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WO2025163281A1 - Procédé et système de fischer-tropsch - Google Patents

Procédé et système de fischer-tropsch

Info

Publication number
WO2025163281A1
WO2025163281A1 PCT/GB2024/053061 GB2024053061W WO2025163281A1 WO 2025163281 A1 WO2025163281 A1 WO 2025163281A1 GB 2024053061 W GB2024053061 W GB 2024053061W WO 2025163281 A1 WO2025163281 A1 WO 2025163281A1
Authority
WO
WIPO (PCT)
Prior art keywords
reformer
electrolyser
fischer
stream
syngas
Prior art date
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.)
Pending
Application number
PCT/GB2024/053061
Other languages
English (en)
Inventor
Graham Charles Hinton
Christopher Jon ROGERS
Joost Johannes SMIT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Johnson Matthey Davy Technologies Ltd
Original Assignee
Johnson Matthey Davy Technologies Ltd
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 Johnson Matthey Davy Technologies Ltd filed Critical Johnson Matthey Davy Technologies Ltd
Publication of WO2025163281A1 publication Critical patent/WO2025163281A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/23—Carbon monoxide or syngas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0495—Composition of the impurity the impurity being water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series

Definitions

  • the present specification relates to a Fischer-Tropsch process and a system for implementing the process.
  • Fischer-Tropsch (FT) plants and their operation are described in WO2021140227A1, WO2018146276A1, WO2017037175A1, W02015140100A1, W02015140099A1, W02015010939A1 and WO2009128865A1.
  • the Fischer-Tropsch process is a collection of chemical reactions that convert a mixture of carbon monoxide and hydrogen (also known as “synthesis gas” or “syngas”) into liquid hydrocarbons. These reactions occur in the presence of metal catalysts, typically at temperatures of 150-300 °C and pressures of one to several tens of atmospheres.
  • the Fischer-Tropsch process involves a series of chemical reactions that produce a variety of hydrocarbons, ideally having the formula (C n H 2n+2 ).
  • the more useful reactions produce alkanes as follows: where n is typically 1-100 or higher.
  • Most of the alkanes produced tend to be straight-chain and are suitable to be upgraded to produce middle distillate fuels such as diesel and jet fuel.
  • competing reactions give small amounts of alkenes, as well as alcohols and other oxygenated hydrocarbons.
  • the syngas fed to the Fischer-Tropsch unit can be prepared by subjecting a feed gas comprising hydrogen and carbon dioxide to a reverse-water-gas-shift reaction to convert some of the carbon dioxide and hydrogen to carbon monoxide and water as follows:
  • Such a reaction can occur together with the reverse-water-gas-shift reaction with a reverse-water- gas-shift reactor.
  • a separate reformer system may be utilized to convert the methane into syngas.
  • Crude syngas from the reverse-water-gas-shift system can be processed to separate carbon dioxide (and also water and other inpurities) in order to produce a purified syngas for the Fischer-Tropsch unit.
  • the separated carbon dioxide can be recycled back into the reverse-water-gas-shift reactor system to produce more crude syngas. Again, this can increase the efficiency of the system while reducing emissions.
  • Yet another adaptation of the reverse-water-gas-shift system is to use an electrolyser to produce hydrogen by electrolysis of water (which may be water recycled from the crude syngas and/or water produced by the Fischer-Tropsch unit) and feed the hydrogen produced by the electrolyser into the reverse-water-gas-shift system to generate more syngas.
  • electrolyser to produce hydrogen by electrolysis of water (which may be water recycled from the crude syngas and/or water produced by the Fischer-Tropsch unit) and feed the hydrogen produced by the electrolyser into the reverse-water-gas-shift system to generate more syngas.
  • This can provide an internal supply of hydrogen for the reverse-water-gas-shift process to produce syngas and water usage can be reduced if the water is internally recycled.
  • syngas can be produced by steam methane reforming of a methane containing gas.
  • tail gas and/or unwanted hydrocarbon products from the Fischer-Tropsch unit can be recycled through one or more pre-reformer or derichment reactors to generate a methane containing gas which is then subjected to steam-methane reforming to generate syngas.
  • SOE solid-oxide electrolyser
  • the solid-oxide electrolyser can thus generate a stream of hydrogen and carbon monoxide (syngas) which can be fed to the Fischer-Tropsch unit.
  • syngas carbon monoxide
  • the paper described three configurations (i) a basic configuration in which a solid oxide electrolyser is used to co-electrolyse carbon dioxide and water to produce syngas for a Fischer-Tropsch process; (ii) a modified version in which tail gas from the Fischer- Tropsch process is subjected to reforming, with the reformed gas recycled into the solid oxide electrolyser; or (iii) a modified version in which tail gas from the Fischer-Tropsch process is recycled into the solid oxide electrolyser without reforming.
  • US2023155150 also discloses the use of a solid-oxide electrolyser to produce syngas for a Fischer- Tropsch process.
  • This document describes a method of operating a solid oxide electrolyser in which water, carbon dioxide, and a hydrocarbon are input to the electrolyzer. It is disclosed that the method can be applied when the solid oxide cell system is connected to a Fischer-Tropsch synthesis process. It is described that a hydrocarbon-rich residual/circulation gas arises which can be converted into H2 and CO directly in a solid oxide electrolyser stack or via a reformer and a solid oxide electrolyser stack in series (similar to the configuration (ii) of the previously discussed paper).
  • the present specification provides a process in which both a reformer system and a co- electrolyser system provide syngas (in parallel) to a Fischer-Tropsch system. That is, instead of the reformer system directing a reformed gas into a co-electrolyser system, both the electrolyser system and the reformer system provide syngas feeds to the Fischer-Tropsch system.
  • One aspect of the present specification provides a method for synthesising hydrocarbons, the method comprising:
  • Another aspect of the present specification provides a system for synthesising hydrocarbons according to the method as defined above, the system comprising:
  • an electrolyser system configured to co-electrolyse water and carbon dioxide producing an electrolyser syngas stream and an oxygen containing stream
  • a Fischer-Tropsch system comprising a Fischer-Tropsch reactor, the Fischer-Tropsch system being configured to receive the electrolyser syngas stream and form a hydrocarbon product stream and a waste stream comprising one or more hydrocarbons
  • Fischer-Tropsch system is configured to receive the reformer syngas stream to form further hydrocarbon product, the system being configured such that both the electrolyser system and the reformer system provide syngas streams to the Fischer-Tropsch system.
  • Such a configuration can have several advantages. For example, hydrocarbon containing waste streams from the Fischer-Tropsch system can be recycled via the reformer system to produce more syngas without risk of contaminating the electrolyser system and reducing performance and/or operational lifetime of the electrolyser. Input streams to the electrolyser system can therefore be better controlled to optimize the performance and lifetime of the electrolyser. At the same time, relatively high purity carbon dioxide which may, for example, be separated from crude syngas from the reformer system, can be safely recycled back into the electrolyser system without undue risk of contaminating the electrolyser system.
  • the electrolyser system for co-electrolysis of water and carbon dioxide produces both a syngas stream and an oxygen stream
  • the oxygen stream from the electrolyser system can be utilized within other parts of the overall system.
  • at least a portion of the oxygen containing stream from the electrolyser system can be passed to the reformer system and combusted to generate heat within the reformer system to drive generation of the reformer syngas stream.
  • the present configuration can ensure that waste streams from various parts of the process can be efficiently recycled back into the overall system.
  • integrating a co-electrolyser system for generating syngas with a reformer system for generating syngas can lead to an improvement in the overall efficiency of the system.
  • Figure 1 shows a flow sheet for a method of synthesising hydrocarbons according to the present specification.
  • Figure 2 shows a more detailed example of a flow sheet for a method of synthesising hydrocarbons according to the present specification with some additional features to those illustrated in Figure 1.
  • the present specification provides a method for synthesising hydrocarbons, the method comprising:
  • the electrolyser system can be a solid oxide electrolyser system. Such systems are known in the art for co-electrolysis of carbon dioxide and water. Alternatively, the electrolyser system can be a more conventional lower temperature liquid electrolyser. However, solid oxide electrolyser systems have been found to have significant power savings over conventional electrolysis in this application.
  • the waste stream from the Fischer-Tropsch system which is recycled to the reformer system can be one or both of: a tail gas stream from the Fischer-Tropsch reactor; and an unwanted portion of the hydrocarbon product stream which is separated from the hydrocarbon product stream (e.g., a naphtha stream).
  • the hydrocarbon containing waste stream(s) from the Fischer-Tropsch system can be recycled via the reformer system to produce more syngas without risk of contaminating the electrolyser system and reducing performance and/or operational lifetime of the electrolyser.
  • Input streams to the electrolyser system can therefore be better controlled to optimize the performance and lifetime of the electrolyser.
  • At least a portion of the oxygen containing stream from the electrolyser system can be passed to the reformer system and combusted to generate heat within the reformer system to drive generation of the reformer syngas stream within the reformer system.
  • the systems can be linked to make use of the oxygen stream from the electrolyser system to drive reformer syngas generation.
  • the heat required for the reformer system can be provided by an alternative heating system (for example, a rotary dynamic heater) in place of burning hydrogen with oxygen. This can lead to further improves in process efficiency.
  • the reformer syngas stream can be treated to remove carbon dioxide prior to passing though the Fischer-Tropsch reactor, and the removed carbon dioxide can be recycled back into the electrolyser system for further generation of the electrolyser syngas stream. While recycling of other waste streams back into the electrolyser system can cause contamination issues and potential loss of performance or lifetime, the carbon dioxide separated from the reformer syngas stream is relatively pure and thus contamination issues can be avoided. Again, this recycle scheme enables the electrolyser, reformer, and FT parts of the system to be linked together in a manner which enables waste streams from various parts of the process to be efficiently recycled back into the overall system while avoiding contamination, performance, and lifetime issues. Further still, it has been found that integrating a co-electrolyser system for generating syngas with a reformer system for generating syngas can lead to an improvement in the overall efficiency of the system.
  • the reformer syngas stream can also be treated to remove water prior to passing though the Fischer-Tropsch reactor.
  • this removed water can be recycled back into the electrolyser system for further generation of the electrolyser syngas stream.
  • the water may be subjected to purification treatment prior to feeding back into the electrolyser.
  • the reformer syngas stream may also be treated to remove further impurities prior to passing though the Fischer-Tropsch reactor, particularly those which may poison the Fischer-Tropsch catalyst material in the Fischer-Tropsch reactor.
  • syngas may typically contain ppm levels of hydrogen cyanide and ammonia, which deactivate the Fischer-Tropsch catalyst, and so ideally the hydrogen cyanide and ammonia are removed down to single-digit ppb levels.
  • Methods of removing water, carbon dioxide, and impurities such as hydrogen cyanide and ammonia are known in the art. The difference here is the integration of these processes into a system which combines production of reformer syngas and electrolyser syngas for a Fischer-Tropsch process, and the reuse of components separated from the reformer syngas in the electrolyser feed.
  • the electrolyser syngas can be of higher purity than the pre-treated crude syngas produced by the reformer system.
  • the electrolyser syngas stream may be passed through the Fischer-Tropsch reactor without treatment to remove one or more of carbon dioxide, water, and other impurities.
  • the reformer syngas stream and the electrolyser syngas stream can be mixed after exiting the syngas and electrolyser systems respectively and prior to passing though the Fischer-Tropsch reactor and said mixing can occur after cooling, and optional carbon dioxide recovery and purification, of the reformer syngas stream.
  • the electrolyser syngas can also be subjected to purification treatments in a similar manner to the reformer syngas. In this case, removed carbon dioxide and/or water can be recycled back into the electrolyser system in a comparable manner to that described above for the reformer syngas treatments. If both the electrolyser syngas and the reformer syngas are to be treated in the same manner, then the syngas streams can optionally be mixed prior to one or more of said treatments.
  • the reformer system may comprise a pre-reformer which generates a methane containing stream from the waste stream of the Fischer-Tropsch system.
  • the reformer system may further comprise one or both of a gas heated reformer and an autothermal reformer for converting the methane containing stream into the reformer syngas stream.
  • the reformer system comprises both a gas heated reformer and an autothermal reformer and heat is recovered from the autothermal reformer by using outlet gas from the autothermal reformer to heat the gas heated reformer.
  • the oxygen containing stream from the electrolyser system can be passed to the autothermal reformer of the reformer system to maintain a sufficiently high temperature to drive generation of reformer syngas.
  • the reformer system may comprise a reverse-water-gas- shift reactor.
  • a reverse-water-gas- shift reactor can create syngas from hydrogen and carbon dioxide feeds and can also optionally perform the steam methane reforming reactions for recycling FT waste streams.
  • Providing such a reactor would enable the Fischer-Tropsch process to operate based on syngas generated from either or both of the reformer and electrolyser systems and thus provide a degree of flexibility and reliability, e.g., in the case of an electrolyser fault.
  • a reverse-water-gas- shift reactor does not have a separate external carbon dioxide feed and supports a reverse water-gas shift reaction based on CO2 within the Fischer-Tropsch waste stream (in addition to steam-methane reforming).
  • such a reverse-water-gas-shift reactor may be provided with a separate external carbon dioxide feed (and a hydrogen feed) in addition to the Fischer-Tropsch waste stream.
  • Fischer-Tropsch reactors typically work optimally at a specified CO to H2 ratio (or operating range) of the syngas passing into the Fischer-Tropsch reactor.
  • the syngas fed to the Fischer-Tropsch reactor is provided from two different sources (reformer and electrolyser).
  • the CO to H2 ratio of the syngas passing into the Fischer-Tropsch reactor can be adjusted at the electrolyser system by increasing or decreasing the carbon dioxide feed to achieve a desired CO to H2 ratio at the Fischer-Tropsch reactor inlet.
  • the present specification also provides a system for synthesising hydrocarbons according to the method as described above.
  • the system comprises:
  • a Fischer-Tropsch system comprising a Fischer-Tropsch reactor, the Fischer-Tropsch system being configured to receive the electrolyser syngas stream and form a hydrocarbon product stream and a waste stream comprising one or more hydrocarbons;
  • Fischer-Tropsch system is configured to receive the reformer syngas stream to form further hydrocarbon product, the system being configured such that both the electrolyser system and the reformer system provide syngas streams to the Fischer-Tropsch system.
  • Figure 1 shows a flow sheet for a method of synthesising hydrocarbons according to the present specification.
  • the method uses a combination of an electrolyser system 2 for co-electrolysis of water 4 and carbon dioxide 6 to produce syngas 8 for a Fischer-Tropsch system 10 and a reformer system 12 to produce a second stream of syngas 14 for the Fischer-Tropsch system 10.
  • the Fischer-Tropsch system 10 generates a hydrocarbon product stream 16.
  • One or more hydrocarbon waste streams from the Fischer-Tropsch system can be recycled via the reformer recycle loop 18 to feed the reformer system 1.
  • Carbon dioxide separated from the crude reformer syngas can be recycled into the electrolyser system 2 via the electrolyser recycle loop 20.
  • Oxygen 22 generated by the electrolyser can be fed into the reformer system 12 to generated heat for driving reformer syngas production.
  • FIG 2 shows a more detailed example of a flow sheet for a method of synthesising hydrocarbons according to the present specification with some additional features to those illustrated in Figure 1.
  • This flow sheet shows that syngas 14 from the reformer system is subjected to cooling and CO2 recovery 24, and further syngas purification 26 prior to entering the Fischer-Tropsch reactor / FT Synthesis loop 28.
  • the recovered CO2 can be recycled via electrolyser recycle loop 20 to the electrolyser 2.
  • Waste streams from the syngas processing and Fischer-Tropsch reactor system include process condensate 30, MP steam 32, and FT produced water 34 (one or more of which may be recycled back into the system, e.g., water/steam streams can be recycled into the electrolyser and/or the reformer systems).
  • the reformer system in this example comprises a pre-reformer 36, a 1 st stage gas heated reformer (GHR) 38 and a 2 nd stage autothermal reformer (ATR) 40.
  • Hydrocarbon waste streams from the Fischer-Tropsch reactor system are recycled via reformer recycle loop 18, mixed with MP steam 42, and fed to the pre-reformer 36 to generate a methane stream 44 which is fed through the 1 st and 2 nd stage reformers 38, 40.
  • Oxygen 22 generated by the electrolyser 2 can be fed into the autothermal reformer 40 and heat is recovered from the autothermal reformer 40 by using outlet gas from the autothermal reformer to heat the gas heated reformer 38.
  • Embodiments of the aforementioned systems provide a Fischer-Tropsch process for production of hydrocarbon products which uses a high temperature solid oxide electrolyser fed with steam and CO2 to produce CO and H2 syngas and a pre-reformer followed by a GHR / ATR reactor set for reforming the FT loop tail gas to CO and H2 syngas.
  • the pre-reformer can convert C2+ paraffinic alkanes to methane.
  • the Pre-reformer is followed by a GHR / ATR reactor set that reforms the methane gas to CO and H2.
  • the GHR / ATR combination is advantageous to: (i) recover the heat from ATR by using the outlet gas to drive the endothermic reaction in the GHR; and (ii) minimise the oxygen gas feed to the ATR which reacts exothermically with H2 to produce H2O.
  • operating parameters for the pre-reformer may be set as follows:
  • Steam to carbonaceous feed ratio is set to 1.8 wt/wt by adding MP Steam.
  • Feed temperature 450°C.
  • the pre-reformer reaction is exothermic. With the aforementioned operating parameters, the gas temperature at the outlet is 567°C. The gas is cooled to 440°C by generating MP Steam (13 bar, 192°C).
  • the GHR / ATR reactor set operating parameters can be set as follows:
  • GHR tube side catalyst side feed gas inlet temperature: 440°C. 2. Inlet pressure: 32 bar.
  • Shell side ATR gas inlet temperature 1000°C.
  • Shell side gas exit temperature 540°C (100°C above feed gas inlet temperature).
  • Oxygen is added at inlet of ATR to maintain the ATR outlet gas temperature at 1000°C (the oxygen can be supplied from the electrolyser).
  • Reformed gas is mixed with the syngas from the solid oxide electrolyser cell after cooling, CO2 recovery, and syngas purification.
  • the CO to H2 ratio is adjusted at the solid oxide electrolyser cell by increasing or decreasing the CO2 gas feed. In this manner, the required CO to H2 ratio is achieved at the inlet to the FT synthesis loop.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

L'invention concerne un procédé de synthèse d'hydrocarbures, le procédé consistant à : (a) introduire de l'eau et du dioxyde de carbone dans un système d'électrolyseur pour coélectrolyser l'eau et le dioxyde de carbone produisant un courant de gaz de synthèse d'électrolyseur et un courant contenant de l'oxygène ; (b) faire passer le courant de gaz de synthèse d'électrolyseur à travers un système Fischer-Tropsch comprenant un réacteur Fischer-Tropsch pour former un courant de produits hydrocarbonés et un courant de déchets comprenant un ou plusieurs hydrocarbures ; (c) faire passer le courant de déchets à travers un système de reformage pour générer un courant de gaz de synthèse de reformeur ; et (d) faire passer le courant de gaz de synthèse de reformeur à travers le système Fischer-Tropsch pour former davantage de produits hydrocarbonés, le système électrolyseur et le système de reformage fournissant tous les deux des courant de gaz de synthèse au système Fischer-Tropsch.
PCT/GB2024/053061 2024-02-01 2024-12-10 Procédé et système de fischer-tropsch Pending WO2025163281A1 (fr)

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GBGB2401332.8A GB202401332D0 (en) 2024-02-01 2024-02-01 Fischer-tropsch process and system
GB2401332.8 2024-02-01

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009128865A1 (fr) 2008-04-16 2009-10-22 Kyrogen Usa, Llc Procédé et appareil pour le démarrage d'un procédé de fischer-tropsch et/ou de synthèse de composés oxygénés
WO2015010939A1 (fr) 2013-07-24 2015-01-29 Shell Internationale Research Maatschappij B.V. Procédé de démarrage d'une réaction fischer-tropsch
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