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WO2025012271A1 - Démarrage d'une installation de décomposition catalytique d'ammoniac - Google Patents

Démarrage d'une installation de décomposition catalytique d'ammoniac Download PDF

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Publication number
WO2025012271A1
WO2025012271A1 PCT/EP2024/069358 EP2024069358W WO2025012271A1 WO 2025012271 A1 WO2025012271 A1 WO 2025012271A1 EP 2024069358 W EP2024069358 W EP 2024069358W WO 2025012271 A1 WO2025012271 A1 WO 2025012271A1
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WIPO (PCT)
Prior art keywords
heat
heat exchanger
combustion
mode
transfer medium
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/EP2024/069358
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German (de)
English (en)
Inventor
Yevgeny Makhynya
Alexander Kleyensteiber
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 LU103170A external-priority patent/LU103170B1/de
Priority claimed from DE102023118576.4A external-priority patent/DE102023118576A1/de
Application filed by ThyssenKrupp AG, ThyssenKrupp Uhde GmbH filed Critical ThyssenKrupp AG
Publication of WO2025012271A1 publication Critical patent/WO2025012271A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/047—Decomposition of ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/2425—Tubular reactors in parallel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the 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
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition 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
    • C01B2203/08—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
    • C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing 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
    • C01B2203/08—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
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • 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
    • C01B2203/1604—Starting up the process

Definitions

  • the invention relates to a plant for producing H2 by catalytic decomposition of NH3 to H2 and N2.
  • the plant according to the invention can be operated in a start-up mode in order to heat devices of the plant to an increased operating temperature using a heat transfer medium, e.g. after an interruption of continuous operation of the plant due to maintenance work. After heating to operating temperature, the plant according to the invention can be operated in a production mode for the continuous production of H2.
  • the invention further relates to a method for starting up a plant for producing H2 by catalytic decomposition of NH3.
  • H2 can be obtained from H2O using renewable energy and then converted into NH3 with N2.
  • NH3 can be stored and transported much more safely than H2.
  • NH3 can then be broken down into H2 and N2. After N2 has been separated, H2 has a wide range of industrial applications.
  • the catalytic decomposition of NH3 to N2 and H2 takes place at high temperature and medium pressure in the gas phase.
  • NH3 Stored NH3 is in liquid form in cooled tanks at atmospheric pressure and -32.8°C. NH3 is fed into the system at system pressure using a pump. The increased system pressure increases the boiling point of the NH3, e.g. at 27.8 bar a to about 62.2°C. In order to convert NH3 into the gas phase, heat must be added to evaporate the NH3. The evaporated NH3 is then heated further until it has reached a sufficiently high temperature at which it can be decomposed on an NH3 decomposition catalyst.
  • this heat is usually provided by the combustion of an energy source (cf. e.g. US 4 704 267 A; FR 1 469 045 A; CN 111 957 270 A; CN 113 896 168 A; WO 2001/087770 Al; WO 2011/107279 Al; WO 2017/160154 Al; WO 2019/038251 Al; WO 2012/039183 Al; WO 2012/090739 Al; WO 2020/095467 A; WO 2021/257944 Al; WO 2022/096529 Al; WO 2022/243410 Al; WO 2022/265647 Al; WO 2022/265648 Al; WHERE 2022/265649 Al; WO 2022/265650 Al; WO 2022/265651 Al).
  • all energy sources can be considered, e.g. natural gas or mixtures of NFF and IE.
  • Plants for producing H2 from NH3 are usually operated continuously for long periods of time without interruption, for example over several weeks or months. Nevertheless, it is occasionally necessary to shut down such plants into a standby mode, for example to carry out safety checks, replace catalyst material or carry out other maintenance work. In the standby mode, the plants cool down to ambient temperature, depending on the duration of the interruption in operation.
  • Warming up can basically be achieved by passing a heat transfer medium through the process side of the system, e.g. N2, water vapor, natural gas or mixtures thereof, and starting to burn the energy carrier to provide the heat for the heating process.
  • a heat transfer medium can either be circulated in the circuit or burned off via a flare.
  • WO 2011/150370 A2 relates to the decomposition of NH3 into an H2 gas mixture, wherein an NH3-rich gas mixture of NH3 and air enters a line in which the combustion and decomposition of a portion of the mixture is initiated, thereby releasing heat and H2.
  • H2 mixes with the majority of the gas mixture and the released heat drives the combustion reaction.
  • the catalyst can be heated electrically, inductively, by briefly burning chemicals on the catalyst and/or the surrounding structure, or by an electric arc. Heating the catalyst can be used to initiate the combustion and decomposition reactions of the NH3 and, if necessary, supply residual heat to the burning gases until the NH3 flame splitter is fully warmed up.
  • the power supply can be turned off or turned down so that the energy required to decompose the NH3 is essentially provided by the combustion of a portion of the NH3 and the combustion of NH3 is essentially sufficient to keep the catalyst hot.
  • WO 2013/119281 A1 relates to the decomposition of NH3 into a gas mixture containing H2, whereby a gas mixture rich in NH3 and air is fed into a heat exchanger. Part of the NH3 is burned, the rest is decomposed, whereby the gas mixture containing H2 is formed.
  • NH3 flame splitters can be brought to operating temperature by burning a starting mixture and then flowing the burned starting mixture through the NH3 flame splitters, so that the burned starting mixture thermally contacts the heat exchangers and/or burners of the NH3 flame splitters during a starting phase.
  • the surface temperatures during the warm-up phase increase, one or more of the following measures can be taken: increasing the total flow of the starting mixture, reducing the oxygen content of the oxidizer component, or increasing the total content of the starting mixture. This allows the NH3 flame splitters to be started quickly even with a comparatively low flow of purified oxygen. The flow of purified oxygen is switched off at or towards the end of the starting phase.
  • the plant should be able to be started up without additional, costly measures and equipment, should not be based on any fossil fuels, should not entail any additional safety risks and should be possible economically and on a large industrial scale.
  • a first aspect of the invention relates to a plant for producing H2 from NH3; wherein the plant can be operated in a production mode (normal operation) at operating temperatures; wherein the plant can be operated in a start-up mode (start-up operation) in order to heat at least one device of the plant from an initial temperature to an operating temperature; wherein the plant for the start-up mode comprises at least the following devices for heating the at least one device to the operating temperature:
  • a heating element for heating NH3 in the flow direction of the NH3 downstream of the heating element, a first NFF combustion device (pre-reactor) for partially catalytically decomposing the heated NH3 to produce a combustion gas comprising H2, N2 and residual NH3; optionally, in the flow direction of the combustion gas downstream of the first NPh reduction device (pre-reactor), a device for metering combustion air into the combustion gas;
  • a combustion device for burning the combustion gas to produce combustion heat and flue gas
  • first heat exchanger preferably flue gas/heat transfer medium heat exchanger for start-up mode
  • a second heat exchanger [preferably flue gas/heat transfer medium heat exchanger for the start-up mode] for heating the heat transfer medium by absorbing heat from the flue gas; and wherein the at least one device of the system is arranged in the flow direction of the heat transfer medium downstream of the first heat exchanger and/or the second heat exchanger and is in fluid communication with the heat transfer medium for absorbing heat from the heat transfer medium.
  • a second aspect of the invention relates to the use of a plant according to the invention for the production of H2.
  • a third aspect of the invention relates to a method for starting up a plant for producing H2 from NH3 comprising the following steps:
  • Steps (a), (b) and (e) of the method according to the invention are optional, independently of one another.
  • steps (a) to (i), if implemented, are carried out in alphabetical order.
  • both the amount and the yield of H2 produced are preferably comparatively high; preferably both the first NtE conversion device (pre-reactor) and the downstream second NtE conversion device (main reactor) are used for the most complete catalytic decomposition of NH3.
  • the intermediate product gas produced in the first Nkh conversion device is not burned as combustion gas, but is preferably fed after heating to the downstream second Nkh conversion device, where the most complete decomposition of the NH3 takes place.
  • H2 is then separated from the product gas produced in the second Nkh conversion device, preferably by pressure swing adsorption, and the remaining gas mixture resulting is burned as combustion gas to generate the required heat. Since in practice the decomposition of NH3 in the second NPh decomposition device is not absolutely complete (100.0%), a residual amount of NH3 remains, which is burned as combustion gas after addition of additional, fresh NH3.
  • the heat exchangers according to the invention serve to transfer heat from one medium to another medium without the media being mixed together.
  • the medium A that releases the heat is mentioned first, followed by the medium B that absorbs the heat.
  • a "flue gas, NH 3 heat exchanger” serves to release heat contained in the flue gas to NH3.
  • the flue gas/NPh heat exchanger is connected accordingly, i.e. its warmer side is flowed through by flue gas, whereas its cooler side is flowed through by NH3.
  • first heat exchanger preferably flue gas/NHi heat exchanger for the production mode; flue gas/heat transfer medium heat exchanger for the start-up mode ['.
  • the first heat exchanger preferably takes on two different functions: In the production mode, the first heat exchanger preferably transfers heat from the flue gas to NH3, in the start-up mode, the first heat exchanger preferably transfers heat from the flue gas to the heat transfer medium. If the heat transfer medium in the start-up mode is NH3, it is ultimately a flue gas/NHs heat exchanger in the start-up mode as well. If such a heat exchanger is described in the context of a specific mode (either production mode or start-up mode), the square brackets after it may only refer to the associated preferred form of heat exchange.
  • water is used for all its states of aggregation, unless expressly stated otherwise, whereby, depending on temperature and pressure, this water can be liquid or gaseous or in the form of a two-phase system, i.e. possibly also as water vapor. This also applies analogously to "NHf.
  • the plant according to the invention comprises a first NFF decomposition device and a second NH3 decomposition device, both of which contain NFh decomposition catalysts.
  • the first NFF decomposition device is preferably a fixed bed reactor.
  • the decomposition of NH3 preferably takes place adiabatically.
  • the downstream second NH3 decomposition device is preferably designed together with a combustion device analogous to a primary reformer, as is used in conventional steam reforming to produce H2, O2 and CO/CO2 from H2O and CH4.
  • the catalytic decomposition of the NH3 takes place in two stages in the first NH3 decomposition device and the downstream second NFF decomposition device.
  • the second heat exchanger preferably flue gas/intermediate product gas heat exchanger for the production mode
  • the second heat exchanger preferably serves to heat the intermediate product gas after leaving the first NHs decomposition facility and before entering the downstream second NHs decomposition facility (main reactor, together with combustion facility analogous to primary reformer).
  • intermediate product gas preferentially absorbs heat from flue gas in the second heat exchanger (see Figure 2, second heat exchanger 67).
  • preheated NH enters the first NHs decomposition device, in which a partial catalytic decomposition of NH; to N2 and H2 takes place to a certain extent.
  • An intermediate product gas is formed which still contains considerable residual amounts of non-decomposed NH3, but also N2 and H2 already formed.
  • the intermediate product gas preferably cools down.
  • the conversion of decomposed NH3 in the first NHs decomposition device is at most 25%, more preferably at most 20% of the total conversion achieved overall.
  • the conversion of decomposed NH3 in the first NHs decomposition device is at least 5%, more preferably at least 10%, even more preferably at least 15% of the total conversion achieved overall.
  • the intermediate product gas is preferably heated again in the second heat exchanger [preferably flue gas/intermediate product gas heat exchanger for the production mode] before it enters the downstream, second NH3 decomposition device.
  • the remaining decomposition of NH3 then takes place in the second NHs decomposition device until the total conversion is achieved.
  • the catalytic decomposition of the NH3 preferably only takes place in one stage, and only in the first NHs decomposition device.
  • the second NHs decomposition device preferably does not yet contribute to the decomposition of NH3, at least during early phases of the start-up mode.
  • preheated NH3 enters the first NHs decomposition device, in which a partial catalytic decomposition of NH3 to N2 and H2 takes place to a certain extent.
  • An intermediate product gas is also formed, which still contains considerable residual amounts of non-decomposed NH3, but also N2 and H2 that have already been formed.
  • the conversion of decomposed NH3 in the first NHs decomposition device is at most 25%, more preferably at most 20% based on the amount of NH3.
  • the conversion of decomposed NH3 in the first NHs decomposition device is at least 5%, more preferably at least 10%, even more preferably at least 15% based on the amount of NH3.
  • the intermediate product gas formed in the first NH s decomposition device is preferably not passed into the second NH s decomposition device, but instead into the combustion device.
  • the amount of H2 formed in the intermediate product gas is sufficient for satisfactory combustion of the NH 3, so that the combustion of the intermediate product gas generates sufficient combustion heat to gradually warm up the system to operating temperature.
  • the NH s stream is divided into a first NH 3 partial stream and a second NH s partial stream. Only the first NH s partial stream is fed to the first decomposition device.
  • the second NH s partial stream flows instead through the second NH 3 decomposition device, whereby the second NFF decomposition device absorbs heat from the second NH s partial stream.
  • the second NFF partial stream therefore initially only functions as a heat transfer medium.
  • the second NH s decomposition device is gradually heated until the start-up temperature (activation temperature) for the catalytic decomposition of NH 3 is reached, so that from this point on additional H 2 is produced in the second NH s decomposition device by catalytic decomposition of NH 3 (see Figure 3).
  • the first NH3 decomposition device can be used for two different purposes, namely in start-up mode for generating the combustion gas and in production mode for the first stage of a total of two-stage decomposition of NH3 for generating the product gas.
  • the system according to the invention preferably does not comprise any further separate NH3 decomposition device, which is used exclusively in start-up mode, but not in production mode.
  • Such separate NH3 decomposition devices are commercially available, possibly already equipped with an electric heater, but even such additional equipment expenditure can be dispensed with according to the invention.
  • the system according to the invention essentially comprises only two devices, which are used exclusively in the start-up mode, but not in the production mode, namely
  • the system according to the invention has a heating element for heating NH3 in the start-up mode.
  • the heating element is preferably electrically operated.
  • the heating of NH3 in step (c) of the method according to the invention preferably takes place using electrical energy.
  • the heating element is only provided for the start-up mode and is switched off in the production mode.
  • the heating element is connected via a line system in a bypass, so that the NH3 can be passed through the heating element via the bypass in the start-up mode in order to be heated there.
  • the NH3 no longer flows through the entire bypass, including the heating element.
  • suitable valves are preferably provided which enable the targeted flow of NH3 through the bypass or not through the bypass.
  • the NH3 is typically provided in liquid form as a starting material and must therefore first be evaporated. This applies not only to the production mode, but also to the start-up mode. According to the invention, the NH3 is preferably evaporated by absorbing heat from water vapor.
  • the water vapor is preferably provided by process heat, in which water as a heat transfer medium absorbs heat from the product gas and/or the flue gas and the thus heated water vapor releases heat to liquid NH3.
  • the system according to the invention preferably comprises an H2O evaporation device for evaporating water to produce water vapor.
  • the H2O evaporation device is preferably arranged upstream of the heating element in the flow direction of the NH3.
  • the H2O evaporation device is preferably heated electrically.
  • the method according to the invention therefore preferably comprises the two optional steps (a) and (b), with the production of water vapor in step (a) of the method according to the invention preferably taking place using electrical energy.
  • the preferably electrically heated H2O evaporation device is only provided for the start-up mode and is switched off in the production mode.
  • the H2O evaporation device is connected via a line system in a bypass, so that in the start-up mode the water can be passed through the bypass through the H2O evaporation device to be heated and evaporated there.
  • the entire bypass including the H2O evaporation device is no longer flowed through by water.
  • suitable valves are preferably provided which enable the targeted flow of the water through the bypass or not through the bypass.
  • the system according to the invention preferably comprises an NFF evaporation device for evaporating liquid NH3 by absorbing heat from the water vapor.
  • the liquid NH3 in the start-up mode, can first be evaporated by absorbing heat from the water vapor, which in turn is generated in the preferably electrically heated H2O evaporation device.
  • the evaporated NH3 is then passed through the preferably electrically heated heating element and heated therein to a temperature which is sufficient for the subsequent partial catalytic decomposition of the NH3 in the first NFF decomposition device.
  • the intermediate product gas thus generated is then burned in the combustion device, thereby generating a flue gas and combustion heat.
  • the heat generated by the combustion of the combustion gases is used not only in the production mode, but also in the start-up mode.
  • the combustion gases can typically have different origins and compositions.
  • the combustion heat essentially serves to heat a heat transfer medium, which is preferably compressed in a compressor and then passed through parts of the system.
  • the heat transfer medium preferably absorbs heat directly from the combustion heat and/or indirectly from the flue gas.
  • the combustion heat preferably in the flow direction of the flue gas downstream of the combustion device and in the flow direction of the heat transfer medium downstream of the compressor
  • the first heat exchanger preferably flue gas/heat transfer medium heat exchanger for start-up mode
  • the second heat exchanger [preferably flue gas/heat transfer medium heat exchanger for start-up mode] arranged to heat the heat transfer medium by absorbing heat from the flue gas.
  • the heat transfer medium comprises N2 or consists essentially of it.
  • N2 is preferably circulated through at least part of the system until the desired operating temperatures of the parts of the system are reached. Once this state has been reached, N2 is preferably discharged from the system and switched to production mode.
  • NH3 is preferably continuously mixed into the N2 and the mixture of N2 and NH3 is optionally burned via a flare. If the content of NH3 in the mixture with N2 is large enough, production mode can be started.
  • the heat transfer medium comprises NH3 or consists essentially thereof.
  • NH3 is preferably circulated through at least part of the system until the desired operating temperatures of the parts of the system are reached. Once this state is reached, the production mode is started.
  • the NHs stream in the start-up mode, is divided into a first NH3 partial stream and a second NHs partial stream. Only the first NHs partial stream is fed to the first decomposition device.
  • the second NHs partial stream flows instead through the second NH3 decomposition device, whereby the second NHs decomposition device extracts heat from the second NHs partial flow.
  • the second NHs partial flow therefore initially only functions as a heat transfer medium.
  • the second NHs decomposition device is gradually heated until the start-up temperature (activation temperature) for the catalytic decomposition of NH3 is reached, so that from this point on additional H2 is produced in the second NHs decomposition device by catalytic decomposition of NH3.
  • the amount of H2 in the combustion gas is increased in the start-up mode compared to the production mode.
  • the larger ratio of H2 to NH3 promotes combustion, whereby the operating temperature can be reached more quickly.
  • At least one device of the system is arranged in the flow direction of the heat transfer medium downstream of the first heat exchanger and/or the second heat exchanger and is in fluid communication with the heat transfer medium for absorbing heat from the heat transfer medium.
  • This at least one device of the system is heated in the start-up mode by absorbing heat from the heat transfer medium.
  • the at least one device which is heated in the start-up mode by absorbing heat from the heat transfer medium is the second NFF reduction device (see Figure 2, second NH3 decomposition device 24).
  • the second NH3 reduction device is preferably connected downstream of the first NH3 decomposition device and preferably serves for the catalytic decomposition of vaporized NH3 to produce a product gas comprising H2 and N2.
  • the system according to the invention preferably comprises corresponding lines and valves which enable a changed connection (see Figure 2).
  • the at least one device which is heated in the start-up mode by absorbing heat from the heat transfer medium is a third heat exchanger [preferably a heat transfer medium/water heat exchanger for the start-up mode] (see Figure 2, third heat exchanger 26).
  • the third heat exchanger preferably a product gas/water heat exchanger for the production mode
  • the system according to the invention preferably comprises corresponding lines and valves which enable a changed connection (see Figure 2).
  • the at least one device which is heated in the start-up mode by absorbing heat from the heat transfer medium is a fourth heat exchanger [preferably heat transfer medium/heat transfer medium heat exchanger for the start-up mode] (see Figure 2, fourth heat exchanger 20).
  • the fourth heat exchanger preferably product gas/NH3 heat exchanger for the production mode] serves to heat NH3 by absorbing of heat from the product gas.
  • the system according to the invention preferably comprises corresponding lines and valves which enable a changed connection (see Figure 2).
  • the at least one device which is heated in the start-up mode by absorbing heat from the heat transfer medium is a fifth heat exchanger [preferably a heat transfer medium/water heat exchanger for the start-up mode] (see Figure 2, fifth heat exchanger 28).
  • the fifth heat exchanger preferably a product gas/water heat exchanger for the production mode
  • the system according to the invention preferably comprises corresponding lines and valves which enable a changed connection (see Figure 2).
  • the at least one device which is heated in the start-up mode by absorbing heat from the heat transfer medium is a sixth heat exchanger [preferably a heat transfer medium/water heat exchanger for the start-up mode] (see Figure 2, sixth heat exchanger 29).
  • the sixth heat exchanger [preferably a product gas/water heat exchanger for the production mode] is preferably used to heat water by absorbing heat from the product gas.
  • the system according to the invention preferably comprises corresponding lines and valves which enable a changed connection (see Figure 2).
  • the flue gas which is generated during the combustion of the combustion gas can also release heat to at least one device in the system.
  • This at least one device is typically arranged in the flue gas duct.
  • This at least one device is preferably arranged in the flow direction of the flue gas downstream of the first heat exchanger and/or the second heat exchanger.
  • the at least one device which is heated in the start-up mode by absorbing heat from the flue gas is a first flue gas/combustion air heat exchanger (cf. Figure 2, first flue gas/combustion air heat exchanger 45), which preferably serves in the start-up mode and/or in the production mode to heat combustion air by absorbing heat from the flue gas.
  • the at least one device which is heated in the start-up mode by absorbing heat from the flue gas is a flue gas denitrification unit (cf. Figure 2, flue gas denitrification unit 50), which preferably serves in the start-up mode and/or in the production mode to clean the flue gas of nitrogen oxides (NOx).
  • the at least one device which is heated in the start-up mode by absorbing heat from the flue gas is a flue gas/water heat exchanger (cf. Figure 2, flue gas/water heat exchanger 52), which preferably serves in the start-up mode and/or in the production mode for heating water, preferably for heating or generating water vapor, by absorbing heat from the flue gas.
  • the at least one device which is heated in the start-up mode by absorbing heat from the flue gas is a second flue gas/combustion air heat exchanger (cf. Figure 2, second flue gas/combustion air heat exchanger 43), which preferably serves in the start-up mode and/or in the production mode to heat combustion air by absorbing heat from the flue gas.
  • the combustion device and the second NH s decomposition device are in heat exchange with one another and are configured for a heat flow from the combustion device into the second NH s decomposition device.
  • they are preferably designed analogously to a primary reformer, as is used in conventional steam reforming to produce H2, O2 and CO/CO2 from H2O and CEE.
  • the plant in production mode (ie during normal operation) is designed for a throughput based on H2 of at least 500 mol-h 1 , preferably at least 1000 mol-h 1 , more preferably at least 5000 mol-h 1 , even more preferably at least 10,000 mol-h 1 , most preferably at least 50,000 mol-h 1 , and in particular at least 100,000 mol-h 1 .
  • the plant comprises a tank for liquid NH3 which has a volume of at least 50 m 3 , preferably at least 100 m 3 , more preferably at least 500 m 3 , even more preferably at least 1000 m 3 , most preferably at least 5000 m 3 , and in particular at least 10,000 m 3 .
  • the plant comprises, in addition to the first NH s decomposition device, a second NH s decomposition device with at least three, preferably at least four, more preferably at least five, even more preferably at least six, most preferably at least seven and in particular at least eight catalyst beds, each of which comprises NH 3 decomposition catalyst; each catalyst bed preferably being present in a tube; the catalyst beds preferably being connected in parallel. Each catalyst bed preferably contains the same NH 3 decomposition catalyst.
  • the plant comprises, in addition to the first NH3 decomposition device, a second NH3 decomposition device with at least one catalyst bed which comprises NH3 decomposition catalyst, wherein the length of the catalyst bed in the flow direction for NH3 is at least 1.0 m, preferably at least 1.5 m, more preferably at least 2.0 m, even more preferably at least 2.5 m, most preferably at least 3.0 m and especially at least 3.5 m; wherein the catalyst bed is preferably present in a tube.
  • the plant comprises a combustion device with at least three, preferably at least four, more preferably at least five, even more preferably at least six, most preferably at least seven and in particular at least eight burners for combustion of the combustion gas.
  • the system comprises a first heat exchanger and/or a second heat exchanger, which are designed independently of one another as tube heat exchangers or tube bundle heat exchangers.
  • a throughput based on H2 of at least 500 mol-h 1 is achieved, preferably at least 1000 mol-h 1 , more preferably at least 5000 mol-h 1 , even more preferably at least 10,000 mol-h 1 , most preferably at least 50,000 mol-h 1 , and in particular at least 100,000 mol-h 1 .
  • the liquid NH3 in the production mode (ie during normal operation), is taken from a tank with a volume of at least 50 m 3 , preferably at least 100 m 3 , more preferably at least 500 m 3 , even more preferably at least 1000 m 3 , most preferably at least 5000 m 3 , and in particular at least 10,000 m 3 .
  • the catalytic decomposition of NH3 takes place on at least three, preferably at least four, more preferably at least five, even more preferably at least six, most preferably at least seven and in particular at least eight catalyst beds, each of which comprises NH3 reduction catalyst; each catalyst bed is preferably present in a tube; the catalyst beds are preferably flowed through in parallel by NH3.
  • the catalytic decomposition in the production mode (i.e. during normal operation), takes place on at least one catalyst bed which comprises NH3 decomposition catalyst, the length of the catalyst bed in the flow direction for NH3 being at least 1.0 m, preferably at least 1.5 m, more preferably at least 2.0 m, even more preferably at least 2.5 m, most preferably at least 3.0 m and in particular at least 3.5 m; the catalyst bed is preferably present in a tube
  • the combustion of the combustion gas is carried out with the aid of at least three, preferably at least four, more preferably at least five, even more preferably at least six, most preferably at least seven and in particular at least eight burners.
  • the catalytic decomposition of NH3 means the formation of N2 and H2, occasionally referred to in the prior art as "cleavage” or "cracking" of NH3.
  • the catalytic decomposition of NH3 is preferably carried out in the absence of O2 .
  • the invention comprises the following measures in the manufacturing mode:
  • H2O is not a product of the reaction and can be present in very small amounts, since H2O is often present in liquid NH3, in concentrations of maximum 0.5 wt.%, typically ⁇ 0.3 wt.%. Due to the evaporation of NH3, it is to be expected that H2O is present in lower concentrations.
  • the NH3 is preferably stored as starting material.
  • the stored NH3 is in liquid form in a cooled tank, at atmospheric pressure and at a temperature below its boiling point of -33.5 °C.
  • NH3 is fed into the system using a pump, preferably at system pressure.
  • the NH3 Before the NH3 can be catalytically decomposed, it is preferably heated successively to several temperature levels according to the invention.
  • NH3 is preferably heated and then evaporated to a medium temperature level ( ⁇ 300°C) by absorbing heat from water or water vapor.
  • the water vapor is preferably generated by absorbing heat from flue gas and/or product gas.
  • the water vapor is preferably generated by an electrically operated H2O evaporation device.
  • a preheater is arranged in the flow direction of the NH3 downstream of the tank and upstream of the NH3 evaporation device, which preheater preferably serves to heat the NH3 to the desired temperature at the inlet to the NH3 evaporation device and in which NH3 absorbs heat from water, which in turn has previously left the NIA evaporation device as water vapor condensate.
  • water vapor and water vapor condensate are passed in countercurrent through the preheater and the NH3 evaporation device.
  • the NH3 is preferably further heated to a high temperature level (>300°C).
  • the further heating of NH3 is preferably carried out by absorbing heat directly from flue gas and/or product gas, ie without water as a heat transfer medium.
  • a first heat exchanger preferably flue gas/NHs heat exchanger for the production mode
  • a second heat exchanger preferably flue gas/intermediate gas heat exchanger for the manufacturing mode.
  • the NH3 decomposition catalyst is nickel-based and the vaporized NH3 is heated to a temperature in the range of preferably 600 to 650°C.
  • the NPh decomposition catalyst is ruthenium-based and the vaporized NH3 is heated to a temperature in the range of preferably 350 to 400°C.
  • NH3 (part or all of it) is passed through the electrical heating element and heated therein above the activation temperature of the Nkh decomposition catalyst in the first NtE decomposition device.
  • the heated NH3 then flows into the first NIE decomposition device, where the NH3 is at least partially decomposed.
  • a conversion of e.g. 18% can be achieved, depending on the preheating temperature.
  • the catalytic decomposition of NH3 is the actual reaction for the formation of H2, which basically takes place thermally, but is accelerated by the use of an NPh decomposition catalyst.
  • the catalytic decomposition of NH3 can be carried out according to the invention under various conditions using various NIE decomposition catalysts and with various connections with different reactor types.
  • the catalytic decomposition of NH3 is preferably carried out by supplying heat in the presence of an NH3 decomposition catalyst.
  • Important parameters for the catalytic decomposition of NH3 are the type of NfE decomposition catalyst, the reaction temperature and the reaction pressure.
  • NH3 decomposition catalyst various materials can be used as NH3 decomposition catalyst.
  • the reaction temperature at which the catalytic decomposition of NH3 takes place is determined in particular by the choice of the NH3 decomposition catalyst.
  • a nickel-based NfE decomposition catalyst is used.
  • the reaction temperature and the reaction pressure determine the equilibrium conversion.
  • the decomposition of NH3 is almost quantitative.
  • the conversion of NH3 is about 98.5%, at 500°C only about 95%.
  • reaction temperatures are preferably set in the range from about 600°C to about 900°C, preferably about 600°C to about 700°C, so that a high conversion is achieved.
  • optimal reaction temperatures are in the range from about 630°C to 640°C.
  • Nickel-based NHs decomposition catalysts are advantageous despite the comparatively high reaction temperature.
  • non-decomposed NH3 Due to the high conversion, the remaining content of non-decomposed NH3 in the product gas is comparatively low, so that separate separation of non-decomposed NH3 for its recovery is preferably avoided. Instead, N2 and non-decomposed NH3 are separated together from the product gas by pressure swing adsorption during the purification of H2.
  • the NH3 decomposition catalyst comprises supported nickel.
  • Preferred carrier materials are selected from the group consisting of Al2O3, MgO, SiCE, mesoporous SiCE (e.g. MCF-17, MCM-41, SBA-15), zeolite (e.g.
  • a ruthenium-based NH3 decomposition catalyst is used.
  • reaction temperatures in the range from about 450°C to about 500°C are preferably set, although somewhat lower conversions of, for example, about 95% can be achieved, so that the remaining residual content of undecomposed NH3 in the product gas is greater.
  • other NH3 decomposition catalysts can also be used at even lower reaction temperatures. The lower the reaction temperature, the lower the conversion and the more non-decomposed NH3 must be separated from the product gas and recycled.
  • the first NH3 decomposition device comprises two catalyst beds connected in series, of which one catalyst bed contains an NH3 decomposition catalyst with a comparatively high activation temperature (preferably a first nickel-based NH3 decomposition catalyst) and the other catalyst bed contains an NFh decomposition catalyst with a comparatively low activation temperature (preferably a second nickel-based NFh decomposition catalyst).
  • NFh decomposition catalysts with different activation temperatures are known to a person skilled in the art (cf. e.g. I. Lucentini et al., Ind. Eng. Chem. Res. 2021, 60, 51, 18560-18611).
  • NFF reduction catalysts based on iron, ruthenium, nickel, cerium, cobalt, chromium, iridium, copper, platinum, molybdenum, palladium, zirconium, tungsten and/or vanadium are preferably used; more preferably based on nickel, iron and/or cerium.
  • the catalytic decomposition of the NH3 preferably takes place in particular on the NFE decomposition catalyst with the comparatively low activation temperature (preferably a second nickel-based NFF decomposition catalyst).
  • the catalytic decomposition of the NH3 preferably takes place first, in particular on the NFF decomposition catalyst with the comparatively high activation temperature (preferably a first nickel-based NHs decomposition catalyst), and optionally additionally or subsequently on the NH3 decomposition catalyst with the comparatively low activation temperature (preferably a second nickel-based NH3 decomposition catalyst).
  • the reaction pressure is preferably about 15 bar a to about 25 bar a.
  • the stoichiometry of the reaction (2 NH3 N2 + 3 H2) increases the volume, which is why an increased reaction pressure generally has a negative effect on the conversion.
  • a reaction pressure of only 1 bar conversions of more than 99% could be achieved at reaction temperatures from 400°C.
  • the system according to the invention is preferably operated at a higher reaction pressure, even if this means that a certain loss in conversion has to be accepted.
  • the reaction pressure is particularly predetermined by the way in which the purification of H2 is carried out.
  • the pressure swing absorption (PSA) preferred according to the invention for purifying H2 can preferably be operated effectively at a pressure in the range from about 15 bar to about 25 bar.
  • the pressure of the product gas when leaving the second NFF reduction device is preferably in the range from about 15 to about 25 bar a, more preferably about 18 bar a to about 22 bar a, even more preferably about 19 bar a to about 21 bar a. In this way, a good balance is found. between the requirements of pressure swing adsorption on the one hand and the achieved conversion on the other.
  • the decomposition of NH3 can basically take place in different reactor types.
  • adiabatic reaction the internal heat of the reaction gas is used as an energy source for the reaction.
  • Suitable reactors for this are autothermal reformers and secondary reformers, which work with internal energy generation. Combustion air is added to the process gas and part of the reaction gas is burned to increase the temperature so that the desired temperature prevails at the reactor outlet.
  • a disadvantage is the presence of water in the process gas that is produced during combustion and must be removed by condensation. Part of the non-decomposed NH3 then dissolves in the condensed water and is lost or must be recycled. In addition, the high temperatures lead to the formation of significant amounts of nitrogen oxides.
  • the decomposition of NH3 according to the invention preferably takes place in two stages in two NPh reduction devices through which the gas flows one after the other.
  • the first NPh reduction device only a portion of the NH3 is initially partially decomposed.
  • the remaining decomposition of NH3 up to the maximum conversion achieved then takes place in the second NH3 decomposition device.
  • the second NPh reduction device together with the combustion device according to the invention preferably forms a reactor, as described in more detail above, designed analogously to a primary reformer.
  • the decomposition of NH3 according to the invention preferably takes place in one stage, namely only in the first NPh reduction device, which can optionally comprise several catalyst beds connected in series.
  • the preheated NH3 enters the first NH3 reduction device, which contains NH3 reduction catalyst and in which a partial catalytic decomposition of NH3 to N2 and H2 takes place to a certain extent.
  • An intermediate product gas is formed which still contains considerable residual amounts of non-decomposed NH3, but also N2 and H2 which have already been formed.
  • the intermediate product gas preferably cools down.
  • the conversion of decomposed NH3 in the first NH3 reduction device is at most 25%, more preferably at most 20% of the total conversion achieved.
  • the conversion of decomposed NH3 in the first NPh reduction device is at least 5%, more preferably at least 10%, even more preferably at least 15% of the total conversion achieved.
  • the intermediate gas After leaving the first NPh reduction device, the intermediate gas is used differently depending on the operating mode. [0115] In the start-up mode, the intermediate gas is optionally mixed with NH3 and then burned in the combustion device with the supply of combustion air.
  • the NFF stream is divided into a first NH3 partial stream and a second NH3 partial stream. Only the first NH3 partial stream is fed to the first decomposition device.
  • the second NH3 partial stream flows through the second NH3 decomposition device instead, whereby the second NH3 decomposition device absorbs heat from the second NH3 partial stream.
  • the second NH3 partial stream therefore initially only functions as a heat transfer medium. In this way, the second NH3 decomposition device is gradually heated until the start-up temperature for the catalytic decomposition of NH3 is reached, so that from this point on additional H2 is produced in the second NH3 decomposition device by catalytic decomposition of NH3.
  • the first NFF part stream is fed to the first NFh decomposition device and the entire intermediate product gas produced (e.g. at 20% conversion: 20 mol% H2 + N2 and 80 mol% undecomposed NH3) is completely burned in the combustion device.
  • the second NFF part stream is neither fed to the first NH3 decomposition device nor burned, but is preferably used as a heat transfer medium, preferably circulated for this purpose, and is preferably used, among other things, to heat the second NFF decomposition device.
  • the intermediate product gas is preferably heated again before it enters the downstream, second NH3 decomposition device.
  • the remaining decomposition of NH3 then takes place in the second NFh decomposition device until the total conversion is achieved.
  • the product gas is formed in the second NFF decomposition device according to the invention by decomposition of NH3 and leaves the second NIE decomposition device via its own outlet.
  • the combustion gas is burned together with combustion air in the combustion device and the flue gas formed thereby also leaves the combustion device via its own outlet, preferably into a flue gas channel.
  • Product gas and flue gas are not mixed with one another, but remain physically separated from one another.
  • Combustion heat formed during the combustion of the combustion gas flows as a heat flow into the second NH3 decomposition device and thus supplies the heat required to maintain the endothermic decomposition of NH3.
  • a mixture of NH3 and H2 is preferably burned as combustion gas together with combustion air (combustion device).
  • combustion air combustion device
  • the N2 formed alongside H2 during the catalytic decomposition of NH3 is inert and serves as an additional heat carrier.
  • the combustion heat generated by the combustion process in the combustion chamber of the combustion device is used to heat the second NIA decomposition device, preferably the pipe or pipes through which the NH3 to be decomposed is passed. For this purpose, a heat flow is passed from the combustion device into the second NFh decomposition device.
  • the NH3 decomposition catalyst in the first NIA decomposition device is preferably the same as in the second NH3 decomposition device. If the first NIA decomposition device comprises several catalyst beds connected in series, preferably at least one of these catalyst beds connected in series contains the same NFF decomposition catalyst as the second NH3 decomposition device.
  • the combustion device preferably has one or more burners, preferably at least two burners, more preferably at least three burners.
  • the combustion gas preferably contains NH3. This applies in particular to the start-up mode.
  • the combustion device according to the invention is therefore preferably an NHs combustion device.
  • the combustion gas preferably contains a mixture of H2 and NH3, since this mixture produces a medium flame temperature and has better combustion properties than pure NH3.
  • a suitable mixing ratio of H2 and NH3 also results in less nitrogen oxide being formed than in the absence of H2.
  • the residual gas mixture which remains after the separation of H2 from the product gas, preferably by pressure swing adsorption, is preferably used as the combustion gas.
  • Fresh NH3 is preferably added to this residual gas mixture. Since pressure swing adsorption typically does not separate the complete amount of H2 from the product gas, the remaining residual amount of H2 in the residual gas mixture preferably serves as a combustion improver for the NH3.
  • the intermediate product gas formed in the first NFh combustion device in the start-up mode contains H2 and is optionally mixed with further NH3 and burned in the combustion device in the start-up mode to form flue gas. Due to the at least partial decomposition of NH3, a sufficient amount of H2 is available to ensure or improve the combustion of the NH3.
  • the preferably electrically operated H2O evaporation device and the electrical heating element require electrical energy to evaporate and further heat the NH; for the catalytic decomposition; the subsequent combustion of NH; together with the H2 formed by the catalytic decomposition then provides the heat to heat the heat transfer medium.
  • the amount of H2 in the combustion gas is increased in the start-up mode compared to the production mode.
  • the higher proportion of H2 in the combustion gas promotes the combustion of the mixture of NH3 and H2, whereby the operating temperature can be reached more quickly.
  • the process according to the invention is preferably operated in the production mode with an H2 proportion Ai and in the start-up mode with an H2 proportion A2, where A2 > Ai.
  • the relative difference between A2 and Ai is at least 1 vol.%, more preferably at least 2 vol.%, even more preferably at least 3 vol.%, most preferably at least 4 vol.%, and in particular at least 5 vol.%.
  • the state during the start-up mode does not have to be statically constant, but can change dynamically, particularly in view of the continuous heating of the system or parts thereof. It is therefore preferred according to the invention that for at least part of the total duration of the start-up mode, the proportion A2 is increased in comparison to the proportion Ai.
  • the combustion device (combustion chamber of the reactor) is supplied with combustion air, which is preferably preheated beforehand in a first flue gas/combustion air heat exchanger and/or a second flue gas/combustion air heat exchanger.
  • the first flue gas/combustion air heat exchanger and/or the second flue gas/combustion air heat exchanger are arranged in the flue gas channel, wherein the combustion air absorbs heat from the flue gas.
  • the combustion air is cleaned via a filter before being fed into the system, compressed to the required pressure using a compressor and then passed through the first flue gas/combustion air heat exchanger and/or the second flue gas/combustion air heat exchanger in the flue gas duct and heated. From there, the heated combustion air flows into the combustion device. Shortly before entering the combustion device or within the combustion device, the combustion air is mixed with the combustion gas (preferably NH3 mixed with H2).
  • the combustion gas preferably NH3 mixed with H2
  • product gas - after catalytic decomposition until purification of H2 [0131]
  • product gas leaves the second NHs decomposition device at a high temperature.
  • at least one heat exchanger is preferably provided in the flow direction of the product gas downstream of the second NHs decomposition device for the production mode, through which the product gas flows before the product gas is fed to a purification of H2:
  • a third heat exchanger [preferably product gas/water heat exchanger for the manufacturing mode]
  • the recovery of NH3 preferred according to the invention preferably serves to separate non-decomposed NH3 from the product gas and to make it available for further use as combustion gas or recovered starting material.
  • a separate recovery of NH3 is preferably dispensed with.
  • the purification of H2 from the product gas preferably takes place by pressure swing adsorption (PSA).
  • PSA pressure swing adsorption
  • Small residual amounts of non-decomposed NH3 can preferably be separated out during the pressure swing adsorption according to the invention, whereby the recovery of NH3 and the purification of H2 are combined into a common step.
  • H2 is particularly preferably purified by pressure swing adsorption (PSA) according to the invention.
  • PSA pressure swing adsorption
  • An adsorptive separation in a pressure swing adsorption device is preferred according to the invention, among other things because it takes place at moderate pressures and also achieves high purity of H2, if required > 99.9%, with a yield of H2 in the range of e.g. approx. 80 to 85%.
  • the pressure swing adsorption can also separate residual amounts of NH3 and possibly H2O in the same work step.
  • the product gas is preferably cooled to the desired temperature using a sixth heat exchanger [preferably product gas/water heat exchanger for the production mode] before entering the pressure swing adsorption device.
  • the corresponding amount of heat is preferably absorbed by the water in the sixth heat exchanger.
  • the cooling water heated in this way is preferably used to preheat NH3 in a preheating device in which NH3 absorbs heat from the water.
  • the cooled product gas is then preferably fed to a pressure swing adsorption device, where the gas mixture is separated under pressure by adsorption. H2 - after purification until storage
  • the separated H2 preferably leaves the pressure swing adsorption device and is preferably brought to an increased pressure, for example to approximately 200 bar, using an H2 compressor.
  • compression of the separated H2 to an increased pressure is not absolutely necessary and, according to the invention, pressures of significantly less than 200 bar are also included.
  • the compressed H2 then preferably flows through a first H2 heat exchanger in which cooling water absorbs heat from the compressed H2.
  • the separated H2 is then brought to a further increased pressure using a second H2 compressor.
  • the further compressed H2 then preferably flows through a second H2 heat exchanger in which cooling water also absorbs heat from the compressed H2.
  • the compressed H2 is then discharged from the system at a pressure of, for example, approximately 70 bar and, for example, stored in a suitable pressure vessel or fed directly for further use.
  • the residual gas mixture is fed to the combustion device so that it can be used to generate combustion heat.
  • the flue gas leaves the combustion device at a high temperature and preferably enters a flue gas channel.
  • heat exchangers are preferably provided in the flow direction of the flue gas downstream of the combustion device, through which the flue gas flows before the flue gas is released into the environment, e.g. via a chimney:
  • a second heat exchanger preferably flue gas/intermediate gas heat exchanger for the production mode; preferably flue gas/heat transfer medium heat exchanger for the start-up mode;
  • a first heat exchanger preferably flue gas/NHs heat exchanger for the production mode; flue gas/heat transfer medium heat exchanger for the start-up mode;
  • the flue gas formed during the combustion of the mixture comprising NH3 and H2 flows through the flue gas channel and thereby preferably heats the second heat exchanger [preferably flue gas/heat transfer medium heat exchanger for the start-up mode] and then preferably the first heat exchanger [preferably flue gas/heat transfer medium heat exchanger for the start-up mode], both of which release heat to the heat transfer medium.
  • the flue gas then flows preferably through the first smoke gas/combustion air heating element, preferably the flue gas denitrification unit, preferably the flue gas/water heat exchanger and preferably the second smoke gas/combustion air heating element. In this way, combustion air or water is heated by absorbing heat from the flue gas.
  • Demineralized water is preferably fed into the plant as water for generating steam. Air and other gases dissolved in the water are preferably removed in a degasser.
  • the water is preheated via a fifth heat exchanger.
  • the fifth heat exchanger preferably product gas/water heat exchanger for the production mode
  • the fifth heat exchanger is preferably flowed through by product gas, so that water absorbs heat from the product gas.
  • the fifth heat exchanger preferably heat transfer medium/water heat exchanger for the start-up mode
  • the fifth heat exchanger is preferably arranged downstream of the third heat exchanger.
  • the water is then passed through a flue gas/water heat exchanger and heated.
  • the flue gas/water heat exchanger cools the flue gases from the combustion device in the flue gas channel, whereby the heat contained in the flue gas is used to heat the water vapor.
  • the steam is then preferably passed into a steam drum.
  • the water is preferably passed through a third heat exchanger and thereby absorbs further heat, in order to then preferably be returned to the steam drum.
  • the third heat exchanger is arranged in the flow direction of the product gas/heat transfer medium downstream of the second NH3 decomposition device.
  • the third heat exchanger [preferably product gas/water heat exchanger for the production mode] preferably serves to cool the product gas after it leaves the second NH3 decomposition device, with heat contained in the product gas also being used to heat the steam.
  • the third heat exchanger [preferably heat transfer medium/water heat exchanger for the start-up mode] preferably serves to release heat from the heat transfer medium to water.
  • hot steam is also generated in an H2O evaporation device and, if necessary, fed to the NH3 evaporation device together with the steam from the steam drum.
  • Heat is obtained by condensing the water vapor in the NH3 evaporation device in order to evaporate the preheated NH3.
  • the steam condensate is preferably fed to the preheater, which serves to preheat the NH3 so that the heat contained in the water vapor is used in two stages to heat the NH3. After flowing through the preheater, the steam condensate can be discharged from the system.
  • the preferably electrically operated H2O evaporation device provides water vapor.
  • the NH3 fed from the tank into the system is preferably preheated in the preheater using the electrically generated water vapor in analogy to the production mode and then evaporated in the NHs evaporation device.
  • a heat transfer medium preferably N2 or NH3
  • the heat transfer medium is preferably circulated and brought to the necessary pressure using a compressor.
  • the system according to the invention preferably comprises several valves at suitable locations in order to close the main process path at several locations in start-up mode and to enable the circulation of the heat transfer medium.
  • the heat transfer medium circulates from the compressor to a fourth heat exchanger [preferably heat transfer medium/heat transfer medium heat exchanger for start-up mode], where it absorbs heat from cross-flow heat transfer medium.
  • a fourth heat exchanger preferably heat transfer medium/heat transfer medium heat exchanger for start-up mode
  • the heat transfer medium in start-up mode preferably flows to a first heat exchanger [preferably flue gas/heat transfer medium heat exchanger for start-up mode], where it absorbs heat from the flue gas.
  • a first heat exchanger preferably flue gas/heat transfer medium heat exchanger for start-up mode
  • the heat transfer medium preferably flows to a second heat exchanger [preferably flue gas/heat transfer medium heat exchanger for start-up mode], where it also absorbs heat from the flue gas.
  • a second heat exchanger preferably flue gas/heat transfer medium heat exchanger for start-up mode
  • the heat transfer medium preferably flows through the second NH3 decomposition device in the start-up mode, where it absorbs combustion heat, which flows as a heat flow from the combustion device into the second Nff decomposition device.
  • the heat transfer medium preferably reaches a third heat exchanger [preferably heat transfer medium/water heat exchanger for start-up mode], where it transfers heat to water.
  • the heat transfer medium preferably flows again through the fourth heat exchanger [preferably heat transfer medium/heat transfer medium heat exchanger for the start-up mode] (ie cross-flow), where it releases heat to the heat transfer medium guided in the cross-flow.
  • the fourth heat exchanger preferably heat transfer medium/heat transfer medium heat exchanger for the start-up mode
  • the heat transfer medium preferably flows through a fifth heat exchanger [preferably heat transfer medium/water heat exchanger for start-up mode], where it transfers heat to water.
  • the heat transfer medium preferably flows through a sixth heat exchanger [preferably heat transfer medium/water heat exchanger for the start-up mode], where it also transfers heat to water.
  • Figures 1, 2 and 3 each show, using flow diagrams, preferred embodiments of systems according to the invention on which preferred embodiments of the method according to the invention can be carried out.
  • the embodiment according to Figure 3 is a variant of the embodiment according to Figure 2 and is only shown as a section; the details not shown in the section of Figure 3 preferably correspond to those of Figure 2.
  • Figure 1 shows a schematic illustration of such a process.
  • Part of the total NIE used is burned in a mixture with FE and O2 (reaction (A)).
  • Combustion releases combustion heat A.
  • the other part of the NH3 is catalytically decomposed to H2 and N2 with the addition of combustion heat, the mixture formed containing a residual amount of undecomposed NH3 in addition to H2 and N2 (reaction (B)).
  • Reactions A and B are preferably carried out separately from one another in a common reactor which is designed analogously to a primary reformer.
  • H2 The majority of the H2 is separated as a product from the mixture formed during the decomposition of NH3, typically by pressure swing adsorption (PSA)), and the remaining mixture of unseparated H2, N2 and undecomposed NH3 is fed to the combustion (recirculation (C)).
  • PSA pressure swing adsorption
  • C combustion
  • H2 can be branched off from the product H2 and also fed to the combustion (recirculation (D)).
  • recirculation (D) the combustion
  • this is not preferred.
  • pressure swing adsorption typically already achieves an excellent purity of H2, and the H2 remaining in the pressure swing adsorption device after separation of the H2
  • the residual gas mixture contains a sufficient amount of H2, which can hardly be avoided for process-related reasons.
  • the amount of NH3 in the combustion gas is preferably increased if necessary, but not the amount of H2 from the purified valuable product.
  • Figure 2 illustrates a preferred system according to the invention. For convenience, the production mode and start-up mode are explained one after the other below.
  • liquid NH3 which is present at low temperature and increased pressure, is passed from tank 10 via line 11 by means of pump 12 through preheater 13 and heated.
  • NH3 evaporation device 14 the NH3 is evaporated and then flows via line 15 to branch 16, where the NPh flow is divided into two partial flows.
  • a first partial flow of NH3 is expanded and fed via line 17 to combustion device 18.
  • a second partial flow of NH3 is passed from branch 16 via line 19 through the fourth heat exchanger [preferably product gas/NPh heat exchanger for the production mode] 20 and then flows via line 21 through the first heat exchanger [preferably flue gas/NIL heat exchanger for the production mode] 22, where the NH3 is further heated.
  • the preheated NH3 is fed to the first NH3 decomposition device 65, where a partial catalytic decomposition takes place, preferably adiabatically.
  • the intermediate product gas leaving the first NIL decomposition device 65 is passed via line 66 to the second heat exchanger [preferably flue gas/intermediate product gas heat exchanger for the production mode] 67, which is arranged in the flue gas channel 49 upstream of the first heat exchanger 22 in the flow direction of the flue gas.
  • the intermediate product gas is heated and then introduced via line 23 into the second NIL decomposition device 24.
  • the flow through the second NH3 decomposition device 24 is preferably from top to bottom.
  • the heat required to maintain the reaction is generated by heating the second NIL decomposition device 24 by burning H2 and NH3 in the combustion device 18.
  • the product gas formed (comprising N2, H2 and possibly remaining NH3) flows through the third heat exchanger [preferably product gas/water heat exchanger for the production mode] 26, then the fourth heat exchanger [preferably product gas/NIL heat exchanger for the production mode] 20, then line 27 and for further cooling a fifth heat exchanger [preferably product gas/water heat exchanger for the production mode] 28, which is preferably operated with water.
  • the product gas is cooled further by means of a sixth heat exchanger [preferably product gas/water heat exchanger for the production mode] 29 and then fed via line 30 to a pressure swing adsorption device 31, where the gas mixture is separated under pressure by adsorption.
  • the H2 separated in this way leaves the pressure swing adsorption device 31 via line 32, is brought to an increased pressure via a first H2 compressor 33, flows through a first H2 heat exchanger 34, a second H2 compressor 35 for further pressure increase, a second H2 heat exchanger 36 and is discharged from the system at a pressure of, for example, about 70 bar via line 37.
  • the residual gas mixture remaining in the pressure swing adsorption device 31 after separation of the H2 contains N2, residual NH3 and H2 and is returned via return line 38 and fed to the combustion device 18 via branching line 39, so that energy contained in the residual gas mixture can be used to generate combustion heat.
  • combustion air for the combustion process in the combustion device 18 is cleaned via filter 40, compressed by means of compressor 41, passed via line 42 through the second combustion gas/combustion air heating element 43 and heated.
  • the combustion air then flows via line 44 and through the first combustion gas/combustion air heating element 45, is further heated there and then flows via line 46 and the two branching branch lines 47 and 48 into the combustion device 18, where the combustion air is fed to the partial flow of NH3 fed via line 17 in order to burn it and thus generate combustion heat.
  • the hot flue gas from the combustion in the combustion device 18 is first cooled via the second heat exchanger [preferably flue gas/intermediate product gas heat exchanger for the production mode] 67, whereby heat is obtained for heating the intermediate product gas supplied to the second NH3 decomposition device 24 after leaving the first NIL decomposition device 65.
  • the flue gas is then further cooled via the first heat exchanger [preferably flue gas/NFL heat exchanger for the production mode] 22, whereby heat is obtained for heating the NH3 supplied to the first NIL decomposition device 65.
  • the flue gas is then passed through flue gas duct 49 via the first flue gas/combustion air heat exchanger 45, by means of which the combustion air is preheated, and then flows through flue gas denitrification unit 50, by means of which the flue gas is cleaned of nitrogen oxides (NOx).
  • the flue gas then flows through flue gas/water heat exchanger 52 via line 51, whereby heat is obtained for heating water, and then flows through the second flue gas/combustion air heating mixer 43, which also serves to heat the combustion air.
  • the flue gas is then compressed in the end region of the flue gas duct 49 by means of the flue gas compressor 53 and leaves the system via chimney 54.
  • water for the production of steam is fed in via line 55, passed through the fifth heat exchanger [preferably product gas/water heat exchanger for the production mode] 28 and then passed at an increased temperature into degasser 56, in which air and other gases dissolved in the water are removed.
  • degasser 56 By means of pump 57, the water is passed through flue gas/water heat exchanger 52 via line 58 and heated.
  • the flue gas/water heat exchanger 52 serves to cool the flue gases from the combustion device 18 in the flue gas channel 49, the thermal energy contained in the flue gas being used to heat the steam, which is then passed into the steam drum 60 via line 59 after passing through the flue gas/water heat exchanger 52.
  • Water can be passed from the steam drum 60 via line 61 through the third heat exchanger [preferably product gas/water heat exchanger for the production mode] 26 and thereby absorb further heat energy in order to then be returned to the steam drum via line 62.
  • the third heat exchanger 26 is arranged in the outlet line 25 in the flow direction of the product gas downstream of the second NHs decomposition device 24 and serves to cool the product gas after it leaves the second NHs decomposition device 24. The heat gained in this way can thus be used to generate further steam.
  • the hot steam generated in the steam drum 60 is introduced via line 63 into the upper area of the NH3 evaporation device 14.
  • the condensation of the steam generates the heat to evaporate the preheated NH3.
  • the steam condensate is fed via line 64 to the preheater 13, which serves to preheat the NH3 so that the heat contained in the steam is used in two stages to heat the NH3.
  • the steam condensate can be discharged from the system.
  • a heat transfer medium preferably N2 or NH3
  • the cold heat transfer medium is preferably circulated and passed through a compressor 77 in order to build up the necessary pressure.
  • the main process path is closed at several points with at least some of the valves 68, 75, 79, 81, 82, 83 in order to enable the circulation of the heat transfer medium.
  • the first NHs decomposition device 65 is excluded from the circulation.
  • the preferably electrically operated H2O evaporation device 84 provides water vapor.
  • the NH3 fed from the tank 10 into the system is preheated with the help of the electrically generated water vapor in analogy to the production mode in preheater 13 and then evaporated in the NH3 evaporation device 14.
  • the evaporated NH3 In order for the evaporated NH3 to be catalytically decomposed, it must be heated to the activation temperature of the NH3 decomposition catalyst, in the case of a nickel-based NFh decomposition catalyst preferably to 600 to 650°C, in the case of a ruthenium-based NFF decomposition catalyst preferably to 350 to 400°C.
  • NH3 (part or all of it) is passed through the electric heating element 74 and heated therein above the activation temperature of the NFF decomposition catalyst in the first NIT decomposition device 65.
  • the heated NH3 then flows via line 73 into the first NIL decomposition device 65, where the NH3 is at least partially decomposed.
  • a conversion of e.g. 18% can be achieved, depending on the preheating temperature.
  • the intermediate product gas thus formed contains H2 and is optionally mixed with further NH3 and burned in the combustion device 18 to form flue gas. Due to the partial decomposition of NH3, a sufficient amount of H2 is available to ensure or improve the combustion of the NH3.
  • the preferably electrically operated H2O evaporation device 84 and the electrical heating element 74 require electrical energy to evaporate and further heat the NH3 for the catalytic decomposition; the subsequent combustion of NH3 together with the H2 formed by the catalytic decomposition then provides the heat to heat the heat transfer medium.
  • the heat transfer medium circulates from the compressor 77 to the fourth heat exchanger [preferably heat transfer medium/heat transfer medium heat exchanger for the start-up mode] 20 on the cold side, from there via line 21 to the first heat exchanger [preferably flue gas/heat transfer medium heat exchanger for the start-up mode] 22, and then via line 80 to the second heat exchanger [preferably flue gas/heat transfer medium heat exchanger for the start-up mode] 67.
  • the heat transfer medium flows through the second NfL circulating device 24 and reaches the third heat exchanger [preferably heat transfer medium/water heat exchanger for the start-up mode] 26 via line 25 and then the fourth heat exchanger [preferably heat transfer medium/heat transfer medium heat exchanger for the Start-up mode] 20 on the hot side. From there, the heat transfer medium flows through the fifth heat exchanger [preferably heat transfer medium/water heat exchanger for the start-up mode] 28 and then the sixth heat exchanger [preferably heat transfer medium/water heat exchanger for the start-up mode] 29, which ensures a constant inlet temperature in the downstream nitrogen compressor, which compensates for the pressure loss across the system.
  • the downstream compressor can also be an N2/NH3 compressor, which fulfils a dual function, i.e. is used to compress both the N2 and the NH3.
  • the NH3 stream in the start-up mode, is divided into a first NH3 partial stream and a second NH3 partial stream. Only the first NH3 partial stream is fed to the first Decomposition device 65.
  • the second NFL partial flow is separated after flowing through the first heat exchanger [preferably flue gas/heat transfer medium heat exchanger for the start-up mode] 22 via line 80, preferably flows through the second heat exchanger [preferably flue gas/heat transfer medium heat exchanger for the start-up mode] 67 and then the second NFL decomposition device 24, whereby the second NHs decomposition device 24 absorbs heat from the second NFL partial flow.
  • the second NFL partial flow therefore initially only has the function of a heat transfer medium.
  • the second NHs decomposition device 24 is gradually heated in this way until the start-up temperature (activation temperature) for the catalytic decomposition of NFL is reached, so that from this point on additional FL is produced in the second NFL decomposition device 24 by catalytic decomposition of NFL.
  • the heat transfer medium is heated in the start-up mode when it flows through the cold side of the fourth heat exchanger [preferably heat transfer medium/heat transfer medium heat exchanger for the start-up mode] 20, where it absorbs heat from the heat transfer medium guided in cross-flow.
  • the heat transfer medium is heated when it flows through the first heat exchanger [preferably flue gas/heat transfer medium heat exchanger for the start-up mode] 22 and the second heat exchanger [preferably flue gas/heat transfer medium heat exchanger for the start-up mode] 67, where it absorbs heat from the flue gas.
  • the heat transfer medium is heated when it flows through the second NFL decomposition device 24, where it absorbs combustion heat, which flows as a heat flow from the combustion device 18 into the second NFL decomposition device 24.
  • the heat transfer medium is cooled in the start-up mode when flowing through the third heat exchanger [preferably heat transfer medium/water heat exchanger for the start-up mode] 26, where it releases heat to water, and when flowing through the warm side of the fourth heat exchanger [preferably heat transfer medium/heat transfer medium heat exchanger for the start-up mode] 20, where it releases heat to the heat transfer medium guided in cross-flow.
  • the heat transfer medium is cooled when flowing through the fifth heat exchanger [preferably heat transfer medium/water heat exchanger for the start-up mode] 28 and then the sixth heat exchanger [preferably heat transfer medium/water heat exchanger for the start-up mode] 29, where it releases heat to water.
  • the flue gas formed during the combustion of the mixture comprising NFL and FL flows through the flue gas channel 49 in the start-up mode and heats the second heat exchanger [preferably flue gas/heat transfer medium heat exchanger for the start-up mode] 67 and then the first heat exchanger [preferably flue gas/heat transfer medium heat exchanger for the start-up mode] 22, both of which release heat to the heat transfer medium.
  • the flue gas then flows through the first flue gas/combustion shift heat exchanger 45, the flue gas denitrification unit 50, the flue gas/water heat exchanger 52 and the second flue gas/combustion shift heat exchanger. In this way, combustion air or water is heated by absorbing heat from the flue gas.
  • NH; or another combustible gas is used as the heat transfer medium, this can be discharged via line 76 and valve 68 and then burned at the flare tower 70.
  • Condensate is preferably separated beforehand in separation device 71. This condensate can comprise water, which is present in small amounts in the NH; ( ⁇ 0.5% by weight), and/or NH; which was not converted in the second NHs decomposition device 24 in the start-up mode.
  • Figure 3 illustrates a preferred variant of the system according to the invention according to Figure 2. Since the production mode according to the variant of Figure 3 largely corresponds to that according to Figure 2, only the start-up mode is expediently explained below.
  • N2 is used as heat transfer medium, NH3 can be added continuously.
  • the electric heating element 74 is arranged in the flow direction of the NH3 downstream of the valve 82 and upstream of the first NH3 decomposition device 65.
  • the valve 82 regulates which proportion of NH3 is fed into the first NHs decomposition device 65 for partial catalytic decomposition and which proportion of NH3 is fed via line 80 into the second NHs decomposition device 24 as a heat transfer medium.
  • valve 75 which is installed downstream in the direction of flow of the NH3 directly after branch 16; this function is performed by the first NHs decomposition device 65 and the valve 82.
  • the circulation of the NH3 as a heat transfer medium then takes place according to the invention as follows: With the valve 75 closed, the NH3 is passed past branch 16 to the fourth heat exchanger 20 (not shown again in Figure 3) and then to the first heat exchanger 22. From there, it is divided into a first NH3 partial flow and a second TML partial flow.
  • the first b L partial stream is passed via valve 82 into the first NH 3 decomposition device 65.
  • Valve 81 is closed so that the intermediate product gas leaving the first NH 3 decomposition device is fed via branching line 39 to the combustion device 18 and burned therein.
  • the second NH 3 partial stream is fed via line 80 with valve 81 closed via the second heat exchanger 67 to the second NH 3 decomposition device 24, where it initially serves as a heat transfer medium (provided that the activation temperature of the NH 3 decomposition catalyst in the second NH 3 decomposition device has not yet been reached).
  • the second NH 3 partial stream leaving the second NH 3 decomposition device 24 is passed via lines 25 and 27 to the fourth heat exchanger 20, then to the fifth heat exchanger 28 and finally to the sixth heat exchanger 29 (all not shown again in Figure 3).
  • Valve 83 and valve 68 are closed so that the second NtL partial stream is passed via line 76 to the compressor 77 (all not shown again in Figure 3).
  • Part of the NH 3; is consumed in this way and intermediate product gas is passed via line 19.
  • first heat exchanger preferably flue gas/NHs heat exchanger for the manufacturing mode; flue gas/heat transfer medium heat exchanger for the start-up mode] 42 line 43 second flue gas/combustion air heat exchanger
  • Line 78 additional tank second heat exchanger [preferably 79 valve flue gas/intermediate product gas heat exchanger for production mode; 80 line flue gas/heat transfer medium heat exchanger for start-up mode] 81 valve 82 valve
  • Valve 84 H2O evaporation device H2O evaporation device.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

L'invention concerne une installation de préparation de H2 par décomposition catalytique de NH3. L'installation selon l'invention peut fonctionner dans un mode de démarrage afin de chauffer des appareils de l'installation à une température de fonctionnement accrue en utilisant un milieu de transfert de chaleur, par exemple suite à l'interruption d'un fonctionnement continu de l'installation en raison d'une opération de maintenance. Après chauffage à la température de fonctionnement, l'installation selon l'invention peut fonctionner dans un mode de production pour la production continue de H2. L'invention concerne également un procédé de démarrage d'une installation de préparation de H2 par décomposition catalytique de NH3.
PCT/EP2024/069358 2023-07-13 2024-07-09 Démarrage d'une installation de décomposition catalytique d'ammoniac Pending WO2025012271A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
LULU103170 2023-07-13
LU103170A LU103170B1 (de) 2023-07-13 2023-07-13 Anfahren einer Anlage zur katalytischen Zersetzung von Ammoniak
DE102023118576.4 2023-07-13
DE102023118576.4A DE102023118576A1 (de) 2023-07-13 2023-07-13 Anfahren einer Anlage zur katalytischen Zersetzung von Ammoniak

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WO2025012271A1 true WO2025012271A1 (fr) 2025-01-16

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Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1469045A (fr) 1965-12-16 1967-02-10 Azote Office Nat Ind Générateur d'hydrogène
US4704267A (en) 1986-05-21 1987-11-03 Air Products And Chemicals, Inc. Production of hydrogen from ammonia
WO2001087770A1 (fr) 2000-05-12 2001-11-22 Gradient Technology Production d'hydrogene par decomposition autothermique d'ammoniac
US20030232224A1 (en) * 2000-07-25 2003-12-18 Apollo Energy Systems, Incorporated Ammonia cracker for production of hydrogen
US20050172556A1 (en) * 2001-04-23 2005-08-11 Michael Powell Hydrogen generation apparatus and method for using same
WO2011107279A1 (fr) 2010-03-02 2011-09-09 Amminex A/S Apppreil pour générer de l'hydrogène à partir de l'ammoniac contenu dans des matériaux solides et intégration de cet appareil dans des piles à combustible basse température
WO2011150370A2 (fr) 2010-05-27 2011-12-01 Grannell, Shawn Système, procédé et appareil de craquage d'ammoniac à flamme
WO2012039183A1 (fr) 2010-09-21 2012-03-29 日立造船株式会社 Procédé de production d'hydrogène à partir d'ammoniac
WO2012090739A1 (fr) 2010-12-30 2012-07-05 株式会社豊田中央研究所 Générateur d'hydrogène et moteur à combustion interne équipé d'un générateur d'hydrogène
WO2013119281A1 (fr) 2012-02-10 2013-08-15 Shawn Grannell Système procédé et appareil de craquage de l'ammoniac par flamme
WO2017160154A1 (fr) 2016-03-14 2017-09-21 Statoil Petroleum As Craquage d'ammoniac
WO2019038251A1 (fr) 2017-08-24 2019-02-28 Haldor Topsøe A/S Procédé de craquage autothermique d'ammoniac
WO2020095467A1 (fr) 2018-11-09 2020-05-14 好朗 岩井 Dispositif de production d'hydrogène gazeux
CN111957270A (zh) 2020-09-03 2020-11-20 福州大学化肥催化剂国家工程研究中心 一种氨分解制氢系统及加氢站系统
CN113294801A (zh) * 2021-05-26 2021-08-24 华中科技大学 一种可实现纯氨高效清洁燃烧的燃烧装置及其控制方法
WO2021257944A1 (fr) 2020-06-18 2021-12-23 Air Products And Chemicals, Inc. Craquage d'ammoniac pour de l'hydrogène vert
CN113896168A (zh) 2021-10-14 2022-01-07 西南化工研究设计院有限公司 一种两段法氨裂解制氢气或制还原气的方法
WO2022096529A1 (fr) 2020-11-04 2022-05-12 Haldor Topsøe A/S Procédé de craquage d'ammoniac
WO2022243410A1 (fr) 2021-05-21 2022-11-24 Casale Sa Craquage d'ammoniac pour la production d'hydrogène
WO2022265648A1 (fr) 2021-06-18 2022-12-22 Air Products And Chemicals, Inc. Craquage d'ammoniac pour hydrogène vert avec élimination de nox
WO2022265650A1 (fr) 2021-06-18 2022-12-22 Air Products And Chemicals, Inc. Procédé de craquage d'ammoniac
WO2022265651A1 (fr) 2021-06-18 2022-12-22 Air Products And Chemicals, Inc. Craquage d'ammoniac pour de l'hydrogène vert
WO2022265649A1 (fr) 2021-06-18 2022-12-22 Air Products And Chemicals, Inc. Craquage d'ammoniac pour hydrogène vert
WO2022265647A1 (fr) 2021-06-18 2022-12-22 Air Products And Chemicals, Inc. Récupération d'un produit d'hydrogène renouvelable à partir d'un processus de craquage d'ammoniac

Patent Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1469045A (fr) 1965-12-16 1967-02-10 Azote Office Nat Ind Générateur d'hydrogène
US4704267A (en) 1986-05-21 1987-11-03 Air Products And Chemicals, Inc. Production of hydrogen from ammonia
WO2001087770A1 (fr) 2000-05-12 2001-11-22 Gradient Technology Production d'hydrogene par decomposition autothermique d'ammoniac
US20030232224A1 (en) * 2000-07-25 2003-12-18 Apollo Energy Systems, Incorporated Ammonia cracker for production of hydrogen
US20050172556A1 (en) * 2001-04-23 2005-08-11 Michael Powell Hydrogen generation apparatus and method for using same
WO2011107279A1 (fr) 2010-03-02 2011-09-09 Amminex A/S Apppreil pour générer de l'hydrogène à partir de l'ammoniac contenu dans des matériaux solides et intégration de cet appareil dans des piles à combustible basse température
WO2011150370A2 (fr) 2010-05-27 2011-12-01 Grannell, Shawn Système, procédé et appareil de craquage d'ammoniac à flamme
WO2012039183A1 (fr) 2010-09-21 2012-03-29 日立造船株式会社 Procédé de production d'hydrogène à partir d'ammoniac
WO2012090739A1 (fr) 2010-12-30 2012-07-05 株式会社豊田中央研究所 Générateur d'hydrogène et moteur à combustion interne équipé d'un générateur d'hydrogène
WO2013119281A1 (fr) 2012-02-10 2013-08-15 Shawn Grannell Système procédé et appareil de craquage de l'ammoniac par flamme
WO2017160154A1 (fr) 2016-03-14 2017-09-21 Statoil Petroleum As Craquage d'ammoniac
WO2019038251A1 (fr) 2017-08-24 2019-02-28 Haldor Topsøe A/S Procédé de craquage autothermique d'ammoniac
WO2020095467A1 (fr) 2018-11-09 2020-05-14 好朗 岩井 Dispositif de production d'hydrogène gazeux
WO2021257944A1 (fr) 2020-06-18 2021-12-23 Air Products And Chemicals, Inc. Craquage d'ammoniac pour de l'hydrogène vert
CN111957270A (zh) 2020-09-03 2020-11-20 福州大学化肥催化剂国家工程研究中心 一种氨分解制氢系统及加氢站系统
WO2022096529A1 (fr) 2020-11-04 2022-05-12 Haldor Topsøe A/S Procédé de craquage d'ammoniac
WO2022243410A1 (fr) 2021-05-21 2022-11-24 Casale Sa Craquage d'ammoniac pour la production d'hydrogène
CN113294801A (zh) * 2021-05-26 2021-08-24 华中科技大学 一种可实现纯氨高效清洁燃烧的燃烧装置及其控制方法
WO2022265648A1 (fr) 2021-06-18 2022-12-22 Air Products And Chemicals, Inc. Craquage d'ammoniac pour hydrogène vert avec élimination de nox
WO2022265650A1 (fr) 2021-06-18 2022-12-22 Air Products And Chemicals, Inc. Procédé de craquage d'ammoniac
WO2022265651A1 (fr) 2021-06-18 2022-12-22 Air Products And Chemicals, Inc. Craquage d'ammoniac pour de l'hydrogène vert
WO2022265649A1 (fr) 2021-06-18 2022-12-22 Air Products And Chemicals, Inc. Craquage d'ammoniac pour hydrogène vert
WO2022265647A1 (fr) 2021-06-18 2022-12-22 Air Products And Chemicals, Inc. Récupération d'un produit d'hydrogène renouvelable à partir d'un processus de craquage d'ammoniac
CN113896168A (zh) 2021-10-14 2022-01-07 西南化工研究设计院有限公司 一种两段法氨裂解制氢气或制还原气的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
I. LUCENTINI ET AL., IND. ENG. CHEM. RES., vol. 60, no. 51, 2021, pages 18560 - 18611

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