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EP4587380A1 - Reformage atr - Google Patents

Reformage atr

Info

Publication number
EP4587380A1
EP4587380A1 EP23769267.8A EP23769267A EP4587380A1 EP 4587380 A1 EP4587380 A1 EP 4587380A1 EP 23769267 A EP23769267 A EP 23769267A EP 4587380 A1 EP4587380 A1 EP 4587380A1
Authority
EP
European Patent Office
Prior art keywords
section
stream
feed
reforming
synthesis gas
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
EP23769267.8A
Other languages
German (de)
English (en)
Inventor
Arunabh SAHAI
Kim Aasberg-Petersen
Thomas Sandahl Christensen
Steffen Spangsberg CHRISTENSEN
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.)
Topsoe AS
Original Assignee
Haldor Topsoe AS
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 Haldor Topsoe AS filed Critical Haldor Topsoe AS
Publication of EP4587380A1 publication Critical patent/EP4587380A1/fr
Pending legal-status Critical Current

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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
    • 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
    • C01B3/382—Multi-step processes
    • 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
    • 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
    • C01B3/48—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 followed 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • 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
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    • 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
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • 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
    • C01B2203/06—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
    • C01B2203/068—Ammonia synthesis
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C01B2203/1264—Catalytic pre-treatment of the feed
    • C01B2203/127—Catalytic desulfurisation
    • 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
    • C10K3/001—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 thermal treatment
    • C10K3/003—Reducing the tar content
    • C10K3/008—Reducing the tar content by cracking

Definitions

  • a synthesis gas stage comprising: a first hydrocarbon feed, a prereformer section, arranged to receive the first hydrocarbon feed and provide a prereformed stream, a reforming section, arranged to receive the prereformed stream and provide a first syngas stream, wherein said synthesis gas stage comprises a first electrical heating unit located between said prereformer section and said reforming section, said first electrical heating unit being arranged to heat the prereformed stream to at least 400 °C, preferably at least 450 °C, prior to being fed to the reforming section.
  • feed refers to means for supplying said gas to the appropriate section, reactor or unit; such as a duct, tubing etc.
  • a “section” comprises one or more “units” which perform a change in the chemical composition of a feed, and may additionally comprise elements such as e.g. heat exchanger, mixer or compressor, which do not change the chemical composition of a feed or stream.
  • a "stage" comprises one or more sections.
  • a prereformer section is arranged to receive the first hydrocarbon feed and provide a prereformed stream. Pre-reforming is the process by which methane and heavier hydrocarbons are steam reformed and the products of the heavier hydrocarbon reforming are methanated.
  • a prereformer section may comprise an adiabatic pre-reformer filled with a catalyst with high nickel content and a main steam reformer. The adiabatic pre-reformer is usually positioned upstream of the main steam reformer. Steam may be added to the stream comprising hydrocarbons upstream the prereforming section.
  • the provided prereformed stream comprises CO 2 , CH 4 , H 2 O and H 2 along with typically lower quantities of CO and possible other components.
  • the prereformers all higher hydrocarbons can be converted to carbon oxides and methane, but the prereformers are also advantageous for light hydrocarbons.
  • Providing the prereformer may have several advantages including reducing the required O 2 consumption in the ATR and allowing higher inlet temperatures to the ATR since cracking risk by preheating is minimized.
  • the prereformers may provide an efficient sulphur guard resulting in a practically sulphur free feed gas entering the ATR and the downstream system.
  • the reforming section comprises at least one of an autothermal reforming (ATR) section, a reverse water gas shift (RWGS) section, optionally, where the reverse water gas shift section is electrically heated, a steam methane reformer (SMR) section, steam methane reformer-b (SMR-b) section, and/or a convection reformer (HTCR) section.
  • ATR autothermal reforming
  • RWGS reverse water gas shift
  • HTCR convection reformer
  • the reforming section comprises an autothermal reforming (ATR) section and the ATR section is arranged to receive a feed comprising an oxidant.
  • a feed comprising an oxidant is provided to the ATR section.
  • the oxidant feed consists essentially of oxygen.
  • the oxidant feed of O 2 is suitably "oxygen-rich" meaning that the major portion of this feed is O 2 ; i.e. over 75% such as over 90% or over 95%, such as over 99% of this feed is O 2 .
  • This oxidant feed may also comprise other components such as nitrogen, argon, CO 2 , and/or steam. This oxidant feed will typically include a minor amount of steam (e.g. 5-10%).
  • the synthesis gas stage thus comprises a reforming section comprising an autothermal reforming (ATR) section and the ATR section is arranged to receive a feed comprising an oxidant.
  • the synthesis gas stage comprises a reforming section comprising an autothermal reforming (ATR) section and further comprises an air separation unit and an air feed, said air separation unit being arranged to separate said air feed into at least an oxygen-rich stream and supply at least a portion of said oxygen-rich stream to the ATR section as said feed comprising an oxidant.
  • the amount of required O2 consumption in the ATR reactor is reduced because the reforming section receives the prereformed stream said stream comprising mostly CO 2 , CH 4 , H 2 O and H 2 compared to the alternative where the reforming section receives a non-prereformed hydrocarbon feed.
  • the synthesis gas stage further comprises a first electrical heating unit located between said prereformer section and said reforming section.
  • the first electrical heating unit is arranged to heat the prereformed stream to at least 400 °C, preferably at least 450 °C, prior to being fed to the reforming section.
  • the presence of said prereformer section upstream said reforming section allows for higher inlet temperatures to the reforming section comprising at least one reactor such as at least one ATR reactor since cracking risk by preheating is minimized.
  • said synthesis gas stage is arranged in such a way that there is no temperature change between the electrical heating unit and the reforming section.
  • the fired heater is provided to preheat the prereformed stream inlet ATR.
  • the inlet temperature of ATR is kept low say below 450 °C such as 400°C.
  • the fired heater can be completely eliminated as well.
  • the plant in the present invention is arranged to have an electric heater to heat the prereformed gas inlet ATR. Coupling the electrical heater with renewable power will also not impact the carbon emission from the plant. Heating the prereformed gas to at least 450 °C such 550 °C or more will reduce the oxygen consumption for the same syngas generation capacity or for the given oxygen flow the syngas generation capacity can be increased without any carbon emission.
  • the reforming section within the synthesis gas stage can comprise a reverse water gas shift (RWGS) section, optionally, where the reverse water gas shift unit is electrically heated.
  • Electrically heated reverse water gas shift (e-RWGS) uses an electric resistance-heated reactor to perform a more efficient reverse water gas shift process and substantially reduce or preferably avoids the use of fossil fuels as a heat source.
  • the e-RWGS section comprise at least one e-RWGS reactor. In the e-RWGS reactor, either selective or non-selective RWGS may take place, wherein "selective RWGS" means that only the reverse water gas shift reaction in accordance with reaction 3,
  • non-selective RWGS means that other reactions such as one or more of the methanation reactions (reverse of reaction 1 and 2) and reverse methanation takes place in addition to reverse water gas shift.
  • said e-RWGS reactor allows increasing temperature over said reactor from relatively low inlet temperature such as 400-600°C to a high product gas temperature in the reactor.
  • the reforming section within the synthesis gas stage comprises an e-RWGS section and a first electrical heating unit located between said prereformer section and said reforming section, said first electrical heating unit being arranged to heat the prereformed stream to at least 400 °C, preferably at least 450 °C, prior to being fed to the reforming section.
  • the reforming section comprises a steam methane reforming (SMR) section or alternatively a SMR-b section, wherein the SMR-b section comprises a SMR section arranged in parallel to an e-RWGS section.
  • SMR section is electrically heated such that it is a e-SMR section.
  • Said e-SMR section comprises at least one SMR reactor wherein methane is heated with steam usually in the presence of a catalyst, to provide a mixture of carbon monoxide and hydrogen in accordance with reaction 1.
  • An e-SMR reactor benefits from receiving a preheated feed such as a preheated prereformed hydrocarbon feed.
  • the reforming section comprises a convection reforming section such as a Haldor Topsoe convection reforming (HTCR) section.
  • HTCR Haldor Topsoe convection reforming
  • SMR and ATR reforming processes are integrated such that the conversion of hydrocarbons and steam to hydrogen and carbon oxides is fully autothermal, thereby avoiding any external fuel-fired heating.
  • said HTCR section comprises an integrated reactor designed in such a way that it comprises a primary reformer zone and a secondary reformer zone.
  • Said primary reformer zone receives the prereformed stream and provide an SMR reformed effluent, which passes through a catalyst bed to the space at the feed end of the secondary reformer zone, at which preheated feed comprising an oxidant such as oxygen is introduced such that the secondary reformer zone provide a secondary reformer effluent.
  • the hot secondary reformer effluent does not leave the reactor but passes on the shell side of the primary reformer zone, thereby applying the heat required for the endothermic SMR reforming reaction that occurs within the catalyst-containing reactor tubes of said primary reformer zone.
  • this convection reforming comprising said integrated reactor benefits from receiving a preheated feed such as a preheated prereformed hydrocarbon feed and thereby by having a first electrical heating unit located between said prereformer section and said reforming section said first electrical heating unit is, in a preferred aspect, arranged to heat the prereformed stream to at least 400 °C, preferably to at least 450 °C, prior to being fed to the reforming section.
  • the synthesis gas stage is composed such that said synthesis gas stage does not comprise a fired heater, in particular, wherein said section does not comprise a fired heater arranged to heat the prereformed stream prior to it being fed to the reforming section.
  • the synthesis gas stage further comprises a sulfur removal section arranged to receive a first hydrocarbon feed and provide a sulfur-depleted first hydrocarbon feed.
  • Sulfur may be present as sulfides in the hydrocarbon feed, however it is not desirable to have sulfur in the stream entering the reforming section, as the presence of sulfur typically leads to contamination of catalysts such as carbon formation on the surface of said catalyst.
  • the synthesis gas stage further comprises the sulfur removal section arranged upstream the reforming section and more preferred upstream the prereformer section.
  • the synthesis gas stage may further comprise a second electrical heating unit located between said sulfur removal section and said prereformer section.
  • the second electrical heating unit is arranged to heat the sulfur-depleted first hydrocarbon feed to at least 400 °C, preferably at least 450 °C, prior to being fed to the prereformer section.
  • the synthesis gas stage further comprises a sulfur removal section arranged to receive a first hydrocarbon feed, and provide a sulfur-depleted first hydrocarbon feed
  • said synthesis gas stage further comprises a second electrical heating unit, arranged to heat the sulfur-depleted first hydrocarbon feed, prior to said sulfur-depleted first hydrocarbon feed, being fed to the prereformer section.
  • the synthesis gas stage may further comprise a hydrogenation section arranged to receive a first hydrocarbon feed and a hydrogen feed, optionally in admixture, and provide a hydrogenated first hydrocarbon feed to the sulfur removal section.
  • the hydrogen feed 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.
  • a part or all of the hydrogen feed may come from at least one electrolyser.
  • An electrolyser means a unit for converting steam or water into hydrogen and oxygen by use of electrical energy.
  • the prereformed stream is heated to a temperature of below 650 °C.
  • the synthesis gas stage comprises an autothermal reforming (ATR) section and said process comprises the step of feeding said feed comprising an oxidant to the ATR section.
  • ATR autothermal reforming
  • a hydrogen plant an ammonia plant, a methanol plant and a synthetic fuel production plant comprising the described synthesis gas stage.
  • an ATR section is arranged for its pressure being lower than what normally would be expected for ATR section operation which typically is 30 bar g or higher, for instance 30-40 bar g such as 37.5 bar g.
  • This enables the capture of even more carbon, e.g. 97% or more of the carbon in the hydrocarbon feed whilst at the same time not compromising the energy efficiency, in particular when combined with the steam-to-carbon ratio in the ATR section being 0.4 or 0.6 or higher such as 0.8.
  • a hydrogen plant comprising the synthesis gas stage described is provided, said hydrogen plant further comprising a shift section and a hydrogen purification section, wherein the shift section is arranged to receive the first syngas stream from the reforming section and provide a second syngas stream, and wherein the hydrogen purification section is arranged to receive the second syngas stream from the shift section and provide a hydrogen-rich stream and an off-gas stream.
  • the shift section comprises a high temperature (HT) shift unit and a low temperature shift unit, said high temperature shift unit being arranged to receive the first syngas stream from the reforming section and to provide a first shifted syngas stream.
  • the first shifted syngas stream is subsequently fed to the low temperature (LT) shift unit for further shifting, thereby providing a second syngas stream, which is shifted according to the water gas shift (WGS) reaction (reaction 3).
  • WGS water gas shift
  • said high temperature (HT) shift unit may comprise a promoted zincaluminum oxide based high temperature shift catalyst.
  • HT high temperature
  • said steam-to-carbon ratio in the reforming and HT shift section are less than 2.6.
  • the advantage of a low steam-to-carbon ratio within the reforming section and shift section is that it enables higher synthesis gas throughput compared to high steam-to-carbon ratio. Additionally, a low steam-to-carbon ratio requires smaller equipment in the front-end due to the lower total mass flow through the plant.
  • the purification section comprises a separation unit in which process condensate comprising mostly water is removed from the product gas.
  • the pressure swing adsorption unit provide a hydrogen-rich stream i.e. a hydrogen product stream and an off-gas stream.
  • the hydrogen plant may be arranged to be operated such that CO 2 emission is further reduced.
  • preheating of feeds reduces the complication of the plant layout and increases the carbon efficiency.
  • Said preheating unit also helps in smooth and fast start-up of the plant.
  • a method for reducing CO 2 emissions in a plant comprising the step of heating a prereformed stream in the first electrical heating unit and heating the prereformed stream to a temperature of at least 400 °C, preferably at least 450 °C, in the first electrical heating unit.
  • At least a portion of the off-gas stream provide by the hydrogen purification section may be arranged to be recycled to the synthesis gas stage such as to the inlet of the prereformer section or to the reforming section as feed gas.
  • the off-gas may be added to the prereformed stream upstream an ATR section.
  • an ammonia plant comprising the synthesis gas stage described is provided, said ammonia plant further comprising a purification section followed by an ammonia synthesis loop, and optionally a shift section is arranged up-steam said purification section.
  • a shift section is arranged to receive the first syngas stream from the reforming section and provide a shifted first syngas stream.
  • the shifted first syngas stream is then fed as a feed to the purification section which is arranged to also receive a nitrogen-rich stream and to provide a process stream and an off-gas stream.
  • the ammonia synthesis loop is then arranged to receive said process stream and to provide an ammonia product stream.
  • the purification section of the ammonia plant may comprise one or more shift sections and CO2 removal section followed by a molecular sieve dryer and a N 2 wash unit (NWU).
  • the CO 2 -depleted stream may contain residual CO and CO2 together with small amounts of CH 4 , Ar, He and H 2 O.
  • the CO 2 and H 2 O are preferably removed before the NWU because they otherwise would freeze at the low operating temperature within the NWU. This may for example be done by adsorption in a molecular sieve dryer consisting of at least two vessels one in operation while the other is being regenerated. Nitrogen may be used as dry gas for re-generation. Provided by the N 2 wash unit is equivalent to earlier aspects said process steam.
  • the nitrogen for the NWU may be supplied by an air separation unit (ASU) which separates atmospheric air into at least a nitrogen-rich stream and an oxygen-rich stream.
  • ASU air separation unit
  • the oxygen-rich stream is used in an ATR section and the nitrogen-rich stream in the NWU.
  • the purification section is arranged to receive the first syngas stream from the reforming section to provide a process stream or, alternatively, wherein a shift section is arranged to receive the first syngas stream from the reforming section and provide a shifted first syngas stream.
  • the shifted first syngas stream is feed to the purification section and the purification section is arranged to provide a process stream, and the ammonia synthesis loop is arranged to receive said process stream and to provide an ammonia product stream.
  • the methanol plant further comprises a methanol synthesis stage.
  • This stage comprises a methanol synthesis section where the first syngas stream from the synthesis gas stage is first converted to a raw methanol stream followed by a methanol purification section where said raw methanol stream is purified to obtain a methanol product stream.
  • the methanol synthesis stage generates a methanol purge gas stream, which typically contains hydrogen, carbon dioxide, carbon monoxide and methane. Additional components such as argon, nitrogen or oxygenates with two or more carbon atoms may also be present in smaller amount.
  • a methanol plant comprising the synthesis gas stage described is also provided, said methanol plant further comprising a methanol synthesis section and a methanol purification section, wherein the methanol synthesis section is arranged to receive the first syngas stream from the reforming section and provide a raw methanol stream, and wherein the methanol purification section is arranged to receive the raw methanol stream from methanol synthesis section and provide a methanol product stream and an purge gas stream.
  • At least a portion of said methanol purge gas stream may be fed as an additional feed to the synthesis gas stage such as upstream an ATR section.
  • the purge gas may be added to the prereformed stream upstream the ATR section. In this way, the purge gas is recycled into the synthesis gas stage thereby increasing the over-all carbon efficiency of the plant.
  • the methanol purge gas stream may be purified prior to feeding it to the synthesis gas section.
  • only a portion of said methanol purge gas stream may be fed to the synthesis gas section; and another portion of the methanol purge gas may be purged and/or used as fuel.
  • a portion of the superheated steam stream is - in the illustrated embodiment - also to be mixed with the first syngas stream (31) downstream the first waste heat boiler.
  • High temperature (HT) shift reactor (210) receives the first syngas stream (31) downstream the first waste heat boiler (110) and provides a first shifted syngas stream (211).
  • Steam superheater (220) is arranged downstream the HT shift reactor, and superheats the first steam stream (121) from the steam drum (120) via heat exchange with the first shifted syngas stream (211) from the HT shift reactor (210).
  • Second waste heat boiler (230) is located between HT and LT shift reactors, as shown to generate second internal steam feed (231) for the steam drum (120) via heat exchange of a boiler water stream from the steam drum (120) with the shifted syngas stream downstream steam superheater (220).
  • steam stream (123) is mixed with oxygen-rich stream (91).
  • the product gas is passed to separator (250) in which process condensate 252 (comprising mostly water) is removed.
  • the product gas (251) is passed to CO 2 removal section 260, where CO 2 is removed in the form of CO 2 -rich stream (262).
  • the product gas is passed to a pressure-swing adsorption (PSA) unit (270) for separation of hydrogen stream (271) and an off-gas stream (272), which can be exported as fuel.
  • PSA pressure-swing adsorption
  • EXAMPLE Examples 1-4 show calculations of various parameters, based on the layout in Fig. 4.
  • Example 1 has no electrical heater at the inlet of the ATR.
  • Examples 2 and 3 differ in terms of the ATR inlet temperature. As can be seen, these three examples provide zero carbon emission from preheating.
  • Example 4 is same as Example 3 but the electrical heaters are replaced with a fired heater. This example shows significant CO2 emission from preheating.
  • the present invention has been described with reference to a number of aspects and figures. However, the skilled person is able to select and combine various aspects within the scope of the invention, which is defined by the appended claims. All documents referenced herein are incorporated by reference.

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Abstract

La présente invention concerne un étage de gaz de synthèse dans lequel une unité de chauffage électrique est située entre une section de pré-reformeur et une section ATR. La première unité de chauffage électrique est conçue pour chauffer le flux pré-formé à au moins 400°C avant son introduction dans la section ATR. L'invention concerne également un procédé de production d'un premier flux de gaz de synthèse, une installation d'hydrogène, qui peut être utilisée dans des installations de production d'hydrogène, d'ammoniac, de méthanol et de carburant synthétique et une méthode de réduction des émissions de CO2 dans une installation d'hydrogène.
EP23769267.8A 2022-09-16 2023-09-15 Reformage atr Pending EP4587380A1 (fr)

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IN202211053160 2022-09-16
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PCT/EP2023/075456 WO2024056870A1 (fr) 2022-09-16 2023-09-15 Reformage atr

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WO2025068513A1 (fr) * 2023-09-28 2025-04-03 Topsoe A/S Méthode de production d'ammoniac bleu
EP4553038A1 (fr) * 2023-11-09 2025-05-14 Linde GmbH Procédé et installation de production d'hydrogène
WO2025219326A1 (fr) * 2024-04-17 2025-10-23 Topsoe A/S Méthode de production d'ammoniac bleu
WO2025223822A1 (fr) * 2024-04-24 2025-10-30 Topsoe A/S Co-production d'ammoniac bleu et d'hydrogène
WO2025247773A1 (fr) * 2024-05-27 2025-12-04 Sabic Global Technologies B.V. Système de reformage autothermique et procédé de production d'hydrogène

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CN119894815A (zh) 2025-04-25

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