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WO2025186101A1 - Procédé et installation de production d'un gaz de synthèse pour la production d'ammoniac - Google Patents

Procédé et installation de production d'un gaz de synthèse pour la production d'ammoniac

Info

Publication number
WO2025186101A1
WO2025186101A1 PCT/EP2025/055377 EP2025055377W WO2025186101A1 WO 2025186101 A1 WO2025186101 A1 WO 2025186101A1 EP 2025055377 W EP2025055377 W EP 2025055377W WO 2025186101 A1 WO2025186101 A1 WO 2025186101A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen
pressure swing
swing adsorption
stream
recovery rate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/055377
Other languages
German (de)
English (en)
Other versions
WO2025186101A8 (fr
Inventor
Katja POSCHLAD
Klaus NÖLKER
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.)
ThyssenKrupp AG
ThyssenKrupp Industrial Solutions AG
Original Assignee
ThyssenKrupp AG
ThyssenKrupp Uhde GmbH
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
Priority claimed from LU103255A external-priority patent/LU103255B1/de
Priority claimed from DE102024106662.8A external-priority patent/DE102024106662A1/de
Application filed by ThyssenKrupp AG, ThyssenKrupp Uhde GmbH filed Critical ThyssenKrupp AG
Publication of WO2025186101A1 publication Critical patent/WO2025186101A1/fr
Publication of WO2025186101A8 publication Critical patent/WO2025186101A8/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • 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
    • C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • 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
    • C01B2203/0415—Purification by absorption in liquids
    • 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
    • C01B2203/06—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
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream

Definitions

  • the invention relates to processes for providing a synthesis gas for producing ammonia, wherein desulfurized natural gas is converted with steam and oxygen-enriched air or with oxygen in a reforming step to a synthesis gas comprising hydrogen, CO and CO2, wherein CO2 is separated from the synthesis gas in a separation step, wherein a hydrogen stream and a hydrogen-rich exhaust gas stream are formed in a pressure swing adsorption, wherein the pressure swing adsorption is operated in an adsorption cycle to provide the hydrogen stream and a regeneration cycle to provide the hydrogen-rich exhaust gas stream, wherein nitrogen is added to the synthesis gas in an enrichment step.
  • Ammonia is one of the most important raw materials. Global annual production currently amounts to approximately 170 million tons. Most of this ammonia is used to produce fertilizers. Ammonia is now also used to transport hydrogen, as it has a higher volumetric energy density than liquid hydrogen. This allows ammonia to transport more energy for the same volume than liquid hydrogen. It is therefore foreseeable that ammonia will continue to gain in importance.
  • Ammonia is produced primarily from the elements hydrogen and nitrogen in the presence of an iron catalyst. Temperatures often range between 400 °C and 500 °C and pressures exceeding 100 bar. The main factor influencing the process costs is the provision of hydrogen from synthesis gas production (Ullmann's, page 139). Accordingly, ammonia is preferably produced in principle as described, for example, in Holleman, Wiberg, Textbook of Inorganic Chemistry, 102nd edition, 2007, pages 662-665 (ISBN 978-3-11-017770-1), based on the “Haber-Bosch process” from the elements according to equation [1]:
  • the reactant nitrogen (N 2 ) can be obtained, for example, by low-temperature air separation.
  • Hydrogen is preferably obtained via the steam reforming process (e.g., as described in Andreas Jess, Peter Wasserscheid, Chemical Technology, An Integrated Textbook, Wiley-VCH, 2013, pages 536 to 539, ISBN 978-3-527-30446-2) according to equation [2]:
  • the object of the present invention is to provide an alternative process and a plant for producing a synthesis gas for the production of ammonia, in which the CO2 emissions can be reduced.
  • a recovery rate is set during operation of the pressure swing adsorption, wherein the recovery rate is formed from the ratio between the amount of hydrogen in the hydrogen stream from the pressure swing adsorption and the amount of hydrogen in the synthesis gas that is introduced into the pressure swing adsorption, wherein the recovery rate is influenced by the duration of the regeneration cycle and wherein the recovery rate is set such that the energy content of the hydrogen-rich exhaust gas stream is sufficient for the hydrogen-rich exhaust gas stream to be used as fuel gas in a burner, through which heat can be introduced into at least one process step of the method.
  • the fuel gas can be used in various burners and/or furnaces that occur or are used to heat various streams or substances within the process.
  • the hydrogen content in the exhaust stream of the pressure swing adsorption process is deliberately increased, either relatively or absolutely, by extending the regeneration cycle. It is not absolutely necessary to change the dimensions of the pressure swing adsorption process. However, it is also conceivable that the dimensions of the pressure swing adsorption process are deliberately lower than those that would be selected for efficient hydrogen yield.
  • Pressure swing adsorption can replace further process steps, such as LT shift conversion, methanation, and even a secondary reformer.
  • Molecular sieves are used as adsorbents in a series of vessels operating in a staggered cyclic mode, alternating between an adsorption phase and various regeneration stages.
  • the regeneration of the loaded adsorbent is achieved by gradual pressure relief and the use of the resulting gas to purge other adsorbers on a different
  • the regeneration cycle is carried out at the pressure level.
  • Hydrogen recovery is typically about 90%, depending on the number of adsorbers in a line. Very high purity can be achieved, with approximately 50 ppm argon and less than 10 ppm of other impurities.
  • the recovery rate is defined by the amount of hydrogen in the product stream of pressure swing adsorption, i.e. the hydrogen stream, in relation to the amount of hydrogen in the inlet stream to pressure swing adsorption, i.e. the synthesis gas introduced into pressure swing adsorption.
  • the hydrogen-rich exhaust stream at a high recovery rate, provides insufficient heat output to fuel a conventional front-end. Conventionally, this is compensated for by blending with natural gas. Combusting natural gas in the fuel gas mixture with the hydrogen-rich exhaust stream generates additional CO2 emissions. To reduce these emissions, the natural gas is replaced with hydrogen by reducing the recovery rate compared to the conventional process.
  • the PSA recovery rate is reduced by extending the regeneration cycle, i.e., extending the backflushing time. This not only increases the amount of hydrogen in the hydrogen-rich exhaust stream, but also the hydrogen purity. By burning the hydrogen-rich exhaust stream in the fired burner or furnace, reactants are preheated and the missing power for steam generation is replaced.
  • furnace is used synonymously with burner in the application.
  • the steam generated in this way has a variety of uses within the plant. A large portion is used to drive the compressors. If these compressors are powered by electricity, the plant's steam demand can be reduced, thus maintaining a higher recovery rate.
  • the question at this point is the CO2 assessment of the electricity: Is this considered CO2-neutral (e.g., electricity from wind power) or must a CO2 equivalent also be taken into account (e.g., electricity generated from fossil fuels).
  • a recovery rate is set in the range between 70% and 85%, preferably between 76% and 82%, particularly preferably between 79.0% and 80.5%. With a recovery rate in this range, the energy content of the hydrogen-rich exhaust gas stream is sufficient to fuel the front end of an ammonia plant without the need for additional admixture of natural gas.
  • the amount of gas in the synthesis gas stream obtained in the reforming step is varied depending on the recovery rate, in particular the amount of gas in the synthesis gas stream obtained in the reforming step is increased when the recovery rate is reduced.
  • Such a change is preferably achieved by changing the capacity or dimensions of the front end. If the front end is enlarged, the same amount of product can be obtained that a plant with an optimal recovery rate for the process can achieve without regard to CO2 emissions. Otherwise, the product amount of hydrogen is reduced. To compensate for this loss, the front end (the part of the plant that supplies the hydrogen) must be enlarged. This leads to additional equipment costs. However, this investment can reduce the CO2 emissions of the entire plant.
  • a chimney temperature and/or a temperature of the heated media is measured and that an adjustment of the recovery rate takes place if the temperature exceeds or falls below a predetermined temperature. Measured variables are then used to determine whether there is a lack of or excess hydrogen in the hydrogen-rich exhaust stream. This can then lead to an adjustment of the regeneration cycle.
  • the regeneration cycle is set at the beginning of the operating period and remains constant during (somewhat) steady-state operation.
  • a reformer comprising a steam reformer with or without a secondary reformer and/or an autothermal reformer is used in the reforming step, and the hydrogen-rich exhaust gas stream is used at least partially as fuel gas to provide the heat for the reforming step.
  • the reformer or the reactants of the reformer can be heated by combustion of the hydrogen-rich exhaust gas stream. In this way, the CO2 emission, which is typically caused during reforming by external heat supply via natural gas firing, can be significantly reduced.
  • hydrogen from an external source is admixed to the hydrogen-rich exhaust gas stream from the pressure swing adsorption.
  • An external source can mean hydrogen that is not already in the process directly as a result of the aforementioned process, for example, hydrogen produced by electrolysis.
  • the additional hydrogen can also be used from a hydrogen-rich stream that is already in the process as a result of reforming. In this way, the dimensioning of the pressure swing adsorption can be adapted to the existing conditions, so that the fuel gas consists entirely of exhaust gases from the pressure swing adsorption and admixed hydrogen-rich streams.
  • the mixed stream can be set at a ratio of 1 to 0.2 of the exhaust gas stream from the pressure swing adsorption and the hydrogen from the external source. If the combustion power of the exhaust gas stream from the pressure swing adsorption is insufficient to realize firing in a subsequent stage of the process, just enough external hydrogen is added to enable complete combustion of the hydrogen in the hydrogen-rich exhaust gas stream.
  • a plant for producing a synthesis gas for producing ammonia comprising at least: a reformer; a carbon monoxide (CO) converter; a carbon dioxide (CO2) scrubber unit with Regeneration; a pressure swing adsorption for providing hydrogen and a hydrogen-rich exhaust gas stream, wherein the pressure swing adsorption is carried out in a
  • Adsorption cycle to provide the hydrogen stream, and a
  • Regeneration cycle for providing the hydrogen-rich exhaust gas stream, is operable. At least one line is provided through which the hydrogen-rich exhaust gas stream from the pressure swing adsorption can be conducted into a section of the plant as fuel gas for a burner or furnace. Furthermore, it is provided that a recovery rate can be adjusted during operation of the pressure swing adsorption, wherein the recovery rate is formed from the ratio between the amount of hydrogen in the hydrogen stream from the pressure swing adsorption and the amount of hydrogen in the synthesis gas that is introduced into the pressure swing adsorption, wherein the recovery rate can be influenced by the duration of the regeneration cycle and wherein the recovery rate can be adjusted such that the energy content of the hydrogen-rich exhaust gas stream can be adjusted, preferably increased.
  • a description of the functioning of a reformer can be found in Ullmann's, Chapter 6.1.1, pages 174 to 179.
  • the system according to the invention comprises a carbon monoxide (CO) converter.
  • CO carbon monoxide
  • a description of the functioning and structure of possible carbon monoxide (CO) converters (“Carbon Monoxide Shift Conversion") can be found in Ullmann's, Chapter 6.1.2, pages 179 to 182.
  • the carbon monoxide (CO) converter is followed by a carbon dioxide (CO2) scrubber unit with regeneration.
  • CO2 carbon dioxide
  • the term "unit” in the sense of the invention encompasses devices and apparatus known to the person skilled in the art for the stated purpose, in this case typically/for example an absorber, a desorber, one or more circulation pumps, and heat exchangers for heating/cooling the solvent.
  • a carbon dioxide (CO2) scrubber unit with regeneration can, for example, be designed as a known device/arrangement in which carbon dioxide is dissolved in a suitable solvent—for example, potassium carbonate or amines—under pressure in an absorber and then expanded ("flashed") separately from the remaining synthesis gas (the synthesis gas depleted of carbon dioxide or freed of carbon dioxide in the carbon dioxide (CO2) scrubber unit with regeneration).
  • a suitable solvent for example, potassium carbonate or amines
  • a recovery rate is set in the range between 75% and 85%, preferably between 78% and 82%, particularly preferably between 79.5% and 80.5%. With a recovery rate in this range, the energy content of the hydrogen-rich exhaust gas stream is sufficient to fire the front-end of an ammonia plant without the need for additional natural gas blending.
  • the reformer comprises a steam reformer with or without a secondary reformer and/or an autothermal reformer. Particularly with a high daily ammonia production, the reformer can also consist of only one or more autothermal reformers.
  • the reformer is dimensioned larger than is necessary for producing a given production quantity of ammonia at a recovery rate in the range of 85% to 95%, preferably approximately 10% larger. If the front end, i.e. the reformer, is enlarged, the same amount of product can be obtained that a plant with an optimal recovery rate for the process can achieve without considering CCh emissions. Otherwise, the product quantity of hydrogen is reduced. To compensate for this loss, the front end (the part of the plant that supplies the hydrogen) must be enlarged. This leads to additional equipment costs. However, this investment can reduce the CCh emissions of the entire plant.
  • a temperature measuring device for measuring a stack temperature and/or a temperature of the heated media. From the measured values, conclusions can then be drawn about missing or oversized H2 in the hydrogen-rich exhaust gas stream. This can then lead to an adjustment of the regeneration cycle. Ideally, the regeneration cycle is set at the beginning of the operating period and remains constant during (somewhat) steady-state operation.
  • an external hydrogen source is included and that a line is provided.
  • External hydrogen from the external hydrogen source can be hydrogen that is not already in the process directly as a result of the aforementioned process, for example, hydrogen produced by electrolysis.
  • the additional hydrogen can, however, also consist of a hydrogen-rich stream that is already in the process as a result of reforming. In this way, the dimensioning of the pressure swing adsorption can be adapted to the existing conditions, so that the Exhaust gas stream can be fully used as fuel gas without the pressure swing adsorption having to be adjusted in its dimensions.
  • a mixing device can be provided by which a molar ratio of 1 to 0.2 of the exhaust gas flow of the pressure swing adsorption and the hydrogen from the external source can be set.
  • a further embodiment provides that the system can be used to carry out a method according to the invention.
  • the above statements regarding the method according to the invention also apply accordingly to the system according to the invention.
  • Fig. 1 is a schematic representation of a process or a plant for producing synthesis gas for ammonia synthesis
  • Fig. 2 shows a further schematic representation of a process or a plant for producing synthesis gas with an additional external hydrogen source
  • Fig. 3 shows a comparison of CO2 emissions between a conventional ammonia plant and a plant according to the invention.
  • FIG. 1 shows a schematic flow diagram of a plant 1 for producing hydrogen-containing synthesis gas.
  • Hydrogen is provided by a reformer 2, preferably a primary and a secondary reformer and/or an autothermal reformer.
  • the heat required for reformer 2 is supplied by reformer burners.
  • the plant includes a carbon monoxide (CO) converter 3.
  • CO carbon monoxide
  • the carbon monoxide (CO) formed which is not required for the actual ammonia synthesis, is converted into carbon dioxide, further producing hydrogen. This is followed by a carbon dioxide (CO2) scrubber unit 4 with regeneration.
  • CO2 carbon dioxide
  • the carbon dioxide (CO2) scrubber unit 4 can, for example, be designed as a known device or arrangement in which carbon dioxide is dissolved in a suitable solvent—for example, potassium carbonate or amines—under pressure in an absorber and then decompressed (“flashed”) separately from the synthesis gas. The solvent can then be reheated and regenerated in a stripping column (desorber). The synthesis gas is subsequently converted to ammonia in an ammonia synthesis unit 6.
  • a suitable solvent for example, potassium carbonate or amines
  • a pressure swing adsorption system 7 which provides a hydrogen stream and a hydrogen-rich exhaust stream.
  • Conduit 8 is advantageously provided, through which the hydrogen-rich exhaust stream from pressure swing adsorption 7 can be conducted as fuel gas into a section of plant 1. It is intended that the hydrogen-rich exhaust stream be used as fuel gas for reformer 2. Reformer 2 can be heated by combustion of the hydrogen-rich exhaust stream. In this way, the CCh release, which is typically caused during reforming, can be significantly reduced. Furthermore, it is not necessary to use natural gas as an additional heating medium.
  • FIG 2 shows a system according to Figure 1, wherein an external hydrogen source 9 is additionally provided in this exemplary embodiment.
  • the hydrogen from the external hydrogen source 9 is admixed with the hydrogen-rich exhaust gas stream of the pressure swing adsorption 7.
  • the external hydrogen source 9 is hydrogen produced by electrolysis. In this way, the dimensioning of the pressure swing adsorption 7 can be adapted to the existing conditions, so that the exhaust gas stream can be fully utilized as fuel gas without the pressure swing adsorption having to be dimensioned larger.
  • an additional line 10 is provided, through which a mixing device 11 can be used to set a mixed flow with a ratio of 1 to 0.2 of the exhaust gas stream from pressure swing adsorption 7 and the hydrogen from the external source. If the combustion power of the exhaust gas stream from pressure swing adsorption 7 is insufficient to realize firing in a subsequent section of the process, just enough external hydrogen is added to enable complete combustion of the hydrogen in the hydrogen-rich exhaust gas stream.
  • the upper section of Figure 3 shows a plant for the production of ammonia. It includes a front end 12 for the production of synthesis gas. The synthesis gas is then fed into a pressure swing adsorption unit 7 and then into an ammonia synthesis unit 6. A balance chamber 13 is arranged around the schematic diagram. Heat is required to operate the plant, for example, to produce steam as a heating medium and to generate sufficient reaction heat. This heat is obtained, among other things, through the use of fuels, the combustion of which, however, often also leads to CCH emissions.
  • FIG. 3 shows a conventional plant for producing ammonia. Natural gas 14 is fed to the front-end 12 and converted to produce a synthesis gas. The synthesis gas is passed into the pressure swing adsorption unit 7, producing a hydrogen stream 15 that is used for the synthesis of ammonia in the ammonia synthesis unit 6. In addition, a hydrogen-rich exhaust gas stream 16 is obtained, which is suitable for use as fuel gas in the front-end 12. Since the energy content of the hydrogen-rich exhaust gas stream 16 is not sufficient to operate the front-end or to supply it with sufficient heat, additional natural gas is burned. The combustion of natural gas produces CO2, which is released into the environment via the balance space. Figure 3 only shows the portion of the CO2 that is actually released into the environment via the balance boundary. Overall, more CO2 is produced than is emitted. The CO2 separated or washed out in the CCH scrubbing process can be compressed. It is then not part of the emissions.
  • FIG. 3 shows a plant with an inventive concept for providing synthesis gas.
  • Pressure swing adsorption 7 is deliberately operated at a lower recovery rate than in a conventional plant for producing ammonia. This increases the energy content of the hydrogen-rich exhaust gas stream 16, as more hydrogen is contained in the hydrogen-rich exhaust gas stream 16.
  • the energy content is sufficient to operate the front end 12 or to supply the front end 12 with heat. It is not necessary to additionally burn natural gas. This way, since primarily hydrogen is burned, CO2 emissions are significantly reduced.
  • the front end in this embodiment is approximately 10% larger. This allows the same amount of product, i.e., ammonia, to be obtained as in the conventional system, while simultaneously significantly reducing CCH emissions.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Separation Of Gases By Adsorption (AREA)

Abstract

L'invention concerne un procédé de fourniture d'un gaz de synthèse pour la production d'ammoniac, le gaz naturel désulfuré étant converti avec de la vapeur et de l'air enrichi en oxygène ou avec de l'oxygène au cours d'une étape de reformage pour former un gaz de synthèse comprenant de l'hydrogène, du CO et du CO2, le CO2 étant séparé du gaz de synthèse au cours d'une étape de séparation, un flux d'hydrogène et un flux de gaz résiduaire riche en hydrogène étant formés dans une adsorption modulée en pression (7), l'adsorption modulée en pression étant actionnée dans un cycle d'adsorption pour fournir le flux d'hydrogène et dans un cycle de régénération pour fournir le flux de gaz résiduaire riche en hydrogène, l'azote étant ajouté au gaz de synthèse au cours d'une étape d'enrichissement. Dans un procédé de production d'un gaz de synthèse pour la production d'ammoniac dans lequel la production de CO2 peut être réduite, la durée du cycle de régénération de l'adsorption modulée en pression (7) est ajustée de telle sorte que la teneur en hydrogène du flux de gaz résiduaire est ajustée, de préférence augmentée, et que le flux de gaz résiduaire est au moins partiellement fourni comme gaz combustible pour une étape du procédé.
PCT/EP2025/055377 2024-03-08 2025-02-27 Procédé et installation de production d'un gaz de synthèse pour la production d'ammoniac Pending WO2025186101A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
LU103255A LU103255B1 (de) 2024-03-08 2024-03-08 Verfahren und Anlage zur Herstellung eines Synthesegases zur Herstellung von Ammoniak
DE102024106662.8 2024-03-08
LULU103255 2024-03-08
DE102024106662.8A DE102024106662A1 (de) 2024-03-08 2024-03-08 Verfahren und Anlage zur Herstellung eines Synthesegases zur Herstellung von Ammoniak

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WO2025186101A1 true WO2025186101A1 (fr) 2025-09-12
WO2025186101A8 WO2025186101A8 (fr) 2025-10-02

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0207620B1 (fr) * 1985-06-04 1990-07-11 Imperial Chemical Industries Plc Récupération de chaleur
EP2085355A1 (fr) * 2006-10-20 2009-08-05 Sumitomo Seika Chemicals CO. LTD. Procédé et appareil de séparation de gaz d'hydrogène
US20230212007A1 (en) * 2021-12-31 2023-07-06 L'air Liquide, Societe Anonyme Pour L'etude Et L?Exploitation Des Procedes Georges Claude Steam methane reforming with process carbon dioxide capture and ammonia firing
WO2023164500A2 (fr) * 2022-02-23 2023-08-31 Jonathan Jay Feinstein Reformage avec capture de carbone

Patent Citations (4)

* Cited by examiner, † Cited by third party
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