WO2024240932A1 - Conversion de co2 et de h2 en combustibles de synthèse - Google Patents

Conversion de co2 et de h2 en combustibles de synthèse Download PDF

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Publication number
WO2024240932A1
WO2024240932A1 PCT/EP2024/064366 EP2024064366W WO2024240932A1 WO 2024240932 A1 WO2024240932 A1 WO 2024240932A1 EP 2024064366 W EP2024064366 W EP 2024064366W WO 2024240932 A1 WO2024240932 A1 WO 2024240932A1
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section
feed
rwgs
stream
syngas
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Inventor
Sudip DE SARKAR
Peter Mølgaard Mortensen
Kim Aasberg-Petersen
Sandahl Thomas CHRISTENSEN
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Topsoe AS
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Haldor Topsoe AS
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Priority to EP24727437.6A priority Critical patent/EP4719973A1/fr
Priority to CN202480027671.9A priority patent/CN121039053A/zh
Publication of WO2024240932A1 publication Critical patent/WO2024240932A1/fr
Anticipated expiration legal-status Critical
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    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/06—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents
    • C01B3/12—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents by reaction of water vapour with carbon monoxide using 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Processes with two or more reaction steps, of which at least one is catalytic, e.g. steam reforming and partial oxidation
    • C—CHEMISTRY; METALLURGY
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • C01B3/586—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being a methanation reaction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/026—Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
    • 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
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • 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
    • C01B2203/0435—Catalytic purification
    • C01B2203/0445—Selective methanation
    • 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
    • C01B2203/061—Methanol production
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/085—Methods of heating the process for making hydrogen or synthesis gas by electric heating
    • 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
    • C01B2203/141—At least two reforming, decomposition or partial oxidation steps in parallel
    • 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
    • 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
    • C01B2203/16—Controlling the process
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to a plant, such as a hydrocarbon plant, with effective use of various streams, in particular carbon dioxide.
  • a method for producing a product stream, such as a hydrocarbon product stream is also provided.
  • the plant and method of the present invention provide overall better utilization of carbon dioxide.
  • CO 2 and H 2 can be converted to synthesis gas (a gas rich in CO and H 2 ) which can be converted further to valuable products like alcohols (including methanol), fuels (such as gasoline, jet fuel, kerosene and/or diesel produced for example by the Fischer-Tropsch (F-T) process), and/or olefins etc.
  • synthesis gas a gas rich in CO and H 2
  • fuels such as gasoline, jet fuel, kerosene and/or diesel produced for example by the Fischer-Tropsch (F-T) process
  • F-T Fischer-Tropsch
  • the RWGS reaction (1) is an endothermic process which requires significant energy input for the desired conversion. High temperatures are needed to obtain sufficient conversion of carbon dioxide into carbon monoxide to make the process economically feasible. However, in traditional reactors, heated by combustion of for example natural gas or other combustibles, the temperature of the reacted gas may be limited to for example 850-900°C. Alternatively, high conversions of carbon dioxide can also be obtained by using a high H 2 /CO 2 -ratio. However, this will often result in a synthesis gas with a (much) too high H 2 /CO-ratio for the downstream synthesis. Furthermore, an increasing use of hydrogen will increase the cost of hydrogen production.
  • the present invention is based on the reactor types, in which it is possible to operate the reverse water gas shift reaction at such high temperature that it is no longer necessary to avoid the methanation reaction, because most of the methane formed will subsequently be converted into hydrogen, CO 2 and CO in the reverse methanation reaction. Furthermore, any methane present in the feed gas can also be converted into synthesis gas according to the reverse methanation reactions.
  • the present invention is further based on the recognition that a prerequisite for this to be possible is that a catalyst capable of catalyzing both reverse water gas shift and methanation is used.
  • hydrocarbons may be available as co-feed.
  • An example is the availability of hydrocarbons from a downstream synthesis stage (e.g. a propane and butane rich stream from an F-T stage; tail gas comprising different hydrocarbons from an F-T stage; naphtha stream from an F-T stage).
  • a downstream synthesis stage e.g. a propane and butane rich stream from an F-T stage; tail gas comprising different hydrocarbons from an F-T stage; naphtha stream from an F-T stage.
  • Such hydrocarbons cannot be processed in an RWGS reactor without a catalyst with activity for steam reforming (e.g. the reverse of reaction (2) or (3)).
  • the hydrocarbon streams from the downstream synthesis stage are not used at least in part for additional production of synthesis gas, the overall process may not be feasible from an economic point of view.
  • a hydrocarbon stream such as natural gas
  • the CO 2 and H 2 feed streams may also comprise smaller amounts of hydrocarbons.
  • this reaction both reduces the partial pressure of the formed CO and increases the partial pressure of H 2 O, both aspects effectively reducing the potential for the CO reduction reaction to take place. Additionally, the risk of carbon formation on the catalyst from the CO reduction reaction is reduced in the case where the methanation reaction also takes place, because catalyst reaction mechanism perspective adsorbed carbon atoms is an intermediate in the methanation reaction scheme (as described by H.S. Bengaard, J.K. Norskov, J. Sehested, B.S. Clausen, L.P. Nielsen, A.M. Molenbroek, J.R.
  • the simultaneous occurrence of methanation in the reverse water gas shift reactor results in release of chemical energy to heat the system and, thereby, a temperature increase because methanation is an exothermic reaction.
  • the increase in temperature created by the methanation reaction results in a reduction of the potential for the CO reduction reaction and when the temperature has risen to a certain level no potential for the CO reduction reaction will be present at all. This exact level will be dependent on the specific reactant concentration, inlet temperature, and pressure, but will typically be in the range from 600-800°C above which the CO reduction reaction will not have a potential to take place.
  • the exotherm generated by the methanation reaction will also give the highest temperature rise at the active site of the catalysts surface on where carbon formation reactions usually take place. Therefore, exotherm from methanation reaction has a positive effect on reduction of the carbon formation potential.
  • e-RWGS reactor allows increasing temperature from relatively low inlet temperature to a high product gas temperature in the reactor.
  • the methanation reaction ((2) and/or (3)) occurs primarily in the first part of the reactor, while produced methane is converted to CO 2 , CO and H 2 in the rest of the reactor when temperature exceeds 600- 800°C.
  • this configuration allows reduction of carbon formation potential (by reducing CO content and increasing H 2 O content) in the first part of the reactor, and the lower part of the same reactor converts produced methane back to CO at high temperature without any potential for carbon formation.
  • CO 2 and H 2 can be converted to syngas with a desired H 2 :CO ratio, suitably without using any external hydrocarbon feed to the plant. If needed, one or more hydrocarbon co-feed to the plant can be used as well.
  • selective RWGS shall mean that only the reverse water gas shift reaction takes place either on a catalyst or in a reactor while “non-selective RWGS” shall mean that other reactions such as one or more of the methanation reactions (including also reverse methanation) take place in addition to reverse water gas shift.
  • the present invention provides a plant (X), said plant comprising : a. a syngas stage (A), said syngas stage comprising an electrically heated reverse water gas shift (e-RWGS) section (I) and a non-electrically heated reactor section (II) , which is an autothermal reactor (ATR) section (Ila) or a fired reactor (SMR) section (lib); b.
  • a syngas stage A
  • said syngas stage comprising an electrically heated reverse water gas shift (e-RWGS) section (I) and a non-electrically heated reactor section (II) , which is an autothermal reactor (ATR) section (Ila) or a fired reactor (SMR) section (lib);
  • ATR autothermal reactor
  • SMR fired reactor
  • a synthesis stage said plant comprising one or more of the following feeds: a first feed (1) comprising hydrogen, a second feed (2) comprising carbon dioxide; a third feed (3) comprising hydrocarbons; wherein the plant is arranged to supply to said e-RWGS section (I) the first (1) feed and/or the second (2) feed and/or the third feed (3), wherein said e-RWGS section (I) is arranged to convert at least a portion of the feed supplied thereto into a first syngas stream (20); wherein the plant is arranged to supply to said non-electrically heated RWGS section (II) the first (1) feed and second (2) feed and optionally the third feed (3), wherein said non- electrically heated reactor section (II) is arranged to convert at least a portion of the feed supplied thereto into a second syngas stream (40); wherein the first feed (1), the second feed (2) and the third feed (3) are supplied to the e- RWGS section (I) and to the non-electrically heated RWGS section (II)
  • the e-RWGS section is preferably operated on the basis of a sustainable source of electricity, e.g. originating from windmills or solar cells etc.
  • a sustainable source of electricity e.g. originating from windmills or solar cells etc.
  • sustainable sources of electricity involve the drawback of unavoidable interruptions in the power production and supply due to variations in weather conditions, which may likely necessitate a temporary shutdown of the plant.
  • the present invention is based on the recognition that it is possible to avoid downtime of the plant due to interruptions on the supply of sustainable power by incorporating a non-electrically heated RWGS reactor section (II) in the plant and by providing the plant with means for switching between two operations modes, hence allowing a shutdown of the eRWGS section (I) while operating the plant solely on the basis of the non- electrically heated reactor section (II) for producing syngas.
  • Figures la and lb show a first layout of the plant of the invention in a first and second operation mode, respectively.
  • Figure 2 shows a variant of the layout of the plant of Figure la in its first operation mode with recycling of hydrocarbon streams from the synthesis stage (B) for use as the third feed (3) comprising hydrocarbons to the syngas stage (A)
  • Figure 2a shows a variation of Figure 2, in which the non-electrically heated reactor section (II) is an autothermal reactor section (Ila).
  • Figure 3 shows a variation of Figure 2a further comprising an electrolysis section (III).
  • any given percentages for gas content are % by volume.
  • Carbon capture and utilization has gained more attention over the years.
  • the proposed layout provides a solution for CO 2 utilization in presence of H 2 to produce syngas and subsequently, conversion of such syngas to valuable products, such as syngas derived liquid fuel, also known as synfuels.
  • syngas derived liquid fuel also known as synfuels.
  • For conversion of CO 2 and H 2 feeds to syngas primarily electrically heated RWGS (e-RWGS) section is used. In the electrically heated RWGS section, either selective or non-selective RWGS may take place.
  • carbon dioxide and hydrogen feeds are primarily processed in an e-RWGS section.
  • a feed comprising hydrocarbons may also be processed in the e-RWGS section.
  • feed comprising hydrocarbons is meant to denote a gas with one or more hydrocarbons and possibly other constituents.
  • typically feed gas comprising hydrocarbons comprises a hydrocarbon gas, such as CH 4 and optionally also higher hydrocarbons often in relatively small amounts, in addition to various amounts of other gasses.
  • Higher hydrocarbons are components with two or more carbon atoms such as ethane and propane.
  • hydrocarbon gas may be natural gas, town gas, naphtha or a mixture of methane and higher hydrocarbons, biogas, biomethane, renewable natural gas (RNG) or LPG.
  • Hydrocarbons may also be components with other atoms than carbon and hydrogen such as oxygenates.
  • feed gas comprising hydrocarbons is meant to denote a feed gas comprising a hydrocarbon gas with one or more hydrocarbons mixed with steam, hydrogen and possibly other constituents, such as carbon monoxide, carbon dioxide, nitrogen and argon.
  • synthesis gas is meant to denote a gas comprising hydrogen, carbon monoxide and also carbon dioxide and small amounts of other gasses, such as argon, nitrogen, methane, etc.
  • a plant comprising : c. a syngas stage (A), said syngas stage comprising an electrically heated reverse water gas shift (e-RWGS) section (I) and a non-electrically heated reactor section (II), which is an autothermal reactor (ATR) section (Ila) or a fired reactor (SMR) section (lib); d.
  • ATR autothermal reactor
  • SMR fired reactor
  • a synthesis stage said plant comprising one or more of the following feeds: a first feed (1) comprising hydrogen, a second feed (2) comprising carbon dioxide; a third feed (3) comprising hydrocarbons; wherein the plant is arranged to supply to said e-RWGS section (I) the first (1) feed and/or the second (2) feed and/or the third feed (3), wherein said e-RWGS section (I) is arranged to convert at least a portion of the feed supplied thereto into a first syngas stream (20); wherein the plant is arranged to supply to said non-electrically heated RWGS section (II) the first (1) feed and second (2) feed and optionally the third feed (3), wherein said non- electrically heated reactor section (II) is arranged to convert at least a portion of the feed supplied thereto into a second syngas stream (40); wherein the first feed (1), the second feed (2) and the third feed (3) are supplied to the e- RWGS section (I) and to the non-electrically heated RWGS section (II)
  • the total feed to e-RWGS section (I) and/or the non-electrically heated reactor RWGS section (II) is in the form of the first and the second feeds, which are supplied to the e-RWGS section (I) and/or the non-electrically heated reactor RWGS section (II) either as separate streams or as a combined stream.
  • the e-RWGS section (I) and/or the non-electrically heated reactor RWGS section (II) is arranged to convert at least a portion of said first feed and at least a portion of said second feed - or at least a portion of said combined feed - into a first syngas stream (20) and a second syngas stream (40), respectively, and feed a syngas stream (e.g. said first and/or second syngas stream) to the synthesis stage (B).
  • a syngas stream e.g. said first and/or second syngas stream
  • the first feed comprising hydrogen and the second feed comprising carbon dioxide are arranged to be mixed to provide a combined feed which is provided to the e- RWGS section and/or the non-electrically heated reactor RWGS section (II).
  • the first syngas stream (20) suitably has the following composition (by volume) :
  • the phrase "the first syngas stream (20) and optionally the second syngas (40) is fed to the synthesis stage (B)” means that operation of non-electrically heated reactor RWGS section (II) is either stopped or reduced to a low production level, e.g. at 40-60%, preferably 30- 40%, more preferably 20-30% of its maximum production capacity, and that no or only a reduced flow of second syngas (40) is fed to the synthesis stage (B) along with first syngas (20).
  • the phrase “the second syngas stream (40) and no first syngas stream (20) is fed to the synthesis stage” means that the operation of the e-RWGS is shut down and that no flow of first syngas is fed to the synthesis stage (B).
  • the plant (X) comprises means for reducing the operation of the e-RWGS reactor to a low production level, e.g. below 30%, in particular below 20%, more particularly below 15%, and most particularly below 10%, of the maximum production capacity of the eRWGS reactor, and for feeding a reduced flow of first syngas corresponding to the reduced production level to the synthesis stage (B).
  • a low production level e.g. below 30%, in particular below 20%, more particularly below 15%, and most particularly below 10%
  • a first feed comprising hydrogen is provided to the syngas stage (A).
  • the first feed consists essentially of hydrogen.
  • the first feed of hydrogen is suitably "hydrogen rich" meaning that the major portion of this feed is hydrogen; i.e. over 75%, such as over 85%, preferably over 90%, more preferably over 95%, even more preferably over 99% of this feed is hydrogen.
  • One source of the first feed of hydrogen can be one or more electrolyser units.
  • the first feed may for example comprise steam, nitrogen, argon, oxygen, carbon monoxide, carbon dioxide, and/or hydrocarbons. In some cases a minor content of oxygen may be present in this feed, typically less than 100 ppm.
  • the first feed suitably comprises only low amounts of hydrocarbon, such as for example less than 5% hydrocarbons or less than 3% hydrocarbons or less than 1% hydrocarbons.
  • a second feed comprising carbon dioxide is provided to the syngas stage (A).
  • the second feed consists essentially of CO 2 .
  • the second feed of CO 2 is suitably "CO 2 rich" meaning that the major portion of this feed is CO 2 , i.e. over 75%, such as over 85%, preferably over 90%, more preferably over 95%, even more preferably over 99% of this feed is CO 2 .
  • One source of the second feed of carbon dioxide can be one or more exhaust stream(s) from one or more chemical plant(s).
  • One source of the second feed of carbon dioxide can also be carbon dioxide captured from one or more process stream(s) or atmospheric air.
  • Another source of the second feed could be CO 2 captured or recovered from the flue gas for example from fired heaters, steam reformers, and/or power plants.
  • the second feed may in addition to CO 2 comprise for example steam, oxygen, nitrogen, oxygenates, amines, ammonia, carbon monoxide, and/or hydrocarbons.
  • the second feed suitably comprises only low amounts of hydrocarbon, such as for example less than 5% hydrocarbons or less than 3% hydrocarbons or less than 1% hydrocarbons.
  • the second feed comprising carbon dioxide may - alternatively or additionally - be a stream comprising CO and CO 2 , which is output from an electrolysis section arranged to convert a feed of CO 2 into a stream comprising CO and CO 2 .
  • a portion of a CO 2 stream is fed directly to the syngas stage (A) as said second feed comprising carbon dioxide, while another portion of this CO 2 stream is fed to an electrolysis section, where it is converted to a stream comprising CO and CO 2 .
  • the stream comprising CO and CO 2 may then be fed to the syngas stage (A).
  • the plant may comprise a combined feed comprising hydrogen and carbon dioxide to the syngas stage (A).
  • the hydrogen content of this combined feed is between 40 and 80%, preferably between 50 and 70%.
  • the carbon dioxide content of this combined feed is between 15 and 50%, preferably between 20 and 40%.
  • the carbon monoxide content of this combined feed is between 0 and 10%.
  • the ratio of hydrogen to carbon dioxide in this combined feed is between 1 and 5, preferably between 2 and 4.
  • Part of the combined feed may be produced by co-electrolysis of a water/steam feed and a CO 2 feed.
  • a third feed comprising hydrocarbons, external to the plant, may be provided to the syngas stage (A).
  • the third feed may additionally comprise other components such as CO 2 and/or CO and/or H 2 and/or steam and/or other components such as nitrogen and/or argon.
  • the third feed consists essentially of hydrocarbons or a mixture of hydrocarbons and steam.
  • the third feed of hydrocarbons is suitably "hydrocarbon rich" meaning that the major portion of this feed is hydrocarbons, i.e. over 25%, e.g. over 50%, e.g. over 75%, such as over 85%, preferably over 90%, more preferably over 95%, even more preferably over 99% of this feed is hydrocarbons.
  • the concentration of hydrocarbons in this third feed is determined prior to steam addition (i.e. determined as "dry concentration").
  • Such third feed can also be a natural gas stream external to the plant.
  • said third feed comprises one or more hydrocarbons selected from methane, ethane, propane or butanes.
  • the source of the third feed comprising hydrocarbons may be external to the plant.
  • the significance of a feed "external to the plant” is that the origin of the feed is from a source external to the plant, i.e. not a recycle stream (or a recycle stream further processed or converted) from any synthesis stage (B) in the plant.
  • Possible sources of a third feed comprising hydrocarbons external to the plant include natural gas, LPG, refinery off-gas, naphtha, and renewables, such as renewable natural gas (RNG), biogas etc., but other options are also conceivable.
  • a gas comprising carbon monoxide, carbon dioxide, hydrogen, and methane is combined with the 3 rd feed comprising hydrocarbons (e.g. recycled tail gas or light end hydrocarbons) to the e-RWGS section (I) and/or non-electrically heated reactor RWGS section (II).
  • the third feed is composed solely of said gas comprising carbon monoxide, carbon dioxide, hydrogen, and methane
  • a tail gas from a Fischer-Tropsch synthesis section Such a gas could for example contain :
  • a particular embodiment of the plant of the invention comprises means arranged for recycling at least a portion of said hydrocarbon-containing off-gas stream (3a, 3b) to the syngas stage (A) as said third feed (3) comprising hydrocarbons or in addition to said third feed (3) comprising hydrocarbons.
  • the recycled hydrocarbon stream is passed through an off-gas conversion section (IV), which may comprise at least one hydrogenation unit and/or at least one water gas shift unit and/or at least one hydrocarbon conversion reactor.
  • the recycled hydrocarbon stream is initially passed through a water gas shift reactor together with steam (reverse of reaction 1 above) :
  • the effluent from the water gas shift reactor may also be directed to another reactor (higher hydrocarbon removal reactor).
  • This higher hydrocarbon removal reactor may be adiabatic or cooled and the catalyst will typically be pellet based.
  • the RWGS reaction (1) or the shift reaction (6)
  • methanation reactions (2-3) or the reverse methanation reactions depending upon the gas composition, temperature, and pressure
  • steam reforming of higher hydrocarbons may take place in this reactor:
  • the conditions of the reactor are preferably adjusted to convert more than 90%, such as more than 95% of the non-methane hydrocarbons present in the feed mixture. Removal or substantial reduction of non-methane hydrocarbons has the advantage that the risk of carbon formation in the e-RWGS section (I) and/or non-electrically heated reactor RWGS section (II) is reduced considerably.
  • the exit temperature from this higher hydrocarbon removal reactor is typically in the range between 400-700°C.
  • the effluent from this reactor is fed to the e-RWGS section (I) and/or non-electrically heated reactor RWGS section (II) optionally after cooling and condensation of part of the formed H 2 O.
  • This has the advantage that the amount of CO 2 in the effluent from the e-RWGS section (I) and/or non-electrically heated reactor RWGS section (II) will be lower.
  • the effluent may be mixed with the first feed and the second feed before being fed to the e-RWGS section (I) and/or non-electrically heated reactor RWGS section (II).
  • the e-RWGS section of the plant of the invention comprises a structured catalyst comprising a macroscopic structure of electrically conductive material capable of catalysing a reverse water gas shift reaction and/or a methanation reaction I steam methane reforming reaction.
  • the e-RWGS section comprises a structured catalyst comprising a macroscopic structure of electrically conductive material capable of catalysing a reverse water gas shift reaction, i.e. reaction (1) above (selective catalyst).
  • reaction (1) reverse water gas shift reaction
  • the total feed to the e-RWGS section (I) is in the form of the first and the second feeds, which are supplied to the e-RWGS section (I) either as separate streams or as a combined stream.
  • the e-RWGS section comprises a structured catalyst comprising a macroscopic structure of electrically conductive material capable of catalysing a methanation reaction I steam methane reforming reaction, i.e. reactions (2) and (3) above in forward and reverse direction (selective catalyst).
  • the total feed to the e-RWGS section (I) is in the form of the third feed, which is supplied to the e-RWGS section (I) as a separate stream.
  • the e-RWGS section is in fact an electrically heated steam methane reforming (e-SMR) section.
  • the e-RWGS section comprises a structured catalyst comprising a macroscopic structure of electrically conductive material capable of catalysing both a reverse water gas shift reaction and a methanation reaction I steam methane reforming reaction (non-selective catalyst).
  • the total feed to the e-RWGS section (I) is in the form of the first, the second feed and the third streams, which are supplied to the e-RWGS section (I) either as separate streams, as a partially combined stream or as one combined stream.
  • the e-RWGS section is in fact a combined e-RWGS and e-SMR section.
  • the primary section in the syngas stage (A) is an electrically heated reverse water gas shift (e-RWGS) section (I).
  • Electrically-heated reverse water gas shift (e-RWGS) uses an electric resistance-heated reactor to perform a more efficient process and substantially reduces or preferably avoids the use of fossil fuels as a heat source.
  • an e-RWGS section (I) is used in the present invention i.a. for carrying out the reverse water-gas shift reaction between CO 2 and H 2 .
  • the e-RWGS section suitably comprises: a structured catalyst comprising a macroscopic structure of electrically conductive material capable of catalysing reverse water gas shift reaction , said structured catalyst comprising a macroscopic structure of electrically conductive material, said macroscopic structure supporting a ceramic coating, wherein said ceramic coating supports a catalytically active material (for selective e-RGWS); a pressure shell housing said structured catalyst; said pressure shell comprising an inlet for letting in said feed and outlet for letting syngas product; wherein said inlet is positioned so that said feed enters said structured catalyst in a first end of said structured catalyst and said syngas product exits said structured catalyst from a second end of said structured catalyst; a heat insulation layer between said structured catalyst and said pressure shell; and at least two conductors electrically connected to said structured catalyst and to an electrical power supply placed outside
  • the e-RWGS section suitably comprises: a structured catalyst comprising a macroscopic structure of electrically conductive material capable of catalysing both reverse water gas shift reaction and methanation reaction, said structured catalyst comprising a macroscopic structure of electrically conductive material, said macroscopic structure supporting a ceramic coating, wherein said ceramic coating supports a catalytically active material (for non-selective e-RWGS); optionally a top layer arranged on top of the structured catalyst, comprising pellet catalyst, capable of catalysing both the methanation reaction and the reverse water gas shift reaction (for non-selective e-RWGS); optionally a bottom layer arranged below the structured catalyst, comprising pellet catalyst, capable of catalysing both the methanation reaction and the reverse water gas shift reaction (for non-selective e-RWGS); a pressure shell housing said structured catalyst; said pressure shell comprising an inlet for letting in said feed and outlet for letting syngas product; wherein
  • the pressure shell suitably has a design pressure of between 2 and 30 bar.
  • the pressure shell may also have a design pressure of between 30 and 200 bar.
  • the at least two conductors are typically led through the pressure shell in a fitting so that the at least two conductors are electrically insulated from the pressure shell.
  • the pressure shell further comprises one or more inlets close to or in combination with at least one fitting in order to allow a cooling gas to flow over, around, close to, or inside at least one conductor within said pressure shell.
  • the exit temperature of the e-RWGS section (I) is suitably 900°C or more, preferably 1000°C or more, even more preferably 1100°C or more.
  • the methanation reaction(s) also occur at and near the inlet of the reactor.
  • the reverse of the methanation reaction will be thermodynamically favoured.
  • methane will be formed and in the second part downstream of the first part methane will be consumed according to the reverse of reactions (2) and/or (3).
  • the eRWGS reactor comprises a structured catalyst.
  • the said structured catalyst has a first reaction zone disposed closest to the first end of said structured catalyst, wherein the first reaction zone has an overall exothermic reaction, and a second reaction zone disposed closest to the second end of said structured catalyst, wherein the second reaction zone has an overall endothermic reaction.
  • said first reaction zone has an extension of between the first 5% to between the first 60% of the length of the total reaction zone in the reactor, wherein reaction zone is understood as the volume of the reactor system catalyzing the methanation and reverse water gas shift reactions as evaluated along the flow path through the catalytic zone.
  • the combined activity for both reverse water gas shift and methanation in an eRWGS reactor of the invention entails that the reaction scheme inside the reactor will start out as exothermic in the first part of the reactor system but end as endothermic towards the exit of the reactor system.
  • This relates to the heat of reaction (Q r ) added or removed during the reaction, according to the general heat balance of the plug flow reactor system:
  • F is the flow rate of process gas
  • C pm is the heat capacity
  • V the volume of the reaction zone
  • T the temperature
  • Q a dd the energy supply/removal from the surrounding
  • Q r the energy supply/removal associated with chemical reactions which are given as the sum of all chemical reactions facilitated within the volume and calculated as the product between the reaction enthalpy and the rate of reaction of a given reaction.
  • the methane concentration by volume in the gas leaving the e-RWGS reactor is lower than 6% such as lower than 4% or preferably less than 3%.
  • High product gas temperature ensures that the final syngas product has low methane concentration, despite the methane concentration has a peak somewhere along the reaction zone. Therefore, this reactor configuration can operated with none, or little, methane in the feed and only little methane in the product gas, but with a peak in methane concentration inside the reaction zone higher than in the feed and/or product gas.
  • the concentration of methane in the synthesis gas is as low as possible as methane does not act as a reactant in downstream synthesis such as methanol or Fischer-Tropsch.
  • the methane concentration in the e-RWGS section is higher than both the concentration of the inlet gas to the e-RWGS section and the concentration of the exit gas from the e-RWGS section.
  • a low concentration of methane can be achieved by a high temperature out of the e-RWGS reactor.
  • a high temperature has the further advantage that a higher conversion of CO 2 into CO.
  • the exit temperature of the gas from the e-RWGS reactor is higher 900°C, such than higher than 1000°C or even higher than 1050°C. It is an advantage of the proposed reactor that a higher temperature can be achieved than what is typically possible with an externally fired reactor.
  • the e-RWGS reactor may further comprise an inner tube in heat exchange relationship with but electrically insulated from the structured catalyst, said inner tube being adapted to withdraw a product gas from the structured catalyst so that the gas flowing through the inner tube is in heat exchange relationship with gas flowing over the structured catalyst.
  • the connection between the structured catalyst and said at least two conductors may be a mechanical connection, a welded connection, a brazed connection or a combination thereof.
  • the electrically conductive material suitably comprises an 3D printed or extruded and sintered macroscopic structure, said macroscopic structure supporting a ceramic coating, wherein said ceramic coating supports a catalytically active material.
  • the structured catalyst may comprise an array of macroscopic structures electrically connected to each other.
  • the macroscopic structure may have a plurality of parallel channels, a plurality of non-parallel channels and/or a plurality of labyrinthic channels.
  • the reactor typically further comprises a bed of a second catalyst material upstream said structured catalyst within said pressure shell.
  • the e-RWGS reactor further comprises a catalyst material in the form of catalyst pellets, extrudates or granulates loaded into the channels of said macroscopic structure.
  • the e-RWGS reactor may further comprise a control system arranged to control the electrical power supply to ensure that the temperature of the gas exiting the pressure shell lies in a predetermined range and/or to ensure that the conversion of the feed gas lies in a predetermined range.
  • the term "macroscopic structure” is meant to denote a structure which is large enough to be visible with the naked eye, without magnifying devices.
  • the dimensions of the macroscopic structure are typically in the range of centimeters or even meters. Dimensions of the macroscopic structure are advantageously made to correspond at least partly to the inner dimensions of the pressure shell, saving room for the heat insulation layer and conductors.
  • a ceramic coating, with or without catalytically active material, may be added directly to a metal surface by wash coating.
  • the wash coating of a metal surface is a well-known process; a description is given in e.g. Cybulski, A., and Moulijn, J. A., Structured catalysts and reactors, Marcel Dekker, Inc, New York, 1998, Chapter 3, and references herein.
  • the ceramic coating may be added to the surface of the macroscopic structure and subsequently the catalytically active material may be added; alternatively, the ceramic coat comprising the catalytically active material is added to the macroscopic structure.
  • the macroscopic structure has been manufactured by extrusion of a mixture of powdered metallic particles and a binder to an extruded structure and subsequent sintering of the extruded structure, thereby providing a material with a high geometric surface area per volume.
  • a ceramic coating which may contain the catalytically active material, is provided onto the macroscopic structure before a second sintering in an oxidizing atmosphere, in order to form chemical bonds between the ceramic coating and the macroscopic structure.
  • the catalytically active material may be impregnated onto the ceramic coating after the second sintering.
  • the conductors are made of different materials than the macroscopic structure.
  • the conductors may for example be of iron, nickel, aluminum, copper, silver, or an alloy thereof.
  • the ceramic coating is an electrically insulating material and will typically have a thickness in the range of around 100 pm, say 10-500 pm.
  • a catalyst may be placed within the pressure shell and in channels within the macroscopic structure, around the macroscopic structure or upstream and/or downstream the macroscopic structure to support the catalytic function of the macroscopic structure.
  • the structured catalyst within said reactor system may have a ratio between the area equivalent diameter of a horizontal cross section through the structured catalyst and the height of the structured catalyst in the range from 0.1 to 2.0.
  • the macroscopic structure comprises Fe, Ni, Cu, Co, Cr, Al, Si or an alloy thereof.
  • Such an alloy may comprise further elements, such as Mn, Y, Zr, C, Co, Mo or combinations thereof.
  • the catalytically active material is particles having a size from 5 nm to 250 nm.
  • the catalytically active material may e.g. comprise copper, nickel, ruthenium, rhodium, iridium, platinum, cobalt, or a combination thereof.
  • one possible catalytically active material is a combination of nickel and rhodium and another combination of nickel and iridium.
  • the ceramic coating may for example be an oxide comprising Al, Zr, Mg, Ce and/or Ca. Exemplary coatings are calcium aluminate or a magnesium aluminum spinel.
  • Such a ceramic coating may comprise further elements, such as La, Y, Ti, K, or combinations thereof.
  • the ratio of moles of carbon in the third feed comprising hydrocarbons, preferably in the case when the third feed is external to the plant, to the moles of carbon in CO 2 in the second feed is less than 0.3, preferably less than 0.25 and more preferably less than 0.20 or even lower than 0.10.
  • the e-RWGS section (I) comprises an e-RWGS reactor and one or more additional reforming reactors (II) selected from the group consisting of an autothermal reforming (ATR) reactor (Ila), a fired steam methane reforming (SMR) reactor (lib), a gas-heated reforming reactor and an electrically heated steam methane reforming (e-SMR) reactor (lie).
  • ATR autothermal reforming
  • SMR fired steam methane reforming
  • e-SMR electrically heated steam methane reforming
  • the additional reforming reactors may be placed in parallel relationship to the e-RWGS reactor or in serial relationship to the e-RWGS reactor in any sequence.
  • the eRWGS section is arranged to operate the one or more additional reforming reactors only in the first operation mode, i.e. the one or more additional reforming reactors are not shared with the non-electrically heated RWGS section (II).
  • the first syngas to be supplied to the synthesis stage (B) is the total of the syngas from the e-RWGs reactor and the one or more additional reforming reactors.
  • the first syngas to be supplied to the synthesis stage (B) is the syngas from the e-RWGS reactor or additional reforming reactor, which is placed most downstream in the e-RWGS section.
  • the first syngas stream (20) is fed to the synthesis stage (B).
  • both the first syngas stream (20) and the second syngas (40) are fed to the synthesis stage (B).
  • the eRWGS section is arranged to operate the one or more additional reforming reactors both in the first and second operation mode, i.e. the one or more additional reforming reactors are shared with the non-electrically heated RWGS section (II).
  • the one or more additional reforming reactors may be selected from the group consisting of an autothermal reforming (ATR) reactor (Ila), a fired steam methane reforming (SMR) reactor (lib) and a gas-heated reforming reactor.
  • ATR autothermal reforming
  • SMR fired steam methane reforming
  • lib gas-heated reforming reactor.
  • the second syngas to be supplied to the synthesis stage (B) together with the first syngas is the total of the syngas from the one or more additional reforming reactors.
  • the second syngas to be supplied to the synthesis stage (B) together with the first syngas is the syngas from the additional reforming reactor, which is placed most downstream.
  • the first and second syngas are fed to the synthesis stage (B) as separate streams.
  • the first and second syngas streams are fed to the synthesis stage (B) as a combined stream.
  • the gas-heated reforming reactor may i.a. be a heat exchange reactor, e.g. a Haldor Topsoe exchange reactor (HTER).
  • HTER Haldor Topsoe exchange reactor
  • the e-RWGs section (I) comprises an electrically heated steam methane reforming (e-SMR) reactor disposed in parallel to the e-RWGS reactor.
  • e-SMR electrically heated steam methane reforming
  • at least one feed comprising hydrocarbons can be processed in the e-SMR section parallel to e-RWGS reactor.
  • the e-RWGS section (I) comprises an autothermal reformer (ATR) reactor downstream the e-RWGS reactor.
  • the ATR reactor typically comprises a burner, a combustion chamber, and a catalyst bed contained within a refractory lined pressure shell.
  • ATR reactor partial combustion of the hydrocarbon containing feed by sub-stoichiometric amounts of oxygen is followed by steam reforming of the partially combusted hydrocarbon feed stream in a fixed bed of steam reforming catalyst.
  • Steam reforming also takes place to some extent in the combustion chamber due to the high temperature.
  • the steam reforming reaction is accompanied by the water gas shift reaction.
  • the gas is at or close to equilibrium at the outlet of the reactor with respect to steam reforming and water gas shift reactions.
  • the exit gas from the e-RWGS reactor is directed to an autothermal reactor.
  • the exit gas from the e-RWGS reactor reacts with an oxidant to produce the final synthesis gas.
  • the final synthesis gas in this embodiment typically has a temperature above 950°C, such as above 1020°C, or 1050°C or above.
  • the exit temperature from the e-RWGS reactor will typically be between 600- 900°C such as between 700-850°C.
  • the e-RWGS reactor may in this embodiment either be selective or preferably be non-selective.
  • a feed gas comprising hydrocarbons is added to the exit gas from the e-RWGS reactor upstream of the autothermal reformer. This could for example be tail gas from a downstream Fischer-Tropsch synthesis unit.
  • the methane concentration leaving the RWGS reactor will preferably be lean, such as less than 20% or preferably less than 12%.
  • a relatively low concentration has the advantage that less oxidant is needed in the autothermal reformer.
  • the gas leaving the RWGS reactor is preferably not cooled (except for heat loss and by mixing with other streams). Cooling of the gas increases the oxygen consumption in the ATR.
  • the advantage of the embodiment with the ATR reactor is that the power needed for the e- RWGS reactor is reduced due to the lower exit temperature.
  • part or all of the oxygen generated by electrolysis of steam to produce hydrogen for the e-RWGS reactor is used in the autothermal reformer.
  • the oxidant for the autothermal reactor may either be oxygen, air, a mixture of air and oxygen, or be an oxidant comprising more than 80% oxygen such as more than 90% oxygen.
  • the oxidant may also comprise other components such as steam, nitrogen, and/or Argon. Typically, the oxidant in this case will comprise 5-20% steam.
  • the e-RWGS section (I) comprises a pre-reforming reactor placed upstream of the e-RWGS reactor.
  • This pre-reforming reactor may be adiabatic or cooled and the catalyst will typically be pellet based. Part or all of the first feed and/or part or all of the second feed and/or part or all of the third feed may be directed to this pre-reforming reactor.
  • pre-reforming reactor can be heated reactor. In the pre-reforming reactor the RWGS and methanation reactions (1-3) and/or steam methane reforming reactions take place. The exit temperature from this pre-reforming reactor is typically in the range between 400-700°C.
  • the effluent from this pre-reforming reactor is fed to the e-RWGS reactor optionally after cooling and condensation of part of the formed H 2 O. This has the advantage that the amount of CO 2 in the effluent from the e-RWGS reactor will be lower.
  • the eRWGS section (I) comprises an e-RWGS reactor and in parallel thereto an autothermal reactor (ATR) section (Ila), comprising one or more autothermal reactors (ATR), wherein first and/or second and/or third, feeds are fed to said ATR section (Ila), and wherein the plant (X) further comprises a fifth feed (5) comprising oxygen and - optionally - a fourth feed (4) comprising steam to the autothermal reactor (ATR) section (Ila).
  • ATR autothermal reactor
  • the plant (X) further comprises a fifth feed (5) comprising oxygen and - optionally - a fourth feed (4) comprising steam to the autothermal reactor (ATR) section (Ila).
  • at least a portion of the combined feed may be fed to the ATR section (Ila).
  • Part or all of the third feed may be desulfurized and pre-reformed. All feeds are preheated as required.
  • the first and second feeds are subjected to a me
  • the ATR reactor typically comprises a burner, a combustion chamber, and a catalyst bed contained within a refractory lined pressure shell.
  • ATR reactor partial combustion of the hydrocarbon containing feed by sub-stoichiometric amounts of oxygen is followed by steam reforming of the partially combusted hydrocarbon feed stream in a fixed bed of steam reforming catalyst.
  • Steam reforming also takes place to some extent in the combustion chamber due to the high temperature.
  • the steam reforming reaction is accompanied by the water gas shift reaction.
  • the gas is at or close to equilibrium at the outlet of the reactor with respect to steam reforming and water gas shift reactions.
  • the syngas stream from the e-RWGS reactor in eRWGS section (I) is arranged to be combined with the second syngas stream from the ATR section (Ila) to provide a combined syngas stream.
  • This combined syngas stream is arranged to be fed to the synthesis stage (B).
  • the effluent gas from the ATR reactor has a temperature of 900-1100°C.
  • the effluent gas normally comprises H 2 , CO, CO 2 , and steam. Other components such as methane, nitrogen, and argon may also be present often in minor amounts.
  • the operating pressure of the ATR reactor will be between 5 and 100 bars or more preferably between 15 and 60 bars.
  • the syngas stream from the ATR is cooled in a cooling train normally comprising a waste heat boiler(s) (WHB) and one or more additional heat exchangers.
  • the cooling medium in the WHB is (boiler feed) water which is evaporated to steam.
  • the syngas stream is further cooled to below the dew point for example by preheating the utilities and/or partial preheating of one or more feed streams and cooling in air cooler and/or water cooler.
  • Condensed H 2 O is taken out as process condensate in a separator to provide a syngas stream with low H 2 O content, which is sent to the synthesis stage.
  • the "ATR section” may be a partial oxidation "POX" section.
  • a POX section is similar to an ATR section except for the fact that the ATR reactor is replaced by a POX reactor.
  • the POX rector generally comprises a burner and a combustion chamber contained in a refractory lined pressure shell.
  • the ATR section could also be a catalytic partial oxidation (cPOX) section.
  • cPOX catalytic partial oxidation
  • the non-electrically heated reactor RWGS section (II) is arranged in parallel to said e-RWGS section (I).
  • the non-electrically heated reactor RWGS section (II) is an autothermal reactor (ATR) section (Ila) or a fired reactor (SMR) section (lib).
  • ATR autothermal reactor
  • SMR fired reactor
  • the non-electrically heated reactor RWGS section (II) is an autothermal reactor (ATR) section (Ila), and the plant (X) further comprises a fifth feed (5) comprising oxygen and - optionally - a fourth feed (4) comprising steam to the autothermal reactor (ATR) section (Ila).
  • the non-electrically heated reactor RWGS section (II) is a fired reactor (SMR) section (lib), and the plant (X) comprises a fourth feed (4) comprising steam to the fired reactor (SMR) section (lib).
  • the plant is arranged to supply to the non-electrically heated reactor RWGS section (II) a total feed comprising d) the second (2) and third (3) feeds either as separate streams or as one combined stream.
  • the second syngas stream produced in the non-electrically heated reactor section may have the following composition (by volume) :
  • At least a portion of the first and second and optionally third feed is fed to the non-electrically heated reactor RWGS section (II).
  • the third feed comprising hydrocarbons may be a natural gas feed.
  • the plant comprises a synthesis stage (B).
  • the synthesis stage (B) is arranged to convert said first syngas stream and/or said second syngas stream into at least a product stream and, optionally, a hydrocarbon-containing off-gas stream.
  • the synthesis stage (B) may comprise other process elements, such as compressor, heat exchanger, separator etc.
  • the syngas stream at the inlet of said synthesis stage (B) has a hydrogen/carbon monoxide ratio in the range 1.00 - 4.00; preferably 1.50 - 3.00, more preferably 1.50 - 2.10.
  • the synthesis stage (B) may be a Fischer-Tropsch (F-T) stage arranged to convert said syngas stream into at least a hydrocarbon product stream and a hydrocarbon- containing off-gas stream in the form of an F-T tail gas stream.
  • F-T Fischer-Tropsch
  • at least a portion of said hydrocarbon-containing off-gas stream may be fed to the syngas stage (A) as said third feed comprising hydrocarbons or in addition to said third feed comprising hydrocarbons. This increases the overall carbon efficiency.
  • the synthesis stage (B) comprises a methanol synthesis stage arranged to provide at least a methanol product stream.
  • the ratio of H 2 :CO 2 provided at the plant inlet may be between 1.0-9.0, preferably 2.5 - 8.0, more preferably 3.0 - 7.0.
  • the ratio of H 2 :CO 2 provided at the plant inlet means the ratio of H 2 :CO 2 calculated on the basis of the total of all feeds provided to the plant.
  • a sixth feed of hydrogen may be arranged to be combined with the first syngas stream and/or the second syngas stream upstream the synthesis stage (B). This allows the required ratio of H 2 :CO 2 to be adjusted as required.
  • the plant further comprises an electrolysis section (III) arranged to convert water or steam into at least a hydrogen stream and an oxygen stream, and at least a part of said hydrogen stream from the electrolysis section is arranged to be fed to the syngas stage (A) as said first feed. Additionally, at least a part of the hydrogen stream from the electrolysis section can be comprised as the sixth feed of hydrogen.
  • a part or all of the water or steam, fed to electrolysis section (III) may come from syngas stage (A) or synthesis stage (B).
  • At least a part of the oxygen stream from the electrolysis section is suitably arranged to be fed to the syngas stage (A) as said fifth feed comprising oxygen.
  • the electrolysis section (III) may also be arranged to convert a feed of CO 2 into a stream comprising CO and CO 2 , wherein at least a part of said stream comprising CO and CO 2 from the electrolysis section (III) is arranged to be fed to the syngas stage (A) as at least a portion of said second feed comprising carbon dioxide.
  • An electrolysis section may also be arranged upstream the eRWGS to convert a feed of CO 2 and a feed of water or steam into part or all of said combined feed comprising hydrogen and carbon dioxide. In other words, a single electrolysis section converts both a feed of CO 2 and a feed of water/steam into the combined feed.
  • the synthesis gas plant further comprises a gas purification unit and/or a pre-reforming reactor for pre-reforming the third feed comprising hydrocarbons upstream the syngas stage (A).
  • the gas purification unit is e.g. a desulfurization unit, such as a hydrodesulfurization unit.
  • the hydrocarbon gas will, together with steam, and potentially also hydrogen and/or other components such as carbon dioxide, undergo prereforming according to reaction (7) in a temperature range of ca. 350-550°C to convert higher hydrocarbons as an initial step in the process, normally taking place downstream the desulfurization step. This removes the risk of carbon formation from higher hydrocarbons on catalyst in the subsequent process steps.
  • carbon dioxide or other components may also be mixed with the gas leaving the pre-reforming step to form the feed gas.
  • the composition of the syngas from the syngas stage of the plant can be adjusted in various ways.
  • the plant may further comprise a carbon dioxide removal section, located between said syngas stage (A) and said synthesis stage (B), and arranged to remove at least part of the carbon dioxide from the syngas stream.
  • a carbon dioxide removal section located between said syngas stage (A) and said synthesis stage (B), and arranged to remove at least part of the carbon dioxide from the syngas stream.
  • at least a portion of the carbon dioxide removed from the syngas stream in said carbon dioxide removal section may be compressed and fed as part of said second feed (2) to the syngas stage (A).
  • Carbon dioxide removal units can be, but not limited to, an amine-based unit or a membrane unit. Such a layout also improves efficiency.
  • the plant may comprise a hydrogen removal section, located between said syngas stage (A) and said synthesis stage (B), arranged to remove at least part of the hydrogen from the syngas stream.
  • a hydrogen removal section located between said syngas stage (A) and said synthesis stage (B), arranged to remove at least part of the hydrogen from the syngas stream.
  • at least a portion of the hydrogen removed from the syngas stream in said hydrogen removal section may be compressed and fed as part of said first feed (1) to the syngas stage (A).
  • Hydrogen removal units can be, but not limited to, pressure swing adsorption (PSA) units or membrane units.
  • a method for producing a product stream, such as a hydrocarbon stream comprises the steps of: providing a plant (X) of the present invention; supplying to each of the e-RWGS section (I) and the non-electrically heated RWGS reactor section (II) the total feed either as separate streams or as partially combined streams or one combined stream; wherein said e-RWGS section (I) is arranged to convert at least a portion of the feeds supplied thereto into a first syngas stream (20), wherein said non-electrically heated reactor RWGS section (II) is arranged to convert at least a portion of the feed supplied thereto into a second syngas stream (40), operating the plant (X) in either a first or a second operation mode; in the first operation mode feeding said first syngas stream (20) and optionally the second syngas stream (40) to the synthesis stage (B) and in the second operation mode feeding the second syngas stream (40) and not the first syngas stream (20) to the synthesis stage (B); converting
  • At least a portion of said hydrocarbon-containing off-gas stream (3a, 3b) is recycled to the syngas stage (A) as said third feed (3) comprising hydrocarbons or in addition to said third feed (3) comprising hydrocarbons.
  • At least a portion of said third feed (3) comprising hydrocarbon is external to said plant (X).
  • the synthesis stage (B) is a Fischer-Tropsch (FT) stage arranged to convert said first syngas stream (20) and/or said second syngas stream (40) into at least a hydrocarbon product stream (500) and a hydrocarbon-containing off-gas stream in the form of an FT tail gas stream.
  • FT Fischer-Tropsch
  • the method suitably comprises the additional steps of providing a third feed comprising hydrocarbons and a fourth feed comprising steam to said additional reforming reactor and converting at least a portion of said third feed into a syngas stream in said additional reforming reactor, and combining said syngas streams from the e-RWGS reactor and the additional reforming reactor to provide a combined first syngas stream and feeding said combined first syngas stream to the synthesis stage (B).
  • l.A plant said plant comprising : e. a syngas stage (A), said syngas stage comprising an electrically heated reverse water gas shift (e-RWGS) section (I) and a non-electrically heated reactor section (II), which is an autothermal reactor (ATR) section (Ila) or a fired reactor (SMR) section (lib); f.
  • a syngas stage said syngas stage comprising an electrically heated reverse water gas shift (e-RWGS) section (I) and a non-electrically heated reactor section (II), which is an autothermal reactor (ATR) section (Ila) or a fired reactor (SMR) section (lib);
  • ATR autothermal reactor
  • SMR fired reactor
  • a synthesis stage said plant comprising one or more of the following feeds: a first feed (1) comprising hydrogen, a second feed (2) comprising carbon dioxide; a third feed (3) comprising hydrocarbons; wherein the plant is arranged to supply to said e-RWGS section (I) the first (1) feed and/or the second (2) feed and/or the third feed (3), wherein said e-RWGS section (I) is arranged to convert at least a portion of the feed supplied thereto into a first syngas stream (20); wherein the plant is arranged to supply to said non-electrically heated RWGS section (II) the first (1) feed and second (2) feed and optionally the third feed (3), wherein said non- electrically heated reactor section (II) is arranged to convert at least a portion of the feed supplied thereto into a second syngas stream (40); wherein the first feed (1), the second feed (2) and the third feed (3) are supplied to the e- RWGS section (I) and to the non-electrically heated RWGS section (II)
  • the third feed (3) is natural gas, town gas, naphtha, or a mixture of methane and higher hydrocarbons or LPG, and wherein the ratio of moles of carbon in the third feed (3) comprising hydrocarbons, when external to the plant, to the moles of carbon in CO 2 in the second feed (2) is less than 0.3, preferably less than 0.25 and more preferably less than 0.20 or even lower than 0.10.
  • non-electrically heated reactor RWGS section (II) is an autothermal reactor (ATR) section (Ila)
  • the plant (X) further comprises a fifth feed (5) comprising oxygen and - optionally - a fourth feed (4) comprising steam to the autothermal reactor (ATR) section (Ila).
  • non-electrically heated reactor RWGS section (II) is a fired reactor (SMR) section (lib)
  • plant (X) further comprises a fourth feed (4) comprising steam and not a feed comprising oxygen to the fired reactor (SMR) section (lib).
  • the operating temperature of the e-RWGS section (I) is 900°C or more, preferably 1000°C or more, even more preferably 1100°C or more.
  • first syngas stream (20) and/or the second syngas stream (40) at the inlet of said synthesis stage (B) has a hydrogen/carbon monoxide ratio in the range 1.00 - 4.00; preferably 1.50 - 3.00, more preferably 1.50 - 2.10.
  • synthesis stage (B) is a Fischer-Tropsch (FT) synthesis stage and the H 2 :CO 2 -ratio provided at the plant inlet is preferably in the range of 3.0 - 7.0 or more preferably from 3.0 - 6.0 and most preferably 2.2 - 4.50.
  • FT Fischer-Tropsch
  • said third feed (3) comprising hydrocarbons is a natural gas feed or renewable natural gas (NG) feed.
  • synthesis stage (B) is arranged to convert said first syngas stream (20) and/or said second syngas stream (40) into at least a product stream (500) and, optionally, at least a hydrocarbon-containing off-gas stream.
  • the synthesis stage (B) is a Fischer-Tropsch (FT) stage arranged to convert said first syngas stream (20) and/or said second syngas stream (40) into at least a hydrocarbon product stream and a hydrocarbon- containing off-gas stream in the form of a FT tail gas stream.
  • FT Fischer-Tropsch
  • the synthesis stage (B) is a methanol synthesis stage arranged to convert said first syngas stream (20) and/or said second syngas stream (40) into at least a hydrocarbon product stream in the form of a methanol product stream and a hydrocarbon-containing off-gas stream.
  • the plant according to any preceding item further comprising an electrolysis section (III) arranged to convert water or steam into at least a hydrogen stream and an oxygen stream (11), and wherein at least a part of said hydrogen stream from the electrolysis section is arranged to be fed to the syngas stage (A) as at least a portion of said first feed (1).
  • non-electrically heated reactor RWGS section (II) being an autothermal reactor (ATR) section (Ila), and wherein at least a part of the oxygen stream (11) from the electrolysis section is arranged to be fed to the syngas stage (A) as said fifth feed (5) comprising oxygen.
  • the electrolysis section (III) is arranged to convert a feed of CO 2 into a stream comprising CO and CO 2 , and wherein at least a part of said stream comprising CO and CO 2 from the electrolysis section (III) is arranged to be fed to the syngas stage (A) as at least a portion of said second feed (2) comprising carbon dioxide.
  • the e-RWGS section comprises a structured catalyst comprising a macroscopic structure of electrically conductive material capable of catalysing both a reverse water gas shift reaction and a methanation reaction I steam methane reforming reaction (non-selective catalyst).
  • the e-RWGs section (I) comprises an e-RWGS reactor and one or more additional reforming reactors (II) selected from the group consisting of an autothermal reforming (ATR) reactor (Ila), a steam methane reforming (SMR) reactor (lib) and an electrically heated steam methane reforming (e-SMR) reactor (lie).
  • ATR autothermal reforming
  • SMR steam methane reforming
  • e-SMR electrically heated steam methane reforming
  • the eRWGS section (I) comprises an e-RWGS reactor and in parallel thereto an autothermal reactor (ATR) section (Ila), comprising one or more autothermal reactors (ATR), wherein first and/or second and/or third, feeds are fed to said ATR section (Ila), and wherein the plant (X) further comprises a fifth feed (5) comprising oxygen and - optionally - a fourth feed (4) comprising steam to the autothermal reactor (ATR) section (Ila).
  • a method for producing a product stream such as a hydrocarbon stream, said method comprising the steps of: providing a plant (X) as defined in any preceding claim; supplying to each of the e-RWGS section (I) and the non-electrically heated reactor RWGS section (II) the total feed either as separate streams or as partially combined streams or one combined stream; wherein said e-RWGS section (I) is arranged to convert at least a portion of the feeds supplied thereto into a first syngas stream (20), wherein said non-electrically heated reactor RWGS section (II) is arranged to convert at least a portion of the feed supplied thereto into a second syngas stream (40), operating the plant (X) in either a first or a second operation mode; in the first operation mode feeding said first syngas stream (20) and optionally the second syngas stream (40) to the synthesis stage (B) and in the second operation mode feeding the second syngas stream (40) and not the first syngas stream (20) to the synthesis stage (B);
  • synthesis stage (B) is a Fischer-Tropsch (FT) stage arranged to convert said first syngas stream (20) and/or said second syngas stream (40) into at least a hydrocarbon product stream (500) and a hydrocarbon-containing off-gas stream in the form of an FT tail gas stream.
  • FT Fischer-Tropsch
  • FIGS la and lb show a specific layout of the plant of the invention in a first and second operation mode, respectively.
  • the plant X comprises a syngas stage (A), and the syngas stage (A) comprises an electrically heated reverse water gas shift (e-RWGS) section (I) and a non- electrically heated reactor RWGS section (II), arranged in parallel to said e-RWGS section (I).
  • the plant also comprises a synthesis stage (B). Plant feeds in Figure 1 are as follows:
  • the first feed (1) comprising hydrogen, the second feed (2) comprising carbon dioxide and the third feed comprising hydrocarbons, are supplied to both the e-RWGS section (I), which converts them to a first syngas stream (20), and to the non-electrically heated reactor section (II), which converts them to a second syngas stream (40).
  • the first syngas stream (20) is fed to the synthesis stage (B).
  • the second syngas stream (40) is combined with the first syngas stream (20) to form a combined syngas stream (100), which is fed to the synthesis stage (B).
  • the mixed syngas can be cooled in a common cooling section (not shown in the figure).
  • the second syngas stream (40) and no first syngas stream (20) is fed to the synthesis stage.
  • the first and/or second syngas stream is converted into at least a hydrocarbon product stream (500).
  • e-RWGS section (I) is the primary source of syngas (20)
  • non-electrically heated reactor section (II) may provide an additional syngas (40) stream to synthesis stage (B).
  • the non-electrically heated reactor section (II) serves as the sole source of syngas to synthesis stage (B) in the plant of the invention.
  • FIG 2 shows a variant of the layout of the plant of Figure la in its first operation mode.
  • Recycled hydrocarbon streams (3a) from synthesis stage (B) and a fourth feed (4) comprising steam are also fed to the e-RWGS section (I), which is arranged to convert the feeds into a first syngas stream (20), and optionally, to the non-electrically heated reactor RWGS section (II), which is arranged to convert the feeds into a second syngas stream (40).
  • the first syngas stream (20) from the e-RWGS section (I) is combined with the second syngas stream (40) from the non-electrically heated reactor RWGS section (II) to provide a combined syngas stream (100) and said combined syngas stream (100) is fed to the synthesis stage (B).
  • FIG 2a shows a variant of the layout in Figure 2, in which the non-electrically heated reactor RWGS section (II) is an autothermal reactor section (Ila).
  • RWGS section (II) is an autothermal reactor section (Ila).
  • fifth feed (5) comprising oxygen is fed to the autothermal reactor (ATR) section (Ila).
  • the recycled hydrocarbon stream (3a) is passed through an off-gas conversion section (IV), which may comprise at least one hydrogenation unit and/or at least one water gas shift unit and/or at least one hydrocarbon conversion reactor.
  • a stream of hydrogen (6) is supplied to the synthesis stage (B).
  • FIG 3 shows a variation of the layout of Figure 2a, i.e. wherein the plant is in its first operation mode and the non-electrically heated reactor RWGS section is an autothermal reactor section (Ila), and wherein the plant further includes an electrolysis section (III).
  • Electrolysis section (III) converts steam or water (60) feed into a hydrogen rich stream and an oxygen rich stream.
  • a part of the hydrogen rich stream from the electrolysis section (III) is fed to the syngas stage (A) as said first feed (1).
  • at least a part of said hydrogen stream from the electrolysis section (III) is comprised as a sixth feed (6) of hydrogen to the synthesis stage (B).
  • a part of the oxygen stream is used in autothermal reactor (ATR) section (Ila) as fifth feed (5), and rest is exported (12).
  • H2 rich and CO2 rich feeds together with hydrocarbon comprising recycled off-gas stream are first converted to syngas and the said syngas is further converted to hydrocarbon product(s) in Fischer-Tropsch (FT) synthesis process.
  • the syngas generation stage comprises an e-RWGS based section (I) and a parallel autothermal reactor section (Ila). Each of these sections has a dedicated waste heat boiler.
  • the plant uses a common cooling train to obtain condensate free syngas to be fed to FT-synthesis stage (B).
  • the numbers shown in the above Table 1 are based on a fixed H2 feed consumption while CO2 feed consumption is adjusted to meet the required syngas quality for FT-synthesis stage (B).
  • the base case is set as operation mode 1 (first operation mode) with no flow through autothermal reactor section (Ila).
  • operation mode 1 first operation mode
  • second row Cl
  • operation loads are approximately equally distributed between section (I) and section (II), i.e. an operation load of 50% for each section.
  • SGU Syngas Generation Unit
  • Production of syngas from H2 and CO2 feeds is more efficient via e-RWGS compared to using any non-electrically heated reactor, including autothermal reactor.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
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  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne une installation, telle qu'une installation d'hydrocarbure, qui comprend un étage de gaz de synthèse (A) pour la génération de gaz de synthèse et un étage de synthèse (B) où ledit gaz de synthèse est synthétisé pour produire un produit dérivé de gaz de synthèse, tel qu'un produit hydrocarboné. L'étage de gaz de synthèse (A) comprend principalement une section de conversion eau-gaz inverse chauffée électriquement (e-RWGS) et une section de réacteur non chauffée électriquement (II). L'installation utilise efficacement divers flux ; en particulier CO2 et H2, et permet une production continue même pendant une indisponibilité partielle ou complète d'électricité renouvelable. L'invention concerne également une méthode de production d'un flux de produit, tel qu'un flux de produit hydrocarboné.
PCT/EP2024/064366 2023-05-25 2024-05-24 Conversion de co2 et de h2 en combustibles de synthèse Ceased WO2024240932A1 (fr)

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EP24727437.6A EP4719973A1 (fr) 2023-05-25 2024-05-24 Conversion de co2 et de h2 en combustibles de synthèse
CN202480027671.9A CN121039053A (zh) 2023-05-25 2024-05-24 将co2和h2转化为合成燃料

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022079098A1 (fr) * 2020-10-14 2022-04-21 Haldor Topsøe A/S Conversion de co2 et de h2 en combustibles de synthèse
WO2022079010A1 (fr) * 2020-10-14 2022-04-21 Haldor Topsøe A/S Installation de synthèse chimique
WO2022253965A1 (fr) * 2021-06-03 2022-12-08 Topsoe A/S Réacteur d'échange de chaleur pour la conversion de co2

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022079098A1 (fr) * 2020-10-14 2022-04-21 Haldor Topsøe A/S Conversion de co2 et de h2 en combustibles de synthèse
WO2022079010A1 (fr) * 2020-10-14 2022-04-21 Haldor Topsøe A/S Installation de synthèse chimique
WO2022253965A1 (fr) * 2021-06-03 2022-12-08 Topsoe A/S Réacteur d'échange de chaleur pour la conversion de co2

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CYBULSKI, A.MOULIJN, J. A.: "Structured catalysts and reactors", 1998, MARCEL DEKKER, INC
H.S. BENGAARDJ.K. NØRSKOVJ. SEHESTEDB.S. CLAUSENL.P. NIELSENA.M. MOLENBROEKJ.R. ROSTRUP-NIELSEN: "Steam Reforming and Graphite Formation on Ni Catalysts", JOURNAL OF CATALYSIS, vol. 209, no. 2, 2002, pages 365 - 384, XP004468881, DOI: 10.1006/jcat.2002.3579

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CN121039053A (zh) 2025-11-28

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