EP0113180B1 - Katalytische Umwandlung von leichten olefinischen Beschickungen in einer Gasanlage von einem katalytischen fluidisierten Krachverfahren - Google Patents

Katalytische Umwandlung von leichten olefinischen Beschickungen in einer Gasanlage von einem katalytischen fluidisierten Krachverfahren Download PDF

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Publication number
EP0113180B1
EP0113180B1 EP19830307095 EP83307095A EP0113180B1 EP 0113180 B1 EP0113180 B1 EP 0113180B1 EP 19830307095 EP19830307095 EP 19830307095 EP 83307095 A EP83307095 A EP 83307095A EP 0113180 B1 EP0113180 B1 EP 0113180B1
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EP
European Patent Office
Prior art keywords
feedstock
zsm
zeolite
fuel oil
olefins
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Legal status (The legal status 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 status listed.)
Expired
Application number
EP19830307095
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English (en)
French (fr)
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EP0113180A3 (en
EP0113180A2 (de
Inventor
Richard George Graven
Stephen James Mcgovern
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ExxonMobil Oil Corp
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Mobil Oil Corp
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    • 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
    • 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
    • C10G2400/02—Gasoline

Definitions

  • This invention relates to the catalytic conversion of olefinic feedstocks in a FCC gas plant to gasoline and fuel all using a ZSM-5 type zeolite catalyst.
  • the present invention provides a process for producing a gasoline fraction and/or a fuel oil fraction by contacting a feedstock comprising C 2 to C s olefins with a crystalline aluminosilicate zeolite having a pore diameter greater than 5x 1 0-10 m, a silica-to-alumina ratio of at least 12 and a constraint index of from 1 to 12 under reaction conditions effective to convert the olefins to a gasoline fraction and/or a fuel oil fraction, characterized by employing as the feedstock the discharge stream from the final stage of the wet gas compressor or the overhead from the high pressure receiver in the gas plant of a fluid catalytic cracking unit and passing the effluent from the zeolite-catalyzed conversion through the separation and recovery facilities of the gas plant to recover the gasoline fraction and/or the fuel oil fraction.
  • Hydrocarbon mixtures containing significant quantities of light olefins are frequently encountered in petrochemical plants and petroleum refineries. Because of the ease with which olefins react, these streams serve as feedstocks in a variety of hydrocarbon conversion processes. Many olefinic conversion processes require that the olefinic feed be provided in a highly purified condition. However, processes which may utilize the olefinic feedstocks without the need for further separation and purification are highly desirable.
  • catalytic cracking Although the main purpose of catalytic cracking is to convert gas oil to compounds of lower molecular weight in the gasoline and middle distillate boiling ranges, significant quantities of C 1 -C 4 hydrocarbons are also produced. These light hydrocarbon gases are rich in olefins which heretofore have made them prime candidates for conversion to gasoline blending stocks by means of polymerization and/or alkylation. Fractionation of the effluent from the fluid catalytic cracking reactor has been employed to effect an initial separation of this stream. The gaseous overhead from the main fractionator is collected and processed in the FCC gas plant.
  • gases are compressed, contacted with a naphtha stream, scrubbed, where necessary, with an amine solution to remove sulfur and then fractionated to provide, for example, light olefins and isobutane for alkylation, light olefins for polymerization, n-butane for gasoline blending and propane for LPG.
  • Light gases are recovered for use as fuel.
  • U.S.-A-3,960,978 teaches conversion of olefins to olefinic gasolines.
  • US-A-4,021,502 discloses conversion of olefins over ZSM-12.
  • US-A-3,760,024 discloses contacting olefins with ZSM-5 type zeolites.
  • US ⁇ A ⁇ 3,775,501 discloses preparation of aromatics by contacting olefins over ZSM-5 type catalysts.
  • US-A-3,827,968 discloses a two-step aromatization process wherein in the first step an olefin is contacted over a ZSM-5 type zeolite.
  • US-A-4,211,640 discloses a process for contacting a highly olefinic gasoline with a ZSM-5 type zeolite to produce fuel oil and gasoline having enhanced gum stability.
  • US-A-4,227,992 discloses a process for separating ethylene from a mixture of C Z -C S olefins by contacting the mixture with a ZSM-5 type zeolite under conditions effective to convert at least 80% of the C 3 +olefins and no more than 20% of the ethylene.
  • FCC fluid catalytic cracking
  • This invention relates to an improvement in the process for producing a gasoline fraction and/or a fuel oil fraction by contacting a feedstock comprising C 2 to C 5 olefins with a crystalline aluminosilicate zeolite having a pore diameter greater than 5xlO-' o m, a silica-to-alumina ratio of at least 12 and a constraint index of from 1 to 12 under reaction conditions effective to convert the olefins to a gasoline fraction and/or a fuel oil fraction, the improvement comprising employing as the feedstock the discharge stream from the final stage of the wet gas compressor or the overhead from the high pressure receiver in the gas plant of a fluid catalytic cracking unit and passing the effluent from the zeolite catalyzed conversion through the separation and recovery facilities of the gas plant to recover the gasoline fraction and/or the fuel oil fraction.
  • the catalysts used in accordance with this invention are crystalline zeolites having a silica/alumina ratio greatsr than 12 and a Constraint Index (C.I.) of from 1 to 12.
  • the zeolites are generally termed ZSM-5 type zeolites. These zeolites and their use as conversion catalysts for olefins are described in the U.S. Patents referred to above, particularly US-A-3,760,024, US-A-3,960,978, US-A-4,021,502, US ⁇ A ⁇ 4,211,640 and US ⁇ A ⁇ 4,227,992.
  • the preferred class of zeolites defined herein are ZSM-5 type zeolites as exemplified by ZSM-5, ZSM-11, ZSM-12, ZSM-35, ZSM-38, with ZSM-5 being particularly preferred.
  • ZSM-5 is described in US ⁇ A ⁇ 3,702,886, ZSM-11 in US-A-3,709,979, ZSM-12 in US-A-3,832,449, ZSM-35 in US-A-4,016,245 and ZSM-38 in US-A-4,046,859.
  • the need for separate processes for the polymerization or alkylation of the olefins in this stream is obviated or reduced.
  • the concept of utilizing a ZSM-5 type zeolite catalyzed conversion instead of the prior art processes for providing Cs+gasoline and/or fuel oil blending stocks has many advantages. Since the ZSM-5 type zeolites can tolerate the poisoning effects of the impurities normally found in raw FCC product streams, extreme purification procedures often encountered in polymerization and alkylation do not have to be employed.
  • the effluent from the catalytic conversion can continue through the gas plant which has the facilities required to separate the gasoline fraction and/or fuel oil fraction as blending stocks from the lighter materials which are recovered at LPG and fuel gas.
  • the only new equipment which must be provided to practice the olefin conversion in accordance with this invention is a catalytic reactor, feed/effluent heat exchangers and a preheat furnace.
  • the discharge stream from the final stage of the wet gas compressor and the overhead from the high pressure receiver are these preferred streams.
  • the multi-stage wet gas compressor in the gas plant is required to increase the pressure of the gaseous overhead from the FCC main fractionator so that it may be effectively processed in the gas plant.
  • the discharge from the final stage is usually from 1308 to 1653 kPa (175 to 225 psig) and 149 to 177°C (300 to 350°F).
  • an amine scrubber employing mono-, di- or triethanol amine or mixtures thereof, may be located between the stages of the wet gas compressor or immediately upstream of the conversion facilities which are the subject of this invention to reduce the sulfur content to acceptable levels.
  • a water wash stage might also be incorporated to reduce ammonia content and to remove traces of entrained amine solution.
  • the overhead from the high pressure receiver associated with the wet gas compressor is the other preferred feedstock for the present process.
  • This gaseous stream does not have the same composition as the discharge from the compressor since other streams, such as the liquid from the interstage receiver and the rich liquid from the primary absorber, as well as the stripper overhead, discharge into this vessel.
  • the gas stream passing from the high pressure receiver is usually at from 1136 to 1480 kPa (150 to 200 psig) and from 32 to 43°C (90 to 110°F).
  • the process of this invention is carried out at a pressure from 1136 to 1825 kPa (150 to 250 psig), a temperature from 149 to 399°C (300 to 750°F) and a space velocity of from 0.1 to 10 WHSV, based on the C 2 to C s olefins.
  • the broad concept of contacting olefins, alone or in admixture with each other or other hydrocarbons, over the identified catalyst with which this invention is concerned is not per se novel.
  • the key to this invention resides in selecting a C 2 to C 6 olefins-containing gas stream in a FCC gas plant as the feedstock for the desired catalytic conversion and the use of the separation and recovery facilities of the gas plant to process the effluent from the catalytic conversion such that gasoline and/or fuel oil fractions useful in gasoline and fuel oil blending may be produced without the necessity of providing product recovery facilities thereby minimizing the capital investment and operating costs for the subject process.
  • the condensed overhead from the FCC main fractionator flow through line 2 into FCC main fractionator overhead accumulator 4 for separation into a gasous phase and a liquid phase.
  • the gaseous portion of the column overhead flows from accumulator 4 to the FCC gas plant through line 6 to the suction of the first stage of wet gas compressor 8 for the initial increase in pressure.
  • the wet gas discharges from the first stage of the compressor through line 10 to interstage receiver 12 and line 14 and then through the second stage of the wet compressor from which it is discharged through line 16 at about 163°C (325°F) and about 1480 kPa (200 psig).
  • an ethanolamine scrubber may be located in line 10 to reduce the sulfur content to acceptable levels.
  • the scrubber may be located upstream of the reactor and equipment depicted in Figure 2, i.e., in lines 16 or 32.
  • the gas stream in line 16 may be employed in the practice of this invention.
  • This stream typically has a composition as shown in Table I.
  • the olefinic stream in line 16 passes through heat exchanger 102 where it is pre-heated by indirect heat exchange with the reactor effluent, described hereinafter.
  • the partially heated olefin stream then flows through line 104 to preheat furnace 106 where it is heated to the reaction temperature in the range of 149-399°C (30o-750°C).
  • the thus heated stream flows through line 108 to reactor 110 which contains a fixed bed 112 of ZSM-5 zeolite catalyst while passing through the reactor at a space velocity of from 0.1 to 10WHSV, the C 2 to C s olefins in the gaseous mixture are converted to hydrocarbons boiling in the gasoline and fuel oil range.
  • the reaction mixture leaves reactor 110 through line 114 and flows to the shell side of heat exchanger 102 where this effluent stream provides some of the preheat to the olefinic feedstream.
  • the reaction mixture then passes to lines 18, 20 and 22 and enters high pressure receiver 24. Several other streams are also passed into this receiver where they are separated into a liquid phase and a gaseous phase.
  • the streams entering high pressure receiver 24 are separated therein into a gaseous phase and a liquid phase.
  • the gaseous phase passes through lines 32 and 34 to primary absorber 36.
  • Dotted square B represents an alternate location for the Figure 2 flowplan and this embodiment will be described hereinafter.
  • the gaseous phase from high pressure receiver 24 passes directly to primary absorber 36 where a C s + liquid stream passing in countercurrent flow to the gas absorbs heavy hydrocarbons from the gas stream.
  • the C s + liquids employed include the liquid phase from FCC main column overhead accumulator 4 and a portion of the final liquid product from the gas plant.
  • These streams are passed to primary absorber 36 through lines 38 and 40, respectively.
  • the rich liquid from absorber 36 flows from the column through lines 30, 28 and 22 and enters high pressure receiver 24, as described above.
  • the unabsorbed gases pass from the top of absorber 36 through line 42 where they are combined with coker gas supplied through line 44.
  • the combined gaseous stream passes through line 46 into sponge absorber 48 where they are contacted in countercurrent fashion with sponge oil which is a stripped heavy naphtha or light fuel oil boiling in the 177-260°C (350-500 * F) range.
  • sponge oil which is a stripped heavy naphtha or light fuel oil boiling in the 177-260°C (350-500 * F) range.
  • the C 3 + gases are absorbed by the sponge oil which passes from sponge absorber 48 through line 50 and discharges into FCC main column (not shown) by means of line 2.
  • the unabsorbed C 2 - gases pass from the absorber through line 52 and are eventually burned as fuel gas.
  • this liquid passes from the receiver through line 54 to stripper 56 where steam is employed to remove the lig ht gases from this stream.
  • the steam and the light gases pass from the top of the stripper through line 31 and eventually discharge into high pressure receiver 24 from which the useful light gases are recovered.
  • the stripped C 3 + liquid passes from stripper 56 through line 58 to debutanizer 60 where a C 4 - fraction is separated and passes from the column as the overhead through line 62 where it is recovered as LPG product.
  • the gasoline and/or fuel oil fraction is removed from debutanizer 60 as the bottoms fraction through line 64. A portion of this fraction is recycled through line 40 to the primary absorber as a portion of the absorbing liquid as described above.
  • the remaining portion of the C s + bottoms is recovered as product through line 66 and is employed as blending stock for gasoline and/or fuel oil following further fractionation, as required.
  • this invention may optionally be practiced employing the overhead from high pressure receiver 24 as the feed for the conversion to gasoline and/or fuel oil.
  • this stream has a composition as shown in Table I.
  • the flowplan of Figure 2 is located at position B of Figure 1 with the feed passing through line 32 and the reaction mixture continuing on to the separation equipment of the gas plant through line 34.
  • the discharge from the wet gas compressor flows directly from line 16 to line 18.
  • this embodiment is practiced in substantially the same manner as the embodiment described above where the Figure 2 flowplan is located at position A of Figure 1.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (6)

1. Verfahren zur Herstellung einer Benzinfraktion und/oder einer Heizölfraktion durch Kontakt eines Zufuhrmaterials, das C2 bis CS-Olefine umfaßt, mit einem kristallinen Aluminosilicatzeolith mit einem Porendurchmesser von größer als 5x10-"m, einem Siliciumdioxid/Aluminiumoxid-Verhältnis von mindestens 12 und einem Zwangsindex von 1 bis 12 bei wirksamen Reaktionsbedingungen, um die Olefine in eine Benzinfraktion und/oder eine Heizölfraktion umzuwandeln, dadurch gekennzeichnet, daß als Zuführmaterial der Abflußstrom aus der Endstufe des Naßgaskompressors oder das Kopfprodukt aus dem Hochdrucksammelgefäß in der Gasanlage einer katalytischen Wirbelschichtorackanlage verwendet wird und der Abfluß aus der durch den Zeolith katalysierten Umwandlung durch diese Abtrennung und die Rückgewinnungseinrichtungen der Gasanlage geleitet wird, um die Benzinfraktion und/oder die Heizölfraktion zu gewinnen.
2. Verfahren nach Anspruch 1, worin das Zufuhrmaterial unter für die Reduzierung das C02- und H2S-Gehaltes des Zufuhrmaterials wirksamen Bedingungen durch einen Aminabsorber oder unter für die Reduzierung des NH3- und des Amingehaltes des Zuführmaterials wirksamen Bedingungen durch einen Wasserrieselturm bzw. Naßreiniger oder durch Kombinationen des Aminabsorbers und des Wasserrieselturms geleitet wird, bevor das Zufuhrmaterial mit dem Zeolith in Kontakt gebracht wird.
3. Verfahren nach Anspruch 1 oder 2, worin der Zeolith ZSM-5, ZSM-11, ZSM-12, ZSM-35 oder Mischungen davon ist.
4. Verfahren nach Anspruch 3, worin der Zeolith ZSM-5 ist.
5. Verfahren nach einem der Ansprüche 1 bis 4, worin die Quelle des Zufuhrmaterials eine katalytische Wirbelschichtcrackanlage ist.
6. Verfahren nach einem der Ansprüche 1 bis 4, worin die Quelle des Zufuhrmaterials ein Verkoker ist.
EP19830307095 1982-12-01 1983-11-21 Katalytische Umwandlung von leichten olefinischen Beschickungen in einer Gasanlage von einem katalytischen fluidisierten Krachverfahren Expired EP0113180B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US44580882A 1982-12-01 1982-12-01
US445808 1982-12-01

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EP0113180A2 EP0113180A2 (de) 1984-07-11
EP0113180A3 EP0113180A3 (en) 1987-01-14
EP0113180B1 true EP0113180B1 (de) 1989-03-08

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EP (1) EP0113180B1 (de)
JP (1) JPS59108090A (de)
AU (1) AU562524B2 (de)
BR (1) BR8306584A (de)
CA (1) CA1213551A (de)
DE (1) DE3379335D1 (de)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL8301747A (nl) * 1983-05-17 1984-12-17 Shell Int Research Werkwijze voor de bereiding van middeldestillaten.
US4605493A (en) * 1984-12-31 1986-08-12 Mobil Oil Corporation Method for minimizing recycling in an unsaturated gas plant
US4746762A (en) * 1985-01-17 1988-05-24 Mobil Oil Corporation Upgrading light olefins in a turbulent fluidized catalyst bed reactor
US4754100A (en) * 1986-03-28 1988-06-28 Mobil Oil Corporation Catalytic conversion of C3 aliphatics to higher hydrocarbons
DE3867245D1 (de) * 1987-01-23 1992-02-13 Mobil Oil Corp Verbesserung von diolefine enthaltenden kohlenwasserstoffen.
AU595706B2 (en) * 1987-06-11 1990-04-05 Mobil Oil Corporation Integrated process for gasoline production
AU2347488A (en) * 1987-10-08 1989-04-13 Mobil Oil Corporation Process for cracking a hydrocarbon feedstock to obtain gasoline and olefins and upgrading the olefins to improve the total gasoline yield
US4831204A (en) * 1987-12-16 1989-05-16 Mobile Oil Corporation Production of gasoline from light olefins with FCC gas plant improvement by olefin upgrading
US4831205A (en) * 1987-12-16 1989-05-16 Mobil Oil Corporation Catalytic conversion of light olefinic feedstocks in a FCC plant
US4831203A (en) * 1987-12-16 1989-05-16 Mobil Oil Corporation Integrated production of gasoline from light olefins in a fluid cracking process plant
US5000837A (en) * 1989-04-17 1991-03-19 Mobil Oil Corporation Multistage integrated process for upgrading olefins
EP2414310A4 (de) * 2009-03-31 2015-04-29 Uop Llc Verfahren zur oligomerisierung von verdünntem ethylen

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB510155A (en) * 1937-11-26 1939-07-26 Standard Oil Co Indiana Improvements relating to the conversion of mineral oils into gasoline
US4211640A (en) * 1979-05-24 1980-07-08 Mobil Oil Corporation Process for the treatment of olefinic gasoline

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Publication number Publication date
BR8306584A (pt) 1984-07-10
JPS59108090A (ja) 1984-06-22
EP0113180A3 (en) 1987-01-14
EP0113180A2 (de) 1984-07-11
DE3379335D1 (en) 1989-04-13
CA1213551A (en) 1986-11-04
AU562524B2 (en) 1987-06-11
AU2167183A (en) 1984-06-07

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