WO2014182440A1 - Régénération de catalyseurs d'alkylation aromatique au moyen de gaz à teneur en hydrogène - Google Patents

Régénération de catalyseurs d'alkylation aromatique au moyen de gaz à teneur en hydrogène Download PDF

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WO2014182440A1
WO2014182440A1 PCT/US2014/035007 US2014035007W WO2014182440A1 WO 2014182440 A1 WO2014182440 A1 WO 2014182440A1 US 2014035007 W US2014035007 W US 2014035007W WO 2014182440 A1 WO2014182440 A1 WO 2014182440A1
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catalyst
hydrogen
mcm
molecular sieve
containing gas
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WO2014182440A8 (fr
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Rainer Kolb
Terry E. Helton
Matthew J. Vincent
Chunshe J. CAO
Dominick A. ZURLO
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Exxonmobil Chemical Patetns Inc.
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • This invention relates to a process for regeneration of an at least partially spent catalyst, preferably an at least partially spent aromatic alkylation or transalkylation catalyst, and a process for alkylating an alkylatable aromatic compound using the regenerated catalyst, in which the at least partially spent catalyst is subjected to regeneration using a hydrogen- containing gas.
  • Zeolite and other porous crystalline molecular sieve catalysts are increasingly being used in low temperature, liquid phase aromatic alkylation processes including ethylbenzene, cumene, and linear polyalkylbenzene synthesis. Operation at lower temperatures improves process economics and, in many cases, product selectivity. However, as in all catalytic processes, the catalyst deactivates with time on stream and needs to be regenerated to recover activity.
  • molecular sieve catalysts commonly known for use as liquid phase alkylation and transalkylation catalysts such as MCM-22 and the related molecular sieves MCM-36, MCM-49 and MCM-56, are uniquely resistant to deactivation by coking, when used in liquid phase alkylation and transalkylation processes, they are susceptible to deactivation as a result of poisons, particularly nitrogen and sulfur compounds, in the feeds.
  • the affinity of these compounds for the active sites in the molecular sieve catalyst can cause rapid deactivation by displacing or neutralizing the acid site.
  • U.S. Patent No. 2,541,044 discloses catalytic alkylation with simultaneous restoration of the alkylation catalyst activity by contacting the catalyst with an alkylatable hydrocarbon while interrupting the flow of alkylating agent.
  • U.S. Patent No. 3,148, 155 describes removing metal poisons from cracking catalysts by contacting the poisoned catalyst with an aqueous solution of sulfurous acid, a water-soluble salt of sulfurous acid or a water- soluble salt of hyposulfurous acid.
  • U.S. Patent No. 4,418,235 provides aromatic alkylation in the presence of steam to enhance or preserve zeolite catalyst activity.
  • 4,550,090 discloses a method for displacing high molecular weight poisons from ZSM-5 catalysts, such as those used in dewaxing, by in-situ treatment with more easily desorbed compounds such as ammonia or by treatment with alkali or alkaline metal cations to effect ion exchange.
  • U.S. Patent No. 4,276, 149 describes passivating metal contaminants on zeolite cracking catalysts by contacting with steam for limited periods.
  • U.S. Patent No. 4,678,764 provides reactivation of noble metal-containing zeolites poisoned with sulfur oxides by contacting with aqueous acid solutions, e.g., nitric, carbon, acetic and formic acids.
  • U.S. Patent No. 5,425,934 teaches treating zeolites with methanol, ethanol or propanol plus nitric or sulfuric acid for the removal of organic templates.
  • U.S. Patent Nos. 4,365, 104 and 4,477,585 disclose enhancing para-selectivity of zeolite alkylation catalysts by treatment with hydrogen sulfide or carbon dioxide.
  • U.S. Patent No. 4,490,570 describes para-selective alkylation of a monoalkylbenzene wherein water in the form of steam can be co-fed with the reactants.
  • U.S. Patent No. 5, 191,135 discloses preparing long chain alkyl substituted aromatic compounds by alkylating naphthalenes with C6+ alkylating agent in the presence of large pore size zeolite such as USY and MCM-22 in the presence of 0.5 to 3.0 wt.% co-fed water to increase selectivity to monoalkyl-substituted products.
  • U.S. Patent No. 5 discloses preparing long chain alkyl substituted aromatic compounds by alkylating naphthalenes with C6+ alkylating agent in the presence of large pore size zeolite such as USY and MCM-22 in the presence of 0.5 to 3.0 wt.% co-fed water to increase selectivity to monoalkyl-substituted products.
  • 6,91 1,568 relates to a process for alkylating an aromatic compound using an alkylation catalyst, in which the spent alkylation catalyst is subjected to regeneration by stripping with a Ci-Cs hydrocarbon.
  • U.S. Patent No. 6,878,654 discloses a process for regenerating a spent aromatics alkylation or transalkylation catalyst comprising a molecular sieve by contacting the spent catalyst with an oxygen-containing gas and then contacting the catalyst with an aqueous medium.
  • 6,909,026 describes a process for liquid phase aromatics alkylation comprising in-situ catalyst reactivation with at least one polar compound having a dipole moment of at least 0.05 Debyes and selected from the group consisting of acetic acid, formic acid, water, and carbon monoxide.
  • the present invention provides a process for regenerating an at least partially spent catalyst comprising a molecular sieve, the process comprising the step of contacting the at least partially spent catalyst with a hydrogen-containing gas under catalyst reactivation conditions.
  • the contacting of the at least partially spent catalyst with the hydrogen-containing gas is conducted in gas phase.
  • the hydrogen-containing gas is free of organic nitrogen containing components.
  • the hydrogen-containing gas is free of sulfur containing components. More preferably, the hydrogen-containing gas is hydrogen.
  • the catalyst reactivation conditions include at least one of the following: (a) a temperature above 300°C, (b) a pressure of about 0.1 to about 1 MPa, and (c) a period of at least 24 hours.
  • the molecular sieve of the catalyst is at least one of a MCM-22 family molecular sieve, faujasite, mordenite, zeolite beta, and zeolite Y.
  • the process further comprises the step of cooling the catalyst treated by the hydrogen-containing gas to room temperature.
  • the present invention encompasses a process for alkylating or transalkylating an alkylatable aromatic compound comprising the step of contacting the alkylatable aromatic compound and an alkylating agent with a regenerated catalyst comprising a molecular sieve under alkylation or trans alkylation conditions, wherein the regenerated catalyst was regenerated by a method comprising the step of contacting an at least partially spent catalyst with a hydrogen-containing gas under catalyst regeneration conditions.
  • the alkylating agent is ethylene, propylene or polyalkylated aromatic compounds and the alkylatable aromatic compound is benzene.
  • the present invention relates to a process for the production of a monoalkylated aromatic compound, particularly ethylbenzene or cumene, by the at least partial liquid phase alkylation of an alkylatable aromatic compound with an alkylating agent in the presence of a regenerated alkylation or a regenerated transalkylation catalyst.
  • the invention is concerned with a process in which, when the alkylation or the transalkylation catalyst has become at least partially spent or deactivated, the catalyst is subjected to an in-situ catalyst regeneration step.
  • the at least partially spent or deactivated catalyst, particularly an alkylation or a transalkylation catalyst is contacted with a hydrogen-containing gas under suitable conditions which effectively regenerate the catalyst.
  • alkylatable aromatic compound as used herein means an aromatic compound that may receive an alkyl group.
  • alkylatable aromatic compound is benzene.
  • alkylating agent means a compound which may donate an alkyl group to an alkylatable aromatic compound.
  • alkylating agent ethylene, propylene, and butylene.
  • Another non-limiting example is any poly- alkylated aromatic compound that is capable of donating an alkyl group to an alkylatable aromatic compound.
  • aromatic in reference to the alkylatable compounds which are useful herein is to be understood in accordance with its art-recognized scope which includes alkyl- substituted and unsubstituted mono-and polynuclear compounds.
  • Compounds of an aromatic character which possess a heteroatom are also useful, provided they do not act as catalyst poisons under the reaction conditions selected.
  • polyalkylated aromatic compound as used herein means an aromatic compound that has more than one alkyl substituent.
  • a non-limiting example of a polyalkylated aromatic compound is poly-alkylated benzene, e.g., di-ethylbenzene, tri- ethylbenzene, di-isopropylbenzene, and tri-isopropylbenzene.
  • Substituted aromatic compounds which can be alkylated herein must possess at least one hydrogen atom directly bonded to the aromatic nucleus.
  • the aromatic rings can be substituted with one or more alkyl, aryl, alkaryl, alkoxy, aryloxy, cycloalkyl, halide, and/or other groups which do not interfere with the alkylation reaction.
  • Suitable aromatic hydrocarbons include benzene, toluene, xylene, naphthalene, anthracene, naphthacene, perylene, coronene and phenanthrene.
  • the alkyl groups which can be present as substituents on the aromatic compound contain from one to about 22 carbon atoms, for example from about one to eight carbon atoms, and in particular from about one to four carbon atoms.
  • Suitable alkyl substituted aromatic compounds include toluene, xylene, isopropylbenzene, normal propylbenzene, alpha-methylnaphthalene, ethylbenzene, cumene, mesitylene, durene, p-cyxene, butylbenzene, pseudocumene, o-diethylbenzene, m- diethylbenzene, p-diethylbenzene, isoainylbenzene, 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-diethyltoluen
  • alkylaromatic hydrocarbons can also be used as starting materials, and these would include aromatic hydrocarbons such as are produced by the alkylation of aromatic hydrocarbons with olefin oligomers.
  • aromatic hydrocarbons such as are produced by the alkylation of aromatic hydrocarbons with olefin oligomers.
  • Such products are frequently referred to in the art as alkylate and include hexylbenzene, nonylbenzene, dodecylbenzene, pentadecylbenzene, hexyltoluene, nonyltoluene, dodecyltoluene, and pentadecyltoluene.
  • alkylate is obtained as a high boiling fraction in which the alkyl group attached to the aromatic nucleus varies in size from about C to about C 12 .
  • cumene or ethylbenzene is the desired product, the present process produces acceptably little by-products such as xy
  • Reformate containing substantial quantities of benzene, toluene and/or xylene constitutes a particularly useful feed for the alkylation process of this invention.
  • the alkylating agents which are useful in the process of this invention generally include any organic compound having at least one available alkylating group capable of reaction with the alkylatable aromatic compound.
  • the alkylating group possesses from 1 to 5 carbon atoms or polyalkylated aromatic compound.
  • Non-limiting examples of suitable alkylating agents are olefins such as ethylene, propylene, the butenes and the pentenes; alcohols (inclusive of monoalcohols, dialcohols, and trialcohols) such as methanol, ethanol, the propanols, the butanols and the pentanols; aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and n-valeraldehyde; and, alkyl halides such as methyl chloride, ethyl chloride, the propyl chlorides, the butyl chlorides and the pentyl chlorides.
  • olefins such as ethylene, propylene, the butenes and the pentenes
  • alcohols inclusivee of monoalcohols, dialcohols, and trialcohols
  • aldehydes such as formaldehyde, acetal
  • alkylating agents are the polyalkylated aromatic compounds.
  • Mixtures of light olefins are especially useful as alkylating agents in the alkylation process of this invention. Accordingly, mixtures of ethylene, propylene, butenes and/or pentenes which are major constituents of a variety of refinery streams, e.g., fuel gas, gas plant off-gas containing ethylene and propylene, naphtha cracker off-gas containing light olefins and refinery FCC propane/propylene streams, are useful alkylating agents herein.
  • a typical FCC light olefin stream possesses the following composition:
  • Reaction products which may be obtained from the process of the invention include ethylbenzene from the reaction of benzene with ethylene, cumene from the reaction of benzene with propylene, ethyltoluene from the reaction of toluene with ethylene, cymenes from the reaction of toluene with propylene, and sec-butylbenzene from the reaction of benzene and n-butenes.
  • the alkylation process of this invention is conducted such that the organic reactants, i.e., the alkylatable aromatic compound and the alkylating agent, are brought into contact with an alkylation catalyst in a suitable reaction zone such as, for example, in a flow reactor containing a fixed bed of the catalyst composition, under effective alkylation conditions.
  • a suitable reaction zone such as, for example, in a flow reactor containing a fixed bed of the catalyst composition, under effective alkylation conditions.
  • Such conditions include a temperature of from about 0°C to about 500°C, and preferably between about 50°C to about 250°C, a pressure of from about 0.2 to about 250 atmospheres (about 20 to about 25330 kPa), and preferably from about 5 to about 100 atmospheres, a molar ratio of alkylatable aromatic compound to alkylating agent of from about 0.1 : 1 to about 50: 1, and preferably can be from about 0.5: 1 to about 10: 1, and a feed weight hourly space velocity (WHSV) of between about 0.1 and 500 hr "1 , preferably between 0.5 and 100 hr "1 .
  • WHSV feed weight hourly space velocity
  • the reactants can be in either the vapor phase or the liquid phase and can be neat, i.e., free from intentional admixture or dilution with other material, or they can be brought into contact with the zeolite catalyst composition with the aid of carrier gases or diluents such as, for example, hydrogen or nitrogen.
  • the alkylation reaction may be carried out in the liquid phase.
  • suitable liquid phase conditions include a temperature between 300°F and 600°F (about 150°C and 316°C), preferably between 400°F and 500°F (about 205°C and 260°C), a pressure up to about 3000 psig (20875 kPa), preferably between 400 and 800 psig (2860 and 5600 kPa), a space velocity between about 0.1 and 20 hr "1 , preferably between 1 and 6 hr "1 , based on the ethylene feed, and a ratio of the benzene to the ethylene in the alkylation reactor from 1 : 1 to 30: 1 molar, preferably from about 1 : 1 to 10: 1 molar.
  • the reaction may also take place under liquid phase conditions including a temperature of up to about 250°C, e.g., a temperature up to about 150°C, e.g., a temperature from about 10°C to about 125°C; a pressure of about 250 atmospheres (25330 kPa) or less, e.g., a pressure from about 1 (101.3 kPa) to about 30 atmospheres (3039.8 kPa); and an aromatic hydrocarbon weight hourly space velocity (WHSV) of from about 5 hr "1 to about 250 hr "1 , preferably from 5 hr "1 to 50 hr " 1 based on the propylene feed.
  • WHSV aromatic hydrocarbon weight hourly space velocity
  • the alkylation catalyst comprises a crystalline molecular sieve preferably selected from MCM-22 family molecular sieves, faujasite, mordenite, zeolite beta (described in detail in U.S. Patent No. 3,308,069), and zeolite Y.
  • MCM-22 family molecular sieve (or "molecular sieve of the MCM-22 family"), as used herein, includes: (i) molecular sieves made from a common first degree crystalline building block "unit cell having the MWW framework topology".
  • a unit cell is a spatial arrangement of atoms which is tiled in three- dimensional space to describe the crystal as described in the "Atlas of Zeolite Framework Types", Fifth edition, 2001, the entire content of which is incorporated as reference; (ii) molecular sieves made from a common second degree building block, a 2-dimensional tiling of such MWW framework type unit cells, forming a "monolayer of one unit cell thickness", preferably one c-unit cell thickness; (iii) molecular sieves made from common second degree building blocks, "layers of one or more than one unit cell thickness", wherein the layer of more than one unit cell thickness is made from stacking, packing, or binding at least two monolayers of one unit cell thick of unit cells having the MWW framework topology.
  • the stacking of such second degree building blocks can be in a regular fashion, an irregular fashion, a random fashion, and any combination thereof; or (iv) molecular sieves made by any regular or random 2-dimensional or 3-dimensional combination of unit cells having the MWW framework topology.
  • the MCM-22 family molecular sieves are characterized by having an X-ray diffraction pattern including d-spacing maxima at 12.4 ⁇ 0.25, 3.57 ⁇ 0.07 and 3.42 ⁇ 0.07 Angstroms (either calcined or as-synthesized).
  • the MCM-22 family molecular sieves may also be characterized by having an X-ray diffraction pattern including d-spacing maxima at 12.4 ⁇ 0.25, 6.9 ⁇ 0.15, 3.57 ⁇ 0.07 and 3.42 ⁇ 0.07 Angstroms (either calcined or as- synthesized).
  • the X-ray diffraction data used to characterize the molecular sieve are obtained by standard techniques using the K-alpha doublet of copper as the incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system.
  • the MCM-22 family molecular sieves include, but are not limited to, MCM-22 (described in detail in U.S. Patent No.
  • the molecular sieve can be combined in conventional manner with an oxide binder, such as alumina, such that the final alkylation catalyst contains between 2 wt.% and 80 wt.% sieve. Alternatively, the molecular sieve can be used in self-bound form that is without a separate oxide binder.
  • the alkylation catalyst will gradually lose its alkylation activity, such that the reaction temperature required to achieve a given performance parameter, for example conversion of the alkylating agent, will increase.
  • the alkylation catalyst is referred to as a "spent" catalyst, or has become at least partially deactivated, i.e., alkylation activity of the catalyst has decreased by some predetermined amount, typically 5-90%, more preferably 20-80% and, most preferably, 40-70%, compared to the initial alkylation activity of the catalyst, the deactivated catalyst is subjected to the regeneration procedure of the present invention.
  • the regeneration procedure of the present invention comprises the step of contacting the at least partially spent catalyst with a hydrogen-containing gas under alkylation or transalkylation catalyst reactivation conditions, preferably in gas phase.
  • a hydrogen-containing gas can be used.
  • the hydrogen-containing gas is free of organic nitrogen containing components and is free of sulfur containing components. More preferably, the hydrogen-containing gas is hydrogen.
  • the alkylation or transalkylation catalyst reactivation conditions include at least one of the following: (a) a temperature above 300°C, preferably about 400°C to 500°C, (b) a pressure of about 0.1 to about 1 MPa, typically at atmospheric pressure, and (c) a period of at least 24 hours, typically about 24 hours.
  • the process further comprises the step of cooling the catalyst treated by the hydrogen-containing gas to room temperature.
  • the catalyst is optionally washed in water or in a water solution comprised of distilled, deionized or demineralized water, and then calcined at a temperature of about 25°C to about 600°C for a period of about 10 minutes to about 48 hours.
  • the regeneration procedure of the present invention is found to be effective in restoring at least about 68% of the original activity of the catalyst, as levels of the heteroatom poisons, particularly nitrogen and sulfur, deposited on the spent catalyst are significantly reduced, while maintaining the monoalkylation selectivity of the catalyst at a level comparable to its fresh state.
  • the process of contacting with the hydrogen-containing gas of the present invention may be repeated a number of times during the lifetime of the alkylation catalyst and, when it fails to achieve the required increase in catalytic activity, the catalyst can be subjected to a conventional air regeneration.
  • the alkylation process of the invention is particularly intended to produce monoalkylated aromatic compounds, such as ethylbenzene and cumene, but the alkylation step will normally produce some polyalkylated aromatic compounds.
  • the process preferably includes the further steps of separating the polyalkylated aromatic compounds from the alkylation effluent and reacting them with additional aromatic feed (i.e., an alkylatable aromatic compound) in a transalkylation reactor over a suitable transalkylation catalyst.
  • the transalkylation catalyst is preferably a molecular sieve which is selective to the production of the desired monoalkylated species and can, for example, employ the same molecular sieve as the alkylation catalyst, such as MCM-22, MCM-49, MCM-36, MCM-56 and zeolite beta.
  • the transalkylation catalyst may be ZSM-5, zeolite X, zeolite Y, and mordenite, such as TEA-mordenite.
  • the transalkylation reaction of the invention is conducted in the liquid phase under suitable conditions such that the polyalkylated aromatics react with the additional aromatic feed to produce additional monoalkylated product.
  • suitable transalkylation conditions include a temperature of about 100°C to about 260°C, a pressure of about 10 bar (1000 kPa) to about 50 bar (5000 kPa), a WHSV of about 1 hr "1 to about 10 hr "1 on total feed, and a benzene/polyalkylated benzene weight ratio of about 1 : 1 to about 6: 1.
  • the transalkylation conditions preferably include a temperature of about 220°C to about 260°C, a pressure of about 20 bar (2000 kPa) to about 30 bar (3000 kPa), a WHSV of about 2 hr "1 to about 6 hr "1 on total feed and a benzene/PEB weight ratio of about 2: 1 to about 6: 1.
  • the transalkylation conditions preferably include a temperature of about 100°C to about 200°C, a pressure of about 20 bar (2000 kPa) to about 30 bar (3000 kPa), a WHSV of about 1 hr "1 to 10 hr _1 on total feed and a benzene/PIPB weight ratio of about 1 : 1 to about 6: 1.
  • transalkylation catalyst As the transalkylation catalyst becomes at least partially deactivated or spent, it may be subjected to the same regeneration process as described above in relation to the alkylation catalyst.
  • Exemplary embodiments can include:
  • a process for regenerating a spent catalyst comprising a molecular sieve comprising the step of contacting the spent catalyst with a hydrogen-containing gas under catalyst reactivation conditions.
  • alkylation or transalkylation catalyst reactivation conditions include at least one of the following: (a) a temperature above 300°C, (b) a pressure of about 0.1 to about 1 MPa, and (c) a period of at least 24 hours.
  • MCM-22 family molecular sieve is at least one of MCM-22, MCM-49, MCM-56, MCM-36, PSH-3, SSZ-25, ERB-1, EMM- 10, EMM- 10-P, EMM-12, EMM- 13, UZM-8, UZM-8HS, ITQ-1, ITQ-2, and ITQ-30.
  • a process for alkylating an aromatic compound comprising the steps of:
  • a process for alkylating an aromatic compound comprising the steps of:
  • said alkylatable aromatic compound is benzene
  • said alkylating agent is ethylene, propylene or polyalkylated aromatic compound
  • the molecular sieve of the catalyst is MCM- 49
  • said step (a) is conducted in liquid phase
  • said step (b) is conducted in gas phase.
  • Catalyst selectivity was determined by the weight ratio of di-isopropyl benzenes produced to cumene produced (DIPB/IPB) and tri-isopropyl benzenes produced to cumene produced (Tri-IPB/IPB) under the reaction conditions (temperature 130°C and pressure 2170 kPa). Relative levels of heteroatoms, including carbon, nitrogen and sulfur, deposited on the catalyst are also provided in normalized percentages.
  • Benzene alkylation with propylene was first conducted using a fresh MCM-49 catalyst with 80 wt.% MCM-49 (as described in U.S. Patent No. 5,236,575) crystal and 20 wt.% alumina in 1/20" quadrulobe extrudate form.
  • One gram of the catalyst was charged to an isothermal well-mixed Parr autoclave reactor along with a mixture comprising benzene (156 g) and propylene (28 g).
  • the reaction was carried out at 130°C and 2170 kPa for 4 hours.
  • a small sample of the product was withdrawn at regular intervals and analyzed by gas chromatography.
  • the catalyst performance was assessed by a kinetic activity rate constant based on propylene conversion and cumene selectivity at 100% propylene conversion, and is shown in Table 1.
  • a spent, 80 wt.% USY (as described in U.S. Patent Nos. 3,293,192 and 3,449,070, and is a form of faujasite) and 20wt.% AI2O 3 catalyst was stripped in hydrogen at a gas hourly space velocity of 300 hr "1 at 200°C, 300°C, 400°C and 500°C for 24 hours in the gas phase. After stripping, the catalyst was cooled to room temperature. The levels of heteroatoms remaining on the regenerated catalyst are shown in Table 4.
  • Monoalkylation selectivity of the regenerated MCM-49-based catalyst was comparable to that of the fresh MCM-49-based catalyst during the regeneration procedure.
  • hot nitrogen treatment of the spent zeolite beta- based alkylation catalyst was more effective at reducing the carbon content of the spent catalysts as compared to hot hydrogen in the 200°C to 500°C temperature range evaluated.
  • hot nitrogen treatment was more effective at temperatures of 400°C and above for reducing the carbon content of the zeolite-beta based catalyst as compared to the spend catalyst.
  • hot hydrogen gas was more effective at reducing the nitrogen levels on the spent zeolite beta-based catalyst as compared to the hot nitrogen gas at temperatures of 300°C and above.
  • the reduction of nitrogen levels using hot hydrogen and hot nitrogen gases were comparable at temperatures of 400°C and 500°C. When evaluated, hot hydrogen and nitrogen gases were both comparable in sulfur removal.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

La présente invention concerne un procédé pour régénérer un catalyseur usé comprenant un tamis moléculaire, le procédé comprend les étapes consistant à mettre en contact ledit catalyseur usé avec un gaz à teneur en hydrogène dans des conditions de réactivation des catalyseurs. Le catalyseur régénéré ainsi formé est, de préférence, utilisé dans des procédés de transalkylation et d'alkylation aromatique.
PCT/US2014/035007 2013-05-09 2014-04-22 Régénération de catalyseurs d'alkylation aromatique au moyen de gaz à teneur en hydrogène WO2014182440A1 (fr)

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WO2017213749A1 (fr) * 2016-06-09 2017-12-14 Exxonmobil Chemical Patents Inc. Procédé de production de composé aromatique mono-alkylé
CN108530246A (zh) * 2017-03-03 2018-09-14 中国石油化工股份有限公司 苯和丙烯生产正丙苯的方法
CN109475859A (zh) * 2016-06-09 2019-03-15 埃克森美孚化学专利公司 单烷基化芳族化合物的制备方法

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TWI634102B (zh) * 2016-06-09 2018-09-01 艾克頌美孚化學專利股份有限公司 芳族烷基化觸媒之處理

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017213749A1 (fr) * 2016-06-09 2017-12-14 Exxonmobil Chemical Patents Inc. Procédé de production de composé aromatique mono-alkylé
KR20190002657A (ko) * 2016-06-09 2019-01-08 엑손모빌 케미칼 패턴츠 인코포레이티드 모노-알킬화 방향족 화합물의 제조 방법
CN109475859A (zh) * 2016-06-09 2019-03-15 埃克森美孚化学专利公司 单烷基化芳族化合物的制备方法
US10821425B2 (en) 2016-06-09 2020-11-03 Exxonmobil Chemical Patents Inc. Treatment of aromatic alkylation catalysts
KR102176960B1 (ko) * 2016-06-09 2020-11-10 엑손모빌 케미칼 패턴츠 인코포레이티드 모노-알킬화 방향족 화합물의 제조 방법
CN109475859B (zh) * 2016-06-09 2022-01-07 埃克森美孚化学专利公司 单烷基化芳族化合物的制备方法
CN108530246A (zh) * 2017-03-03 2018-09-14 中国石油化工股份有限公司 苯和丙烯生产正丙苯的方法
CN108530246B (zh) * 2017-03-03 2021-03-30 中国石油化工股份有限公司 苯和丙烯生产正丙苯的方法

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