WO2007009987A1 - Procede de synthese d'hydrocarbures - Google Patents

Procede de synthese d'hydrocarbures Download PDF

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Publication number
WO2007009987A1
WO2007009987A1 PCT/EP2006/064364 EP2006064364W WO2007009987A1 WO 2007009987 A1 WO2007009987 A1 WO 2007009987A1 EP 2006064364 W EP2006064364 W EP 2006064364W WO 2007009987 A1 WO2007009987 A1 WO 2007009987A1
Authority
WO
WIPO (PCT)
Prior art keywords
stream
reactor
syngas
waxy hydrocarbon
oxygenates
Prior art date
Application number
PCT/EP2006/064364
Other languages
English (en)
Inventor
Robert Martijn Van Hardeveld
Lip Piang Kueh
Thomas Joris Remans
Original Assignee
Shell Internationale Research Maatschappij B.V.
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 Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Publication of WO2007009987A1 publication Critical patent/WO2007009987A1/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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/34—Apparatus, reactors
    • C10G2/342—Apparatus, reactors with moving solid catalysts
    • C10G2/343—Apparatus, reactors with moving solid catalysts according to the "moving-bed" method
    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/34—Apparatus, reactors
    • C10G2/342—Apparatus, reactors with moving solid catalysts
    • C10G2/344—Apparatus, reactors with moving solid catalysts according to the "fluidised-bed" technique
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions

Definitions

  • the present invention relates to a hydrocarbon synthesis process, particularly but not exclusively to a Fischer-Tropsch process.
  • liquid recycles as a means of improving the overall performance in a fixed-bed design are described in the art.
  • a system is also called a "trickle flow" reactor (as part of a sub-set of fixed-bed reactor systems) in which both reactant gas and liquid are introduced (preferably in an up flow or down flow orientation with respect to the catalyst) simultaneously.
  • the presence of the flowing reactant gas and the liquid improves heat removal and temperature control, thus enhancing the reactor performance with respect to CO conversion and product selectivity.
  • the Fischer-Tropsch reaction is improved in the art, longer (and therefore heavier) hydrocarbons are being formed, meaning that the percentage of the heavy tail fractions formed by the reaction is increasing.
  • the present invention provides a process for the synthesis of hydrocarbon products from syngas in one or more syngas conversion reactors, the or each conversion reactor having: a fixed bed of hydrocarbon synthesis catalyst; a syngas entry stream system comprising one or more entry streams into the reactor; two or more reactor product exit streams, one of which is a liquid waxy hydrocarbon stream having a heavy tail fraction including oxygenates, another one being a gaseous product stream comprising unconverted syngas, gaseous hydrocarbons, steam and optionally inert gaseous compounds; and a system for recycling at least a portion of the waxy hydrocarbon stream back into the reactor, by contacting syngas with the hydrocarbon synthesis catalyst and converting syngas into liquid and gaseous hydrocarbons, wherein in that portion of the liquid waxy hydrocarbon stream being recycled, the oxygenates in the heavy tail fraction are removed before said stream is reintroduced as a recycle stream into the conversion reactor.
  • Catalysts as discussed above are susceptible to various substances, which include oxygenates, olefins and water. Such substances are found in many fractions of hydrocarbon products, but their presence in heavy tail fractions is of greater concern, which presence is increasing in recycle streams as the Fischer-Tropsch reaction is made more efficient in the art.
  • Option A involves passing the waxy hydrocarbon feed 12 to a separation unit (SU) 14, which in this example could be a distillation unit .
  • the distillation will create a number of product streams therefrom.
  • that fraction which is generally boiling in the range 350-490 0 C can be taken from the separation unit 14 and passed along line 24 into a recycle stream 30 passing back into the HS 10.

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)

Abstract

L'invention concerne un procédé de synthèse de produits d'hydrocarbures à partir de gaz de synthèse dans un ou plusieurs réacteurs de conversion de gaz de synthèse. Le ou chaque réacteur de conversion est doté d'un système de flux d'entrée de gaz de synthèse comprenant un ou plusieurs flux d'entrée dans le réacteur; deux ou plusieurs flux de sortie de produits du réacteur, l'un étant un flux d'hydrocarbure paraffineux ayant une fraction résiduaire lourde comportant des composés oxygénés; et un système permettant de recycler au moins une partie du flux d'hydrocarbure paraffineux dans le réacteur. Pendant le recyclage de ladite partie du flux d'hydrocarbure paraffineux, les composés oxygénés de la fraction résiduaire lourde sont évacués avant la réintroduction du flux en question comme flux de recyclage dans le réacteur de conversion.
PCT/EP2006/064364 2005-07-20 2006-07-18 Procede de synthese d'hydrocarbures WO2007009987A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP05254534.0 2005-07-20
EP05254534 2005-07-20

Publications (1)

Publication Number Publication Date
WO2007009987A1 true WO2007009987A1 (fr) 2007-01-25

Family

ID=35395737

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/064364 WO2007009987A1 (fr) 2005-07-20 2006-07-18 Procede de synthese d'hydrocarbures

Country Status (1)

Country Link
WO (1) WO2007009987A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2199370A4 (fr) * 2007-09-28 2015-11-04 Japan Oil Gas & Metals Jogmec Procédés de fabrication de naphte synthétique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2617816A (en) * 1950-10-11 1952-11-11 Joyce H Crowell Catalytic conversion of carbon monoxide and hydrogen to hydrocarbons and oxygenated organic compounds
EP0583836A1 (fr) * 1992-08-18 1994-02-23 Shell Internationale Researchmaatschappij B.V. Procédé de préparation de combustibles hydrocarbonés
US20030195264A1 (en) * 2000-06-06 2003-10-16 David Newton Fischer-tropsch process
US20040044090A1 (en) * 2000-10-13 2004-03-04 Font Freide Josephus Johannes Helena Maria Fischer-tropsch synthesis process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2617816A (en) * 1950-10-11 1952-11-11 Joyce H Crowell Catalytic conversion of carbon monoxide and hydrogen to hydrocarbons and oxygenated organic compounds
EP0583836A1 (fr) * 1992-08-18 1994-02-23 Shell Internationale Researchmaatschappij B.V. Procédé de préparation de combustibles hydrocarbonés
US20030195264A1 (en) * 2000-06-06 2003-10-16 David Newton Fischer-tropsch process
US20040044090A1 (en) * 2000-10-13 2004-03-04 Font Freide Josephus Johannes Helena Maria Fischer-tropsch synthesis process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2199370A4 (fr) * 2007-09-28 2015-11-04 Japan Oil Gas & Metals Jogmec Procédés de fabrication de naphte synthétique

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