EP0439865B1 - Verfahren zur Herstellung von normalerweise flüssigen Kohlenwasserstoffen - Google Patents

Verfahren zur Herstellung von normalerweise flüssigen Kohlenwasserstoffen Download PDF

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Publication number
EP0439865B1
EP0439865B1 EP90203479A EP90203479A EP0439865B1 EP 0439865 B1 EP0439865 B1 EP 0439865B1 EP 90203479 A EP90203479 A EP 90203479A EP 90203479 A EP90203479 A EP 90203479A EP 0439865 B1 EP0439865 B1 EP 0439865B1
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EP
European Patent Office
Prior art keywords
catalyst
feedstock
process according
reactor
normally liquid
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Expired - Lifetime
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EP90203479A
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English (en)
French (fr)
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EP0439865A1 (de
Inventor
Johannes Petrus Van Den Berg
Karl-Heinz Wilhelm Röbschläger
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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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

Definitions

  • the present invention relates to a process for preparing normally liquid hydrocarbons from a hydrocarbonaceous feedstock comprising olefins containing 2-6 carbon atoms and to hydrocarbons obtained in such process.
  • the invention therefore relates to a process for preparing normally liquid hydrocarbons from a hydrocarbonaceous feedstock comprising olefins containing 2-6 carbon atoms, which process comprises passing the feedstock upwardly at elevated pressure and at a temperature of from 150 to 295 °C through a reactor containing catalyst particles comprising a crystalline support, which catalyst particles stay in the reactor for at least 1 hour at reaction conditions.
  • the process is preferably carried out at a temperature from 180 °C to 295 °C, and more preferably at a temperature from 180 to 280 °C. Further, the process is preferably carried out at a pressure of from 2 to 100 bar, more preferably of from 10 to 50 bar and at a space velocity of from 0.1 to 10 kg feed/kg catalyst.hour, more preferably of from 0.2 to 5 kg feed/kg catalyst.hour.
  • the feedstock is passed upwardly through a reactor.
  • upwardly is understood that the feedstock is inserted in the reactor at a place situated below the one where the product is withdrawn from the reactor.
  • Different kinds of catalyst beds can be used in such process, e.g. a fixed bed or a fluidized bed.
  • a fixed bed is understood a catalyst bed having a catalyst volume density in the catalyst bed of from 0.45 to 0.70, catalyst volume density being the fraction of the volume of the catalyst bed which is taken up by catalyst particles, the internal pore volume of the catalyst particles not being taken into account; more preferably the fixed bed has a catalyst volume density of from 0.50 to 0.65.
  • fluidized bed is understood a catalyst bed having a catalyst volume density of from 0.35 to 0.50.
  • the process is carried out in a fixed bed of catalyst particles.
  • the process according to the invention is preferably carried out at such process conditions that the formation of substantial gas bubbles, e.g. as in pulse flow, is prevented.
  • a description of pulse flow is given in the article by Fukushima and Kusaka, J. Chem. Eng. Japan, vol.12, 296, 1979.
  • the catalyst suitably used comprises a crystalline refractory oxide, optionally containing a metal selected from the Group 1b, 2a, 2b, 4b, 5b, 6b, 7b and 8 metals of the Periodic Table of the Elements, preferably a Group 8 metal such as nickel.
  • Crystalline supports are understood to have their atoms or molecules arranged in a regularly ordered structure as observed by diffraction techniques.
  • the catalyst contains a crystalline aluminosilicate.
  • Suitable refractory oxides are faujasite, zeolite-L, ferrierite, mordenite, zeolite-beta, ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-20, ZSM-21 and ZSM-35; most suitably ZSM-5 and/or mordenite are applied.
  • the following compounds can suitably be used as catalysts: mordenite in the hydrogen form, optionally comprising nickel, and/or ZSM-5 in the hydrogen form, optionally comprising nickel.
  • the amount of metal present on the catalyst can be up to 20% by weight (%wt), based on the amount of refractory oxide, suitably from 0.1 to 20 %wt, preferably from 0.1 to 10 %wt.
  • the catalyst may further contain binder, such as alumina, in an amount ranging from 10 to 80% by weight, based on total amount of catalyst including binder.
  • the catalyst will not need continuous regeneration. Therefore the catalyst particles can stay in the reactor at reaction conditions for at least 1 hour, suitably more than 10 hours, preferably more than 100 hours.
  • the feedstock consists for more than 50% by weight of olefins containing 2-6 carbon atoms, such as ethene, propene, n-butenes, isobutene, n-pentenes, isopentenes, n-hexenes and isohexenes; in addition to said olefins, hydrocarbons such as (cyclic) paraffins and mono-olefins having more than six carbon atoms per molecule can be present in the feedstock.
  • olefins containing 2-6 carbon atoms such as ethene, propene, n-butenes, isobutene, n-pentenes, isopentenes, n-hexenes and isohexenes
  • hydrocarbons such as (cyclic) paraffins and mono-olefins having more than six carbon atoms per molecule can be present in the feedstock.
  • propene- and/or butene-containing feedstocks which are suitably obtained in (fluid) catalytic cracking processes, thermal cracking processes, coking- and/or pyrolysis processes.
  • Suitable feedstocks for the present process can also be prepared starting from synthesis gas which is first converted into methanol and subsequently into a product substantially consisting of olefins containing from 2-6 carbon atoms.
  • the synthesis gas can be converted in the presence of a Fischer-Tropsch type of catalyst into a product which in addition to paraffinic hydrocarbons contains a considerable amount of olefins containing 2-6 carbon atoms.
  • normally liquid hydrocarbons which are prepared in the process according to the present invention, are meant hydrocarbons which are in the liquid phase at a temperature of 15 °C and atmospheric pressure.
  • Such liquid hydrocarbons include products boiling in the gasoline range (40-150 °C), in the middle distillate range (kerosene- and gasoil fractions boiling from 150-370 °C) and in the lubricating base oil range (above 370 °C).
  • Part of the product obtained in the process e.g. products boiling below the gasoline boiling range and unconverted feedstock, if any, can be separated from the normally liquid products, combined with the feedstock and again passed through the reactor.
  • the feedstock according to the present invention separate the effluent obtained into at least two fractions of which at least one has a boiling range above that of the olefins present in the feedstock and recycle at least part of such fraction to the process, as described in European patent publication 0334428.
  • the part of the fraction being recycled to the first stage can be a relatively light part or a relatively heavy part.
  • the catalyst volume density was 0.54.
  • the process was carried out at a temperature of 215 °C, a pressure of 32 bar and a WHSV of 1 (kg/kg.hr) (weight feedstock/weight catalyst). After 170 hours on stream, 71 %wt of the butene present in the feedstock was observed to be converted into normally liquid hydrocarbons.
  • Example II A comparative experiment was carried out in which a process substantially as described in Example I was carried out at a temperature of 300 °C and a pressure of 35 bar. After 170 hours on stream, 30 %wt of the butene present in the feedstock was observed to be converted into normally liquid hydrocarbons.
  • the catalyst volume density was 0.54.
  • the process was carried out at a temperature of 215 °C, a pressure of 31 bar and a WHSV of 2.5 (kg/kg.hr) (weight feedstock/weight catalyst). After 260 hours on stream 45 %wt of the butene present in the feedstock was observed to be converted into normally liquid hydrocarbons.
  • the catalyst was present as a fixed bed during operation. The process was carried out at a temperature of 215 °C, a pressure of 30 bar and a WHSV of 1 (kg/kg.hr) (weight feedstock/weight catalyst). After 210 hours on stream, 76 %wt of the butene present in the feedstock was observed to be converted into normally liquid hydrocarbons.
  • Example III A comparative experiment was carried out in which a process substantially as described in Example III was carried out, differing in that the feedstock was passed downwardly through the reactor. After 210 hours on stream, 30 %wt of the butene present in the feedstock was observed to be converted into normally liquid hydrocarbons.
  • the catalyst was present as a fixed bed during operation. The process was carried out at a temperature of 215 °C, a pressure of 30 bar and a WHSV of 1 (kg/kg.hr) (weight feedstock/weight catalyst). After 160 hours on stream, 75 %wt of the butene present in the feedstock was observed to be converted into normally liquid hydrocarbons.

Landscapes

  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (9)

  1. Verfahren zur Herstellung normalerweise flüssiger Kohlenwasserstoffe aus einem kohlenwasserstoffhaltigen Ausgangsmaterial, umfassend Olefine mit 2 bis 6 Kohlenstoffatomen, welches Verfahren das Leiten des Ausgangsmaterials bei erhöhtem Druck und einer Temperatur von 150 bis 295°C in Aufwärtsrichtung durch einen Reaktor, der Katalysatorteilchen, umfassend einen kristallinen Träger enthält, welche Katalysatorteilchen mindestens 1 Stunde lang bei Reaktionsbedingungen im Reaktor verbleiben, umfaßt.
  2. Verfahren nach Anspruch 1, in welchem das Verfahren bei einer Temperatur von 180 bis 280°C durchgeführt wird.
  3. Verfahren nach Anspruch 1 und/oder 2, in welchem der Katalysator ein kristallines Aluminosilikat enthält.
  4. Verfahren nach Anspruch 3, in welchem das kristalline Aluminosilikat ZSM-5 ist.
  5. Verfahren nach Anspruch 3, in welchem das kristalline Aluminosilikat Mordenit ist.
  6. Verfahren nach einem der Ansprüche 1 bis 5, in welchem der Katalysator Nickel enthält.
  7. Verfahren nach einem der Ansprüche 1 bis 6, in welchem das kristalline Aluminosilikat in der Wasserstofform vorliegt.
  8. Verfahren nach einem der Ansprüche 1 bis 7, in welchem die Katalysatorvolumendichte 0,50 bis 0,65 beträgt.
  9. Verfahren nach einem der Ansprüche 1 bis 8, in welchem der erhaltene Abstrom in mindestens 2 Fraktionen aufgetrennt wird, von welchen mindestens eine einen Siedebereich oberhalb der im Ausgangsmaterial vorliegenden Olefine aufweist, und mindestens ein Teil einer solchen Fraktion zum Verfahren im Kreislauf rückgeführt wird.
EP90203479A 1990-01-02 1990-12-20 Verfahren zur Herstellung von normalerweise flüssigen Kohlenwasserstoffen Expired - Lifetime EP0439865B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB909000025A GB9000025D0 (en) 1990-01-02 1990-01-02 Process for preparing normally liquid hydrocarbons
GB9000025 1990-01-02

Publications (2)

Publication Number Publication Date
EP0439865A1 EP0439865A1 (de) 1991-08-07
EP0439865B1 true EP0439865B1 (de) 1994-10-19

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EP90203479A Expired - Lifetime EP0439865B1 (de) 1990-01-02 1990-12-20 Verfahren zur Herstellung von normalerweise flüssigen Kohlenwasserstoffen

Country Status (6)

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EP (1) EP0439865B1 (de)
JP (1) JPH04132793A (de)
CA (1) CA2031933A1 (de)
DE (1) DE69013489T2 (de)
GB (1) GB9000025D0 (de)
ZA (1) ZA919B (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5231043A (en) * 1991-08-21 1993-07-27 Sgs-Thomson Microelectronics, Inc. Contact alignment for integrated circuits
KR102329122B1 (ko) 2014-10-23 2021-11-19 에스케이이노베이션 주식회사 Ｃ4, ｃ5, ｃ6 스트림을 이용한 탄화수소의 업그레이드 방법

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3515769A (en) 1967-06-30 1970-06-02 Universal Oil Prod Co Polymerization process
FR2620724B1 (fr) * 1987-09-17 1994-04-15 Institut Francais Petrole Procede de production d'oligomeres d'olefines, utilisant un catalyseur a base de mordenite modifiee
US4827069A (en) 1988-02-19 1989-05-02 Mobil Oil Corporation Upgrading light olefin fuel gas and catalytic reformate in a turbulent fluidized bed catalyst reactor
GB8806675D0 (en) 1988-03-21 1988-04-20 Shell Int Research Process for preparing liquid hydrocarbons
ZA892236B (en) 1988-03-29 1989-11-29 Csir Catalytic process for the oligomerization of olefins

Also Published As

Publication number Publication date
GB9000025D0 (en) 1990-03-07
JPH04132793A (ja) 1992-05-07
EP0439865A1 (de) 1991-08-07
DE69013489D1 (de) 1994-11-24
CA2031933A1 (en) 1991-07-03
DE69013489T2 (de) 1995-03-23
ZA919B (en) 1991-10-30

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