EP2099727B1 - Verfahren zur optimierung des betriebs einer einheit für die synthese von kohlenwasserstoffen aus einem synthesegas - Google Patents

Verfahren zur optimierung des betriebs einer einheit für die synthese von kohlenwasserstoffen aus einem synthesegas Download PDF

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EP2099727B1
EP2099727B1 EP07866482A EP07866482A EP2099727B1 EP 2099727 B1 EP2099727 B1 EP 2099727B1 EP 07866482 A EP07866482 A EP 07866482A EP 07866482 A EP07866482 A EP 07866482A EP 2099727 B1 EP2099727 B1 EP 2099727B1
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ratio
synthesis
reaction
gas
fischer
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EP2099727A1 (de
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Marie-Claire Marion
François Hugues
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IFP Energies Nouvelles IFPEN
Eni SpA
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Eni SpA
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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
    • 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

Definitions

  • the present invention relates to the field of hydrocarbon synthesis from a mixture comprising carbon monoxide (CO), hydrogen (H2) and optionally carbon dioxide (CO2), generally called synthesis gas.
  • CO carbon monoxide
  • H2 hydrogen
  • CO2 carbon dioxide
  • the method according to the invention makes it possible to optimize the operation of a hydrocarbon synthesis unit from synthesis gas (also called Fischer-Tropsch synthesis), or to restore stable operation in order to maximize the hydrocarbon yield.
  • synthesis gas also called Fischer-Tropsch synthesis
  • the process according to the invention is a process for controlling Fischer-Tropsch synthesis in which the ratio of partial pressures of water and hydrogen P H 2 O : P H 2 is used as the control parameter of this synthesis.
  • catalysts comprising cobalt can develop a CO conversion activity (WGSR), which then comes into competition with the Fischer-Tropsch synthesis reaction and strongly penalize this synthesis.
  • WGSR CO conversion reaction
  • the CO conversion reaction (WGSR) consumes some of the CO reagent by forming CO2 instead of the desired hydrocarbons and simultaneously produces an excess of hydrogen which modifies the H2: CO ratio and gives rise to a degradation of the selectivity of the reaction towards the lightest products.
  • the selectivities in methane and C2 to C4 hydrocarbons are therefore increased.
  • the patent US 6,534,552 B2 describes a process for the production of hydrocarbons from natural gas in which natural gas is converted to synthesis gas which is fed to a Fischer-Tropsch synthesis section to produce hydrocarbons and a tail gas (tail gas according to the terminology Anglo-Saxon).
  • a separation section makes it possible to separate hydrogen from a fraction of this gas, said hydrogen being recycled continuously, either to the Fischer-Tropsch section or to the synthesis gas production section.
  • the patent US 4,626,552 describes a procedure for starting a Fischer-Tropsch reactor in which the H2: CO ratio is maintained at a low value by imposing a hydrogen flow rate of between 15% and 90% of the flow rate in the stabilized state. Then gradually increases the gas load flow, pressure and temperature and finally the H2: CO ratio is adjusted to the desired optimum value by increasing the flow of hydrogen input.
  • Requirement WO 2005/123882 describes a method for producing liquid hydrocarbons by Fischer-Tropsch synthesis in which the difference between the H2 / CO ratio at the inlet and the H2 / CO ratio in the effuent is kept substantially constant.
  • the method according to the invention is a method for optimizing the operation of a hydrocarbon synthesis unit from a feedstock comprising synthesis gas, in which one operates in the presence of a catalyst comprising cobalt.
  • the method according to the invention relates to a process for the synthesis of hydrocarbons from a feedstock comprising synthesis gas operated with a catalyst comprising cobalt.
  • Said method comprises the following steps: the determination of the theoretical molar ratio of the partial pressures of water and of hydrogen P H2O : P H2 in the Fischer-Tropsch reaction section, followed by a possible adjustment of this ratio and then the determination of the new value of this report. These steps are optionally repeated until said ratio has a value less than 1.1, preferably strictly less than 1 and very preferably strictly less than 0.9, even more preferably strictly less than 0.8. or even strictly less than 0.65.
  • This method of controlling the Fischer-Tropsch synthesis makes it possible to maintain high performances, particularly in terms of yield of heavy products (C5 + hydrocarbons). It also makes it possible to maximize the selectivity of the heavier hydrocarbons according to the Fischer-Tropsch reaction and to avoid the degradation of the selectivity by the development of the CO conversion reaction (in English WGSR).
  • the method according to the invention is a method for controlling and optimizing Fischer-Tropsch synthesis in which the molar ratio of the partial pressures of water and hydrogen P H 2 O : P H 2 in the Fischer-Tropsch reaction section is used. as a parameter for controlling and optimizing this synthesis.
  • the method according to the invention makes it possible to improve the operation of the Fischer-Tropsch synthesis unit by optimizing its yield and avoiding any selectivity drift towards the CO conversion reaction ("Water Gas Shift Reaction” or “WGS Reaction”). according to the English terminology).
  • This new method of control and optimization is particularly relevant during transitional phases, especially when starting a unit or during a temporary malfunction of the unit (for example, when an incident such as the rupture of part of the load supply, disrupts the operation of the reaction section).
  • the objective is the synthesis of a mixture of hydrocarbons comprising mainly paraffins, and mainly long-chain carbon compounds (hydrocarbons having more than 5 carbon atoms per molecule and preferably having more than 20 carbon atoms per molecule) in the presence of a catalyst comprising cobalt, also called Fischer-Tropsch synthesis.
  • a catalyst comprising cobalt also called Fischer-Tropsch synthesis.
  • it is important to minimize as much as possible the aforementioned transitional phases during which the conversion and or the selectivity of the Fischer-Tropsch reaction are generally not optimal.
  • the method for controlling and optimizing the operation of a hydrocarbon synthesis unit according to the invention makes it possible to maintain high performances, particularly in terms of yield of heavy products (C5 + hydrocarbons). More precisely, it makes it possible to maximize the selectivity for the heavier hydrocarbons according to the Fischer-Tropsch reaction and to avoid the degradation of the selectivity by the development of the CO conversion reaction.
  • said catalyst can be used in a fixed bed (reactor with a fixed bed catalyst, with one or more catalyst beds in the same reactor) or preferably in a reactor.
  • triphasic reactor (implementation in "slurry” according to the English terminology) comprising the catalyst in suspension in a substantially inert liquid phase and the reactive gas phase (synthesis gas).
  • the synthesis gas used in the Fischer-Tropsch synthesis step according to the invention can be obtained via the transformation of natural gas, coal, or biomass by processes such as steam reforming or partial oxidation, or via the decomposition of methanol, or from any other method known to those skilled in the art. Any charge comprising at least hydrogen and carbon monoxide may therefore be suitable.
  • the synthesis gas used in Fischer-Tropsch synthesis has a H 2: CO molar ratio of between 1: 2 and 5: 1, more preferably between 1.2: 2 and 3: 1, and more preferably between 1.5: 1 and 2.6: 1.
  • the Fischer-Tropsch synthesis is generally carried out under a pressure of between 0.1 MPa and 15 MPa, preferably between 1 MPa and 10 MPa and more preferably between 1.5 MPa and 5 MPa.
  • the hourly volumetric velocity of the synthesis gas is generally between 100 and 20000 h -1 (volume of synthesis gas per volume of catalyst per hour), preferably between 400 and 10,000 h -1 .
  • Any catalyst comprising cobalt known to those skilled in the art is suitable for the process according to the invention, especially those mentioned in the "prior art" part of this application.
  • Catalysts comprising cobalt deposited on a support selected from among the following oxides are preferably used: alumina, silica, zirconia, titanium oxide, magnesium oxide or their mixtures.
  • Various promoters known to those skilled in the art can also be added, in particular those selected from the following elements: rhenium, ruthenium, molybdenum, tungsten, chromium. It is also possible to add at least one alkali or alkaline earth metal to these catalytic formulations.
  • step a) The determination of the ratio P H2O : P H2 according to step a) can be carried out using any means known to those skilled in the art.
  • the reaction section may consist of one or more reactors.
  • Step a) is performed using a means selected from the means detailed below.
  • a preferred means consists in measuring the amount of carbon monoxide in the gaseous effluent and estimating the theoretical P H2O : P H2 ratio from the conversion rate of carbon monoxide in the whole of the reaction section comprising one or more reactors. , the H2: CO ratio in the feedstock and the H2: CO ratio for the gas consumed by the reaction (also called the use ratio).
  • the conversion rate of carbon monoxide is defined from measurements of carbon monoxide entering the hydrocarbon synthesis reaction section (CO input) and carbon monoxide leaving said reaction section (CO output ). These measurements are generally performed by gas chromatography using a katharometer detector. Similarly, hydrogen is measured with a specific column and detector in the gas streams entering and leaving the hydrocarbon synthesis reaction section to calculate the various H2 / CO ratios.
  • the Rft usage ratio qualifies in a certain way the intrinsic selectivity of the Fischer-Tropsch synthesis catalyst. It is generally determined beforehand under normal Fischer-Tropsch synthesis conditions, that is to say when the Shift reaction (WGSR) is a minority and practically negligible. By default, it can be taken equal to 2.0, according to the stoichiometry of the general Fischer-Tropsch synthesis reaction [1] recalled below, knowing that then the estimation of the ratio P H2O : P H2 theoretical will be conservative (c that is, slightly underestimated).
  • step c When the ratio P H2O : P H2 has been adjusted in step b), its new theoretical value is again determined (step c) in order to check that it is strictly less than 1.1, preferably strictly less than 1 , 0 and very preferably strictly less than 0.9, even more preferably strictly less than 0.8, or even strictly less than 0.65.
  • steps a to c are repeated (step d) until the criterion P H2O is met: P H2 theoretical strictly less than 1.1, preferably strictly less than 1.0 and very preferably strictly less than 0.9, even more preferably strictly less than 0.8, or even strictly less than 0.65.
  • Said reaction section may comprise one or more hydrocarbon synthesis reactors.
  • the Fischer-Tropsch synthesis reaction is carried out in a device comprising a perfectly stirred three-phase reactor of the autoclave type (CSTR according to the English abbreviations).
  • This reactor can be maintained under pressure and temperature and operated continuously.
  • the reactor is fed with a synthesis gas having an H2 / CO ratio which can be adjusted between 1.5 and 2.5.
  • the charge rate (synthesis gas) is controlled and can also be adjusted to increase or decrease the reaction time.
  • the Fischer-Tropsch synthesis is carried out at 230 ° C., 2 MPa, in the presence of 35 g of a catalyst containing 13% by weight of cobalt deposited on an alumina support having a specific surface area of approximately 150 m 2 / g and having a gamma structure. cubic.
  • the catalytic performances are evaluated by material balance from the analysis and the measurement of the various outgoing flows of the reactor.
  • the compositions of the various outgoing streams are determined by gas chromatography.
  • Example 2 Example of readjustment of the report after a setpoint change.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Gas Separation By Absorption (AREA)

Claims (10)

  1. Verfahren zum Optimieren des Betriebs einer Reaktionseinheit zur Synthese von Kohlenwasserstoffen ausgehend von einer Beschickung, die Synthesegas umfasst, wobei in Gegenwart eines Katalysators gearbeitet wird, der Cobalt umfasst, wobei das Verfahren die folgenden Schritte umfasst:
    a) Bestimmen des theoretischen Molverhältnisses PH2O:PH2 in der Reaktionseinheit durch die folgende Berechnung: theoretisches P H ⁢ 2 ⁢ O : P H ⁢ 2 = Cv / R ⁢ 1 - Rft * Cv
    Figure imgb0005
    mit Cv = (CO Einlass - CO Auslass) / CO Einlass
    R1 = H2/CO Beschickung = H2 Einlass / CO Einlass (mol/mol)
    Rft = H2/CO Reaktion = (H2 Einlass - H2 Auslass) / (CO Einlass - CO Auslass),
    b) Gegebenenfalls Anpassen des in Schritt a) bestimmten PH2O:PH2-Verhältnisses an einen Wert, der exakt kleiner als 1,1 ist, mit Hilfe eines Mittels, das aus den folgenden Mitteln ausgewählt ist:
    i. Erhöhen der Durchflussrate der Beschickung,
    ii. Falls die Reaktionseinheit oder mindestens ein Reaktor der Einheit mit einer Rückführung des nicht umgewandelten Gases ausgestattet ist, Erhöhung der Rückführungsrate,
    iii. Kontinuierliches Entfernen des gesamten oder eines Teils des Wassers, das durch die Reaktion gebildet wurde,
    iv. Verändern des H2/CO-Verhältnisses am Einlass der Reaktionseinheit zur Kohlenwasserstoffsynthese oder mindestens eines Reaktors zur Kohlenwasserstoffsynthese,
    v. Verringern der Betriebstemperatur,
    vi. Verringern des Drucks,
    c) Bestimmen des neuen Werts des theoretischen PH2O:PH2-Verhältnisses in der Reaktionseinheit.
  2. Verfahren nach Anspruch 1, wobei das gegebenenfalls erforderliche Anpassen des PH2O:PH2-Verhältnisses (Schritt b) mit Hilfe eines Mittels ausgeführt wird, das aus den folgenden Mitteln ausgewählt ist:
    i. Erhöhen der Durchflussrate der Beschickung,
    ii. Falls der Reaktor mit einer Rückführung des nicht umgewandelten Gases ausgestattet ist, Erhöhen der Rückführungsrate,
    iii. Kontinuierliches Entfernen des gesamten oder eines Teils des Wassers, das durch die Reaktion gebildet wurde.
  3. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Bestimmen des PH2O:PH2-Molverhältnisses (Schritte a und c) mit Hilfe eines Mittels ausgeführt wird, das aus den folgenden Mitteln ausgewählt ist:
    i. Analyse des gasförmigen Stroms am Auslass der Reaktionseinheit,
    ii. Messen der Menge an Kohlenmonoxid in dem gasförmigen Abfluss und Berechnen des Verhältnisses ausgehend von der Umwandlungsrate des Kohlenmonoxids und des H2:CO-Verhältnisses in der Beschickung.
  4. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Bestimmen des PH2O:PH2-Molverhältnisses (Schritte a und c) mit Hilfe des Messens der Menge an Kohlenmonoxid in dem gasförmigen Abfluss und Berechnen des Verhältnisses ausgehend von der Umwandlungsrate des Kohlenmonoxids und des H2:CO-Verhältnisses in der Beschickung ausgeführt wird, und das gegebenenfalls erforderliche Anpassen des PH2O:PH2-Verhältnisses (Schritt b) mit Hilfe eines Mittels ausgeführt wird, ausgewählt aus den folgenden Mitteln:
    i. Erhöhen der Durchflussrate der Beschickung,
    ii. Falls der Reaktor mit einer Rückführung des nicht umgewandelten Gases ausgestattet ist, Erhöhen der Rückführungsrate.
  5. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Kohlenwasserstoffsynthese in mindestens einem Reaktor mit einem Katalysator im Festbett durchgeführt wird.
  6. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Kohlenwasserstoffsynthese in mindestens einem Dreiphasenreaktor durchgeführt wird, der den Katalysator in Suspension in einer im Wesentlichen inerten flüssigen Phase und die reaktive gasförmige Phase umfasst.
  7. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Synthesegas, das in der Fischer-Tropsch-Synthese verwendet wird, ein H2:CO-Molverhältnis im Bereich zwischen 1:2 und 5:1 aufweist und die Fischer-Tropsch-Synthese unter einem Druck im Bereich zwischen 0,1 MPa und 15 MPa, mit einer Raumgeschwindigkeit pro Stunde des Synthesegases im Bereich zwischen 100 und 20.000 h-1 durchgeführt wird.
  8. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Synthesegas, das in der Fischer-Tropsch-Synthese verwendet wird, ein H2:CO-Molverhältnis im Bereich zwischen 1,5:1 und 2,6:1 aufweist und die Fischer-Tropsch-Synthese unter einem Druck im Bereich zwischen 1,5 MPa und 5 MPa, mit einer Raumgeschwindigkeit pro Stunde des Synthesegases im Bereich zwischen 400 und 10.000 h-1 durchgeführt wird.
  9. Verfahren nach einem der vorhergehenden Ansprüche, wobei am Ende des Schritts c) das Verhältnis der Partialdrücke von Wasser und Wasserstoff PH2O:PH2 einen Wert aufweist, der exakt kleiner als 1 ist.
  10. Verfahren nach einem der vorhergehenden Ansprüche, wobei am Ende des Schritts c) das Verhältnis der Partialdrücke von Wasser und Wasserstoff PH2O:PH2 einen Wert aufweist, der exakt kleiner als 0,65 ist.
EP07866482A 2006-11-13 2007-11-02 Verfahren zur optimierung des betriebs einer einheit für die synthese von kohlenwasserstoffen aus einem synthesegas Active EP2099727B1 (de)

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FR0609879A FR2908421B1 (fr) 2006-11-13 2006-11-13 Methode pour optimiser le fonctionnement d'une unite de synthese d'hydrocarbures a partir de gaz de synthese.
PCT/FR2007/001816 WO2008065268A1 (fr) 2006-11-13 2007-11-02 Methode pour optimiser le fonctionnement d'une unite de synthese d'hydrocarbures a partir de gaz de synthese

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DE (1) DE602007009313D1 (de)
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FR2908421B1 (fr) 2006-11-13 2009-02-06 Inst Francais Du Petrole Methode pour optimiser le fonctionnement d'une unite de synthese d'hydrocarbures a partir de gaz de synthese.
ITMI20080007A1 (it) * 2008-01-04 2009-07-05 Eni Spa Procedimento per stabilizzare le prestazioni di un catalizzatore per la reazione di fischer tropsch
FR2946659B1 (fr) * 2009-06-10 2011-07-01 Inst Francais Du Petrole Methode pour optimiser le fonctionnement d'une unite de synthese d'hydrocarbures a partir de gaz de synthese par controle de la pression partielle en co
US9393543B2 (en) 2012-03-09 2016-07-19 EVOenergy, LLC Plasma chemical device for conversion of hydrocarbon gases to liquid fuel
FR2991991B1 (fr) 2012-06-18 2014-06-13 IFP Energies Nouvelles Procede de synthese d'hydrocarbures a partir de gaz de synthese avec controle de la temperature de la boucle externe
WO2023174861A1 (en) * 2022-03-14 2023-09-21 Topsoe A/S Conversion of methanol to a hydrocarbon product stream
WO2024072544A1 (en) 2022-09-29 2024-04-04 Exxonmobil Chemical Patents Inc. Foamable branched polypropylene compositions and foamed products therefrom

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FR2870544B1 (fr) * 2004-05-19 2006-06-30 Inst Francais Du Petrole Procede de synthese fischer-tropsch comprenant une regulation amelioree
FR2908421B1 (fr) 2006-11-13 2009-02-06 Inst Francais Du Petrole Methode pour optimiser le fonctionnement d'une unite de synthese d'hydrocarbures a partir de gaz de synthese.

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CA2669301A1 (fr) 2008-06-05
CN101605744A (zh) 2009-12-16
EP2099727A1 (de) 2009-09-16
NO341790B1 (no) 2018-01-22
ATE481372T1 (de) 2010-10-15
US8399526B2 (en) 2013-03-19
DE602007009313D1 (de) 2010-10-28
PL2099727T3 (pl) 2011-04-29
CA2669301C (fr) 2015-01-13
FR2908421B1 (fr) 2009-02-06
FR2908421A1 (fr) 2008-05-16
WO2008065268A1 (fr) 2008-06-05
CN101605744B (zh) 2013-06-19
US20110009502A1 (en) 2011-01-13
NO20092043L (no) 2009-07-31

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