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WO1993002025A1 - Oligomerisation d'olefines par catalyse a lit fluidise - Google Patents

Oligomerisation d'olefines par catalyse a lit fluidise Download PDF

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Publication number
WO1993002025A1
WO1993002025A1 PCT/US1991/005161 US9105161W WO9302025A1 WO 1993002025 A1 WO1993002025 A1 WO 1993002025A1 US 9105161 W US9105161 W US 9105161W WO 9302025 A1 WO9302025 A1 WO 9302025A1
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WO
WIPO (PCT)
Prior art keywords
catalyst particles
reaction zone
primary
stream
hydrocarbons
Prior art date
Application number
PCT/US1991/005161
Other languages
English (en)
Inventor
Mohsen Nadimi Harandi
Hartley Owen
Original Assignee
Mobil Oil Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mobil Oil Corporation filed Critical Mobil Oil Corporation
Priority to PCT/US1991/005161 priority Critical patent/WO1993002025A1/fr
Publication of WO1993002025A1 publication Critical patent/WO1993002025A1/fr

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Classifications

    • 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
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • 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
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising 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
    • 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
    • C10G57/02—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 polymerisation
    • 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
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11

Definitions

  • This invention relates to olefin upgrading by fluidized bed catalysis.
  • Conversion of lower olefins, especially propene (propylene) and butenes, over HZSM-5 is effective at moderately elevated temperatures and pressures.
  • the conversion products are sought as liquid fuels, especially the C_+ aliphatic and aromatic hydrocarbons.
  • Product distribution for liquid hydrocarbons can be varied by controlling process conditions, such as temperature, pressure and space velocity.
  • Gasoline ( C 5 ⁇ c ⁇ n ⁇ is rea ⁇ -i 1 _ r formed at elevated temperature
  • Olefinic gasoline can be produced in good yield and may be recovered as a product or fed to a low severity, high pressure reactor system for further conversion to heavier distillate-range products.
  • Distillate mode operation can be employed to maximize production of C 1Q + aliphatics by reacting the lower and intermediate olefins at high pressure and moderate temperature.
  • Operating details for typical "MOGD" oligomerization units are disclosed in U.S. Pat. Nos. 4,456,779; 4,497,968 (Owen et al) and 4,433,185 (Tabak) .
  • the conversion conditions favor distillate-range product having a boiling point of at least 165°C (330°F).
  • Lower olefinic feedstocks containing C,-C 6 alkenes may be converted selectively; however, the low severity distillate mode conditions do not convert a major fraction of ethene (ethylene) .
  • Ethene can also be converted at moderate temperature with a bifunctional nickel catalyst.
  • ethene-containing light gas can be upgraded to liquid hydrocarbons rich in isobutane and gasoline or benzene, toluene, xylene (BTX) by catalytic conversion in a turbulent fluidized bed of solid acid zeolite catalyst under high severity reaction conditions in a single pass or with recycle of gas product.
  • This technique is particularly useful for upgrading FCC light gas, which usually contains significant amounts of ethene, propene, paraffins and hydrogen produced in cracking heavy petroleum oils and the like.
  • gasoline yield of FCC units can be significantly increased. Accordingly, it is a primary object of the present invention to provide a novel technique for upgrading ethene-containing light gas.
  • 4,090,949 discloses dual riser reactors operating in parallel and containing zeolite catalyst particles obtained from a common regeneration zone.
  • a gas oil feed material is contacted with catalyst in a first riser reactor and a C 2 ⁇ c 5 olefinic stream is contacted with catalyst in a second riser reactor.
  • Hydrogen contributors are injected into both riser reactors at multiple positions along each riser.
  • U.S. Patent No. 4,456,779 discloses process for upgrading C 2 ⁇ 5 olef i--i c feedstocks in a reaction zone containing zeolite ZSM-5 catalyst particles.
  • the feedstock is mixed initially with a recycled C.-C. paraffinic material obtained from a debutanizer.
  • U.S. Patent No. 4,487,985 discloses a reactor sequencing technique useful for multi-stage hydrocarbon conversion systems. Fixed bed catalytic reactors are employed. Catalyst partially inactivated in a primary stage is employed in a secondary stage to effect hydrocarbon conversion at a higher temperature.
  • U.S. Patent No. 4,497,968 discloses a multistage process for converting lower olefins to gasoline boiling range hydrocarbons.
  • An olefinic feedstock is prefractionated to obtain an ethene containing stream and a stream comprising C_+ olefins such as propene, butene and the like.
  • the ethene-containing stream is added to a high severity reaction system and the C 3 + olefinic stream is added to a distillate mode reaction system.
  • the olefinic feedstock is obtained from an oxygenates conversion reaction system such as the methanol to-olefins (MTO) process.
  • MTO methanol to-olefins
  • the distillate mode reaction system preferably comprises a series of fixed bed reactors.
  • U.S. Patent No. 4,831,203 discloses a fluidized bed process for upgrading ethene-containing hydrocarbons to gasoline products.
  • process conditions can be varied to favor the formation of either gasoline or distillate range products.
  • the conversion conditions favor distillate range product having a normal boiling point of at least 165*C (330 ⁇ F).
  • Lower olefinic feedstocks containing C_-C 8 alkenes may be converted selectively; however, the distillate mode conditions do not convert a major fraction of ethylene.
  • ethylene and the other lower olefins are catalytically oligomerized at higher temperature and moderate pressure.
  • coking of the catalyst is accelerated by the higher temperature.
  • ethylene conversion rate is greatly increased and lower olefin conversion is nearly complete to produce an olefinic gasoline comprising pentane, pentene and C g + hydrocarbons in good yield.
  • the lower olefinic feed may be diluted.
  • olefinic gasoline may be recycled and further oligomerized, as disclosed in U.S. Patent No. 4,211,640 (Garwood and Lee).
  • the diluent may contain light hydrocarbons, such as C_-C. alkanes, present in the feedstock and/or recycled from the debutanized product.
  • the present invention takes advantage of the accelerated aging rate for hydrocarbon conversion catalyst operating under process conditions which produce coke deposits. Increased coking decreases conversion at a given temperature, and it is conventional practice to increase process temperature to maintain the desired level of conversion.
  • partially deactivated coked catalyst from a high severity reaction zone is transferred to a low severity reaction zone operating in parallel.
  • the partially deactivated catalyst retains enough acid activity to convert more reactive olefins under low severity conditions.
  • highly active ZSM-5 type catalyst is used in the high severity reaction zone for conversion of ethylene (C-H. ethene) .
  • the ZSM-5 type catalyst When the ZSM-5 type catalyst is deactivated to a point below which efficient conversion of ethene can be achieved, the catalyst or a portion thereof is removed to the low severity reaction zone for contact with more reactive olefins such as propene, butene and the like. Under low severity conditions C.+ olefinic reactants are efficiently converted in major amount to gasoline product.
  • An improved process for continuous conversion of ethene-containing feedstock to heavier hydrocarbon products such as gasoline, distillate and the like wherein the feedstock is contacted with fluidized zeolite catalysts under oligomerization conditions.
  • the improvement comprises separating the feedstock into a C_ hydrocarbon stream rich in ethene and a -C olefinic hydrocarbon stream.
  • the ethene-rich stream is added to a high severity fluidized bed reaction zone operating under conditions sufficient to oligo erize ethene by contacting with acid zeolite catalyst particles.
  • the ,-C 4 olefinic stream containing propene, butene and the like is added to a low severity fluidized bed reaction zone containing acid zeolite catalyst particles and operating under conditions which yield only a minor amount of methane and ethane cracking products.
  • the process further comprises withdrawing an amount of partially coked and deactivated zeolite catalyst from the high severity reaction zone. At least a portion of withdrawn catalyst is added to the low severity zone where it is employed for the efficient conversion of C 3 ⁇ * C A olefins to heavier hydrocarbon products.
  • the present continuous process for upgrading lower olefins comprises adding a primary stream comprising relatively unreactive olefins to a primary fluidized reaction zone comprising solid crystalline zeolite catalyst particles in a reactor, preferably operating under turbulent regime high severity conditions.
  • a secondary stream comprising readily reactive olefins is added to a secondary fluidized reaction zone comprising solid crystalline zeolite catalyst particles in a reactor, also preferably operating under turbulent regime low severity conditions.
  • a portion of partially deactivated catalyst particles is withdrawn from the primary high severity fluidized reaction zone and added to the secondary low severity fluidized reaction zone where the portion contacts readily reactive olefins.
  • a common regeneration system is employed for the high severity and low severity reaction zones.
  • the regeneration system comprises a common regenerator and stripper.
  • an integrated product recovery system is used.
  • a common gasoline debutanizer or product liquid filter is an essential part of the integrated product recovery system.
  • the regeneration system is operated at equal or lower pressure than the high severity and low severity reaction zones.
  • Catalyst versatility permits the same zeolite to be used in both the high severity fluidized reaction zone and the low severity reaction zone. While it is within the inventive concept to employ substantially different catalysts in these zones, it is advantageous to employ a standard ZSM-5 having a silica:alumina molar ratio of 25:1 to 70:1.
  • Oligomerization catalysts preferred for use herein include the medium pore shape selective crystalline aluminosilicate zeolites having a silica:alumina ratio of at least 12, a constraint index of 1 to 12 and acid cracking activity of 1 to 250.
  • Representative of the ZSM-5 type zeolites are ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-48.
  • ZSM-5 is disclosed in U.S. Patent No. 3,702,886 and U.S. Patent No. Re. 29,948.
  • Other, suitable zeolites are disclosed in U.S. Patent No.
  • a typical zeolite catalyst component having Bronsted acid sites may consist essentially of aluminosilicate ZSM-5 zeolite with 5 to 95 wt.% silica and/or alumina binder.
  • siliceous zeolites may be employed in their acid forms, ion exchanged or impregnated with one or more suitable metals, such as Ga, Pd, Zn, Ni, Co and/or other metals of Periodic Groups III to VIII.
  • the zeolite may include a hydrogenation-dehydrogenation component (sometimes referred to as a hydrogenation component) which is generally one or more metals of Group IB, IIB, IIIB, VA, VIA or VIIIA of the Periodic Table (IUPAC) , especially aromatization metals such as Ga, Pd, etc.
  • IUPAC Periodic Table
  • Useful hydrogenation components include the noble metals of Group VIIIA, especially platinum, but other noble metals, such as palladium, gold, silver, rhenium, or rhodium may also be used.
  • Base metal hydrogenation components may also be used, especially nickel, cobalt, molybdenum, tungsten, copper or zinc.
  • the catalyst material may include two or more catalytic components, such as metallic oligomerization component (e.g., ionic Ni +2 and a shape-selective medium pore acidic oligomerization catalyst, such as
  • ZSM-5 zeolite which components may be present in admixture or combined in a unitary bifunctional solid particle. It is possible to utilize an ethene dimerization metal or oligomerization agent to effectively convert feedstock ethene in a continuous reaction zone.
  • Certain ZSM-5 type medium pore shape selective catalyst are sometimes known as pentasils.
  • the borosilicate, ferrosilicate and "silicalite” materials may be employed. It is advantageous to employ a standard ZSM-5 having a silica:alumina molar ratio of 25:1 to 70:1 with an apparent alpha value of 10-80 to convert 60 to 100 percent, preferably at least 70%, of the olefins in the feedstock.
  • ZSM-5 type pentasil zeolites are particularly useful in the process because of their regenerability, long life and stability under extreme conditions of operation.
  • the zeolite crystals have a crystal size from 0.01 to over 2 ⁇ m or more, with 0.02-1 ⁇ m being preferred.
  • the zeolite catalyst crystals are bound with a suitable inorganic oxide, such as silica, alumina, and the like, to provide a zeolite concentration of 5 to 95 wt%.
  • a 25% H-ZSM-5 catalyst contained within a silica-alumina matrix and having a fresh alpha value of 80 is employed unless otherwise stated.
  • Particle size distribution can be a significant factor in achieving overall homogeneity in turbulent regime fluidization. It is desired to operate the process with particles that will mix well throughout the bed. Large particles having a particle size greater than 250 ⁇ m hould be avoided, and it is advantageous to employ a particle size range consisting essentially of 1 to 150 ⁇ m. Average particle size is usually 20 to 100 ⁇ m, preferably 40 to 80 ⁇ m. Particle distribution may be enhanced by having a mixture of larger and smaller particles within the operative range, and it is particularly desirable to have a significant amount of fines. Close control of distribution can be maintained to keep about 10 to 25 wt% of the total catalyst in the reaction zone in the size range less than 32 ⁇ m.
  • This class of fluidizable particles is classified as Geldart Group A. Accordingly, the fluidization regime is controlled to assure operation between the transition velocity and transport velocity. Fluidization conditions are substantially different from those found in non-turbulent dense beds or transport beds. Although fluid bed reactors are preferred for both the high severity and low severity reaction zones, it is within the scope of the present process to utilize riser reactors in either one or both zones.
  • a portion of partially deactivated catalyst particles from the secondary low severity fluidized bed reaction zone is withdrawn and then added to the primary high severity reaction zone.
  • Catalyst flow in this manner can be employed when conditions dictate, e.g., when flow rates of feeds are such that it is more beneficial to proceed in such a manner.
  • a continuous process for upgrading lower olefins to increase gasoline yield and ease of liquid petroleum gas (LPG) recovery.
  • the process comprises separating a C_-C. cracked olefinic gas into a primary overhead stream containing C. hydrocarbons typically having at least 10-30 wt.% ethene and up to 20% heavier olefins and a secondary stream comprising C -C. olefinic hydrocarbons.
  • the primary stream is amine treated and the secondary stream is a ine and Merox treated.
  • the treated primary stream containing C, hydrocarbons is added to a primary fluidized bed reaction zone which contains solid crystalline zeolite catalyst particles in a reactor bed operating under turbulent regime high severity conditions.
  • the treated secondary stream comprising C_-C olefinic hydrocarbons is added to a secondary fluidized bed reaction zone which contains solid crystalline zeolite catalyst particles in a reactor bed operating under turbulent regime and low severity conditions.
  • a portion of partially deactivated catalyst particles from the primary high severity fluidized bed reaction zone is withdrawn and then added to the secondary low severity fluidized bed reaction zone.
  • the withdrawn partially deactivated catalyst particles contact the C 3 -C 4 olefinic hydrocarbons in the secondary reaction zone.
  • an amount of deactivated catalyst particles can be withdrawn from the secondary low severity fluidized bed reaction zone and added to a catalyst regeneration zone. Oxidative regeneration restores the catalytic activity to provide reactivated catalyst particles.
  • the reactivated catalyst particles are withdrawn from the catalyst regeneration zone and at least a portion of the catalyst particles are added to the primary high severity reaction zone.
  • the present process further comprises withdrawing from the primary high severity reaction zone a primary effluent comprising unseparated light gas and C_+ hydrocarbons boiling in the gasoline range. From the secondary low severity reaction zone a secondary effluent comprising unseparated LPG and C_+ hydrocarbons boiling in the gasoline and/or distillate range is withdrawn.
  • Primary effluent is added to a primary separation zone to obtain a noncondensible primary separation overhead stream comprising light gas and a primary separation bottoms stream comprising C ⁇ + hydrocarbons.
  • Secondary effluent is added to a secondary separation zone to obtain a secondary separation liquid overhead stream consisting essentially of C 3 -C. hydrocarbons substantially free of C_- components and a secondary separation bottoms stream comprising C_.+ hydrocarbons. Both primary and secondary separation bottoms streams can be recovered as product in an integrated separation system.
  • the process of the present invention is an improvement on a continuous process for upgrading C_-C- olefinic offgas from a fluidized catalytic cracking (FCC) unit comprising contacting C.-C. olefinic hydrocarbons with solid crystalline acid zeolite catalyst particles in a fluidized reaction zone under olefins oligomerization conditions to obtain hydrocarbons boiling in the gasoline and/or distillate range.
  • FCC fluidized catalytic cracking
  • C--C. olefinic offgas from an FCC unit and separating the offgas in a separation zone to obtain a primary overhead stream comprising noncondensible C_ hydrocarbons rich in ethene and a secondary stream comprising C--C olefinic hydrocarbons.
  • a primary high severity fluidized olefins oligomerization reaction zone is maintained at a predetermined pressure of 100 kPa to 3000 kPa and a temperature of 300"C to 500"C.
  • the primary reaction zone contains solid crystalline acid zeolite catalyst particles having an apparent average acid cracking activity of 2 to 100.
  • a secondary low severity fluidized bed olefins oligomerization reaction zone is maintained preferably at about the same predetermined pressure as the primary reaction zone and a temperature of 250 ⁇ C to 450*C.
  • the secondary reaction zone contains solid crystalline acid zeolite catalyst particles having an apparent average acid cracking activity of 1 to 50.
  • Feedstock for the secondary reaction zone is the secondary stream comprising C--C. olefinic hydrocarbons.
  • a primary effluent comprising unseparated fuel gas and C_+ hydrocarbons boiling in the gasoline range is withdrawn from the primary reaction zone; and a secondary effluent comprising C 3 ⁇ C 4 saturated and unsaturated hydrocarbons and C g + hydrocarbons boiling in the gasoline and/or distillate range is withdrawn from the secondary reaction zone.
  • An advantage of the invention is that the reaction severity is controlled to produce an effluent from the secondary reaction zone substantially free of methane and ethane cracking products so that the condensed C--C 4 product meet the required vapor pressure specification. Downstream fractionation requirements are therefore substantially reduced.
  • C_-alkanes present in the effluent from the secondary reaction zone, it can be substantially purged from the separation system and added to the FCC gas plant feed, primary reactor feed, or noncondensible stream from the primary reaction zone effluent at no additionally significant cost to the overall process.
  • a portion of partially deactivated zeolite catalyst particles is withdrawn from the primary high severity reaction zone and added to the secondary low severity reaction zone where the portion of partially deactivated catalyst particles contacts C 3 ⁇ C 4 olefinic hydrocarbon feedstock under oligomerization conditions.
  • An amount of deactivated zeolite catalyst particles is then withdrawn from the secondary low severity reaction zone and added to a catalyst regeneration zone where the deactivated catalyst particles are oxidatively regenerated to provide reactivated zeolite catalyst particles.
  • Reactivated catalyst particles are withdrawn from the oxidative regeneration zone and at least a portion of the reactivated particles are added to the primary high severity reaction zone.
  • the deactivated zeolite catalyst particles are stripped in a common stripping zone before entering the catalyst regeneration zone.
  • the present process is a continuous process for upgrading a C_-C 4 olefinic hydrocarbon stream to more valuable C-.+ hydrocarbons.
  • a C_-C 4 olefinic hydrocarbon stream is separated into at least two reactive streams having different chemical reactivity.
  • At least two fluidized bed reaction zones containing solid crystalline zeolite catalyst particles in a turbulent reactor bed are maintained under oligomerization reaction conditions.
  • One of the reaction zones is maintained under high severity reaction conditions.
  • the reactive streams are added as feedstock to the fluidized reaction zones operating in parallel.
  • the feedstreams are added in a manner such that each reactive stream enters a separate reaction zone operating under conditions which optimize olefins oligomerization reactions for each stream.
  • An oligo erized product is withdrawn from each of the fluidized bed reaction zones.
  • At least a portion of partially deactivated zeolite catalyst particles is withdrawn from the reaction zone operating under high severity oligomerization reaction conditions.
  • the portion of withdrawn partially deactivated catalyst particles is added to at least one parallel reaction zone.
  • a reactive stream then contacts the partially deactivated catalyst particles to provide oligomerized product and deactivated catalyst particles.
  • An amount of deactivated catalyst particles is withdrawn from the at least one parallel reaction zone containing the added partially deactivated catalyst particles.
  • Withdrawn deactivated catalyst particles are then added to a catalyst regeneration zone and oxidatively regenerated therein to provide reactivated catalyst particles.
  • Reactivated catalyst particles are withdrawn from the regeneration zone and at least a portion of said particles are added to the reaction zone operated under high severity oligomerization reaction conditions.
  • an olefinic feedstock such as FCC main fractionator overhead product enters separation zone 2 as by line 1.
  • the heavy products are recovered via line 80.
  • a C- hydrocarbon stream rich in ethene is withdrawn in vapor phase as noncondensible overhead from separation zone 2 via line 3.
  • the C_ hydrocarbon stream enters high severity fluidized bed oligomerization reaction zone 4 via line 3 where oligomerizable C, hydrocarbons contact fresh shape selective acid zeolite catalyst particles under ethene oligomerization conditions.
  • the fresh zeolite catalyst particles have an apparent average acid cracking value of 2 to 100. In a preferred embodiment, the apparent average acid cracking value is 3 to 7.
  • Deactivated catalyst particles are withdrawn from reaction zone 4 via line 30.
  • deactivated catalyst particles are added to the low severity reaction zone 6 as by line 33.
  • a portion of deactivated catalyst can be added directly to the catalyst regeneration zone 8 via line 39.
  • Fresh catalyst particles are added as needed to high severity reaction zone 4 as by line 31.
  • Oxidatively regenerated catalyst particles are added to high severity reaction zone 4 as by line 37.
  • a treated liquid bottoms stream comprising C 3 -C. olefinic hydrocarbons.
  • the liquid bottoms stream is added via line 5 to a fluidized reaction zone operated under low severity oligomerization conditions. Such conditions typically do not favor very high conversion of ethene.
  • C 3 -C 4 olefins contact solid acid zeolite catalyst particles in the reaction zone 6.
  • the apparent average acid cracking value of the catalyst particles in reaction zone 6 is 1 to 50.
  • olefins such as rea ⁇ tant propene and butene are e ficiently upgraded to C-.+ hydrocarbons boiling in the gasoline range. Only a minor amount of propene undergoes cracking to less valuable methane, ethene and ethane. Depending on the operating conditions various amounts of distillate components are also produced.
  • Deactivated catalyst particles are withdrawn from reaction zone 6 and added to common catalyst regeneration unit 8 via line 35. Oligomerized effluent is withdrawn from reaction zone 6 via line 9. Effluent enters heat exchange unit 16 where it is cooled prior to entering separation zone 12 as by line 13. From separation zone 12 is withdrawn a liquid overhead comprising C_-C 4 saturated and unsaturated hydrocarbons via line 19 and a liquid bottoms stream comprising C-.+ hydrocarbons boiling in the gasoline and/or distillate range as by line 21.
  • Oligomerized effluent is withdrawn from reaction zone 4 via line 7 and enters heat exchanger 14 for cooling. Effluent then enters separation zone 10 via line 11 to obtain a noncondensible overhead comprising fuel gas which is withdrawn via line 15 and a liquid bottoms stream comprising C-.+ gasoline-range hydrocarbons as by line 17.
  • the hydrocarbon stream of line 17 can be recycled to fractionation zone 2 to be separated into light gas, C 3 -C 4 hydrocarbons, and a gasoline fraction.
  • the C -C 4 hydrocarbons can be added to reaction zone 6 for further upgrading.
  • separation zone 10 operates to produce a relatively pure stream 17 lean in C.hydrocarbons, which stream is added to common fractionator 12.
  • a common liquid filter can be employed to remove catalyst fines from the combined gasoline product stream.
  • C_+ hydrocarbons withdrawn from separation zone 12 can be added to a fixed bed MOGD (Mobil Olefins to Gasoline) reactor containing solid crystalline acid zeolite catalyst such as ZSM-5 to obtain a product comprising C- 0 + hydrocarbons boiling in the distillate range.
  • MOGD Mobil Olefins to Gasoline
  • ZSM-5 solid crystalline acid zeolite catalyst
  • C,-C 4 saturated and unsaturated hydrocarbons withdrawn from separation zone 12 via line 19 can be recycled to separation zone 2, to reaction zone 4, or directly to reaction zone 6 for upgrading to more valuable C 5 + hydrocarbon product.
  • the C--C hydrocarbons withdrawn via line 19 can be sent to a dehydrogenation reaction zone for upgrading to olefins which could be used to make ethers or recycled to zone 6.
  • the present process is not limited to processing only an ethene fraction in a high severity reaction zone and specifically a propene/butene-containing fraction in a lower severity reaction zone.
  • any light olefins-containing feed can be added to either reaction zone, so long as one reaction zone is operated at a significantly higher severity than the other zone.
  • An alternative example is a process comprising adding a propene-rich feed to a primary reaction zone; withdrawing from the primary reaction zone a primary effluent comprising C_+ hydrocarbons and unreacted propene; adding at least a portion of the primary effluent to a feed rich in n-butene to obtain a mixed feedstream containing n-butene, C 5 + hydrocarbons and propene; and adding the mixed feedstream to a secondary reaction zone operated at higher severity than said primary reaction zone.
  • Other alternative arrangements are obvious to one skilled in the art and are within the scope of the present invention.

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Abstract

Procédé multiphases continu destiné à convertir des oléfines normalement gazeuses (3) contenant une certaine quantité d'éthène en essence et/ou en hydrocarbures de la gamme des distillats (17), qui emploie au moins deux zones de réaction d'oligomérisation d'oléfines fluidisées (4 et 6) fonctionnant en parallèle, une des zones de réaction fonctionnant dans des conditions de réaction à haute sévérité efficaces pour convertir l'éthène.
PCT/US1991/005161 1991-07-22 1991-07-22 Oligomerisation d'olefines par catalyse a lit fluidise WO1993002025A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010023369A1 (fr) * 2008-08-29 2010-03-04 Ifp Procédé de conversion d'une charge lourde en essence et en propylène présentant une structure de rendement modulable
US11072749B2 (en) 2019-03-25 2021-07-27 Exxonmobil Chemical Patents Inc. Process and system for processing petroleum feed

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4886925A (en) * 1988-05-02 1989-12-12 Mobil Oil Corp Olefins interconversion and etherification process
US4929780A (en) * 1988-05-12 1990-05-29 Mobil Oil Corporation Multistage process for converting oxygenates to liquid hydrocarbons and ethene
US5043499A (en) * 1990-02-15 1991-08-27 Mobil Oil Corporation Fluid bed oligomerization of olefins

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4886925A (en) * 1988-05-02 1989-12-12 Mobil Oil Corp Olefins interconversion and etherification process
US4929780A (en) * 1988-05-12 1990-05-29 Mobil Oil Corporation Multistage process for converting oxygenates to liquid hydrocarbons and ethene
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WO2010023369A1 (fr) * 2008-08-29 2010-03-04 Ifp Procédé de conversion d'une charge lourde en essence et en propylène présentant une structure de rendement modulable
FR2935377A1 (fr) * 2008-08-29 2010-03-05 Inst Francais Du Petrole Procede de conversion d'une charge lourde en essence et en propylene presentant une structure de rendement modulable
CN102137914B (zh) * 2008-08-29 2014-02-26 Ifp新能源公司 具有可变的收率结构的将重质进料转化成汽油和丙烯的方法
US11072749B2 (en) 2019-03-25 2021-07-27 Exxonmobil Chemical Patents Inc. Process and system for processing petroleum feed

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