EP1765956B1 - Fischer-tropsch-syntheseverfahren mit verbesserter steuerung - Google Patents

Fischer-tropsch-syntheseverfahren mit verbesserter steuerung Download PDF

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Publication number
EP1765956B1
EP1765956B1 EP05771067A EP05771067A EP1765956B1 EP 1765956 B1 EP1765956 B1 EP 1765956B1 EP 05771067 A EP05771067 A EP 05771067A EP 05771067 A EP05771067 A EP 05771067A EP 1765956 B1 EP1765956 B1 EP 1765956B1
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Prior art keywords
hydrogen
carbon monoxide
synthesis gas
fischer
ratio
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French (fr)
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EP1765956A1 (de
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Marie-Claire Marion
Eric Lemaire
Jean-Marc Schweitzer
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IFP Energies Nouvelles IFPEN
Eni SpA
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IFP Energies Nouvelles IFPEN
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
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • 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

Definitions

  • the invention relates to the field of liquid hydrocarbon production processes comprising a Fischer-Tropsch synthesis step. It relates more particularly to an improved Fischer-Tropsch synthesis process that maximizes production and minimizes production costs.
  • Fischer-Tropsch synthesis is a reaction that makes it possible to synthesize paraffinic, olefinic liquid hydrocarbons and / or oxygenated derivatives from a synthesis gas, the latter being obtained, for example, from natural gas or coal. This reaction, exploited industrially in Europe during the Second World War and also in South Africa since the 1950s, has regained a spectacular renewal of interest since the 1980s to 1990, following the evolution of oil and gas costs, but also for environmental reasons.
  • One of the concerns of those skilled in the art using such methods is to maximize the conversion rate reagents, that is to say maximize the conversion rate of carbon monoxide to liquid hydrocarbons. It is often difficult to maximize the conversion rate of the reactants in a single reactor and in a single pass, that is to say in a single passage of said reagents in said reactor. Indeed, by seeking a high level of conversion, the operation of the catalyst used during the synthesis can be degraded given the operating conditions and, in particular, high partial pressures of water. For example, a marked decrease in selectivity can be observed in products having at least five carbon atoms when, using a cobalt-based catalyst, the carbon monoxide conversion level is increased to above about 80%. weight.
  • one solution may consist in carrying out said synthesis in several steps, for example using several reactors in series.
  • Another solution may be to carry out the Fischer-Tropsch synthesis in a single reactor by implementing an internal recycling loop around said reactor, which may make it possible to maintain a moderate conversion level, for example of the order of 60 to 70% by weight, while achieving a high overall conversion level, for example greater than or equal to 90% conversion.
  • the use ratio is generally defined as the stoichiometric ratio (or molar ratio) between hydrogen and carbon monoxide consumed by the Fischer-Tropsch synthesis.
  • the usage ratio is generally variable. This ratio may depend on the nature of the catalyst as well as the operating conditions used during the synthesis. This usage ratio can change over time, depending for example on the stability of the catalyst. This usage ratio can also reflect the selectivity of the catalyst. For example, in the case of a Fischer-Tropsch process using a cobalt catalyst and aimed at producing long chain paraffinic hydrocarbons, the duty ratio can range from 2.0 to 2.3 mol.
  • the ratio of hydrogen and carbon monoxide introduced into a reaction zone where Fischer-Tropsch synthesis is performed plays on the reaction mechanisms of said synthesis, in particular on the kinetics and selectivity of the catalyst used.
  • margin of error is a function of the control system implemented and the response times of the adjustment means. Said margin of error is less than or equal to plus or minus 5%, preferably less than or equal to plus or minus 2%, more preferably less than or equal to plus or minus 1%, for example less than or equal to more than less than 0.5%.
  • concentration ratios A1 and A2 can then be determined by simple calculation from the concentration measurements.
  • A1 corresponds to a molar ratio of hydrogen and carbon monoxide concentrations in the feed of the Fischer-Tropsch synthesis step (b).
  • This feed is generally a mixture comprising the synthesis gas produced in step (a) and the effluent enriched in hydrogen and carbon monoxide recycled during step (e).
  • A2 corresponds, for its part, to a molar ratio of concentrations of hydrogen and carbon monoxide in any of the gaseous effluents obtained in steps (b) to (e).
  • A2 is calculated from measurements made at any gaseous flow from the gaseous effluent obtained in step (b) and directed to the recycled effluent during step (e). These streams generally have concentrations of hydrogen and carbon monoxide in the same proportions.
  • the concentrations of hydrogen and / or carbon monoxide in the synthesis gas obtained in step (a) are adjusted so as to keep the difference between the two substantially constant.
  • This adjustment can be carried out by any means known to those skilled in the art, such as, for example, by means of a control system or a connected automaton, on the one hand, to the means for measuring the concentrations of hydrogen and carbon monoxide. carbon at the base of which are calculated the A1 and A2 ratios, and secondly to means for adjusting the concentrations of hydrogen and / or carbon monoxide in the synthesis gas obtained in step (a)
  • the regulation of the method of the invention makes adjustments in step (a) of the process in order to enrich the synthesis gas with carbon monoxide or to deplete it in hydrogen so as to minimize or maintain constant the difference between A1 and A2.
  • the regulation of the process of the invention makes adjustments in step (a) of the process in order to enrich the synthesis gas with hydrogen or to deplete it in carbon monoxide so as to equalize A1 and A2.
  • the implementation of the method of the invention advantageously avoids having to perform the regulation with respect to a given value of the duty ratio.
  • the regulation is done by minimizing or maintaining a constant value of the difference between two concentration ratios, in this case those measured by A1 and A2.
  • the concentrations of hydrogen and / or carbon monoxide in the synthesis gas obtained in step (a) are adjusted so as to maintain substantially constant between the two ratios A1 and A2.
  • the concentrations of hydrogen and / or carbon monoxide in the synthesis gas obtained in step (a) can be adjusted so as to keep the difference between the two ratios A1 and A2 constant.
  • This mode makes it possible to adjust the selectivity of the reaction to obtain the desired product distribution.
  • the aging of the catalyst over time may induce a change in the duty ratio giving rise to a change in the product distribution.
  • the ratio of use in the reaction zone of the Fischer-Tropsch synthesis step (b) may vary over time. For example, this ratio of use tends to increase with time, which may reflect some deactivation of the catalyst, and more particularly a decrease in its selectivity to long-chain hydrocarbon products. Similarly, the use ratio can increase with temperature, which favors the formation of light products at the expense of heavy products. There can therefore also be an impact of any change in capacity, in terms of changes in space velocity and / or change in operating temperature, on the duty ratio in the Fischer-Tropsch synthesis reaction zone.
  • the process of the invention is carried out so as to regulate the operating conditions in order to regulate the H2 / CO concentration ratio at a level corresponding to a required duty ratio in accordance with a targeted product distribution.
  • the present invention may advantageously be used in processes for converting natural gas into liquid hydrocarbons, processes known as "gas to liquid", or abbreviated to GTL. These processes have a natural gas recovery pathway that allows, among other things, to produce high quality, sulfur-free diesel fuels from natural gas. These processes generally use a catalyst based on cobalt or iron, preferably based on cobalt.
  • the method of the invention therefore comprises a step (a) of generating the synthesis gas essentially comprising carbon monoxide and hydrogen.
  • This generation of a synthesis gas can be made from natural gas, coal or obtained by any other transformation route known to those skilled in the art, for example by decomposition of methanol in the presence of copper-based catalyst.
  • the generation of a synthesis gas is made from natural gas.
  • this step (a) may comprise a step of reforming with methane vapor or a partial oxidation step of methane, or a combination of these two steps, such as the autothermal reforming process, for example, the ATR process marketed by the company TOPSOE.
  • This first step may comprise a combination of a methane steam reforming step with a partial methane oxidation step.
  • this embodiment provides a means of adjusting the concentrations of hydrogen and carbon monoxide in the synthesis gas, in particular the ratio of concentrations of hydrogen and carbon monoxide, H2 / CO. These means generally result from the implementation of a conversion reaction of carbon monoxide in the presence of water to carbon dioxide and hydrogen.
  • the step (a) of generating a synthesis gas may comprise means dedicated to adjusting the concentrations of hydrogen and / or carbon monoxide in the synthesis gas.
  • these means may be controlled flow injection means of water and / or carbon dioxide.
  • step (a) comprises an autothermal reforming
  • the injection of controlled rate steam is particularly well suited.
  • step (a) of generating a synthesis gas is followed by a step (a ') dedicated to adjusting the concentrations of hydrogen and / or monoxide. of carbon in the synthesis gas.
  • step (a ') can be carried out from a feed of all or part of the synthesis gas produced in step (a).
  • step (a ') is carried out from a feed of a portion of the synthesis gas produced in step (a), which may range from 1 to 50% by weight, preferably 10 to 30% by weight. % by weight of the synthesis gas produced in step (a).
  • this step (a ') may comprise the use of a means for extracting hydrogen or carbon monoxide, such as, for example, a membrane which preferably extracts hydrogen from a mixture comprising hydrogen and carbon monoxide.
  • a means for extracting hydrogen or carbon monoxide such as, for example, a membrane which preferably extracts hydrogen from a mixture comprising hydrogen and carbon monoxide.
  • This step (a ') can comprise the implementation of means allowing a supplementation of hydrogen or carbon monoxide, such as, for example, a hydrogen make-up line from a catalytic reforming auxiliary unit.
  • This adjustment can also be achieved through the control system which is one of the objects of the invention.
  • the concentration ratio H2 / CO at the output of step (a') can equal to, greater than or less than the ratio of H2 / CO concentrations in the synthesis gas from step (a).
  • step (a ') makes it possible to improve the regulation of the concentration ratio H2 / CO of the supply of the reaction section of step (b). Indeed, even if it is often possible to adjust this H2 / CO concentration ratio directly during step (a) for generating the synthesis gas, the regulation actions on this step (a) can have significant response times that may be too slow to establish a regulation effective or even incompatible with the control system of the present invention.
  • the preferred embodiment implementing a step (a ') provides flexibility in the operation of the method of the invention. The adjustments made in this step (a ') are simple and fast corrective actions, which considerably improves the overall performance of the method of the invention.
  • the Fischer-Tropsch synthesis step (b) of the process according to the invention is carried out from a feed comprising at least a part of the synthesis gas resulting from steps (a) or (a ') and allowing the production an effluent comprising synthetic liquid hydrocarbons and at least one gaseous effluent.
  • step (b) Thanks to the H2 / CO concentration ratio control system in step (b), the operation of this Fischer-Tropsch synthesis step is optimized.
  • the Fischer-Tropsch synthesis step (b) is carried out in a reaction zone comprising one or more suitable reactors, the technology of which is known to those skilled in the art. It may be, for example, fixed bed multitubular reactors, moving bed reactors or bubble column type reactors, known in English as “slurry bubble column", or abbreviated as "SBC”. .
  • step (b) uses one or more bubble column type reactors.
  • the synthesis being strongly exothermic, this mode of realization allows, among other things, to improve the thermal control of the reactor, especially in the case of high capacity units.
  • the catalyst used in this step (b) is generally any catalytic solid known to those skilled in the art for performing the Fischer-Tropsch synthesis.
  • the catalyst used in this step (b) comprises cobalt or iron, more preferably cobalt.
  • the catalyst used in this step (b) is generally a supported catalyst.
  • the support may be, for example, based on alumina, silica or titanium.
  • the conditions of temperature and pressure are variable and adapted to the catalyst used in this step (b).
  • the pressure can generally be between 0.1 and 10 MPa.
  • the temperature can generally be between 200 and 400 ° C.
  • the temperature is preferably between about 200 and 250 ° C and the pressure is preferably between about 1 and 4 MPa.
  • the feed of step (b) of the invention comprises carbon monoxide and hydrogen with a ratio of molar concentrations H2 / CO which may be between 0.5 and 3, preferably between 1 and 2 , 5, more preferably between 2.0 and 2.3.
  • the liquid effluent from step (b) comprising synthetic liquid hydrocarbons is generally intended to be treated in various purification and / or conversion stages with a view to producing, for example, fuels and in particular diesel fuel. of very high quality.
  • a gaseous effluent obtained during step (b) is condensed.
  • This effluent may comprise all or part of the effluent obtained in step (b).
  • This condensation step can be carried out so as to achieve a temperature ranging from -20 to 300 ° C, preferably from 0 to 200 ° C, more preferably from 30 to 60 ° C.
  • the condensation step (c) is carried out so as to condense at least a portion of the effluent sent in said step, which makes it possible to obtain a two-phase flow.
  • the condensed portion may represent at most 50%, preferably at most 15% by weight, of the portion of the effluent sent in the condensation step.
  • the condensation step (c) can be carried out by any means known to those skilled in the art such as, for example, a conventional air-condenser or a conventional water-heat exchanger, preferably an air condenser.
  • the condensed effluent is sent during step (c) to a separation zone making it possible to obtain a gaseous effluent enriched with carbon monoxide and hydrogen. , an aqueous phase and liquid hydrocarbons.
  • the separation zone in which the separation step (d) is carried out can be equipped by any means known to those skilled in the art, such as, for example, by one or more separation flasks.
  • step (e) at least a portion of the gaseous effluent enriched in carbon monoxide and hydrogen obtained during step (d) is recycled to step (b) of synthesis.
  • Fischer-Tropsch synthesis at least a portion of the gaseous effluent enriched in carbon monoxide and hydrogen obtained during step (d) is recycled to step (b) of synthesis.
  • the portion of the enriched gaseous effluent recycled to the Fischer-Tropsch synthesis stage (b) may comprise at least 50% by volume, preferably at least 75% by volume, more preferably at least 85% by volume.
  • the portion of the enriched effluent recycled to step (b) may have a flow rate ranging from 0 (excluded) to 2 times, preferably from 0.5 to 1.5 times that of the synthesis gas resulting from the step (a) or (a ').
  • the portion of the effluent enriched with carbon monoxide and hydrogen is compressed by any means known to those skilled in the art at a pressure ranging from 0.1 to 10 MPa, preferably from 1 to 4 MPa, more preferably from 2 to 3 MPa.
  • the recycling step (e) may comprise means for extracting carbon dioxide.
  • These means can be any means known to those skilled in the art, such as, for example, washing with an aqueous solution of amines.
  • the extraction of carbon dioxide can be partial or total. This extraction can be carried out on all or part of the recycled enriched effluent.
  • the recycled enriched effluent may be optionally heated or cooled by any means known to those skilled in the art.
  • a hydrocarbon feedstock is sent via a conduit 1 into a synthesis gas generation zone 2, said gas then being fed into a conduit 3.
  • the generation zone 2 is equipped with means for adjust the hydrogen and carbon monoxide concentrations of the synthesis gas thus produced.
  • These means are diagrammatically represented by a hydrogen supply duct 4 equipped with a valve 5 and a hydrogen evacuation duct 6 equipped with a valve 7.
  • the two valves 5 and 7 can be operated at the same time. distance by a PLC 51.
  • the synthesis gas is sent through the conduit 3 and a conduit 11 into a Fischer-Tropsch synthesis reactor 12.
  • This reactor is equipped with a discharge pipe 13 of an effluent comprising liquid hydrocarbons to unrepresented purification and / or conversion steps.
  • a gaseous effluent is also discharged through a conduit 21 of the Fischer-Tropsch synthesis reactor 12. This gaseous effluent is directed to a cooling unit 22.
  • the cooled effluent is directed by a conduit 31 to separation means, in this case a separator tank 32.
  • An aqueous effluent enriched with water is withdrawn at the bottom of this flask via a conduit 33.
  • a liquid effluent enriched in hydrocarbons is also withdrawn by a conduit 34.
  • an effluent enriched in carbon monoxide and hydrogen is discharged through a conduit 35.
  • Part of the enriched effluent is sent, via a conduit 41, to a compressor 42.
  • the other part of the enriched effluent is discharged through a conduit 43.
  • the part of the enriched and compressed effluent is sent, via a conduit 44, to means 45 for extracting carbon dioxide before being recycled to the Fischer-Tropsch synthesis reactor via a conduit 46 through through the conduit 11.
  • the carbon dioxide is extracted via a conduit 47.
  • a programmable controller 51 makes it possible to regulate the opening and the closing of the valves 5 and 7 as a function of the measurements of concentrations of hydrogen and of carbon monoxide produced by means of chromatographic analyzers 52 and 53 respectively located on the conduits 11 and 41.
  • the valves 5 and 7, and the analyzers 52 and 53 are connected to the programmable controller 51 respectively via the lines 54, 55, 56 and 57.
  • the Figure 2 contains elements already represented in Figure 1 .
  • the embodiment shown in FIG. Figure 2 comprises adjustment means 61 for the ratio of the concentrations of hydrogen and carbon monoxide in the synthesis gas, said means being dissociated from the zone 2 for generating the synthesis gas.
  • These adjustment means are connected to the synthesis gas generation zone 2 via a conduit 62.
  • Means (4, 5, 6 and 7) for adjusting the hydrogen and carbon monoxide concentrations of the Figure 1 are replaced in the Figure 2 by a hydrogen supply duct 63 equipped with a valve 64 and a hydrogen evacuation duct 65 equipped with a valve 66.
  • the two valves 64 and 66 are operated remotely by a programmable controller.
  • the programmable logic controller 51 makes it possible to regulate the opening and the closing of the valves 64 and 66 as a function of the measurements of concentrations of hydrogen and carbon monoxide. carbon generated by chromatographic analyzers 52 and 53 which are, in this embodiment, respectively located on the ducts 11 and 43.
  • the valves 64 and 66, and the analyzers 52 and 53 are connected to the programmable controller 51 respectively via lines 54, 55, 56 and 57.
  • the Figure 3 contains elements already represented in Figure 2 .
  • the adjustment means 61 for the ratio of the concentrations of hydrogen and carbon monoxide in the synthesis gas are directly connected to the synthesis gas duct 3 via a supply duct 71 and a exhaust duct 72.
  • step of adjusting the ratio of the concentrations of hydrogen and carbon monoxide is implemented only on a portion of the synthesis gas produced in step (a).
  • the programmable logic controller 51 makes it possible to regulate the opening and the closing of the valves 64 and 66 as a function of the measurements of concentrations of hydrogen and of carbon monoxide produced by means of chromatographic analyzers 52 and 53 which are in this case, respectively located on the ducts 11 and 46.
  • the valves 64 and 66, and the analyzers 52 and 53 are connected to the programmable controller 51 respectively via the lines 54, 55, 56 and 57.
  • the scheme of the figure 3 was used as a basis for these examples.
  • the reaction section of the Fischer-Tropsch synthesis used in these examples was fed with a synthesis gas comprising hydrogen and carbon monoxide.
  • This synthesis gas is produced by a generating device and an adjustment device making it possible to maintain the hydrogen / monoxide concentration ratio H2 / CO at a value determined by a programmable logic controller. carbon of this synthesis gas.
  • the recycling rate defined by the ratio of the flow rate in the recycling loop to the flow rate of synthesis gas leaving the synthesis gas generation zone, is maintained around a value equal to 1.0.
  • the Fischer-Tropsch synthesis reaction is carried out at 220 ° C. and at 2 MPa, in the presence of a cobalt catalytic solid. Under the conditions used in the reaction zone, the duty ratio is about 2.10 and the initial conversion level per pass is 60% by weight.
  • the Fischer-Tropsch reaction section is fed with a synthesis gas having a ratio of molar concentrations H2 / CO equal to 2.0.
  • the Fischer-Tropsch reaction section is fed with a synthesis gas having a ratio of molar concentrations H2 / CO equal to 2.2.
  • the method implemented corresponds to the diagram of the figure 3 wherein the control system according to the invention (adjustment means 61, PLC 51, valves 64 and 66) is not implemented (comparative cases).
  • the Fischer-Tropsch reaction section is fed with a synthesis gas having a ratio of molar concentrations H2 / CO regulated thanks inter alia to the adjustment means 61, to the controller 51 and to the valves 64 and 66 according to the invention ( figure 3 ).
  • Table 1 1st case 2nd case 3 rd case H2 / CO ratio in synthesis gas (3) 2.0 2.2 2.0 Initial H2 / CO ratio in the feed of the Fischer-Tropsch reaction zone (11) 2.0 2.2 2.1 Initial conversion of carbon monoxide (% by weight) 60 60 60 H2 / CO ratio of use 2.1 2.1 2.1 H2 / CO A2 ratio of the gaseous effluent of the Fischer-Tropsch synthesis (21) 1.85 2.35 2.1 H2 / CO ratio A1 in the feed of the Fischer-Tropsch reaction zone (11), immediately after mixing between synthesis gas (3) and recycling (46). 1.92 2.27 2.1
  • Figure 4 shows the impact of H2 / CO concentration ratio on carbon monoxide conversion.
  • Figure 5 shows the impact of the H2 / CO concentration ratio on the selectivity to hydrocarbons having at least five carbon atoms.
  • the control method according to the invention not only allows a stable operation, but it also allows, in a simple, fast and precise way, to adjust the ratio of H2 / CO concentrations in the reactor to a level approximately equal to the usage ratio. .
  • This operation thus makes it possible to obtain a good compromise between the conversion of carbon monoxide and the selectivity into hydrocarbons having at least 5 carbon atoms.

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Claims (12)

  1. Verfahren zur Herstellung von flüssigen Kohlenwasserstoffen durch Fischer-Tropsch-Synthese, umfassend einen Schritt (a) der Erzeugung eines Synthesegases, das im Wesentlichen Kohlenmonoxid und Wasserstoff umfasst, einen Schritt (b) der Fischer-Tropsch-Synthese, ausgehend von einer Beschickung, die mindestens einen Teil des Synthesegases umfasst, der die Herstellung eines Abflusses ermöglicht, der flüssige Synthesekohlenwasserstoffe und mindestens einen gasförmigen Abfluss umfasst, einen Schritt (c) der Kondensation des gasförmigen Abflusses, der während des Schritts (b) erhalten wurde, einen Schritt (d) der Trennung des während des Schritts (c) kondensierten Abflusses, der es ermöglicht, einen gasförmigen Abfluss, der mit Kohlenmonoxid und mit Wasserstoff angereichert ist, eine wässrige Phase und flüssige Kohlenwasserstoffe zu erhalten, und einen Schritt (e) zum Recycling mindestens eines Teils des während des Schritts (d) angereicherten gasförmigen Abflusses zum Schritt (b) der Fischer-Tropsch-Synthese, dadurch gekennzeichnet, dass:
    1) zwei Molverhältnisse der Konzentrationen, A1 und A2, zwischen dem Wasserstoff und dem Kohlenmonoxid (H2/CO) bestimmt werden, wobei A1 der Wert des Verhältnisses in der Beschickung aus dem Syntheseschritt (b) ist, und A2 der Wert des Verhältnisses in irgendeinem der gasförmigen Abflüsse ist, die während der Schritte (b) bis (e) erhalten wurden,
    2) die Verhältnisse A1 und A2 verglichen werden, und
    3) die Wasserstoff- und/oder Kohlenmonoxidkonzentrationen in dem Synthesegas angepasst werden, um den Abstand zwischen den beiden Verhältnissen A1 und A2 im Wesentlichen konstant zu halten.
  2. Verfahren nach Anspruch 1, wobei das Konzentrationsverhältnis A2 auf der Basis von Messungen berechnet wird, die ausgeführt werden:
    - am gasförmigen Abfluss, der während des Schritts (b) erhalten wurde,
    - am abgekühlten Abfluss, der während des Schritts (c) erhalten wurde,
    - am gasförmigen Abfluss, der mit Kohlenmonoxid und Wasserstoff angereichert ist, der während des Schritts (d) erhalten wurde, oder
    - am Abfluss, der zum Schritt (b) der Fischer-Tropsch-Synthese recycelt wurde.
  3. Verfahren nach einem der Ansprüche 1 oder 2, wobei die Wasserstoff- und/oder Kohlenmonoxidkonzentrationen in dem Synthesegas, das in Schritt (a) erhalten wurde, angepasst werden, um den Abstand zwischen den beiden Verhältnissen A1 und A2 zu minimieren.
  4. Verfahren nach einem der Ansprüche 1 bis 3, wobei die Betriebsbedingungen eingestellt werden, um das H2/CO-Konzentrationsverhältnis auf ein Niveau einzustellen, das einem Anwendungsverhältnis entspricht, das in Übereinstimmung mit einer gesuchten Produktverteilung erforderlich ist.
  5. Verfahren nach einem der Ansprüche 1 bis 4, wobei die Erzeugung eines Synthesegases ausgehend von Erdgas realisiert wird.
  6. Verfahren nach einem der Ansprüche 1 bis 5, wobei auf den Schritt (a) der Erzeugung eines Synthesegases ein Schritt (a') folgt, der der Anpassung der Wasserstoff- und/oder Kohlenmonoxidkonzentrationen in dem Synthesegas dient.
  7. Verfahren nach Anspruch 6, wobei der Schritt (a') ausgehend von einer Beschickung eines Teils des in Schritt (a) hergestellten Synthesegases realisiert wird, der von 1 bis 50 Gew.-% des in Schritt (a) hergestellten Synthesegases reicht.
  8. Verfahren nach einem der Ansprüche 6 oder 7, wobei der Schritt (a') das Einsetzen eines Mittels zur Extraktion des Wasserstoffs oder des Kohlenmonoxids umfasst.
  9. Verfahren nach Anspruch 8, wobei der Schritt (a') das Einsetzen einer Membran umfasst, die den Wasserstoff aus einem Gemisch extrahiert, das Wasserstoff und Kohlenmonoxid enthält.
  10. Verfahren nach einem der Ansprüche 1 bis 9, wobei in Schritt (b) ein oder mehrere Reaktoren des Blasensäulentyps eingesetzt werden.
  11. Verfahren nach einem der Ansprüche 1 bis 10, wobei der in Schritt (b) eingesetzte Katalysator Cobalt oder Eisen umfasst.
  12. Verfahren nach einem der Ansprüche 1 bis 11, wobei der in Schritt (b) eingesetzte Katalysator (b) auf Cobalt basiert, die Temperatur des Schritts (b) im Bereich zwischen 200 und 250 °C liegt, und der Druck des Schritts (b) im Bereich zwischen etwa 1 und 4 MPa liegt.
EP05771067A 2004-05-19 2005-05-17 Fischer-tropsch-syntheseverfahren mit verbesserter steuerung Expired - Fee Related EP1765956B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0405551A FR2870544B1 (fr) 2004-05-19 2004-05-19 Procede de synthese fischer-tropsch comprenant une regulation amelioree
PCT/FR2005/001234 WO2005123882A1 (fr) 2004-05-19 2005-05-17 Procede de synthese fischer-tropsch comprenant une regulation amelioree

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EP1765956A1 EP1765956A1 (de) 2007-03-28
EP1765956B1 true EP1765956B1 (de) 2010-08-04

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EP (1) EP1765956B1 (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.
US20100175320A1 (en) * 2006-12-29 2010-07-15 Pacific Renewable Fuels Llc Energy efficient system and process for the continuous production of fuels and energy from syngas
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
PE20141819A1 (es) 2012-02-24 2014-12-08 Sasol Technology Propietary Ltd Sintesis de fischer-tropsch
GB201206196D0 (en) 2012-04-05 2012-05-23 Ingengtl Production of liquid hydrocarbons
CN114061035B (zh) * 2021-11-02 2023-01-13 青岛海尔空调器有限总公司 用于控制电化学空调除霜的方法及装置、电化学空调

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US5023276A (en) * 1982-09-30 1991-06-11 Engelhard Corporation Preparation of normally liquid hydrocarbons and a synthesis gas to make the same, from a normally gaseous hydrocarbon feed
GB0023781D0 (en) * 2000-09-28 2000-11-08 Kvaerner Process Tech Ltd Process
GB0027575D0 (en) * 2000-11-10 2000-12-27 Sasol Tech Pty Ltd Production of liquid hydrocarbon roducts

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WO2005123882A1 (fr) 2005-12-29
FR2870544A1 (fr) 2005-11-25
US20080200569A1 (en) 2008-08-21
DE602005022712D1 (de) 2010-09-16
ZA200609577B (en) 2008-04-30
FR2870544B1 (fr) 2006-06-30
EP1765956A1 (de) 2007-03-28
US7776932B2 (en) 2010-08-17

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