about 150° C. to 300° C., or about 200° C. to 260° C., about 20000 kPa or less, preferably about 200 kPa to about 5600 kPa. Pressure, WHSV from about 0.1 hr ^-1 to about 50 hr ^-1 , or from about 1 hr ^-1 to about 10 hr ^-1 , and 1:1 to 30:1 moles, preferably about 1: It can be carried out under at least partially liquid phase alkylation conditions comprising a benzene to ethylene ratio in the alkylation reactor of 1 to 10:1 moles.

When benzene is alkylated with propylene to produce cumene, the reaction may be at a temperature of about 250°C or less, preferably about 10°C to about 200°C; A pressure of about 25000 kPa or less, preferably about 100 kPa to about 3000 kPa; And a WHSV of about 1 hr ^-1 to about 250 hr ^-1 , preferably 5 hr ^-1 to 50 hr ^-1 , preferably about 5 hr ^-1 to about 10 hr ^-1 based on ethylene feed. It can be carried out under at least partially liquid alkylation conditions.

At least partially liquid transalkylation conditions may include at least one of the following: a temperature of about 100° C. to about 300° C., or about 100° C. to about 275° C., about 200 kPa to about 600 kPa, or about 200 kPa to about Pressure of 500 kPa, weight space velocity per hour based on total feed (WHSV) from about 0.5 hr ^-1 to about 100 hr ^-1 , and aromatic/poly-alkylated aromatic compound weight ratios from 1:1 to 6:1.

When the poly-alkylated aromatic compound is polyethylbenzene and reacts with benzene to produce ethylbenzene, the transalkylation conditions are based on a temperature of about 220° C. to about 260° C., a pressure of about 300 kPa to about 400 kPa, and the total feed. As a 2-6 hourly weight space rate and a benzene/PEB weight ratio of 2:1 to 6:1.

When the poly-alkylated aromatic compound is poly-isopropylbenzene (PIPB) and reacts with benzene to produce cumene, the transalkylation conditions are at a temperature of about 100° C. to about 200° C., a pressure of about 300 kPa to about 400 kPa, total And a weight space rate of 1 to 10 per hour and a benzene/PIPB weight ratio of 1:1 to 6:1 based on the feed.

Guard layer

In general, the alkylatable aromatic compounds and alkylating agents supplied to the process of the present invention are small enough to enter the pores of the catalyst, preferably the alkylation catalyst and/or the transalkylation catalyst, which is a catalyst poison, such as a nitrogen compound (as defined above). As such) contains some reactive impurities. In addition, it is customary to supply all of the alkylatable aromatic compounds to the first alkylation and/or transalkylation reaction zone, and to supply the alkylation agent divided between the alkylation and/or transalkylation catalyst beds. Therefore, the catalyst in the first reaction zone is more susceptible to poisoning by impurities. Thus, 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 is preferably a separate guard bed in the first alkylation and/or transalkylation reaction zone. ) Is used. Alternatively, the guard layer can be present upstream of the first reaction zone separately. The effluent from the guard bed is, for example, a treated feed such as a treated alkylatable aromatic compound and/or a treated alkylating agent, which is subsequently fed to the process of the 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 treating material to remove at least a portion of any impurities from the alkylatable aromatic compound or the alkylating agent. Include. The treatment material may be selected from the group consisting of clay, resin, activated alumina, molecular sieve, and combinations thereof. Molecular sieves include Linde X, Linde A, zeolite beta, sporesite, zeolite Y, superstability Y (USY), dealuminated Y (Deal Y), rare earth Y (REY), superhydrophobic Y (UHP-Y), It may be selected from the group consisting of mordenite, TEA-mordenite, ZSM-3, ZSM-4, ZSM-14, ZSM-18, ZSM-20, and combinations thereof.

The invention is more specifically disclosed in the numbered paragraphs below.

Paragraph 1. A method of treating a catalyst comprising molecular sieve, comprising heating the catalyst in the presence of a gas stream having a dew point temperature of 5° C. or less to form a treated catalyst.

Paragraph 2. The method of Paragraph 1, wherein the gas stream comprises air.

Paragraph 3. The method of any of the preceding paragraphs, wherein the gas stream comprises oxygen in the range of about 1 v/v% to about 21 v/v%.

Paragraph 4. The method of any preceding paragraph, wherein the gas stream further comprises one or more diluents.

Paragraph 5. The method of Paragraph 4, wherein the diluent is either nitrogen, helium, or a mixture of two or more thereof.

Paragraph 6. The flow rate of the gas stream is at least 1 vol./vol. Catalyst/min, the method of any of the preceding paragraphs.

Paragraph 7. The method of any of the preceding paragraphs, wherein the catalyst is heated for a period of at least 1 hour and no more than about 48 hours.

Paragraph 8. The method of any of the preceding paragraphs, wherein the catalyst is heated to a temperature greater than 300°C and no greater than about 600°C.

Paragraph 9. The method of any preceding paragraph, wherein the catalyst is an acidic catalyst having a proton.

Paragraph 10. The method of any of the preceding paragraphs, wherein the catalyst further comprises greater than 0% to 99% by weight of a binder, based on the weight of the catalyst.

Paragraph 11. The method of Paragraph 10, wherein the binder is a metal or mixed metal oxide.

Paragraph 12. The method of Paragraph 10, wherein the binder is any one of alumina, silica, titania, zirconia, tungsten oxide, ceria, niobia, or a mixture of two or more thereof.

Paragraph 13. The method of any preceding paragraph, wherein said molecular sieve comprises an aluminosilicate.

Paragraph 14. The method of Paragraph 13, wherein the aluminosilicate is any one of an MCM-22 class molecular sieve, sporesite, mordenite, zeolite-beta, or a combination of two or more thereof.

Paragraph 15.MCM-22 class molecular sieves are 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, or any one of a combination of two or more thereof, the method of paragraph 14.

Paragraph 16. A catalyst treated by the method of any of Paragraphs 1-15.

Paragraph 17. A method for producing a mono-alkylated aromatic compound comprising contacting an alkylatable aromatic compound and an alkylating agent with a treated catalyst under at least partially liquid alkylation or transalkylation conditions to produce an effluent comprising the mono-alkylated aromatic compound. Wherein the treated catalyst is prepared by the method of any one of paragraphs 1 to 15, or is the catalyst of paragraph 16.

Paragraph 18. The method of Paragraph 17, further comprising the step of contacting the alkylatable aromatic compound or the alkylating agent with a treatment material to remove at least a portion of any impurities from the alkylatable aromatic compound or the alkylating agent.

Paragraph 19. The method of Paragraph 18, wherein the treating material is any one of clay, resin, activated alumina, molecular sieve, and combinations of two or more of them.

Paragraph 20. Said molecular sieve is Linde X, Linde A, zeolite beta, sporesite, zeolite Y, superstability Y, dealumination Y, rare earth Y, superhydrophobic Y, mordenite, TEA-modenite, ZSM-3 , ZSM-4, ZSM-14, ZSM-18, ZSM-20, or a combination of two or more thereof, the method of paragraph 19.

Paragraph 21. The method of any of paragraphs 17-20, wherein the alkylatable aromatic compound is benzene or toluene or mixtures thereof.

Paragraph 22. The method of any of paragraphs 17 to 21, wherein the alkylating agent comprises an olefin group having 1 to 5 carbon atoms or a poly-alkylated aromatic compound.

Paragraph 23. The method of any of paragraphs 17 to 21, wherein the alkylating agent is either ethylene, propylene or mixtures thereof.

Paragraph 24. The method of any of paragraphs 17-22, wherein the effluent further comprises a poly-alkylated aromatic compound.

Paragraph 25. The method of Paragraph 24, further comprising separating the poly-alkylated aromatic compound from the effluent.

Paragraph 26. Further comprising contacting the poly-alkylated aromatic compound and the additional alkylatable aromatic compound with a transalkylation catalyst under at least partial liquid phase conditions to produce the effluent comprising the additional mono-alkylated aromatic compound. The method of paragraph 25 is to do.

Paragraph 27. Paragraph 26, wherein the transalkylation catalyst comprises an aluminosilicate, and the aluminosilicate is any one of a class MCM-22 molecular sieve, sporesite, mordenite, zeolite-beta, or a combination of two or more thereof. Way.

Paragraph 28.MCM-22 class molecular sieves are 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, or any one of a combination of two or more thereof, the method of paragraph 27.

Paragraph 29. The method of any of paragraphs 17-28, wherein the at least partially liquid phase alkylation conditions comprise a temperature of about 10° C. to about 400° C. and a pressure of about 25000 kPa or less.

Paragraph 30. The method of any one of paragraphs 17-29, wherein the at least partially liquid transalkylation conditions comprise a temperature of about 100°C to about 300°C and a pressure of about 200 kPa to about 600 kPa.

Example

Now, the present invention will be described in more detail with reference to the following examples.

Catalyst preparation

The catalyst contained 80% by weight of MCM-49 and 20% by weight of alumina or MCM-56 and 20% by weight of alumina, which was treated with ammonium nitrate for high temperature treatment in pre-flowing nitrogen and conversion to the acidic form. It has undergone ion exchange. These catalysts were then calcined in dilute air containing varying concentrations of water at high temperatures. The calcination procedure exposed the material to a flow of about 1200 sccm with an oxygen concentration ranging from 1% to 13% using air and a diluent such as nitrogen. In addition, the flow also contained moisture that produced a dew point in the range of -40°F (-40°C) to 80°F (26.7°C). The highest temperature reached during the calcination procedure is generally 1000°F (538°C) or higher. The calcination procedure was the same for all materials reviewed.

Catalyst activity and selectivity evaluation

After catalyst preparation, the activity and selectivity of each aromatic alkylation catalyst was determined by testing the material for benzene alkylation with propylene. The test consisted of charging the dried catalyst with benzene into a batch reactor. The reactor was then heated to 266° F. (130° C.) and then propylene was added under an inert gas pressure of 300 psig (2068.43 kPa). Samples were periodically removed during the test period and analyzed by gas chromatography to determine the activity and selectivity of benzene alkylation with propylene. The activity of the catalyst was assessed by monitoring the conversion of benzene and propylene over time and determining the rate constant (k), which is 10 ³ times the rate constant in units of cc gmol ^-1 hr ^-1 . The selectivity of di-isopropylbenzene (DIPB) and tri-isopropylbenzene (TIPB) of the catalyst was determined by calculating the ratio of DIPB production to cumene and TIPB production to cumene, respectively. Thus, catalysts with lower selectivity for poly-alkylated aromatic compounds such as DIPB and TIPB are more selective catalysts for mono-alkylated aromatic compounds such as cumene.

Table II below shows the effect of the dew point temperature of the air used during the final calcination of the catalyst containing MCM-49 on the DIPB and TIPB/IPB selectivity in the cumene production process. The increase in the moisture content of the air (e.g., higher dew point) during the final calcination of the catalyst compared to the production of isopropylbenzene (IPB), the desired mono-alkylated aromatic compound, di-isopropylbenzene (DIPB), the unwanted poly- Significantly increases the production of alkylated aromatic compounds. When the dew point temperature of the final calcined air is -40° F. (-40° C.), the percent reduction in DIPB/IPB selectivity of the catalyst is more than 37% compared to the dew point temperature of 80° F. (26.7° C.). The same trend was seen in the reduction of the DIPB/IPB selectivity and TIPB/IPB selectivity of the catalyst, with a decrease in the dew point temperature of the final calcined air. Percentage of DIPB/IPB as a function of final calcined air dew point at -20°F (-28.9°C), 0°F (-17.8°C), 20°F (-6.7°C), 40°F (4.4°C) and 60°F (15.6°C) See the data in Table II for the reduction and percent reduction in TIPB/IPB. Thus, significantly more monoselective MCM-49 based catalysts can be produced by treating the catalyst with air having a lower dew point, preferably less than -20° F. (-28.9° C.).

The effect on the relative activity of the MCM-49 containing catalyst used in the cumene production process, depending on the moisture content (eg, dew point) of the final calcined air, is also shown in Table II. As can be seen, the relative activity of the catalyst increased with decreasing moisture. In fact, the percent increase in the relative activity of the catalyst with final calcined air at -40°F (-40°C) was 52% compared to final calcined air at 80°F (26.7°C). The same trend in increasing relative activity was observed with decreasing dew point temperature of the final calcined air. Percentage of relative activity as a function of final calcined air dew point at -20°F (-28.9°C), 0°F (-17.8°C), 20°F (-6.7°C), 40°F (4.4°C), and 60°F (15.6°C) See the data in Table II for the increase. As can be seen, the higher moisture content of the air during the hot calcination treatment (eg at 80° F. (26.7° C.)) not only reduced the monoselectivity of the catalyst, but also reduced the activity of the aromatic alkylation catalyst. Thus, it is possible to produce a material with higher activity by reducing the moisture content of the final air treatment, preferably below 40° F. (4.4° C.).

Similarly, Table III below shows an increase in relative activity with a decrease in the moisture content of the final calcined air for a catalyst containing MCM-56 and DIPB/IPB and TIPB/IPB selectivity (indicating an increase in monoselectivity for the desired cumene product). Indicates a decrease. When the dew point temperature of the final calcined air was -40°F (-40°C), the percent reduction in DIPB/IPB and TIPB/IPB selectivity was 31% and 58.1%, respectively, compared to the dew point temperature of 80°F (26.7°C). The same trend was found in the decrease in the DIPB/IPB selectivity and TIPB/IPB selectivity of the MCM-56-based catalyst, as the dew point temperature of the final calcined air decreased. DIPB/IPB as a function of final calcined air dew point at -20°F (-28.9°C), 0°F (-17.8°C), 20°F (-6.7°C), 40°F (4.4°C), and 60°F (15.6°C) See the data in Table III below for the percent reduction in TIPB/IPB and the percent reduction in TIPB/IPB. Consistent with the previous findings, significantly more monoselective MCM-56 based catalysts can be prepared by treating the catalyst with air with a lower dew point, preferably less than -20°F (-28.9°C). .

As with the MCM-49-based catalyst, the catalyst containing MCM-56 had a 25% increase in relative activity at a dew point of -40°F (-40°C) compared to 80°F (26.7°C). The MCM-56-based catalyst showed the same tendency in increasing the relative activity as the dew point temperature of the final calcined air decreased. Percentage of relative activity as a function of final calcined air dew point at -20°F (-28.9°C), 0°F (-17.8°C), 20°F (-6.7°C), 40°F (4.4°C), and 60°F (15.6°C) See Table III for the increase.

First, by probing the acid site of the catalyst with pyridine and then collidine, and then measuring the adsorption of molecules on the Bronsted acid site by infrared spectroscopy (IR), the final calcined air is -40°F (-40°C) and 0°F ( Advanced characterization of MCM-49-containing catalysts treated at dew point temperatures of -17.8° C.) and 80° F. (26.7° C.) was performed. The catalyst was treated with pyridine to obtain the total amount of Bronsted acid sites (B _Tot ). By replacing pyridine with collidine, the amount of external Bronsted acid site (B _Ext ) was obtained. The IR results in Table IV below show that during the final calcination, as the moisture content of the air increased from -40°F (-40°C) to 80°F (26.7°C), the external Bronsted acid site and the total Bronsted acid site It shows that the amount ratio increases significantly. Further, as shown in Table IV, as the moisture content of the air increased from -40°F (-40°C) to 80°F (26.7°C) during the final calcination, the relative total Bronsted acid site decreased by 50%. MCM-49-based catalysts treated at 40° F. (4.40° C.) and 80° F. (26.7° C.) final calcination dew point temperature air are external to those treated with 0° F. (-17.8° C.) dew point temperature or lower moisture content of air. The ratio of the Bronsted acid site to the total Bronsted acid site was higher. The increase in B _Ext /B _Tot is the preferential loss of the Bronsted acid site within the micropores resulting from dealumination of the zeolite, or 40° F. (4.4), as observed in the 80° F. (26.7° C.) calcined sample. °C) As observed in the calcined sample, it appears to direct the reaction of the alumina binder with the zeolitic component potentially forming an external Bronsted acid site.

Thus, by controlling the moisture content of the air during the final high-temperature calcination to a dew point temperature of 0° F. (-17.8° C.) or a lower temperature, B _Ext /B _Tot is less than 0.19, preferably less than 0.15, with high monoselectivity and high alkylation activity. It has been found that these higher catalysts can be produced.

Certain embodiments and features have been disclosed using an upper set of numerical limits and a set of lower numerical limits. It is to be understood that, unless stated otherwise, ranges from any lower limit to any upper limit are contemplated. Certain lower, upper, and ranges appear in one or more claims below. All numerical values take into account experimental errors and variations predicted by those skilled in the art.

The term “comprising” (and its grammatical variations), as used herein, is not used in the exclusive sense of “consisting of” but in the inclusive sense of “having” or “including”. The singular form, as used herein, is understood to encompass the singular as well as the plural.

Several terms have been defined above. To the extent that a term used in the claims is not defined above, it is to be construed as the broadest definition for which one of ordinary skill in the art has given the term, as reflected in one or more printed publications or issued patents. In addition, all patents, testing procedures, and other documents cited in this application are incorporated by reference in their entirety to the extent that such disclosure is not inconsistent with this application and to all jurisdictions where inclusion thereof is permitted.

The description of the above disclosure is to illustrate and describe the present disclosure. In addition, the present disclosure has presented and described only preferred embodiments, but as mentioned above, the present disclosure may utilize various other combinations, modifications, and environments, and is based on the teachings and/or skills or knowledge in the field. It should be understood that variations or modifications are possible within the scope of the concepts as expressed herein, correspondingly.

Claims (25)

A method for treating a catalyst comprising more than 0% by weight to 99% by weight of a binder and molecular sieve based on the weight of the catalyst, the method comprising: heating the catalyst in the presence of a gas stream having a dew point temperature of 5°C or less , Forming a treated catalyst having a ratio of the amount of external Bronsted acid sites (BExt) to the amount of total Bronsted acid sites (BTot) is less than 0.19,
The molecular sieve is any one of MCM-22 molecular sieve, sporesite, mordenite, zeolite-beta, or a combination of two or more thereof,
The gas stream comprises air and has an oxygen concentration in the range of 1 v/v% to 21 v/v%,
The treatment method of the catalyst is heated to a temperature of more than 300 ℃ 600 ℃ or less for a time of 1 hour or more and 48 hours or less. delete The method of claim 1, wherein the binder is any one of alumina, silica, titania, zirconia, tungsten oxide, ceria, niobia, or a mixture of two or more thereof. The method of claim 1, wherein the MCM-22 class molecular sieve is 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, or any one of a combination of two or more thereof. The treatment method according to claim 1, wherein the catalyst is an acidic catalyst having a proton. delete The ratio of the amount of the external Bronsted acid moiety (B _Ext ) to the amount of the total Bronsted acid moiety (B _Tot ) is the alkylatable aromatic compound comprising the alkylating agent and benzene, under at least partially liquid phase alkylation or transalkylation conditions. A method for producing a mono-alkylated aromatic compound comprising contacting with a treated catalyst of less than 0.19 to produce an effluent comprising a mono-alkylated aromatic compound, wherein the treated catalyst comprises 0 weight based on the weight of the catalyst. % To 99% by weight of a binder and molecular sieve, comprising heating the untreated catalyst in the presence of a gas stream having a dew point temperature of 5° C. or less to form the treated catalyst, The molecular sieve is any one of MCM-22 class molecular sieve, sporesite, mordenite, zeolite-beta, or a combination of two or more of them, and the gas stream contains air and is 1 v/v% to 21 v/v It has an oxygen concentration in the range of %, and the catalyst is heated to a temperature of more than 300° C. and not more than 600° C. for a period of 1 hour or more and 48 hours or less. 8. The method of claim 7, wherein the gas stream further comprises one or more diluents, wherein the diluent is any one of nitrogen, helium, or mixtures thereof. The method of claim 7, wherein the alkylatable aromatic compound or the alkylating agent supplied to the method comprises an impurity, and the method comprises contacting the alkylatable aromatic compound or the alkylating agent with a treatment material to remove at least a portion of the impurities. The method further comprises a step, wherein the treatment material is any one of clay, resin, activated alumina, molecular sieve, and a combination of two or more of them. 8. The method of claim 7, wherein the alkylatable aromatic compound is benzene, the alkylating agent is ethylene, and the mono-alkylated aromatic compound is ethylbenzene. 8. The method of claim 7, wherein the alkylatable aromatic compound is benzene, the alkylating agent is propylene, and the mono-alkylated aromatic compound is cumene. 8. The method of claim 7, wherein the effluent further comprises a poly-alkylated aromatic compound, the method further comprising separating the poly-alkylated aromatic compound from the effluent. The effluent according to claim 12, wherein the poly-alkylated aromatic compound and an additional alkylatable aromatic compound comprising benzene are contacted with a transalkylation catalyst under at least partial liquid phase conditions to contain the additional mono-alkylated aromatic compound. The manufacturing method further comprising the step of producing water. The method of claim 13, wherein the transalkylation catalyst comprises an aluminosilicate, and the aluminosilicate is any one of MCM-22 molecular sieve, sporesite, mordenite, zeolite-beta, or a combination of two or more thereof. Manufacturing method. The method of claim 7, wherein the at least partial liquid phase alkylation conditions include a temperature of 10°C to 400°C and a pressure of 25000 kPa or less, or the at least partial liquid phase transalkylation conditions include a temperature of 100°C to 300°C and a temperature of 200 kPa to The manufacturing method comprising a pressure of 600 kPa. delete delete delete delete delete delete delete delete delete delete