WO2013169465A1 - Procédé de production de xylènes - Google Patents

Procédé de production de xylènes Download PDF

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WO2013169465A1
WO2013169465A1 PCT/US2013/037211 US2013037211W WO2013169465A1 WO 2013169465 A1 WO2013169465 A1 WO 2013169465A1 US 2013037211 W US2013037211 W US 2013037211W WO 2013169465 A1 WO2013169465 A1 WO 2013169465A1
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stream
zsm
molecular sieve
aliphatic
hydrocarbon
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PCT/US2013/037211
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English (en)
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Larry L. Iaccino
Glenn C. Wood
Jesus A. RAMOS
Lane L. McMORRIS
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Exxonmobil Chemical Patents Inc.
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Priority claimed from US13/465,766 external-priority patent/US8937205B2/en
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Publication of WO2013169465A1 publication Critical patent/WO2013169465A1/fr

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    • 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
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
    • C07C4/12—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene
    • C07C4/14—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene splitting taking place at an aromatic-aliphatic bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
    • C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
    • C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C10G51/026—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only only catalytic cracking steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C10G51/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only including only thermal and catalytic cracking steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
    • C10G57/005—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process with alkylation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
    • C10G69/123—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step alkylation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics

Definitions

  • the invention relates to a process for the production of xylenes from naphtha feedstocks.
  • Xylene isomers find wide and varied application. They are especially valuable as intermediates in chemical processes.
  • ara-xylene PX
  • MX meto-xylene
  • OX ort/zo-xylene
  • PX is currently the most valuable of the xylene isomers and, although research related to obtaining (e.g., producing or purifying) PX is too voluminous to mention, there is still intensive research in the area.
  • catalytic cracking particularly fluid catalytic cracking (FCC)
  • FCC fluid catalytic cracking
  • U.S. Patent No. 6,635,792 discloses a process for producing BTX and liquefied petroleum gas (LPG) from a hydrocarbon feedstock having boiling points of 30°C to 250°C, such as reformate and pyrolysis gasoline.
  • aromatic components in the hydrocarbon feedstock are converted to BTX-enriched components in the liquid phase through hydrodealkylation and/or transalkylation, and non-aromatic components are converted to LPG-enriched gaseous materials through hydrocracking.
  • the process employs a catalyst comprising platinum/tin or platinum/lead on mordenite, zeolite beta or ZSM-5 and is said to have the advantage of avoiding the need of a solvent extraction step to remove aliphatic compounds from the hydrocarbon feedstock.
  • U.S. Patent Nos. 7,297,831 and 7,301,063 disclose similar processes.
  • U.S. Patent No. 7, 176,339 discloses a process for producing xylenes from reformate, which process comprises: (a) providing a reformate containing hydrogen, C ⁇ to C 5 hydrocarbons, C ⁇ to C 7 hydrocarbons comprising benzene, toluene or mixtures thereof, and Cg+ hydrocarbons; (b) removing at least a portion of said hydrogen from said reformate to produce a product containing C ⁇ to C 7 hydrocarbons comprising benzene, toluene or mixtures thereof, and Cg+ hydrocarbons; and (c) methylating at least a portion of the benzene, toluene, or mixtures thereof present in said product with a methylating agent under vapor phase conditions and in the presence of a catalyst effective for the methylation to produce a resulting product having a higher para-xylsns content than the reformate, wherein the catalyst comprises a zeolite-bound-zeolite catalyst and/or a selectivated
  • U.S. Patent No. 7,563,358 discloses a process for producing BTX-enriched product from a hydrocarbon feed comprising: (a) C ⁇ + non-aromatic cyclic hydrocarbons; (b) Cg+ single-ring aromatic hydrocarbons having at least one alkyl group containing two or more carbon atoms; and (c) C9+ single-ring aromatic hydrocarbons having at least three methyl groups, by contacting the feed in the presence of hydrogen with a catalyst comprising at least one Group VIII metal and a large or intermediate pore molecular sieve having an alpha value, before incorporation of the Group VIII metal, from about 2 to less than 100 under conditions sufficient for (i) forming aromatic hydrocarbons from C ⁇ + non-aromatic cyclic hydrocarbons; (ii) dealkylating Cg+ single-ring aromatic hydrocarbons having at least one alkyl group containing two or more carbon atoms; (iii) transalkylating C9+ single-ring aromatic hydrocarbons having at least three methyl groups
  • U.S. Published Patent Application No. 2009/000988 discloses a process of manufacturing para-xylene, comprising: (a) contacting a pygas feedstock and methylating agent with a catalyst under reaction conditions to produce a product having para-xylene, wherein said product has higher para-xylene content than the para-xylene content of the pygas feedstock; and (f) separating said para-xylene from the product of the step (a), wherein said catalyst comprises a molecular sieve having a Diffusion Parameter for 2,2- dimethylbutane of about 0.1 to 15 sec -1 when measured at a temperature of 120°C and a 2,2- dimethylbutane pressure of 8 kPa-a and said pygas comprises from about 1 wt% to about 65 wt% benzene and from about 5 wt% to 35 wt% toluene.
  • a hydrocarbon upgrading process comprising (a) treating a first hydrocarbon stream in at least one of a steam cracker, catalytic cracker, coker, hydrocracker, reformer, and the like, under suitable conditions to produce a second stream comprising to C[Q+ aromatic hydrocarbons; (b) dealkylating and/or transalkylating and/or cracking (D/T/C) the second stream by contact with a suitable catalyst under suitable reaction conditions to produce a third stream having an increased benzene and/or toluene content compared with the second stream and a light paraffin by-product; and (c) methylating at least a portion of the third stream with a methylating agent to selectively produce para-xylene.
  • this process offers significant advantages in terms of higher petrochemical yields and lower energy consumption as compared with existing processes for enriching the BTX content of hydrocarbon streams.
  • the invention resides in a hydrocarbon upgrading process comprising:
  • said aliphatic hydrocarbons are removed in (c) by solvent extraction or selective adsorption.
  • the second hydrocarbon stream is fractionated, prior to (c), to produce an overhead stream containing C 7 - hydrocarbons and a bottoms stream containing Cg+ hydrocarbons and said aliphatic hydrocarbons are removed from said overhead stream in
  • the catalyst in (d) comprises at least a first and second catalyst compositions, wherein the first catalyst composition comprises a first molecular sieve having a Constraint Index in the range of about 3 to about 12 and at least one metal or compound thereof of Groups 6 to 10 of the Periodic Table of the Elements, and wherein the second catalyst composition comprises a second molecular sieve having a Constraint Index less than
  • the first molecular sieve comprises at least one of ZSM-5, ZSM-1 1, ZSM-22, ZSM-23, ZSM-35, and ZSM-48.
  • the first molecular sieve has an alpha value in the range of 100 to 1500.
  • the second molecular sieve comprises at least one of zeolite beta, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), mordenite, NU-87, ZSM-3, ZSM-
  • the second molecular sieve has an alpha value in the range of
  • the first molecular sieve is ZSM-5 and the second molecular sieve is ZSM-12.
  • the methylating agent comprises methanol.
  • the process further comprises recovering para-xylene from said xylene- enriched stream to leave a ara-xylene-depleted stream. At least part of said ara-xylene- depleted stream may be recycled to (d).
  • the process further comprises feeding additional benzene to (d). At least part of said additional benzene may be removed from said third stream.
  • the invention resides in a hydrocarbon upgrading process comprising:
  • the first hydrocarbon stream is selected from natural gas liquids, natural gas condensate, naphtha, distillate, gas oils, crude oils, and/or resid.
  • Figure 1 is a schematic drawing of part of a hydrocarbon upgrading process according to one embodiment of the present invention.
  • C N hydrocarbon wherein n is a positive integer, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9,
  • C N - hydrocarbon wherein n is a positive integer, e.g., 1, 2,
  • 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, as used herein, means a hydrocarbon having no more than n number of carbon atom(s) per molecule.
  • resid refers to the complex mixture of heavy petroleum compounds otherwise known in the art as residuum or residual.
  • Atmospheric resid is the bottoms product produced in atmospheric distillation where the endpoint of the heaviest distilled product is nominally 650°F (343°C), and is referred to as 650°F + (343°C + ) resid.
  • Vacuum resid is the bottoms product from a column under vacuum where the heaviest distilled product is nominally 1050°F (566°C), and is referred to as 1050°F + (566°C + ) resid.
  • resid means the 650°F + (343°C + ) resid and 1050°F + (566°C + ) resid unless otherwise specified (note that 650°F + resid comprises 1050°F + resid).
  • hydrocarbon upgrading process in which a hydrocarbon feed is treated in at least one of a steam cracker, catalytic cracker, coker, hydrocracker, and reformer under suitable conditions to produce a first stream enriched in olefinic and/or aromatic hydrocarbons.
  • a second stream composed mainly of to C9 aliphatic and aromatic hydrocarbons is separated from the first stream and at least part of the second stream is then supplied to an extraction unit, where aliphatic hydrocarbons are selectively removed to produce an aromatic hydrocarbon-enriched stream.
  • the aromatic hydrocarbon-enriched stream together with ]3 ⁇ 4 is subsequently fed to a catalytic reactor where the Cg+ components of the stream are dealkylated, trans alkylated and/or cracked (D/T/C) in the presence of a catalyst to produce a third stream having an increased benzene and/or toluene content compared with said aromatic hydrocarbon-enriched stream and a light paraffin by-product.
  • the light paraffin by-product is recovered and the benzene and/or toluene are separated from the third stream and are methylated typically by reaction with methanol to produce a xylene- enriched product.
  • said methylation is ara-selective meaning that para-xylene is produced at greater than equilibrium ratio with respect to ortho-xylene and meta-xylene.
  • hydrocarbon feed can comprise a natural gas liquid or condensate, naphtha, gas oil or any distillate fraction of whole crude oil, including in some cases, the residual fraction remaining after an atmospheric or vacuum distillation process (i.e. resid).
  • Treating the hydrocarbon feed in the steam cracker, catalytic cracker, coker, hydrocracker, or reformer produces a first hydrocarbon stream having a broad spectrum of olefinic and aromatic hydrocarbons depending on the initial composition of the hydrocarbon feed and also on the unit used to process the feed.
  • the first hydrocarbon stream is then subjected to one or more separation operations to recover C3- olefins, such as ethylene and propylene, fuel gas and CIQ+ hydrocarbons and leave a second hydrocarbon stream composed mainly to C9 aliphatic and aromatic hydrocarbons.
  • the precise composition of the second hydrocarbon stream will depend on the initial composition of the hydrocarbon feed and on the unit used to process the feed.
  • the second hydrocarbon stream may contain quantities (generally less than 20 wt%) of C5- and CIQ+ hydrocarbons.
  • the second hydrocarbon stream is a pyrolysis gasoline containing from about 15 wt% to about 65 wt% benzene, from about 5 wt% to about 35 wt% toluene, from about 1 wt% to about 15 wt% of Cg+ aromatic compounds and up to 50 wt%, typically about 1 wt% to about 15 wt%, non-aromatics depending on the composition of feedstock to the steam cracker, the intensity of the pyrolysis reaction, and the separation and processing scheme for the pygas stream.
  • Naphthas and gasoils are conventional feedstocks to steam crackers, including virgin and hydrotreated streams.
  • Resid-containing feeds (considerable portion of 1050°F+) can be processed by first passing through the convection section of the steam cracking furnace, then passing to a vapor/liquid separating drum, which can optionally be integrated with the pyrolysis furnace, to drop out the heaviest fraction.
  • part or all of the second hydrocarbon stream undergoes an initial aliphatics extraction step.
  • this requires the addition of a costly aliphatics extraction unit, it has surprisingly been found that the resultant reduction in the level of aliphatics in the feed to the D/T/C and other downstream process units allows the overall capital cost of the system to be reduced.
  • the entire second hydrocarbon stream can be fed to the aliphatics extraction step.
  • the second hydrocarbon stream since the Cg+ portion of the stream typically has a lower non-aromatics content, it is preferable to subject the second hydrocarbon stream to a fractionation step to remove the C 7 - hydrocarbons.
  • the C 7 - overhead fraction is then passed to the aliphatics extraction step and the Cg+ bottoms fraction is fed directly to the D/T/C reactor.
  • the second hydrocarbon stream is subjected to hydrotreating, for example with a cobalt/molybdenum catalyst, to reduce the content of olefins, diolefins, and acetylenes in the second stream prior to aliphatics extraction step.
  • Reduction of the aliphatic content of the second hydrocarbon stream or the effraction thereof can be effected by any known process and especially by solvent extraction or selective adsorption.
  • the product of the aliphatics extraction step is an aliphatic hydrocarbon-depleted stream which, as used herein, is intended to mean a hydrocarbon stream containing less than 20 wt%, such as less than 10 wt%, for example less than 5 wt%, even less than 1 wt% of aliphatic hydrocarbons.
  • the aliphatic hydrocarbons removed by the aliphatics extraction step can then be recycled to a steam cracker, or more preferably are recovered as a product, for example, for use as a gasoline blending stock.
  • the entire aliphatic hydrocarbon-depleted product remaining after removal of the aliphatic component can then be fed to the D/T/C reactor but generally the product is initially passed to a distillation system where at least a toluene-containing fraction is removed from the product and fed to the methylation reactor.
  • a benzene-containing fraction is also removed by the distillation system and can be recovered as a product of the process or fed to the methylation reactor together with the toluene-containing fraction.
  • the feed to the D/T/C reactor is mainly benzene, Cg aromatics and C9 aromatics.
  • Hydrogen is also supplied to the D/T/C reactor.
  • the reactor includes a plurality of different catalyst compositions.
  • the D/T/C catalyst system typically includes a first catalyst composition comprising a first molecular sieve having a Constraint Index in the range of about 3 to about 12 and at least one metal or compound thereof from Groups 6 to 12 of the Periodic Table of the Elements.
  • Constraint Index is a convenient measure of the extent to which an aluminosilicate or other molecular sieve provides controlled access to molecules of varying sizes to its internal structure.
  • molecular sieves which provide a highly restricted access to and egress from its internal structure have a high value for the Constraint Index.
  • Molecular sieves of this kind usually have pores of small diameter, e.g., less than 5 Angstroms.
  • molecular sieves which provide relatively free access to their internal pore structure have a low value for the Constraint Index, and usually pores of large size.
  • the method by which Constraint Index is determined is described fully in U.S. Patent No. 4,016,218, which is incorporated herein by reference for the details of the method including that Constraint Index is determined on the zeolite alone without any treatment to adjust the diffusivity of the catalyst.
  • Suitable molecular sieves for use in the first catalyst composition comprise at least one of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57 and ZSM-58.
  • ZSM- 5 is described in detail in U.S. Patent No. 3,702,886 and Re. 29,948.
  • ZSM-1 1 is described in detail in U.S. Patent. No 3,709,979.
  • ZSM-22 is described in U.S. Patent Nos. 4,556,477 and 5,336,478.
  • ZSM-23 is described in U.S. Patent No. 4,076,842.
  • ZSM-35 is described in U.S. Patent No. 4,016,245.
  • ZSM-48 is more particularly described in U.S. Patent Nos. 4,234,231 and 4,375,573.
  • ZSM-57 is described in U.S. Patent No. 4,873,067.
  • ZSM-58 is described in U.S. Patent No. 4,698,2
  • the first molecular sieve comprises ZSM-5 and especially ZSM-5 having an average crystal size of less than 0. 1 micron, such as about 0.05 micron.
  • the first molecular sieve has an alpha value in the range of about 100 to about 1500, such as about 150 to about 1000, for example about 300 to about 600.
  • Alpha value is a measure of the cracking activity of a catalyst and is described in U.S. Patent No. 3,354,078 and in the Journal of Catalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); and Vol. 61, p. 395 (1980), each incorporated herein by reference as to that description.
  • the experimental conditions of the test used herein include a constant temperature of 538°C and a variable flow rate as described in detail in the Journal of Catalysis, Vol. 61, page 395.
  • the first molecular sieve is an aluminosilicate having a silica to alumina molar ratio of less than 1000, typically from about 10 to about 100.
  • the first catalyst composition comprises at least 1 wt%, preferably at least 10 wt%, more preferably at least 50 wt%, of the first molecular sieve.
  • the first catalyst composition comprises at least a first metal, and generally first and second different metals, or compounds thereof of Groups 6 to 12 of the Periodic Table of the Elements.
  • the first metal is generally selected from platinum, palladium, iridium, rhenium and mixtures thereof, whereas the second metal, if present, is chosen so as to lower the benzene saturation activity of the first metal and is conveniently selected from at least one of copper, silver, gold, ruthenium, iron, tungsten, molybdenum, cobalt, nickel, tin, and zinc.
  • the first metal comprises platinum and said second metal comprises copper.
  • the first metal is present in the first catalyst in amount between about 0.01 wt% and about 5 wt% of the first catalyst and the optional second metal is present in the first catalyst in amount between about 0.01 wt% and about 1 wt% of the first catalyst.
  • the first catalyst composition also comprises a binder or matrix material that is resistant to the temperatures and other conditions employed in the D/T/C reactor.
  • a binder or matrix material that is resistant to the temperatures and other conditions employed in the D/T/C reactor.
  • Such materials include active and inactive materials and synthetic or naturally occurring zeolites, as well as inorganic materials such as clays, silica and/or metal oxides such as alumina.
  • the inorganic material may be either naturally occurring, or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.
  • Use of a binder or matrix material which itself is catalytically active may change the conversion and/or selectivity of the catalyst composition.
  • Inactive materials suitably serve as diluents to control the amount of conversion so that transalkylated products can be obtained in an economical and orderly manner without employing other means for controlling the rate of reaction.
  • These catalytically active or inactive materials may include, for example, naturally occurring clays, e.g., bentonite and kaolin, to improve the crush strength of the catalyst composition under commercial operating conditions.
  • Naturally occurring clays that can be composited with the first molecular sieve as a binder for the first catalyst composition include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia, and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite.
  • Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
  • the first molecular sieve can be composited with a porous matrix binder material, such as an inorganic oxide selected from the group consisting of silica, alumina, zirconia, titania, thoria, beryllia, magnesia, and combinations thereof, such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, as well as ternary compositions such as silica-alumina-thoria, silica-alumina- zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia. It may also be advantageous to provide at least a part of the foregoing porous matrix binder material in colloidal form so as to facilitate extrusion of the catalyst composition.
  • a porous matrix binder material such as an inorganic oxide selected from the group consisting of silica, a
  • the first molecular sieve is admixed with the binder or matrix material so that the first catalyst composition contains the binder or matrix material in an amount ranging from 5 wt% to 95 wt%, and typically from 10 wt% to 60 wt%.
  • the first catalyst bed composition is effective to dealkylate Cg+ single-ring aromatic hydrocarbons having at least one alkyl group containing two or more carbon atoms in the D/T/C feed.
  • exemplary reactions proceeding in the presence of the first catalyst composition are cracking of ethyltoluene, ethylxylene and cumene to toluene, xylene and benzene respectively.
  • the cracking is of course accompanied by production of ethylene and propylene but these are immediately hydrogenated to the corresponding alkanes.
  • the D/T/C catalyst system also includes a second catalyst composition comprising a second molecular sieve having a Constraint Index less than 3 and optionally one or more metals or compounds thereof of Groups 6 to 12 of the Periodic Table of the Elements.
  • Suitable molecular sieves for use in the second catalyst composition comprise at least one of zeolite beta, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), mordenite, MJ-87, ZSM-3, ZSM-4 (Mazzite), ZSM-12, ZSM-18, MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, EMM- 10, EMM-10-P and ZSM-20.
  • Zeolite ZSM-4 is described in U.S. Patent No. 3,923,636.
  • Zeolite ZSM-12 is described in U.S. Patent No. 3,832,449.
  • Zeolite ZSM-20 is described in U.S. Patent No. 3,972,983.
  • Zeolite Beta is described in U.S. Patent Nos. 3,308,069, and Re. No. 28,341.
  • Low sodium Ultrastable Y molecular sieve (USY) is described in U.S. Patent Nos. 3,293, 192 and 3,449,070.
  • Dealuminized Y zeolite (Deal Y) may be prepared by the method found in U.S. Patent No. 3,442,795.
  • Zeolite UHP-Y is described in U.S. Patent No. 4,401,556.
  • Rare earth exchanged Y (REY) is described in U.S. Patent No. 3,524,820.
  • Mordenite is a naturally occurring material but is also available in synthetic forms, such as TEA-mordenite (i.e., synthetic mordenite prepared from a reaction mixture comprising a tetraethylammonium directing agent).
  • TEA-mordenite is disclosed in U.S. Patent Nos. 3,766,093 and 3,894, 104.
  • MCM-22 is described in U.S. Patent No. 4,954,325.
  • PSH-3 is described in U.S. Patent No. 4,439,409.
  • SSZ-25 is described in U.S. Patent No. 4,826,667.
  • MCM-36 is described in U.S. Patent No. 5,250,277.
  • MCM-49 is described in U.S. Patent No. 5,236,575.
  • MCM-56 is described in U.S. Patent No. 5,362,697.
  • the second molecular sieve comprises ZSM-12 and especially ZSM-12 having an average crystal size of less than 0.1 micron, such as about 0.05 micron.
  • the second molecular sieve has an alpha value of at least 20, such as from about 20 to about 500, for example from about 30 to about 100.
  • the second molecular sieve is an aluminosilicate having a silica to alumina molar ratio of less than 500, typically from about 50 to about 300.
  • the second catalyst composition comprises at least 1 wt%, preferably at least 10 wt%, more preferably at least 50 wt%, and most preferably at least 65 wt%, of the second molecular sieve.
  • the second catalyst composition comprises at least one and preferably at least two metals or compounds thereof of Groups 6 to 12 of the Periodic Table of the Elements.
  • the second catalyst composition comprises the same first and second metals present in the same amounts as contained by the first catalyst composition.
  • the second catalyst composition also contains a binder or matrix material, which can be any of the materials listed as being suitable for the first catalyst and can be present in an amount ranging from 5 wt% to 95 wt%, and typically from 10 wt% to 60 wt%, of the second catalyst composition.
  • a binder or matrix material which can be any of the materials listed as being suitable for the first catalyst and can be present in an amount ranging from 5 wt% to 95 wt%, and typically from 10 wt% to 60 wt%, of the second catalyst composition.
  • the weight ratio of the first catalyst composition to the second catalyst composition is typically in the range of 5:95 to 75:25.
  • the second catalyst composition is effective to transalkylate C9+ single-ring aromatic hydrocarbons having at least three methyl groups in the D/T/C feed.
  • an exemplary reaction proceeding in the presence of the second catalyst composition is trans alky lation of xylene with benzene to produce two molecules of toluene.
  • the D/T/C catalyst system includes a third catalyst composition comprising a third molecular sieve having a Constraint Index from about 1 to 12.
  • Suitable molecular sieves for use in the third catalyst comprise at least one of ZSM-5, ZSM-1 1, ZSM- 12, zeolite beta, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, and ZSM-58, with ZSM-5 being preferred.
  • the third catalyst composition also contains a binder or matrix material, which can be any of the materials listed as being suitable for the first catalyst and can be present in an amount ranging from 5 wt% to 95 wt%, and typically from 10 wt% to 60 wt%, of the third catalyst composition.
  • a binder or matrix material which can be any of the materials listed as being suitable for the first catalyst and can be present in an amount ranging from 5 wt% to 95 wt%, and typically from 10 wt% to 60 wt%, of the third catalyst composition.
  • the third catalyst composition is effective to crack non-aromatic cyclic hydrocarbons in the effluent from the first and second catalyst beds.
  • the third catalyst composition is effective to crack benzene co-boilers, such as cyclohexane, so as to facilitate the recovery of a high purity benzene product from the D/T/C effluent.
  • the D/T/C catalyst system comprises (a) a first catalyst composition comprising a 50 wt% ZSM-5:50 wt% AI2O3 extrudate which has been impregnated with 0.115 wt% Pt and steamed to a target alpha value of 350; (b) a second catalyst composition comprising a 65 wt% ZSM-12:35 wt% AI2O3 extrudate which has been impregnated with 0.1 wt% Pt; and (c) a third catalyst composition comprising a metal-free 65 wt% ZSM-5 :35 wt% A1 2 0 3 extrudate.
  • the D/T/C catalyst system comprises (a) a first catalyst composition comprising a 50 wt% ZSM-5:50 wt% AI2O3 extrudate which has been impregnated with 0.1 15 wt% Pt and 0.0375 wt% copper and steamed to a target alpha value of 350; (b) a second catalyst composition comprising a 65 wt% ZSM-12:35 wt% AI2O3 extrudate which has been impregnated with 0.1 wt% Pt and 0.0326 wt% copper; and (c) a third catalyst composition comprising a metal-free 65 wt% ZSM-5:35 wt% AI2O3 extrudate.
  • the various catalyst compositions may be contained within a single bed; mounted within multiple beds in a single reactor, or located within multiple reactor shells.
  • the product of the D/T/C reactor is a third hydrocarbon stream having an increased molar concentration of benzene and/or toluene as compared with the feed and a C3- paraffin by-product, which is recovered for use as fuel or sent to a steam cracker as supplemental feed.
  • the third hydrocarbon stream is fed to a distillation system where the stream is divided into at least a toluene-containing fraction is removed from the product and fed to the methylation reactor.
  • a benzene-containing fraction is also removed by the distillation system and can be recovered as a product of the process or fed to the methylation reactor together with the toluene-containing fraction.
  • the toluene and, where present, benzene removed from the third hydrocarbon stream is fed to a methylation reactor where the aromatic feed is methylated, generally with methanol in the presence of a specific zeolite catalyst at a temperature between about 500°C and about 700°C, preferably between about 500°C and about 600°C, a pressure of between about 1 atmosphere and 1000 psig (100 kPa and 7000 kPa), a weight hourly space velocity of between about 0.5 and 1000, and a molar ratio of toluene to methanol (in the reactor charge) of at least about 0.2, e.g., from about 0.2 to about 20.
  • the process is preferably conducted in the presence of added water such that the molar ratio of water to benzene/toluene + methanol in the feed is between about 0.01 and about 10.
  • the zeolite catalyst employed in the alkylation process is selected to have a Diffusion Parameter for 2,2-dimethylbutane of about 0.1 to 15 sec -1 , and preferably 0.5 to 10 sec -1 , when measured at a temperature of 120°C and a 2,2-dimethylbutane pressure of 60 torr (8 kPa).
  • the Diffusion Parameter of a particular porous crystalline material is defined as D/r 2 x 10 6 , wherein D is the diffusion coefficient (cm 2 /sec) and r is the crystal radius (cm).
  • the required diffusion parameters can be derived from sorption measurements provided the assumption is made that the plane sheet model describes the diffusion process.
  • the value Q/Q ⁇ is mathematically related to (Dt/r 2 ) 1/2 where t is the time (sec) required to reach the sorbate loading Q, D is the diffusion coefficient (cm 2 /sec) and r is the crystal radius (cm).
  • t is the time (sec) required to reach the sorbate loading Q
  • D is the diffusion coefficient (cm 2 /sec)
  • r is the crystal radius (cm).
  • Medium pore zeolites are generally defined as those having a pore size of about 5 to 7 Angstroms, such that the zeolite freely sorbs molecules such as n- hexane, 3-methylpentane, benzene, and p-xylene.
  • medium pore zeolites have a Constraint Index of about 3 to 12, as measured on the zeolite alone without the introduction of oxide modifiers and prior to any steaming to adjust the diffusivity of the catalyst.
  • suitable medium pore zeolites include ZSM-5, ZSM-1 1, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, and MCM-22, with ZSM-5 and ZSM-1 1 being particularly preferred.
  • the medium pore zeolites described above are preferred for the present alkylation process since the size and shape of their pores favor the production of p-xylene over the other xylene isomers.
  • conventional forms of these zeolites have Diffusion Parameter values in excess of the 0.1 to 15 sec -1 range referred to above.
  • the required diffusivity for the catalyst can be achieved by severely steaming the catalyst so as to effect a controlled reduction in the micropore volume of the catalyst to not less than 50%, and preferably 50% to 90%, of that of the unsteamed catalyst.
  • Reduction in micropore volume is derived by measuring the n-hexane adsorption capacity of the catalyst, before and after steaming, at 90°C and 75 torr n-hexane pressure.
  • Steaming of the zeolite is effected at a temperature of at least about 950°C, preferably about 950°C to about 1075°C, and most preferably about 1000°C to about 1050°C for about 10 minutes to about 10 hours, preferably from 30 minutes to 5 hours.
  • the zeolite prior to steaming, with at least one oxide modifier, preferably selected from oxides of the elements of Groups IIA, IIIA, IIIB, IVA, IVB, VA, and VIA of the Periodic Table (IUPAC version).
  • said at least one oxide modifier is selected from oxides of boron, magnesium, calcium, lanthanum and most preferably phosphorus.
  • the total amount of oxide modifier present in the catalyst may be between about 0.05 wt% and about 20 wt%, and preferably is between about 0.1 wt% and about 10 wt%, based on the weight of the final catalyst.
  • the modifier includes phosphorus
  • incorporation of modifier into the catalyst is conveniently achieved by the methods described in U.S. Patent Nos. 4,356,338; 5, 110,776; 5,231,064; and 5,348,643, the entire disclosures of which are incorporated herein by reference.
  • Treatment with phosphorus-containing compounds can readily be accomplished by contacting the zeolite, either alone or in combination with a binder or matrix material, with a solution of an appropriate phosphorus compound, followed by drying and calcining to convert the phosphorus to its oxide form.
  • Contact with the phosphorus-containing compound is generally conducted at a temperature of about 25°C and about 125°C for a time between about 15 minutes and about 20 hours.
  • the concentration of the phosphorus in the contact mixture may be between about 0.01 wt% and about 30 wt%.
  • Suitable phosphorus compounds include, but are not limited to, phosphonic, phosphinous, phosphorus and phosphoric acids, salts and esters of such acids and phosphorous halides.
  • the porous crystalline material may be dried and calcined to convert the phosphorus to an oxide form. Calcination can be carried out in an inert atmosphere or in the presence of oxygen, for example, in air at a temperature of about 150°C to 750°C, preferably about 300°C to 500°C, for at least 1 hour, preferably 3 to 5 hours. Similar techniques known in the art can be used to incorporate other modifying oxides into the catalyst employed in the alkylation process.
  • the catalyst employed in the alkylation process may include one or more binder or matrix materials resistant to the temperatures and other conditions employed in the process.
  • binder or matrix materials resistant to the temperatures and other conditions employed in the process.
  • Such materials include active and inactive materials such as clays, silica and/or metal oxides such as alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.
  • active materials such as clays, silica and/or metal oxides such as alumina.
  • the latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.
  • Use of a material which is active tends to change the conversion and/or selectivity of the catalyst and hence is generally not preferred.
  • Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate of reaction.
  • These materials may be incorporated into naturally occurring clays, e.g., bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions.
  • Said materials i.e., clays, oxides, etc., function as binders for the catalyst. It is desirable to provide a catalyst having good crush strength because in commercial use it is desirable to prevent the catalyst from breaking down into powder-like materials.
  • These clay and/or oxide binders have been employed normally only for the purpose of improving the crush strength of the catalyst.
  • Naturally occurring clays which can be composited with the porous crystalline material include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia, and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite.
  • Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment, or chemical modification.
  • the porous crystalline material can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica- zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia, and silica-magnesia- zirconia.
  • a porous matrix material such as silica-alumina, silica-magnesia, silica- zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia, and silica-magnesia- zirconia.
  • the relative proportions of porous crystalline material and inorganic oxide matrix vary widely, with the content of the former ranging from about 1 wt% to about 90 wt% and more usually, particularly when the composite is prepared in the form of beads, in the range of about 2 wt% to about 80 wt% of the composite.
  • the matrix material comprises silica or a kaolin clay.
  • the alkylation catalyst used in the present process may optionally be precoked.
  • the precoking step is preferably carried out by initially utilizing the uncoked catalyst in the toluene methylation reaction, during which coke is deposited on the catalyst surface and thereafter controlled within a desired range, typically from about 1 wt% to about 20 wt% and preferably from about 1 wt% to about 5 wt%, by periodic regeneration by exposure to an oxygen-containing atmosphere at an elevated temperature.
  • One of the advantages of the catalyst described herein is its ease of regenerability.
  • the catalyst after the catalyst accumulates coke as it catalyzes the toluene methylation reaction, it can easily be regenerated by burning off a controlled amount of coke in a partial combustion atmosphere in a regenerator at temperatures in the range of from about 400°C to about 700°C.
  • the coke loading on the catalyst may thereby be reduced or substantially eliminated in the regenerator.
  • the regeneration step may be controlled such that the regenerated catalyst returning to the toluene methylation reaction zone is coke-loaded at the desired level.
  • the present process may suitably be carried out in fixed, moving, or fluid catalyst beds. If it is desired to continuously control the extent of coke loading, moving or fluid bed configurations are preferred. With moving or fluid bed configurations, the extent of coke loading can be controlled by varying the severity and/or the frequency of continuous oxidative regeneration in the catalyst regenerator.
  • toluene can be alkylated with methanol so as to produce para-xylene at a selectivity of at least about 80 wt% (based on total Cg aromatic product) at a per-pass toluene conversion of at least about 15 wt% and a trimethylbenzene production level less than 1 wt%.
  • the olefin-rich light gas by-product may be recovered in a dedicated olefins recovery unit or routed to a steam cracker olefins recovery section. Unreacted toluene, methanol and a portion of the water product may be recycled to the methylation reactor and heavy byproducts routed to fuels dispositions.
  • the Cs fraction is routed to a para-xylene recovery unit, which typically operates by fractional crystallization or by selective adsorption (e.g., Parex or Eluxyl) to recover a para-xylene product stream from the alkylation effluent and leave a ara-xylene-depleted stream containing mainly C 7 and Cg hydrocarbons.
  • the ara-xylene-depleted stream is conveniently recycled to the D/T/C reactor, generally after removal of any toluene for recycle to methylation step.
  • the para-xylene- depleted stream may be isomerized and recycled to the para-xylene recovery unit.
  • a to C9 aliphatic and aromatic hydrocarbon product from a steam cracker (not shown) is fed by line 11 to a first fractionation system 12, where the product is separated into an overhead stream containing C 7 - hydrocarbons and a bottoms stream containing Cg+ hydrocarbons.
  • the C 7 - overhead stream is then fed by line 13 to a solvent extraction unit 14, while the Cg+ bottoms stream is fed by line 15 to a D/T/C reactor 16.
  • the solvent extraction unit 14 removes aliphatic hydrocarbons from the C 7 - overhead stream to leave an aliphatic hydrocarbon-depleted stream which is fed by line 17 to a second fractionation system 18.
  • the aliphatic hydrocarbons removed by the extraction unit 14 are recovered and fed by line 36 either for recycle to the steam cracker or for use as a gasoline blending stock.
  • the second fractionation system 18 also receives the C ⁇ + product stream from the D/T/C reactor 16 and a ara-xylene-depleted effluent stream from a methylation reactor 19.
  • the second fractionation system 18 divides these various hydrocarbon streams into a benzene-rich stream in first overhead line 21, a toluene-rich steam in second overhead line 22, a Cg and C ⁇ rich steam in first bottoms line 23 and a C ⁇ +'rich stream in second bottoms line 24.
  • the toluene-rich steam in second overhead line 22 and part of the benzene-rich stream in first overhead line 21 are fed together with methanol in line 25 to the methylation reactor 19 where the benzene and toluene are converted to xylenes.
  • the xylene-enriched effluent stream from the methylation reactor 19 is then fed by line 26 to a para-xylsns recovery unit 27, where a para-xylene product stream is recovered in line 28, to leave a para-xylene- depleted stream which is recycled to the second fractionation system 18 via line 29.
  • the methylation reactor 19 also produces an olefin-rich light gas, which is recovered by line 31 and can be combined with the light olefins produced in the steam cracker.
  • the Cg and Cg-rich steam in first bottoms line 23 is fed with the Cg+ bottoms stream in line 15 to the D/T/C reactor 16, which also receives part of the benzene-rich stream in first overhead line 21 via slipstream 32 and also receives make-up hydrogen via line 33.
  • the D/T/C reactor 16 converts the various Cg and C9 hydrocarbons in the lines 15 and 23 to a product enriched in benzene and/or toluene and a light paraffin by-product.
  • the benzene and/or toluene-enriched product is recycled by line 34 to the second fractionation system 18, whereas the light paraffin by-product is recovered in line 35 for use as a fuel.
  • this invention relates to:
  • a hydrocarbon upgrading process comprising:
  • the catalyst in (d) comprises at least a first and second catalyst composition
  • the first catalyst composition comprising a first molecular sieve having a Constraint Index in the range of about 3 to about 12 and at least one metal or compound thereof of Groups 6 to 10 of the Periodic Table of the Elements
  • the second catalyst composition comprising a second molecular sieve having a Constraint Index less than 3 and at least one metal or compound thereof of Groups 6 to 10 of the Periodic Table of the Elements.
  • said first molecular sieve comprises at least one of ZSM-5, ZSM-1 1, ZSM-22, ZSM-23, ZSM-35, and ZSM-48.
  • said second molecular sieve comprises at least one of zeolite beta, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), mordenite, NU-87, ZSM-3, ZSM-4 (Mazzite), ZSM-12, ZSM-18, MCM-22, MCM-36, MCM-49, MCM-56, EMM-10, EMM-10-P, and ZSM-20.
  • hydrocarbon feed is selected from natural gas liquids, natural gas condensate, naphtha, distillate, gas oils, crude oils, and/or resid.
  • a hydrocarbon upgrading process comprising:
  • the catalyst in (f) comprises at least a first and second catalyst composition, wherein the first catalyst composition comprising a first molecular sieve having a Constraint Index in the range of about 3 to about 12 and at least one metal or compound thereof of Groups 6 to 10 of the Periodic Table of the Elements, and wherein the second catalyst composition comprising a second molecular sieve having a Constraint Index less than 3 and at least one metal or compound thereof of Groups 6 to 10 of the Periodic Table of the Elements.
  • said first molecular sieve comprises at least one of ZSM-5, ZSM-1 1, ZSM-22, ZSM-23, ZSM-35, and ZSM-48.
  • said second molecular sieve comprises at least one of zeolite beta, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), mordenite, NU-87, ZSM-3, ZSM-4 (Mazzite), ZSM-12, ZSM-18, MCM-22, MCM-36, MCM-49, MCM-56, EMM-10, EMM-10-P, and ZSM-20.
  • hydrocarbon feed is selected from natural gas liquids, natural gas condensate, naphtha, distillate, gas oils, crude oils, and/or resid.
  • Table 1 provides the estimated aromatics material balance for a hydrocarbon upgrading process as described in our co-pending U.S. Application Serial No. 13/303,855, filed November 23, 201 1 (which claims the benefit of and priority to USSN 61/421,917 filed December 10, 2010), in which the entire to C9 aliphatic and aromatic hydrocarbon feed from the steam cracker is fed to the D/T/C reactor without removal of the C 7 - aliphatic component. All amounts specified in Table 1 are in kilotons per annum (kTa).
  • Table 2 provides the estimated aromatics material balance for a hydrocarbon upgrading process as described in Example 1 but with extraction of the C 7 - aliphatic component before the D/T/C step.
  • Example 1 required 45.5 kTa of make-up hydrogen and produced 133.5 kTa of low value LPG, with the hydrogen purge being 167.2 kTa.
  • the process of Example 2 required only 23.3 kTa of make-up hydrogen and produced only 86.7 kTa of low value LPG and 244.2 kTa of higher value C 7 - aliphatics, with the hydrogen purge being only 54.7 kTa.
  • the process of Example 2 produced 626.5 kTa of ara-xylene product as compared with only 617.4 kTa in Example 1.
  • Example 3 provides the results of conducting the D/T/C reaction on two different feeds, one being substantially entirely aromatic and the other containing 83.6 wt% aromatics and 16.4 wt% non-aromatics.
  • the reaction was conducting using 30 gm of a dual bed catalyst composed of (a) 90 wt% of a first catalyst comprising a 50 wt% ZSM-5:50 wt% AI2O3 extrudate impregnated with 0.1 15 wt% Pt and steamed to a target alpha value of 350 and (b) 10 wt% of a second comprising a 65 wt% ZSM-12:35 wt% A1 2 0 3 extrudate impregnated with 0.1 wt% Pt. Details and results of the tests are summarized in Table 3 and show significantly higher light gas make with the non-aromatic containing feed and higher hydrogen consumption with the non-aromatic containing feed.
  • compositions, an element or a group of elements are preceded with the transitional phrase “comprising”, it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of, “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.
  • the term “comprising” encompasses the terms “consisting essentially of,” “is,” and “consisting of and anyplace “comprising” is used “consisting essentially of,” “is,” or consisting of may be substituted therefor.

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Abstract

L'invention concerne un procédé de valorisation d'hydrocarbures, dans lequel une charge d'hydrocarbures est traitée dans un vapocraqueur, et/ou un craqueur catalytique, et/ou un cokeur, et/ou un hydrocraqueur, et/ou un reformeur, dans des conditions appropriées pour produire un premier flux comprenant des hydrocarbures oléfiniques et aromatiques. Un deuxième flux comprenant des hydrocarbures aliphatiques et aromatiques C6-C9 est récupéré dans le premier flux et les hydrocarbures aliphatiques sont retirés d'au moins une partie du deuxième flux pour produire un flux pauvre en hydrocarbures aliphatiques. Le flux pauvre en hydrocarbures aliphatiques est ensuite désalkylé et/ou transalkylé et/ou craqué (D/T/C) par contact avec un catalyseur, dans des conditions de réaction appropriées pour produire un troisième flux présentant une teneur en benzène et/ou en toluène accrue par comparaison avec ledit flux pauvre en hydrocarbure aliphatique et contenant un sous-produit de paraffine légère. Le benzène et/ou le toluène provenant du troisième flux est/sont ensuite méthylé(s) avec un agent de méthylation pour produire un courant enrichi en xylène.
PCT/US2013/037211 2012-05-07 2013-04-18 Procédé de production de xylènes WO2013169465A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017052858A1 (fr) * 2015-09-25 2017-03-30 Exxonmobile Chemical Patents Inc. Conversion d'hydrocarbure non-aromatique
US10196329B2 (en) 2014-11-21 2019-02-05 Exxonmobil Chemical Patents Inc. Process for making para-xylene
CN111072445A (zh) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 由甲苯和甲醇合成二甲苯的工艺方法
WO2021082579A1 (fr) * 2019-10-30 2021-05-06 中国石油化工股份有限公司 Procédé de production de composé aromatique léger
US11192834B2 (en) 2018-06-25 2021-12-07 Sabic Global Technologies B.V. Process and system for producing para-xylene

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5932777A (en) * 1997-07-23 1999-08-03 Phillips Petroleum Company Hydrocarbon conversion
US20030105372A1 (en) * 2001-06-15 2003-06-05 Xiaobing Feng Process for selectively producing aromatic compounds
US20040049093A1 (en) * 1999-09-30 2004-03-11 Phillips Petroleum Company Hydrocarbon upgrading process
US20060194996A1 (en) * 2005-02-28 2006-08-31 Umansky Benjamin S Liquid phase aromatics alkylation process
US20100040517A1 (en) * 2007-06-28 2010-02-18 Stephen Harold Brown Process Of Manufacturing Para-Xylene

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5932777A (en) * 1997-07-23 1999-08-03 Phillips Petroleum Company Hydrocarbon conversion
US20040049093A1 (en) * 1999-09-30 2004-03-11 Phillips Petroleum Company Hydrocarbon upgrading process
US20030105372A1 (en) * 2001-06-15 2003-06-05 Xiaobing Feng Process for selectively producing aromatic compounds
US20060194996A1 (en) * 2005-02-28 2006-08-31 Umansky Benjamin S Liquid phase aromatics alkylation process
US20100040517A1 (en) * 2007-06-28 2010-02-18 Stephen Harold Brown Process Of Manufacturing Para-Xylene

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10196329B2 (en) 2014-11-21 2019-02-05 Exxonmobil Chemical Patents Inc. Process for making para-xylene
WO2017052858A1 (fr) * 2015-09-25 2017-03-30 Exxonmobile Chemical Patents Inc. Conversion d'hydrocarbure non-aromatique
CN108137434A (zh) * 2015-09-25 2018-06-08 埃克森美孚化学专利公司 非芳族烃的转化
US10059641B2 (en) 2015-09-25 2018-08-28 Exxonmobil Chemical Patents Inc. Conversion of non-aromatic hydrocarbon
CN108137434B (zh) * 2015-09-25 2020-07-03 埃克森美孚化学专利公司 非芳族烃的转化
US11192834B2 (en) 2018-06-25 2021-12-07 Sabic Global Technologies B.V. Process and system for producing para-xylene
CN111072445A (zh) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 由甲苯和甲醇合成二甲苯的工艺方法
CN111072445B (zh) * 2018-10-18 2022-07-12 中国石油化工股份有限公司 由甲苯和甲醇合成二甲苯的工艺方法
WO2021082579A1 (fr) * 2019-10-30 2021-05-06 中国石油化工股份有限公司 Procédé de production de composé aromatique léger
US12054680B2 (en) 2019-10-30 2024-08-06 China Petroleum & Chemical Corporation Method for producing light aromatic

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