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WO2025073609A1 - Synthèse d'ammoniac vert à débit variable - Google Patents

Synthèse d'ammoniac vert à débit variable Download PDF

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Publication number
WO2025073609A1
WO2025073609A1 PCT/EP2024/077390 EP2024077390W WO2025073609A1 WO 2025073609 A1 WO2025073609 A1 WO 2025073609A1 EP 2024077390 W EP2024077390 W EP 2024077390W WO 2025073609 A1 WO2025073609 A1 WO 2025073609A1
Authority
WO
WIPO (PCT)
Prior art keywords
synthesis units
synthesis
reactant gas
units
synthesized
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/EP2024/077390
Other languages
German (de)
English (en)
Inventor
Evgeni Gorval
Bernd Keil
Reinhard Heun
Stephan Buß
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 DE102023126893.7A external-priority patent/DE102023126893A1/de
Priority claimed from LU103199A external-priority patent/LU103199B1/de
Application filed by ThyssenKrupp AG, ThyssenKrupp Uhde GmbH filed Critical ThyssenKrupp AG
Publication of WO2025073609A1 publication Critical patent/WO2025073609A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0482—Process control; Start-up or cooling-down procedures
    • 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
    • B01J19/2445—Stationary reactors without moving elements inside placed 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
    • 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
    • B01J8/04—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 the fluid passing successively through two or more beds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00026—Controlling or regulating the heat exchange system
    • B01J2208/00035—Controlling or regulating the heat exchange system involving measured parameters
    • B01J2208/00044—Temperature measurement
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00026—Controlling or regulating the heat exchange system
    • B01J2208/00035—Controlling or regulating the heat exchange system involving measured parameters
    • B01J2208/00044—Temperature measurement
    • B01J2208/00061—Temperature measurement of the reactants
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B01J2208/023—Details
    • B01J2208/027—Beds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the invention relates to a process for the synthesis of NH 3 at variable throughput in a plant comprising several synthesis units connected in parallel.
  • a reactant gas stream comprises H 2 , which is provided by electrolysis of water using electricity from renewable energy. The currently available amount of H 2 varies depending on the currently available amount of renewable energy.
  • the reactant gas stream is introduced as such into a single synthesis unit or divided into independent substreams into several or all of the synthesis units, where NH3 is subsequently synthesized from H2 and N2.
  • the invention also relates to a plant configured to carry out the process.
  • H2 is often obtained by steam reforming hydrocarbons.
  • the hydrocarbons can be stored safely and for extended periods of time so that they can be made available in sufficient quantities at any time. Therefore, a sufficient amount of H2 can also be obtained from them at any time by steam reforming.
  • the electrical power used for the electrolysis is generated from renewable energy, in particular from wind power, hydropower, solar energy, or combinations thereof.
  • Renewable energy is not continuously available in constant quantities.
  • the availability of wind power and solar energy is subject to considerable fluctuations, which are caused primarily by the weather and the day-night cycle.
  • For the electrolysis of water such fluctuations are a minor problem, because the performance of modern electrolysis cells can be quickly adjusted to such fluctuations.
  • H 2 which is obtained by electrolysis of water with electricity from renewable energy, simultaneously (or slightly delayed) with the fluctuation in the availability of renewable energy.
  • the electrical power generated from renewable energy can also hardly be temporarily stored in accumulators in the quantity that would be required for the large-scale synthesis of NH3.
  • the required storage capacity of the accumulators would be so great that the investment costs for the accumulators would not allow for an economical process.
  • H2 produced by electrolysis of water can in principle be stored temporarily, this then represents a considerable safety risk, particularly in view of the quantity required for the large-scale synthesis of NH3.
  • EP 2589574 A1 relates to a method for controlling an NH3 plant, in which a purge gas containing inert substances is taken from the NH 3 -synthesis cycle and in which the NH 3 -plant is operated at partial load by the NH 3 -synthesis circuit is maintained at a nominal high pressure and reducing the purge rate to reduce the concentration of inert substances in the NH 3 -synthesis cycle and to avoid overheating of the reactor.
  • US 7892511 relates to systems and methods for producing one or more products from synthesis gas.
  • WO 2017153304 A1 relates to a process and a plant for synthesizing a product gas from a first reactant gas and a second reactant gas, wherein product gas is discharged and unreacted reactant gas is circulated, and wherein the volume flow of the first reactant gas, the second reactant gas, and/or the discharged product gas is varied during the process.
  • the amount of product gas formed per unit of time can be temporarily throttled (partial load operation) or its synthesis can be temporarily completely stopped (standby operation) without the plant on which the process is carried out having to be completely shut down.
  • WO 2021060985 A1 relates to a process for producing NH 3 , depending on the availability of H 2 switching between a first operating mode and a second operating mode occurs.
  • WO 2021089276 A1 relates to a method for synthesizing NH3, including generating make-up gas in a front end and converting the make-up gas in an NH3 synthesis loop.
  • the loop When the loop is operated at partial load and the flow rate of the make-up gas is reduced, the loop is controlled by separating a gas stream from a converter feed line at a point upstream of a converter, thus forming a bypass stream, which is reintroduced into the loop at the suction side of a circulator or at a point in a loop downstream of a separation section.
  • WO 2021151672 A1 relates to a method for NH3 synthesis in a synthesis circuit, wherein a gas mixture comprising N2, H2, and NH3 is circulated in the synthesis circuit using a conveying device, wherein N2 and H2 are at least partially converted to NH3 in a converter, and wherein the gas mixture is cooled in a cooling device such that NH3 condenses out of the gas mixture.
  • WO 2022173794 A1 relates to a method for the synthesis of renewable ammonia.
  • WO 2022256907 A1 relates to a container system for producing anhydrous ammonia from air, water, and an energy source.
  • WO 2023006291 A1 relates to an integrated process for the synthesis of NH3 and nitric acid, including the production of H2 from the electrolysis of water.
  • the process is controlled by selectively switching between a first operating mode and a second operating mode, whereby in the first operating mode NH3 produced in excess is used and in a suitable NH 3 -storage; and in the second operating mode the NH 3 from the NH 3 storage is used to provide an additional supply of NH 3 for nitric acid production. Switching between the first mode and the second mode is based on the amount of energy transferred to electrolyze water.
  • WO 2023036560 A1 relates to a method for controlling an ammonia plant comprising an ammonia synthesis section with an ammonia converter and a hydrogen generation section connected to a hydrogen storage unit.
  • the methods and plants known from the prior art for the synthesis of NH 3 are not satisfactory in all respects and it is an object of the invention to provide improved methods and improved plants.
  • the methods and plants should use H2, which is obtained by electrolysis of water with electrical power from renewable energy, wherein the methods and plants can compensate for a temporarily reduced or interrupted availability of renewable energy (and thus of electrical power generated therefrom and of H obtained by electrolysis of water). 2 ) without having to temporarily store large amounts of renewable energy, electrical power generated therefrom, or H2 obtained by electrolysis of water.
  • a first aspect of the invention relates to a process for the synthesis of NH3 at variable throughput in a plant comprising several NH3 synthesis units connected in parallel, the process comprising the steps of: (a) providing H2 by electrolysis of H2O with electrical power from renewable energy; (b) providing a reactant gas stream comprising the H2; preferably in a mixture with N2; (c) introducing the reactant gas stream as a function of the currently available amount of H2 (i) as such into a single one of the NH3 synthesis units; or divided into independent partial streams (ii) into several of the NH3 synthesis units or (iii) into all of the NH3 synthesis units, wherein (ii) one of the partial streams is introduced into each of the several NH3 synthesis units or (iii) into all of the NH3 synthesis units independently of one another; and (d) synthesizing NH3 from H2 and N
  • the instantaneous availability of H2 changes, preferably due to external influences such as, for example, the day-night cycle, weather, etc.
  • the instantaneous availability of H2 is high, during another time interval the availability of H 2 moderate, during a further time interval the instantaneous availability of H 2 low.
  • Step (c) occurs, i.e. the process reacts to fluctuations in the availability of H 2 with a modified procedure in Step (c), and as a consequence also in step (d).
  • the change in the procedure due to fluctuations in the availability of H 2 results in a variable throughput.
  • Step (c) addresses the following three alternative possibilities for introducing the reactant gas stream: Alternative (i): the reactant gas stream is introduced as such (i.e., completely) into a single NH3 synthesis unit; or Alternative (ii): the reactant gas stream is divided into independent substreams in several of the NH 3 -synthesis units, wherein in each of the several NH 3 -synthesis units, one of the partial streams is introduced independently of each other; or alternative (iii): the reactant gas stream is divided into independent partial streams in all of the NH 3 -synthesis units, wherein one of the partial streams is introduced into each of the NH3 synthesis units independently of one another.
  • each time interval comprises at least 15 minutes, more preferably at least 30 minutes, even more preferably at least 45 minutes, most preferably at least 1 hour.
  • the maximum length of the time interval depends on the ratio of heating rate and cooling rate under the given conditions.
  • each time interval comprises at most 24 hours, more preferably at most 18 hours, even more preferably at most 12 hours, most preferably at most 6 hours.
  • the parallel-connected NH3 synthesis units are designed as single-bed reactors, with each NH3 synthesis unit preferably being arranged in its own pressure vessel.
  • the plant preferably comprises at least two parallel-connected NH3 synthesis units, preferably single-bed reactors; more preferably at least three parallel-connected NH 3 -synthesis units, preferably single-bed reactors; more preferably exactly three NH 3 -synthesis units, preferably single-bed reactors.
  • NH 3 - Synthesis units cool down slowly and are also preferably insulated. Towards the end of the temporary shutdown, process heat is then preferably extracted from at least one still active NH 3 -Synthesis unit for warming up the not yet active NH 3 -synthesis units are used.
  • the temporary shutdown of the first NH3 synthesis unit means a reduction of the total plant load by 33% to 67% of the nominal plant load. If the second NH 3 -synthesis unit (reactor) is switched off, the total load of the plant is reduced by a further 33% to only 33% of the nominal load of the plant.
  • individual NH 3 -synthesis units independent of the other NH 3 -synthesis units are throttled by reducing the individual throughput on this NH3 synthesis unit (partial load operation).
  • each NH3 synthesis unit it is therefore not necessary for each NH3 synthesis unit to be operated constantly and permanently at the maximum possible throughput (full load operation). Rather, conventional NH3 synthesis units are perfectly capable of maintaining NH3 synthesis even at a lower than maximum throughput (partial load operation). According to the invention, preference is given to using NH3 synthesis units in which the individual partial load can be continuously reduced to approximately 30% of the maximum possible throughput by reducing the throughput, without the synthesis of NH3 from H2 and N2 coming to a standstill. [0032] It has surprisingly been found that the shutdown of individual NH3 synthesis units and the individual throttling of individual NH3 synthesis units can be advantageously combined with one another.
  • the total load of the plant can be significantly reduced from 100% of its nominal load, e.g., to 40% of its nominal load or even to 30% of its nominal load, without having to temporarily shut down one of the NH3 synthesis units.
  • the reactant gas stream as such is preferably fed to another of the NH3 synthesis units.
  • the previously operated NH3 synthesis units is preferably no longer flowed through, i.e., switched off, and the newly fed NH 3 -synthesis unit is preferably reheated by the exothermic reaction to a predetermined temperature.
  • Another parallel NH 3 -synthesis unit can be reheated in the same way. For example, with three NH 3 -synthesis units, the total load of the plant can thus be reduced to only approximately 10% of its nominal load, even over longer periods.
  • the NH3 synthesis units can be operated in a temperature range.
  • the temperature in none of the NH3 synthesis units preferably falls below the minimum light-off temperature. It has been found that the heating rate can be 50 K/h, with the cooling rate being significantly slower. Therefore, according to the invention, two NH3 synthesis units can preferably always be switched off and cooled down, while one NH3 synthesis unit is heated by its reaction heat (process heat). Preferably, none of the NH3 synthesis units cools below the light-off temperature. All NH3 synthesis units then preferably have a different temperature at a given time. The temperature of the reactors is preferably monitored, e.g., by thermocouples.
  • the NH3 synthesis units are in heat exchange with one another. If the NH3 synthesis units are each arranged in their own pressure vessels, three different pressure vessels are required for three NH3 synthesis units. This results in increased costs. [0038] It was surprisingly found that the three NH3 synthesis units can be accommodated together in one pressure vessel in such a way that they can be flowed to evenly but separately. The separation of the NH3 synthesis units is preferably not thermally insulated, so that the NH3 synthesis units which are temporarily not flowed through, i.e. are switched off, can be kept at least at the start-up temperature.
  • the process according to the invention comprises steps (a) to (d), which are preferably carried out in alphabetical order.
  • the method according to the invention can comprise any additional steps before the steps, after the steps or between the steps, which can be carried out independently of one another in time or at least partially simultaneously.
  • a distinction is made between the total load of the system on the one hand and the individual load of a single NH 3 -synthesis unit on the other hand.
  • the individual Load of a single NH 3 -Synthesis unit a distinction is further made between full load operation and partial load operation.
  • the nominal load of the system means the maximum load when all NH 3 -synthesis units in full-load operation without any throttling, i.e. the maximum possible throughput for which the plant as a whole is designed.
  • "NH3 synthesis unit” means, in the simplest case, a spatially defined collection of catalyst material suitable for the conversion of H 2 and N 2 to NH 3 This can be, for example, a catalyst bed or a reactor. If each of the NH 3 If several NH3 synthesis units are arranged in a separate pressure vessel, this pressure vessel can be regarded as a reactor.
  • This pressure vessel can optionally comprise a plurality of catalyst beds connected in series, which are then preferably regarded together as an NH3 synthesis unit. If the plurality of NH3 synthesis units are arranged together in a pressure vessel, this pressure vessel can be regarded as a reactor in which the plurality of NH3 synthesis units are preferably present as catalyst beds connected in parallel, which preferably exchange heat with one another. It is possible for further catalyst beds to be connected in series, independently of one another, downstream of the plurality of NH3 synthesis units, which are present as catalyst beds connected in parallel, so that each of the NH3 synthesis units can in turn optionally comprise a plurality of catalyst beds connected in series. However, each of the NH3 synthesis units preferably comprises only a single catalyst bed.
  • each of the NH3 synthesis units comprises at least one catalyst bed, preferably only a single catalyst bed, through which the reactant gas stream preferably flows axially.
  • each catalyst bed independently of one another has a substantially cylindrical shape, so that in this context "axial" means in a direction substantially parallel to the cylinder jacket.
  • each catalyst bed can also be independently subjected to radial flow, although this is less preferred according to the invention.
  • the multiple NH3 synthesis units are connected in parallel, i.e., not in series.
  • the parallel connection of the NH3 synthesis units comes into effect when the reactant gas stream is divided into independent substreams and introduced into several of the NH3 synthesis units or into all of the NH3 synthesis units in parallel. In this case, each substream is introduced into its own NH3 synthesis unit independently of the other substreams.
  • the conversion of H 2 and N 2 to NH 3 does not proceed completely in large-scale ammonia production plants, so that the process gas is usually circulated, possibly recompressed, and the NH 3 -synthesis units several times. Fresh reactant gas is then introduced into the circuit.
  • the terms "reactant gas stream” and "partial stream” refer to both circulated process gas and fresh reactant gas (make-up gas).
  • step (d) of the process according to the invention comprises synthesizing NH 3 from H 2 and N 2 in one, several or all of the NH 3 - synthesis units into which, in step (c), reactant gas stream or a partial stream thereof is introduced to obtain a product gas stream or partial product gas stream which contains NH 3 and possibly unreacted H2 and N2; and - recycling the product gas stream or product gas substream to the one, several or all of the NH 3 -synthesis units.
  • the product gas stream or partial product gas stream is preferably only used for those of the NH 3 -synthesis units into which reactant gas stream or a partial stream thereof was also previously introduced.
  • the plant preferably comprises three NH3 synthesis units connected in parallel; preferably no more than three NH3 synthesis units connected in parallel.
  • the NH3 synthesis units preferably each have essentially the same structure.
  • each of the NH3 synthesis units is arranged separately in its own pressure vessel.
  • the NH3 synthesis units are arranged in a common pressure vessel.
  • the NH3 synthesis units are preferably in heat exchange with one another.
  • Each of the NH3 synthesis units preferably contains at least one catalyst bed.
  • Each of the NH3 synthesis units preferably contains only a single catalyst bed.
  • step (a) of the process according to the invention H2 is provided by electrolysis of H2O with electrical power from renewable energy.
  • the electrical power is generated from wind power; preferably, the currently available amount of H2 depends on the current availability of wind power.
  • the electrical power is generated from hydropower; preferably, the currently available amount of H2 depends on the current availability of hydropower.
  • the electrical power is generated from solar energy; preferably, the currently available amount of H2 depends on the current availability of solar energy.
  • step (a) comprises the intermediate storage of electrical power from renewable energy, preferably in an accumulator.
  • step (a) comprises the intermediate storage of H 2 ; preferably in a tank.
  • a reactant gas stream is provided which comprises the H2 provided in step (a).
  • the reactant gas stream is fed with a throughput depending on the currently available amount of H 2
  • the reactant gas stream provided in step (b) comprises, in addition to H 2 also N 2 .
  • the reactant gas stream provided in step (b) consists essentially of H 2 and N 2 .
  • the reactant gas stream provided in step (b) comprises H2, N2 and NH3.
  • step (b) comprises compressing the reactant gas stream to elevated pressure, preferably to a pressure of at least 150 bar.
  • step (b) comprises heating the reactant gas stream to elevated temperature, preferably to a temperature of at least 300°C.
  • step (c) of the process according to the invention the reactant gas stream is introduced into NH3 synthesis unit(s) depending on the currently available amount of H2.
  • the reactant gas stream is not divided into substreams, but is introduced as such into a single one of the NH3 synthesis units; then, neither the reactant gas stream nor a substream thereof is introduced into all the remaining NH3 synthesis units; or (2) the reactant gas stream is divided into independent substreams and the substreams are introduced into several, but not all, of the NH3 synthesis units, with one of the substreams being introduced independently into each of the several NH3 synthesis units; then neither the reactant gas stream nor a substream thereof is introduced into the remaining NH3 synthesis units; or (3) the reactant gas stream is divided into independent substreams and the substreams are introduced into all of the NH3 synthesis units, with one of the substreams being introduced independently into each of the NH3 synthesis units; then there are no NH3 synthesis units remaining into which neither the reactant gas stream nor a substream thereof is introduced.
  • step (d) of the process according to the invention in one, in several or in all of the NH 3 -synthesis units into which in step (c) reactant gas stream or a partial stream thereof is introduced, NH 3 from H 2 and N 2 synthesized.
  • NH3 is synthesized in each of the NH3 synthesis units into which the reactant gas stream is introduced as such; in all other NH3 synthesis units into which neither reactant gas stream nor a partial stream thereof is introduced, no NH 3 synthesized, i.e.
  • step (c) of the method according to the invention the introduction of the reactant gas stream takes place as a function of the currently available amount of H2.
  • “As a function” means that the currently available amount of H2 is monitored, either directly as such, and/or indirectly via the currently available amount of electrical power, and/or via the currently available amount of renewable energy. Monitoring may also include predictions, for example, predictions of the day-night cycle, or weather forecasts that predict expected precipitation, expected wind, and/or expected hours of sunshine.
  • the feed gas stream is then introduced according to one of the three alternative operating modes (1), (2), and (3).
  • "Currently" refers to a current state that only lasts for a certain period of time and then passes.
  • the overall load of the system is preferably reduced.
  • the overall load of the system is preferably increased.
  • the synthesis of NH 3 with variable throughput With currently high availability of H 2 the total load of the system is preferably higher than when there is currently low availability of H 2 .
  • Step (c) of the process according to the invention can also be determined depending on the expected future availability of H 2
  • the current availability of H 2 is then not the only parameter depending on which step (c) is carried out.
  • the expected future available amount of H 2 preferably results from predictions.
  • the onset of the next twilight can be predicted very accurately and reliably.
  • the change in the availability of solar energy that accompanies twilight influences the availability of electrical power generated from solar energy and thus of electricity generated by electrolysis of H 2 O H obtained with this electric current 2 .
  • a time offset may have to be taken into account which the electrolysis of H2O with this electrical current requires before the H2 thus obtained can be made available.
  • the expected future available amount of H2 is preferably also taken into account for the control of the process, with the future 4 hours being preferably taken into account.
  • the expected future available amount of H2 is preferably also taken into account for the control of the process, with at least the future 4 hours being taken into account in terms of time, more preferably the future 6 hours, even more preferably the future 12 hours.
  • the method according to the invention is preferably controlled as a function of the currently available amount of H2, wherein the control preferably selects one of the three alternative operating modes (1), (2) and (3) as a function of the currently available amount of H2 and comparison with a specified threshold value or several specified threshold values.
  • different threshold values may be relevant.
  • the change from operating mode (1) to operating mode (2) ((1)->(2)) can thus take place at a different specified threshold value than the converse change from operating mode (2) to operating mode (1) ((2)->(1)).
  • the control takes place as a function of both the currently available amount of H 2 as well as the expected future availability of H 2 , which results from predictions.
  • control of the method within this selected alternative operating mode (1), (2) or (3) is also preferred, wherein this control is preferably also dependent on the current available amount of H 2 is carried out, whereby preferably also a comparison of the currently available amount of H 2 with a fixed threshold value or several fixed threshold values.
  • the introduction preferably takes place according to the alternative operating mode (3), when H2 is available in large quantities.
  • all NH3 synthesis units can be operated at full load, i.e. at maximum throughput, so that the maximum achievable total load of the plant in this operating mode is 100% of its nominal load.
  • all NH 3 Synthesis units can also be operated independently of each other in partial load mode, i.e. at reduced throughput, so that in this mode of operation the total load of the plant can be less than 100% of its nominal load.
  • the introduction preferably takes place according to the alternative operating mode (2), when H2 is available in medium quantities.
  • the plurality of NH3 synthesis units can each be operated in full load operation, i.e. at maximum throughput, in which case the total load of the plant is already less than 100% of its nominal load because at least one of the NH3 synthesis units is switched off.
  • the plurality of NH3 synthesis units can also be operated independently of one another in partial load operation, i.e.
  • the individual NH3 synthesis unit can be operated at full load, i.e. at maximum throughput, in which case the total load of the plant is already less than 100% of its nominal load because the remaining NH3 synthesis units are switched off.
  • the individual NH3 synthesis unit can also be operated at partial load, i.e. at reduced throughput, so that the total load of the plant is reduced even further.
  • a change from one of the alternative operating modes to another of the alternative operating modes takes place during the process according to the invention.
  • This change is preferably made depending on a corresponding change in the availability of H 2
  • the following nine states of NH 3 -synthesis units can be distinguished: (0) into none of the NH 3 -Synthesis units are fed with a reactant gas stream, neither as such nor divided into independent substreams;(1a) The reactant gas stream is introduced as such into a single NH 3 synthesis units, which are operated at reduced throughput (partial load operation); (1b) the reactant gas stream is introduced as such into a single one of the NH 3 -synthesis units, which are operated at maximum throughput (full load operation); (2a) the reactant gas stream is divided into independent partial streams into several, but not all, of the NH3 synthesis units, which are each operated independently of one another at reduced throughput (partial load operation); (2b) the reactant gas stream is divided into independent
  • the subscript suffix "decreases" means that the respective threshold is relevant for the case where the current availability of H 2 is currently decreasing, i.e. the temporal course of the current availability of H 2 has a negative slope.
  • the above-mentioned states are passed through successively, preferably starting from state (1a), but in reverse order.
  • the relevant threshold values determined for this purpose can be quantitatively the same threshold values as for reducing the total load, but they can also be above or below them independently of one another.
  • [17] to [32] starting from a reduced nominal load (e.g. (1a), (2b) or (3a)), the following states are passed through one after the other, wherein a threshold value S rises is preferably defined for the transition from one state to the next state (according to the table above): [17] (3b) -> S rises -> (3c); [18] (1a) -> S rises -> (3b) -> S rises -> (3c); [19] (3a) -> S rises -> (3b) -> S rises -> (3c); [20] (2b) -> S rises -> (3a) -> S rises -> (3b) -> S rises -> (3c); [21] (1a) -> S rises -> (3a) -> S rises -> (3b) -> S rises -> (3c); [22] (2b) -> S rises
  • step (c) the reactant gas stream is introduced into all of the NH3 synthesis units during a first time interval, divided into independent partial streams, so that in all of the NH 3 -Synthesis units each NH 3 is synthesized (alternative mode of operation (3)); and - during a second time interval, which immediately follows the first time interval, divided into independent partial streams into several of the NH 3 -synthesis units, but not in all of the NH 3 -synthesis units, so that NH3 is synthesized in each of the several NH3 synthesis units, but not in all of the NH3 synthesis units (alternative operating mode (2)).
  • the availability of H2 is preferably lower during the second time interval than during the first time interval.
  • the order of the two aforementioned time intervals is exactly reversed.
  • the availability of H2 is preferably greater during the second time interval than during the first time interval.
  • step (c) the reactant gas stream is introduced into all of the NH3 synthesis units during a first time interval, divided into independent substreams, so that NH3 is synthesized in each of the NH3 synthesis units (alternative operating mode (3)); and - during a second time interval, which immediately follows the first time interval, introduced as such into a single one of the NH3 synthesis units, so that NH3 is synthesized only in the single one of the NH3 synthesis units (alternative operating mode (1)).
  • the availability of H2 is preferably lower than during the first time interval.
  • step (c) the reactant gas stream - during a first time interval, is divided into independent substreams into several of the NH 3 -synthesis units, but not in all of the NH 3 -synthesis units are initiated, so that in several of the NH 3 -synthesis units, but not in all of the NH 3 -Synthesis units each NH 3 is synthesized (alternative mode of operation (2)); and - during a second time interval immediately following the first time interval, as such into a single one of the NH 3 -synthesis units are initiated, so that only in the individual NH 3 -synthesis units NH3 is synthesized (alternative operating mode (1)).
  • the availability of H2 is preferably lower than during the first time interval.
  • the order of the two aforementioned time intervals is exactly reversed.
  • the availability of H 2 preferably greater than during the first time interval.
  • the first time interval and the second time interval each independently comprise at least 15 minutes, more preferably at least 30 minutes, even more preferably at least 45 minutes, most preferably at least 1 hour.
  • the first time interval and the second time interval each independently comprise at most 24 hours, more preferably at most 18 hours, even more preferably at most 12 hours, most preferably at most 6 hours.
  • step (c) comprises the substeps: (c1) determining the currently available amount of H2; (c2) comparing the determined currently available amount of H2 with a specified threshold value for the amount of H2 (e.g. threshold value As decreases when the current availability of H2 decreases, or threshold value A increases when the current availability of H2 increases).
  • Determining the currently available amount of H2 in sub-step (c1) preferably comprises determining the currently available amount of H2 as such, and/or determining the currently available amount of electrical power, and/or determining the currently available amount of renewable energy.
  • Forecasts can also be taken into account, for example, forecasts of the day-night cycle, or weather forecasts that predict the expected precipitation, the expected wind, and/or the expected hours of sunshine.
  • the process is then preferably controlled, in particular the division of the reactant gas stream into two or more sub-streams, and the introduction of the reactant gas stream as such or divided into sub-streams into a single one, into several or into all of the NH 3 -synthesis units.
  • step (c) comprises the substep: (c) 3 ) Determine the temporal change in the currently available amount of H 2 , i.e. whether the currently available amount of H 2 just decreases or increases.
  • step (c) the amount of H 2 a threshold B sinks and a threshold value B rises; where - first, the reactant gas flow is divided into independent sub-flows and the sub-flows are introduced into several or all of the NH3 synthesis units; and where, in the event of a decrease in the instantaneous availability of H 2 and falling below threshold B sinks the reactant gas stream as such into a single NH 3 -synthesis units; or - first the reactant gas stream as such is introduced into a single one of the NH 3 -synthesis units is initiated; and in the case of an increase in the instantaneous availability of H 2 and exceeding the threshold value B rises, the reactant gas stream is divided into independent substreams and the substreams are introduced into several or
  • the n NH3 synthesis units can each be throttled independently of one another by reducing the individual throughput (partial load operation), wherein preferably the individual partial load can be continuously reduced to about 30% of the maximum possible throughput (throttling) without the synthesis of NH3 from H2 and N2 coming to a standstill.
  • the individual throughput partial load operation
  • the individual partial load can be continuously reduced to about 30% of the maximum possible throughput (throttling) without the synthesis of NH3 from H2 and N2 coming to a standstill.
  • any reduction in the instantaneous availability of H2 can be compensated by throttling the individual throughput on one, several or all of the n NH3 synthesis units in the range between - the maximum possible total load of the plant (100% of the nominal load of the plant), and - the minimum possible total load of the plant in this operating mode, i.e.
  • a first threshold value for the instantaneous availability of H2 is preferably set for the start of the throughput throttling (transition from state (3c) to state (3b) or state (3a)), preferably the amount of H possible or required for full load operation (100% of the nominal load of the plant).
  • a second threshold value for the instantaneous availability of H2 is preferably set for the transition to the alternative operating mode (2) or to the alternative operating mode (1), preferably the amount of H2 at which, for the alternative operating mode (3), a supply of all NH 3 -synthesis units is possible at throttling (e.g. 30% of the nominal load of the plant).
  • the minimum possible total load of the plant for this example is 30%/n (the only NH 3 -
  • the synthesis unit only contributes 1/n to the maximum possible total load of the plant and is additionally throttled to an individual throughput of, for example, 30% of its maximum possible throughput.
  • the minimum possible total load of the plant for this operating mode is then preferably 10% of its nominal load.
  • the temporary shutdown of at least one NH3 synthesis unit (alternative operating mode (2)) or all but one NH3 synthesis unit (alternative operating mode (1)) is therefore particularly relevant if the current availability of H 2 falls below the second threshold value, up to which, in alternative operating mode (3), all NH 3 -synthesis units is possible when throttling, e.g., 30% of the nominal load of the plant.
  • this aforementioned second threshold value e.g., threshold value Bsinkt
  • the amount of H2 possible or required for full-load operation is limited by the design of the plant, resulting in a maximum value.
  • the synthesis of NH3 from H2 and N2 is exothermic, i.e., the NH3 synthesis units heat up as a result of the synthesis, provided they have not (yet) reached their respective normal operating temperatures, at which the inflow of heat (process heat) as a result of the synthesis and the outflow of heat are in equilibrium.
  • conventional catalysts for the Haber-Bosch process require a minimum temperature (light-off temperature) to be catalytically effective. Once this temperature is reached, synthesis takes place, and the NH3 synthesis unit continues to heat itself.
  • the following temperatures or temperature ranges are distinguished in particular, which are independent for each of the NH3 synthesis units: (i) temperatures below the light-off temperature: if the reactant gas stream or a partial stream thereof is introduced into an NH3 synthesis unit at such temperatures, practically no synthesis of NH3 from H2 and N3 takes place; (ii) light-off temperature: at this temperature, the synthesis of NH3 from H2 and N3 starts and subsequently heats the NH3 synthesis unit as a result of the reaction heat (process heat) formed; typical light-off temperatures can, for example, be in the range of approximately 300-350°C, but also below or above; and (iii) usual operating temperature: at this temperature, at maximum possible throughput (full load operation), the inflow of heat due to the synthesis and the outflow of heat are in equilibrium with each other; Typical operating temperatures can be in the range of approximately 420-500°C, but also lower or higher.
  • the temperatures inside the NH 3 -synthesis units preferably using suitable thermocouples.
  • the temperature is preferably measured at one or more locations (as an average value) which are representative of the thermal state of the respective NH 3 -synthesis facility is meaningful, preferably in the center of the respective NH 3 -Synthesis unit.
  • the respective light-off temperature and usual operating temperature depend on the type and age of the catalyst used and other factors, such as the structure of the NH3 synthesis unit, its insulation, etc., and can be determined for a given NH3 synthesis unit by usual routine tests. Since the NH 3 -synthesis units preferably have essentially the same structure, they preferably also have essentially the same light-off temperature and usual operating temperature.
  • At least one of the NH3 synthesis units is permanently kept at a temperature above its light-off temperature. This prevents the respective temperature in all NH3 synthesis units from simultaneously falling below the respective light-off temperature, which is required for the respective NH 3 -synthesis unit is crucial. Otherwise, it would no longer be possible to synthesize NH without the external supply of heat, e.g., from a heater. 3 from H2 and N2.
  • the process is preferably controlled or regulated such that at any given time at least one of the NH3 synthesis units, preferably several of the NH3 synthesis units independently of one another, more preferably all NH3 synthesis units independently of one another, has or have a temperature above their respective start-up temperature.
  • the appropriate process control in particular the time for the revolving change from one operating state to the next operating state, depends, among other things, on the total number of NH 3 -synthesis units, the relative temperature difference ⁇ T between the operating temperature at full load (T B ) and the light-off temperature (T A ) (i.e.
  • the heating rate at full load operation the heating rate at partial load operation, and the cooling rate.
  • the reactant gas flow is not temporarily completely interrupted, i.e., at any time, the reactant gas flow is either introduced as such into a single NH3 synthesis unit or divided into several substreams and introduced into several or all of the NH3 synthesis units.
  • a preferred system according to the invention is particularly suitable for carrying out such a revolving operation.
  • several NH 3 -synthesis units preferably exactly two NH 3 -synthesis units, more preferably exactly three NH3 synthesis units, are arranged in a common pressure vessel.
  • the plurality of NH3 synthesis units are in heat exchange with one another.
  • the common pressure vessel has a substantially circular cross-sectional area and thus a substantially cylindrical shape.
  • the reactant gas stream can be introduced into the pressure vessel in the axial direction, wherein targeted introduction into a single, several, or all of the NH3 synthesis units is possible.
  • the interior of the common pressure vessel is divided into several cylinder sectors, which preferably have substantially the same shape and size.
  • one of the NH3 synthesis units is arranged in each of the cylinder sectors.
  • the number of cylinder sectors thus preferably corresponds to the number of NH3 synthesis units in the common pressure vessel.
  • the cylinder sectors are preferably delimited by walls which separate the NH3 synthesis units from one another. These walls are preferably substantially gas-tight.
  • the interior of the common pressure vessel is therefore preferably divided into two preferably substantially equal-sized semicircular cylinder halves (cylinder sectors), each of which describes an angle of 180° and which each extend over the entire length of the interior of the common pressure vessel.
  • the boundary between the two semicircular cylinder halves runs as the diameter of the preferably circular cross-sectional area through its center point (cylinder sector with an angle of 180°).
  • the interior of the common pressure vessel is preferably divided into three cylinder thirds (cylinder sectors), each of which preferably has essentially the same size, each defining an angle of 120° and each extending over the entire length of the interior of the common pressure vessel or the cylindrical part of the common pressure vessel.
  • the boundary between the three cylinder thirds runs as Three-pointed star in the circular cross-sectional area through its center (cylindrical sector with an angle of 120°).
  • the interior of the common pressure vessel is therefore preferably divided into four cylinder quarters (cylinder sectors), each of which is preferably essentially the same size, each of which describes an angle of 90° and which each extend over the entire length of the interior of the common pressure vessel or of the cylindrical part of the common pressure vessel.
  • the boundary between the four cylinder quarters runs as a four-pointed star in the circular cross-sectional area through its center (cylinder sector with an angle of 90°).
  • each of the NH 3 -synthesis units are characterized independently of one another by a maximum possible throughput of the reactant gas stream or the partial stream and are operable either at full load or at partial load, wherein the throughput of the reactant gas stream or the partial stream thereof is - undiminished at full load and - reduced at partial load compared to the maximum possible throughput.
  • a threshold value Csinkt and a threshold value Castronom are defined for the amount of H2, wherein - firstly the throughput of the reactant gas stream or the partial stream thereof, which is fed into at least one of the NH3 synthesis units, is undiminished compared to the maximum possible throughput for this at least one of the NH3 synthesis units, so that in step (d) NH3 is synthesized in this at least one of the NH3 synthesis units with undiminished throughput (full load operation); and wherein in the event of a decrease in the instantaneous availability of H2 and falling below the threshold value C, the throughput of the reactant gas stream or the partial stream thereof which is introduced into said at least one of the NH3 synthesis units is reduced compared to the maximum possible throughput for said at least one of the NH3 synthesis units, so that in step (d) NH3 is synthesized in said at least one of the NH3 synthesis units with a reduced through
  • the threshold values C sinks and C rises differently from each other.
  • C sinks > C increases.
  • C sinks ⁇ C rises.
  • this is at least one of the NH3 synthesis units, which switches from full load operation to partial load operation, - the only NH 3 -synthesis unit (alternative mode of operation (1)), or - one of several but not all loaded NH 3 -synthesis units (alternative mode of operation (2)), or - one of all NH 3 -synthesis units (alternative operating mode (3)).
  • the above-mentioned threshold value Csinkt or Csinkt is then preferably decisive for the transition of this at least one of the NH3 synthesis units from full-load operation to partial-load operation, i.e.
  • H2 for the transition of the following states with decreasing instantaneous availability of H2: - in alternative operating mode (1): - (1b) -> Csinkt -> (1a); - in alternative operating mode (2): - (2c) -> Csinkt -> (2b); - (2c) -> Csinkt -> (2a); or - (2b) -> Csinkt -> (2a); - in alternative operating mode (3): - (3c) -> Csinkt -> (3b); - (3c) -> Csinkt -> (3a); or - (3b) -> Csinkt -> (3a).
  • the throughput of the reactant gas stream which is introduced into several of the NH3 synthesis units in a divided manner into independent substreams, is reduced in each case independently of one another compared to the respective maximum possible throughput for the plurality of NH3 synthesis units, so that in step (d) NH3 is synthesized in the plurality of NH3 synthesis units with a reduced throughput (partial load operation).
  • the throughput of the reactant gas stream which is divided into independent Partial flows into all of the NH 3 synthesis units, each independently reduced compared to the maximum possible throughput for all of the NH 3 -synthesis units, so that in step (d) in all NH 3 -Synthesis units with reduced throughput NH 3 is synthesized (partial load operation).
  • a threshold value Dsinkt and a threshold value D defend are defined for the amount of H2; wherein - firstly, the reactant gas stream is divided into independent partial streams in all of the NH 3 synthesis units, so that in step (d) in all of the NH 3 -Synthesis units NH 3 is synthesized; and in the event of a decrease in the current availability of H 2 and falling below the threshold value D sinks the reactant gas flow for at least one of the NH 3 -synthesis units is interrupted, so that in step (d) no NH3 is synthesized in at least one of the NH3 synthesis units; preferably with the proviso that the reactant gas flow is not interrupted simultaneously for all of the NH3 synthesis units, so that in step (d) NH3 is synthesized in at least one of the NH3 synthesis units; or - initially the reactant gas flow is interrupted for at least one of the NH3 synthesis units, so that in step (d)
  • the threshold values D rises, falls and D are different from one another.
  • these aforementioned threshold values D rises and D rises are independently 67 ⁇ 15%, more preferably 67 ⁇ 10%, even more preferably 67 ⁇ 5%, most preferably 67% of the maximum possible amount of H2 for full load operation (100% of the nominal load of the plant).
  • these aforementioned threshold values Dsinkt and D ceremonies are independently 50 ⁇ 15%, more preferably 50 ⁇ 10%, even more preferably 50 ⁇ 5%, most preferably 50% of the maximum possible amount of H for full load operation (100% of the nominal load of the plant). 2 .
  • these above-mentioned threshold values D sinks and D increases independently of each other 20 ⁇ 15%, more preferably 20 ⁇ 10%, even more preferably 20 ⁇ 5%, preferably 20% of the maximum possible amount of H for full load operation (100% of the nominal load of the plant). 2 .
  • step (c) the amount of H 2 a threshold D sinks and a threshold value D rises; wherein - firstly, the reactant gas stream is divided into independent partial streams and passed into all of the NH3 synthesis units, so that in step (d) NH3 is synthesized in all of the NH3 synthesis units; and wherein in the event of a decrease in the instantaneous availability of H 2 and falling below the threshold value D sinks the reactant gas flow for several of the NH 3 -synthesis units is interrupted, so that in step (d) in the plurality of the NH 3 -Synthesis units no NH 3 is synthesized; preferably with the proviso that the reactant gas stream is not simultaneously used for all of the NH 3 -synthesis units is interrupted, so that in step (d) NH3 is synthesized in at least one of the NH3 synthesis units; or - initially the reactant gas flow for several of the NH3 synthesis units is interrupted, so that in step (
  • a threshold value D increases and decreases for the amount of H2; wherein - firstly the reactant gas stream is divided into independent partial streams and passed into all of the NH3 synthesis units, so that in step (d) NH3 is synthesized in all of the NH3 synthesis units; and wherein in the event of a decrease in the instantaneous availability of H2 and the threshold value D decreases, the reactant gas stream as such is introduced into a single one of the NH3 synthesis units, so that in step (d) NH3 is synthesized in the single one of the NH3 synthesis units; and wherein the reactant gas stream is interrupted for all the remaining NH3 synthesis units, so that in step (d) no NH3 is synthesized in any of the remaining NH3 synthesis units; or - initially the feed gas flow is interrupted for all but one of the NH3 synthesis units, so that in step (d) in all but one of the NH 3 -Syn
  • the reactant gas flow for several of the NH 3 -synthesis units are interrupted, so that in step (d) in the several NH 3 -Synthesis units no NH 3 is synthesized; preferably with the proviso that the reactant gas stream is not simultaneously used for all of the NH 3 -synthesis units is interrupted, so that in step (d) NH3 is synthesized in at least one of the NH3 synthesis units.
  • the above-mentioned threshold values e.g.
  • the threshold value e.g.
  • step (d) the reactant gas flow as such into a single one of the NH 3 -synthesis units, so that in step (d) NH3 is synthesized in each of the NH3 synthesis units; and wherein the reactant gas flow for all remaining NH3 synthesis units is interrupted, so that in step (d) no NH3 is synthesized in any of the remaining NH3 synthesis units.
  • the above-mentioned threshold values e.g.
  • the threshold values D decreases and D increases) are then independently of one another 20 ⁇ 15%, more preferably 20 ⁇ 10%, even more preferably 20 ⁇ 5%, most preferably 20% of the maximum possible amount of H2 for full-load operation (100% of the nominal load of the plant).
  • the throughput of the reactant gas stream, which is introduced as such into the individual NH3 synthesis units is reduced compared to the maximum possible throughput for the individual NH3 synthesis units, so that in step (d) NH3 is synthesized in the individual NH3 synthesis units with a reduced throughput (partial load operation).
  • the reactant gas stream for all of the NH3 synthesis units is interrupted, so that in step (d) NH3 is not synthesized in any of the NH3 synthesis units.
  • at least one of the above-mentioned pairs of threshold values e.g.
  • a increases increases increases decreases and A , B decreases and B , C decreases and C , or D increases decreases d D is fixed for the amount of H2 and the control of the method according to the invention is carried out on the basis of these two threshold values, which are preferably each independently of one another (i) 20 ⁇ 15%, more preferably 20 ⁇ 10%, even more preferably 20 ⁇ 5%, most preferably 20%; (ii) 25 ⁇ 15%, more preferably 25 ⁇ 10%, even more preferably 25 ⁇ 5%, most preferably 25%; (iii) 33 ⁇ 15%, more preferably 33 ⁇ 10%, even more preferably 33 ⁇ 5%, most preferably 33%; (iv) 50 ⁇ 15%, more preferably 50 ⁇ 10%, even more preferably 50 ⁇ 5%, most preferably 50%; or (v) 67 ⁇ 15%, more preferably 67 ⁇ 10%, even more preferably 67 ⁇ 5%, most preferably 67% the maximum possible amount of H for full-load operation (100% of the nominal load of the system) 2 [0155] In preferred embodiment
  • the first time interval ends and the second time interval begins as soon as the temperature of the at least one other of the NH3 synthesis units falls below a specified first threshold value; and wherein the second time interval ends and the third time interval begins as soon as the temperature of the at least one other of the NH3 synthesis units exceeds a specified second threshold value.
  • the reactant gas stream as such is introduced into a single one of the NH3 synthesis units, so that in step (d) NH3 is synthesized in the single one of the NH3 synthesis units; wherein the reactant gas stream is interrupted for all the remaining NH3 synthesis units, so that in step (d) no NH3 is synthesized in all the remaining NH3 synthesis units, as a result of which all the remaining NH3 synthesis units cool down; - during a second time interval, which immediately follows the first time interval, process heat is extracted from the single one of the NH 3 -synthesis units in all the other NH 3 -synthesis units, whereby the remaining NH 3 -synthesis units are heated; and - during a third time interval, which immediately follows the second time interval, the reactant gas stream is divided into independent partial streams into the individual NH 3 -synthesis units as well as all other NH 3 -synthesis units are initiated, so that in step (d) in the individual
  • the first time interval ends and the second time interval begins as soon as the temperature of all the remaining NH 3 -synthesis units falls below a specified first threshold value (e.g., a threshold value E); and wherein the second time interval ends and the third time interval begins as soon as the temperature of all the remaining NH3 synthesis units exceeds a specified second threshold value (e.g., a threshold value F).
  • a specified first threshold value e.g., a threshold value E
  • a specified second threshold value e.g., a threshold value F
  • the plurality of parallel-connected NH 3 -Synthesis units operated in a revolving manner.
  • the reactant gas stream is introduced as such into a single one of the NH3 synthesis units, so that in step (d) NH3 is synthesized in the single one of the NH3 synthesis units; wherein the reactant gas stream is interrupted for all the remaining NH3 synthesis units, so that in step (d) no NH3 is synthesized in the all the remaining NH3 synthesis units, as a result of which all the remaining NH3 synthesis units cool down; and - during a second time interval, which immediately follows the first time interval, the reactant gas stream is introduced as such into another single one of the NH3 synthesis units, so that in step (d) NH3 is synthesized in the other single one of the NH3 synthesis units, as a result of which the other single one of the NH3 synthesis units is heated; wherein the reactant gas flow for all remaining NH3 synthesis units is interrupted, so that in step (d) no NH3 is synthesized
  • the reactant gas flow as such is introduced into a further individual one of the NH3 synthesis units, so that in step (d) NH3 is synthesized in the further individual one of the NH3 synthesis units, as a result of which the further individual one of the NH3 synthesis units is heated; wherein the reactant gas flow for all remaining NH3 synthesis units is interrupted, so that in step (d) no NH3 is synthesized in all remaining NH3 synthesis units, as a result of which all remaining NH3 synthesis units cool down.
  • the throughput of the reactant gas stream, which as such is introduced into the individual NH 3 synthesis units is reduced compared to the maximum possible throughput for each of the NH 3 -synthesis units, so that in step (d) in each of the NH 3 -Synthesis units with reduced throughput NH 3 is synthesized (partial load operation); and/or - during the second time interval, the flow rate of the reactant gas stream, which as such is fed into the other individual NH 3 synthesis units is reduced compared to the maximum possible throughput for the other individual NH 3 -synthesis units, so that in step (d) in the other individual of the NH 3 -Synthesis units with reduced throughput NH 3 is synthesized (partial load operation); and/or - if necessary during the third time interval, the throughput of the reactant gas stream, which as such is fed into the further individual NH 3 -synthesis units is reduced compared to the maximum possible throughput for the further individual NH 3
  • the first time interval, the second time interval and optionally the third time interval are selected such that the temperature in none of the NH3 synthesis units falls below the minimum light-off temperature for the synthesis of NH3 from H2 and N2.
  • the NH3 synthesis units are arranged in a common pressure vessel.
  • the NH3 synthesis units are uniformly flowed to by the reactant gas stream as such, separately and one after the other.
  • the NH3 synthesis units are in heat exchange with one another, so that - during the first time interval, a heat flow flows from the individual NH3 synthesis units into one or more of the remaining NH3 synthesis units; and/or - during the second time interval, a heat flow flows from the other individual NH3 synthesis unit into one or more of the remaining NH3 synthesis units; and/or - optionally during the third time interval, a heat flow flows from the further individual NH3 synthesis unit into one or more of the remaining NH3 synthesis units.
  • the plurality of NH3 synthesis units comprise a first NH3 synthesis unit and a second NH3 synthesis unit; wherein - during a first time interval, the reactant gas flow for the first NH3 synthesis unit is interrupted, so that in step (d) no NH3 is synthesized in the first NH3 synthesis unit; and - during a second time interval, which immediately follows the first time interval, the reactant gas flow for the second NH3 synthesis unit is interrupted, so that in step (d) in the second NH 3 -Synthesis unit no NH 3 is synthesized.
  • the reactant gas stream is not simultaneously for all of the NH 3 -synthesis units are interrupted, so that in step (d) in at least one of the NH 3 -Synthesis units NH 3 is synthesized.
  • the reactant gas stream as such or as a partial stream thereof is preferably introduced into the second NH 3 -synthesis unit, so that in step (d) in the second NH 3 - Synthesis unit NH 3 is synthesized.
  • the throughput of the reactant gas stream which is introduced as such or as a partial stream thereof into the second NH3 synthesis unit, is reduced compared to the maximum possible throughput for the second NH3 synthesis unit, so that in the second NH3 synthesis unit with reduced throughput NH 3 is synthesized (partial load operation).
  • the reactant gas stream as such or as a partial stream thereof is fed into the first NH 3 -synthesis unit, so that in step (d) in the first NH 3 -Synthesis unit NH 3 is synthesized.
  • the throughput of the reactant gas stream which is introduced as such or as a partial stream thereof into the first NH3 synthesis unit, is reduced compared to the maximum possible throughput for the first NH3 synthesis unit, so that NH3 is synthesized in the first NH3 synthesis unit with a reduced throughput (partial load operation).
  • the first NH3 synthesis unit cools down during the first time interval; the first time interval ends and the second time interval begins as soon as the temperature of the first NH3 synthesis unit falls below a specified threshold value (e.g., a threshold value G); and - during the second time interval, the reactant gas stream as such or as a partial stream thereof is introduced into the first NH3 synthesis unit, so that in step (d) NH3 is synthesized in the first NH3 synthesis unit and the temperature of the first NH3 synthesis unit rises again.
  • a specified threshold value e.g., a threshold value G
  • the plurality of NH3 synthesis units comprise a first NH3 synthesis unit, a second NH3 synthesis unit, and a third NH3 synthesis unit; and - during a first time interval, the reactant gas stream for the first NH3 synthesis unit is interrupted, so that in step (d) no NH3 is synthesized in the first NH3 synthesis unit; and - during a second time interval, which immediately follows the first time interval, the reactant gas flow for the second NH3 synthesis unit is interrupted, so that in step (d) no NH3 is synthesized in the second NH3 synthesis unit; and - during a third time interval, which immediately follows the second time interval, the reactant gas flow for the third NH3 synthesis unit is interrupted, so that in step (d) no NH3 is synthesized in the third NH 3 -Synthesis unit no NH 3 is synthesized.
  • the reactant gas stream is not simultaneously for all of the NH 3 - Synthesis units are interrupted so that in step (d) in at least one of the NH 3 -Synthesis units NH 3 is synthesized.
  • the reactant gas stream is introduced alternately into an individual one of the NH3 synthesis units so that none of the NH3 synthesis units cools down too much, preferably so that the temperature in none of the NH3 synthesis units falls below the respective start-up temperature.
  • the temperature rises again, whereas in the remaining NH 3 -synthesis units, into which no reactant gas stream is then temporarily introduced, the temperature drops.
  • the change preferably takes place starting from that of the NH3 synthesis units which has the highest temperature at the time of the change to that of the NH3 synthesis units which has the lowest temperature at the time of the change.
  • the NH3 synthesis units are preferably each configured such that the short-term heating rate when the reactant gas flow is introduced is significantly faster than the cooling rate when the reactant gas flow is interrupted.
  • the heating rate is preferably at least twice as fast as the cooling rate, more preferably at least three times as fast.
  • the heating preferably lasts very briefly, typically only a few minutes, after which the temperature preferably remains constant.
  • the reactant gas stream is introduced as such or as a partial stream thereof into the second NH3 synthesis unit, so that NH3 is synthesized in the second NH3 synthesis unit in step (d).
  • the reactant gas stream for the second NH3 synthesis unit is interrupted, so that no NH3 is synthesized in the second NH3 synthesis unit in step (d).
  • the reactant gas stream is introduced as such or as a partial stream thereof into the third NH3 synthesis unit, so that NH3 is synthesized in the third NH3 synthesis unit in step (d).
  • the reactant gas flow for the third NH3 synthesis unit is interrupted, so that in step (d) no NH3 is synthesized in the third NH3 synthesis unit.
  • the reactant gas flow as such or as a partial flow thereof is introduced into the first NH3 synthesis unit, so that in step (d) in the first NH 3 -Synthesis unit NH 3 is synthesized.
  • the reactant gas stream for the first NH 3 -synthesis unit is interrupted, so that in step (d) in the first NH 3 -Synthesis unit no NH 3 is synthesized.
  • the reactant gas stream as such or as a partial stream thereof is introduced into the third NH 3 -synthesis unit, so that in step (d) in the third NH 3 -Synthesis unit NH 3 is synthesized.
  • the reactant gas stream for the third NH 3 -synthesis unit is interrupted, so that in step (d) in the third NH 3 -Synthesis unit no NH 3 is synthesized.
  • the reactant gas stream as such or as a partial stream thereof is introduced into the first NH3 synthesis unit, so that in step (d) NH3 is synthesized in the first NH3 synthesis unit.
  • the reactant gas stream for the first NH 3 -synthesis unit is interrupted, so that in step (d) in the first NH 3 -Synthesis unit no NH 3 is synthesized.
  • the reactant gas stream as such or as a partial stream thereof is introduced into the second NH 3 -synthesis unit, so that in step (d) NH3 is synthesized in the second NH3 synthesis unit.
  • the reactant gas flow for the second NH3 synthesis unit is interrupted, so that in step (d) no NH3 is synthesized in the second NH3 synthesis unit.
  • the reactant gas flow as such is introduced into the third NH3 synthesis unit, so that in step (d) NH3 is synthesized in the third NH3 synthesis unit;
  • the reactant gas flow for the second NH3 synthesis unit and for the third NH3 synthesis unit is interrupted, so that in step (d) no NH3 is synthesized in the second NH3 synthesis unit and in the third NH3 synthesis unit; wherein the reactant gas flow as such is
  • the throughput of the reactant gas stream, which is introduced as such into the third NH 3 synthesis unit is reduced compared to the maximum possible throughput for the third NH 3 -synthesis unit, so that in the third NH 3 -Synthesis unit with reduced throughput NH 3 is synthesized (partial load operation); and/or - during the second time interval, the flow rate of the reactant gas stream, which as such is fed into the first NH 3 synthesis unit is reduced compared to the maximum possible throughput for the first NH 3 -synthesis unit, so that in the first NH 3 -Synthesis unit NH 3 with reduced throughput NH 3 is synthesized (partial load operation); and/or - during the third time interval, the throughput of the reactant gas stream, which is introduced as such into the second NH3 synthesis unit, is reduced compared to the maximum possible throughput for the second NH 3 -synthesis unit, so that in the second NH 3 -Synthesis
  • the first NH 3 -synthesis unit and the second NH 3 -synthesis unit wherein the first time interval ends and the second time interval begins as soon as the temperature of the first NH3 synthesis unit falls below a specified threshold value (e.g.
  • a threshold value H a threshold value H
  • the reactant gas stream as such or as a partial stream thereof is introduced into the first NH3 synthesis unit, so that in step (d) NH3 is synthesized in the first NH3 synthesis unit and the temperature of the first NH3 synthesis unit rises again; wherein during the second time interval, the second NH3 synthesis unit and the third NH3 synthesis unit cool down; and wherein the second time interval ends and the third time interval begins as soon as the temperature of the second NH3 synthesis unit falls below a specified threshold value (e.g.
  • a threshold value I a threshold value I
  • the reactant gas stream as such or as a partial stream thereof is introduced into the second NH3 synthesis unit, so that in step (d) NH3 is synthesized in the second NH3 synthesis unit and the temperature of the second NH3 synthesis unit rises again; wherein during the third time interval, the third NH3 synthesis unit and the first NH3 synthesis unit cool down; and wherein the third time interval ends as soon as the temperature of the third NH3 synthesis unit falls below a specified threshold value (e.g. a threshold value J).
  • a specified threshold value e.g. a threshold value J
  • the above-mentioned threshold value H for the temperature of the first NH3 synthesis unit, the above-mentioned threshold value I for the temperature of the second NH3 synthesis unit and the above-mentioned threshold value J for the temperature of the third NH3 synthesis unit are defined, wherein the control of the method according to the invention is carried out on the basis of these threshold values, and wherein each of these threshold values is preferably each independently of one another by at least 10°C, more preferably by at least 20°C, even more preferably by at least 30°C, most preferably by at least 40°C above the respective light-off temperature of the first, second or third NH 3 -synthesis unit.
  • the first time interval, the second time interval, and the third time interval each independently comprise at least 15 minutes, more preferably at least 30 minutes, even more preferably at least 45 minutes, most preferably at least 1 hour.
  • the first time interval, the second time interval, and the third time interval each independently comprise at most 24 hours, more preferably at most 18 hours, even more preferably at most 12 hours, most preferably at most 6 hours.
  • a further aspect of the invention relates to a plant for the synthesis of NH 3 at variable throughput, the plant comprising: - a device configured to provide H 2 by electrolysis of H 2 O with electrical power from renewable energy; - a device configured to provide a reactant gas stream comprising the H2; preferably in a mixture with N2; - a plurality of NH3 synthesis units connected in parallel, configured to synthesize NH3 from H2 and N2; and - a device configured to introduce the reactant gas stream, depending on the currently available amount of H2 - as such into a single one of the NH3 synthesis units; or - divided into independent partial streams into several of the NH3 synthesis units or into all of the NH3 synthesis units.
  • the plant comprises three NH3 synthesis units connected in parallel, preferably no more than three NH3 synthesis units connected in parallel.
  • the NH3 synthesis units have essentially the same structure.
  • each of the NH3 synthesis units is arranged separately in its own pressure vessel.
  • the NH3 synthesis units are preferably arranged in a common pressure vessel.
  • the NH3 synthesis units are preferably in heat exchange with one another.
  • Each of the NH3 synthesis units preferably contains at least one catalyst bed; preferably, the reactant gas stream can flow axially against the catalyst bed.
  • Each of the NH3 synthesis units preferably contains only a single catalyst bed; preferably, the reactant gas stream can flow axially against the catalyst bed.
  • the plant according to the invention is preferably configured to carry out the process according to the invention described above.
  • Sentence 1 A process for the synthesis of NH 3 with variable throughput on a system comprising several parallel connected NH 3 -synthesis units, the method comprising the steps of: (a) providing H2 by electrolysis of H2O with electrical power from renewable energy; (b) providing a reactant gas stream comprising the H2; (c) introducing the reactant gas stream depending on the currently available amount of H 2 - as such in a single one of the NH 3 -synthesis units; or - divided into independent substreams in several of the NH 3 -synthesis units or in all of the NH 3 -synthesis units, wherein in each of the plurality of NH 3 -synthesis units or in all of the NH 3 -synthesis units, one of the partial streams is introduced independently of one another; and (d) synthesizing NH3 from H2 and N2 in one, in several or in all of the NH3 synthesis units into which
  • Sentence 2 The process according to sentence 1, wherein the plant comprises three NH3 synthesis units connected in parallel; preferably no more than three NH3 synthesis units connected in parallel.
  • Sentence 3 The process according to one of the preceding sentences, wherein the NH3 synthesis units each have essentially the same structure.
  • Sentence 4 The process according to one of the preceding sentences, wherein each of the NH3 synthesis units is arranged separately in its own pressure vessel.
  • Sentence 5 The process according to one of sentences 1 to 3, wherein the NH3 synthesis units are arranged in a common pressure vessel.
  • Sentence 6 The process according to one of the preceding sentences, wherein the NH3 synthesis units are in heat exchange with one another.
  • Sentence 7 The process according to one of the preceding sentences, wherein each of the NH3 synthesis units contains at least one catalyst bed; preferably wherein the reactant gas stream flows axially against the catalyst bed.
  • Sentence 8 The process according to one of the preceding sentences, wherein each of the NH3 synthesis units contains only a single catalyst bed; preferably wherein the reactant gas stream flows axially against the catalyst bed.
  • Sentence 9 The process according to one of the preceding sentences, wherein in step (a) the electrical power is generated from wind power; preferably wherein the currently available amount of H2 depends on the current availability of wind power.
  • Sentence 10 The process according to one of the preceding sentences, wherein in step (a) the electrical power is generated from hydropower; preferably wherein the currently available amount of H 2 depends on the current availability of hydropower.
  • Sentence 11 The method according to any one of the preceding sentences, wherein in step (a) the electrical power is generated from solar energy; preferably wherein the currently available amount of H 2 depends on the current availability of solar energy.
  • Sentence 12 The method according to one of the preceding sentences, wherein step (a) comprises the intermediate storage of electrical power from renewable energy; preferably in an accumulator.
  • Sentence 13 The method according to one of the preceding sentences, wherein step (a) comprises the intermediate storage of H 2 comprises; preferably in a tank.
  • Sentence 14 The process according to any one of the preceding sentences, wherein in step (b) the reactant gas stream is fed at a throughput depending on the currently available amount of H 2
  • Sentence 15 The process according to one of the preceding sentences, wherein the reactant gas stream provided in step (b) comprises N2 in addition to H2; preferably consists essentially of H2 and N2, or preferably comprises H2, N2 and NH3.
  • Sentence 16 The process according to one of the preceding sentences, wherein step (b) comprises compressing the reactant gas stream to elevated pressure, preferably to a pressure of at least 150 bar.
  • Sentence 17 The process according to one of the preceding sentences, wherein step (b) comprises heating the reactant gas stream to elevated temperature, preferably to a temperature of at least 300°C.
  • Sentence 18 The process according to one of the preceding sentences, wherein step (c) comprises the substeps: (c1) determining the currently available amount of H2; (c2) comparing the determined currently available amount of H2 with a specified threshold value for the amount of H2.
  • Sentence 19 The method according to one of the preceding sentences, wherein in step (c) a threshold value Bsinkt and a threshold value Bschreib are specified for the amount of H2; wherein - firstly the reactant gas stream is divided into independent sub-streams and the sub-streams are introduced into several or all of the NH3 synthesis units; and wherein in the event of a decrease in the instantaneous availability of H2 and the threshold value Bsinkt being undershot, the reactant gas stream as such is introduced into a single one of the NH3 synthesis units; or - firstly the reactant gas stream as such is introduced into a single one of the NH3 synthesis units; and wherein in the event of an increase in the instantaneous availability of H2 and the threshold value B is exceeded, the reactant gas stream is divided into independent sub-streams and the sub-streams are introduced into several or all of the NH3 synthesis units.
  • Sentence 20 The process according to one of the preceding sentences, wherein each of the NH3 synthesis units is characterized independently of one another by a maximum possible throughput of the reactant gas stream or the partial stream and is operable either at full load or at partial load, wherein the throughput of the reactant gas stream or the partial stream thereof is - undiminished at full load and - reduced at partial load compared to the maximum possible throughput.
  • Sentence 21 The method according to any one of the preceding sentences, wherein in step (c) the amount of H 2 a threshold value C sinks and a threshold value C rises, where - firstly the throughput of the reactant gas stream or the partial stream thereof, which is fed into at least one of the NH 3 -synthesis units is conducted, is undiminished compared to the maximum possible throughput for this at least one of the NH3 synthesis units, so that in step (d) NH3 is synthesized in this at least one of the NH3 synthesis units with undiminished throughput (full load operation); and wherein in the event of a decrease in the instantaneous availability of H 2 and falling below the threshold C sinks the throughput of the reactant gas stream or the partial stream thereof which is fed into said at least one of the NH 3 - synthesis units is reduced compared to the maximum possible throughput for these at least one of the NH 3 -synthesis units, so that in step (d) NH3 is synthesized in at least one of
  • Sentence 22 The method according to sentence 21, wherein below the threshold values C increases decreases and C the throughput of the reactant gas stream, which is divided into independent partial streams and is introduced into several of the NH3 synthesis units, is each independently reduced compared to the respective maximum possible throughput for the plurality of NH3 synthesis units, so that in step (d) NH3 is synthesized in the plurality of NH3 synthesis units with reduced throughput (partial load operation).
  • Sentence 23 The method according to sentence 21 or 22, wherein below the threshold values C increases decreases and C the throughput of the reactant gas stream, which is divided into independent partial streams and is introduced into all of the NH3 synthesis units, is each independently reduced compared to the respective maximum possible throughput for all of the NH 3 -synthesis units, so that in step (d) in all NH 3 - Synthesis units with reduced throughput NH 3 is synthesized (partial load operation).
  • Sentence 24 The process according to any one of the preceding sentences, wherein in step (c) the amount of H 2 a threshold D sinks and a threshold value D rises; where - first the reactant gas flow is divided into independent partial flows in all of the NH 3 synthesis units, so that in step (d) in all of the NH 3 -Synthesis units NH 3 is synthesized; and in the event of a decrease in the current availability of H 2 and falling below the threshold D sinks the Educt gas stream for at least one of the NH 3 -synthesis units is interrupted, so that in step (d) in the at least one of the NH 3 -Synthesis units no NH 3 is synthesized; preferably with the proviso that the reactant gas stream is not used simultaneously for all of the NH 3 -synthesis units is interrupted, so that in step (d) in at least one of the NH 3 -Synthesis units NH 3 is synthesized; or - initially the reactant gas flow for at least one of the NH
  • Sentence 25 The process according to sentence 24, wherein in step (c) a threshold value for the amount of H2 and a threshold value D rises; wherein - the reactant gas stream is first divided into independent substreams and fed into all of the NH3 synthesis units, so that NH3 is synthesized in all of the NH3 synthesis units in step (d); and wherein, in the event of a decrease in the instantaneous availability of H2 and the threshold value D sinks, the reactant gas stream is interrupted for several of the NH3 synthesis units, so that no NH3 is synthesized in the several of the NH3 synthesis units in step (d); preferably with the proviso that the reactant gas stream is not interrupted simultaneously for all of the NH3 synthesis units, so that NH3 is synthesized in at least one of the NH3 synthesis units in step (d); or - initially the reactant gas flow is interrupted for several of the NH3 synthesis units, so that in step (d) no NH3 is synthesized
  • Sentence 26 The process according to sentence 24 or 25, wherein - firstly the reactant gas stream is divided into independent partial streams and passed into all of the NH3 synthesis units, so that in step (d) in all of the NH 3 -Synthesis units NH 3 is synthesized; and in the event of a decrease in the current availability of H 2 and falling below the threshold D sinks the reactant gas stream as such into a single one of the NH 3 -synthesis units is introduced, so that in step (d) in the individual NH 3 - Synthesis units NH 3 is synthesized; and wherein the reactant gas flow for all other NH 3 -synthesis units is interrupted, so that in step (d) in all the remaining NH 3 -Synthesis units no NH 3 is synthesized; or - first the reactant gas stream for all but one of the NH 3 -synthesis units is interrupted, so that in step (d) in all but one of the NH 3 -Synthesis units no NH 3 is synthesized; and in
  • Sentence 27 The process according to sentence 26, wherein the throughput of the reactant gas stream, which is introduced as such into the individual NH3 synthesis units, is reduced compared to the maximum possible throughput for the individual NH 3 -synthesis units, so that in step (d) in each of the NH 3 -Synthesis units with reduced throughput NH 3 is synthesized (partial load operation).
  • Sentence 28 The method according to one of the sentences 24 to 27, where below the threshold values D sinks and Dthe reactant gas flow increases for all of the NH 3 -synthesis units is interrupted, so that in step (d) no NH3 is synthesized in any of the NH3 synthesis units.
  • Sentence 29 The process according to one of the preceding sentences, wherein - during a first time interval the reactant gas stream as such or as a partial stream thereof is introduced into at least one of the NH3 synthesis units, so that in step (d) NH3 is synthesized in the at least one of the NH3 synthesis units; wherein the reactant gas stream for at least one other of the NH3 synthesis units is interrupted, so that in step (d) no NH3 is synthesized in the at least one other of the NH3 synthesis units, whereby the at least one other of the NH3 synthesis units cools down; - during a second time interval, which immediately follows the first time interval, process heat is transferred from the at least one of the NH3 synthesis units to the at least one other of the NH3 synthesis units, whereby the at least one other of the NH3 synthesis units is heated; and - during a third time interval, which immediately follows the second time interval, the reactant gas stream is divided into independent partial streams and introduced into the
  • Sentence 30 The method according to sentence 29, wherein the first time interval ends and the second time interval begins as soon as the temperature of the at least one other of the NH3 synthesis units falls below a specified first threshold value; and wherein the second time interval ends and the third time interval begins as soon as the temperature of the at least one other of the NH3 synthesis units exceeds a specified second threshold value.
  • Sentence 31 The method according to one of the preceding sentences, wherein - during a first time interval, the reactant gas stream as such is introduced into a single one of the NH 3 -synthesis units is introduced, so that in step (d) in the individual NH 3 -Synthesis units NH 3 is synthesized; the reactant gas flow for all other NH 3 -synthesis units is interrupted, so that in step (d) in all the remaining NH 3 -Synthesis units no NH 3 is synthesized, whereby the remaining NH 3 -synthesis units cool down; - during a second time interval immediately following the first Time interval follows, process heat from the individual NH 3 -synthesis units in the remaining NH 3 -synthesis units, whereby the remaining NH 3 -synthesis units are heated; and - during a third time interval, which immediately follows the second time interval, the reactant gas stream is divided into independent partial streams into the individual NH 3 -synthesis units as well as into all the remaining NH3 synthesis units, so that in step (d
  • Sentence 32 The method according to Sentence 31, wherein the first time interval ends and the second time interval begins as soon as the temperature of all the remaining NH 3 -synthesis units falls below a specified first threshold value; and wherein the second time interval ends and the third time interval begins as soon as the temperature of all the remaining NH3 synthesis units exceeds a specified second threshold value.
  • Sentence 33 The method according to one of the preceding sentences, wherein the plurality of NH3 synthesis units connected in parallel are operated in a revolving manner.
  • Sentence 34 The method according to one of the preceding sentences, wherein - during a first time interval, the reactant gas stream as such is introduced into a single one of the NH3 synthesis units, so that in step (d) NH3 is synthesized in the single one of the NH3 synthesis units; wherein the reactant gas stream for all the remaining NH3 synthesis units is interrupted, so that in step (d) no NH3 is synthesized in all the remaining NH3 synthesis units, as a result of which all the remaining NH3 synthesis units cool down; - during a second time interval, which immediately follows the first time interval, the reactant gas flow as such is introduced into another individual one of the NH3 synthesis units, so that in step (d) NH3 is synthesized in the other individual one of the NH3 synthesis units, whereby the other individual one of the NH3 synthesis units is heated; wherein the reactant gas flow for all the remaining NH3 synthesis units is interrupted, so that in step (d) no NH
  • Sentence 35 The process according to sentence 34, wherein - during a third time interval, which immediately follows the second time interval, the reactant gas stream as such is introduced into a further individual one of the NH3 synthesis units, so that in step (d) NH3 is synthesized in the further individual one of the NH3 synthesis units, whereby the further individual one of the NH3 synthesis units is heated; wherein the reactant gas stream for all remaining NH 3 -synthesis units is interrupted, so that in step (d) in all the remaining NH 3 -Synthesis units no NH 3 is synthesized, whereby the remaining NH 3 -synthesis units.
  • Sentence 36 The process according to one of the sentences 33 to 35, wherein - during the first time interval, the throughput of the reactant gas stream, which as such is fed into the individual NH 3 -synthesis units is reduced compared to the maximum possible throughput for the individual NH 3 - Synthesis units, so that in step (d) in each of the NH 3 -Synthesis units with reduced throughput NH 3 is synthesized (partial load operation); and/or - during the second time interval, the throughput of the reactant gas stream, which as such is fed into the other individual NH 3 -synthesis units is reduced compared to the maximum possible throughput for the other individual NH3 synthesis units, so that in step (d) NH3 is synthesized in the other individual NH3 synthesis units with reduced throughput (partial load operation); and/or - if appropriate during the third time interval, the throughput of the reactant gas stream, which as such is introduced into the further individual NH 3 -synthesis units is reduced compared to the maximum possible throughput for
  • Clause 37 The process according to any one of clauses 33 to 36, wherein the first time interval, the second time interval and optionally the third time interval are selected such that the temperature in none of the NH3 synthesis units falls below the minimum light-off temperature for the synthesis of NH3 from H2 and N2.
  • Clause 38 The process according to any one of clauses 33 to 37, wherein the NH3 synthesis units are arranged in a common pressure vessel.
  • Clause 39 The process according to clause 38, wherein the NH3 synthesis units are uniformly supplied with the reactant gas stream as such, separately and one after the other.
  • Sentence 40 The method according to one of sentences 33 to 39, wherein the NH3 synthesis units are in heat exchange with one another, so that - during the first time interval, a heat flow flows from the individual NH3 synthesis units into one or more of the remaining NH3 synthesis units; and/or - during the second time interval, a heat flow flows from the other individual NH3 synthesis units into one or more of the remaining NH3 synthesis units; and/or - optionally during the third time interval, a heat flow flows from the further individual NH3 synthesis units into one or more of the remaining NH3 synthesis units.
  • Sentence 41 The method according to one of the preceding sentences, wherein the plurality of NH3 synthesis units comprise a first NH3 synthesis unit and a second NH3 synthesis unit; and wherein - during a first time interval, the reactant gas flow for the first NH3 synthesis unit is interrupted, so that in step (d) no NH3 is synthesized in the first NH3 synthesis unit; and - during a second time interval, which immediately follows the first time interval, the reactant gas flow for the second NH 3 -synthesis unit is interrupted, so that in step (d) in the second NH 3 -Synthesis unit no NH 3 is synthesized.
  • Theorem 42 The process according to theorem 41, wherein during the first time interval and during the second time interval the reactant gas flow is not simultaneously for all of the NH 3 -synthesis units is interrupted, so that in step (d) in at least one of the NH 3 -Synthesis units NH 3 is synthesized.
  • Sentence 43 The process according to sentence 41 or 42, wherein during the first time interval the reactant gas stream as such or as a partial stream thereof is introduced into the second NH 3 -synthesis unit is introduced, so that in step (d) in the second NH 3 -Synthesis unit NH 3 is synthesized.
  • Sentence 44 The process according to sentence 43, wherein the throughput of the reactant gas stream, which is introduced as such or as a partial stream thereof into the second NH3 synthesis unit, is reduced in comparison to the maximum possible throughput for the second NH3 synthesis unit, so that in the second NH 3 -Synthesis unit with reduced throughput NH 3 is synthesized (partial load operation).
  • Clause 45 The process according to any one of clauses 41 to 44, wherein during the second time interval the reactant gas stream as such or as a partial stream thereof is introduced into the first NH 3 -synthesis unit is introduced, so that in step (d) in the first NH 3 -Synthesis unit NH 3 is synthesized.
  • Sentence 46 The method according to sentence 45, wherein the throughput of the reactant gas stream, which is introduced as such or as a partial stream thereof into the first NH3 synthesis unit, is reduced compared to the maximum possible throughput for the first NH3 synthesis unit, so that NH3 is synthesized in the first NH3 synthesis unit with a reduced throughput (partial load operation).
  • Sentence 47 The method according to one of sentences 41 to 46, wherein - during the first time interval, the first NH3 synthesis unit cools down; wherein the first time interval ends and the second time interval begins as soon as the temperature of the first NH3 synthesis unit falls below a specified threshold value; and - wherein during the second time interval, the reactant gas stream as such or as a partial stream thereof is introduced into the first NH3 synthesis unit, so that in step (d) NH3 is synthesized in the first NH3 synthesis unit and the temperature of the first NH3 synthesis unit rises again.
  • Sentence 48 The method according to one of the preceding sentences, wherein the plurality of NH3 synthesis units comprise a first NH3 synthesis unit, a second NH3 synthesis unit, and a third NH3 synthesis unit; and wherein - during a first time interval, the reactant gas stream for the first NH3 synthesis unit is interrupted, so that in step (d) no NH3 is synthesized in the first NH3 synthesis unit; and - during a second time interval, which immediately follows the first time interval, the reactant gas flow for the second NH3 synthesis unit is interrupted, so that in step (d) no NH3 is synthesized in the second NH3 synthesis unit; and - during a third time interval, which immediately follows the second time interval, the reactant gas flow for the third NH3 synthesis unit is interrupted, so that in step (d) no NH 3 is synthesized.
  • Theorem 49 The process according to theorem 48, wherein during the first time interval, during the second time interval and during the third time interval the reactant gas flow is not simultaneously for all of the NH 3 -synthesis units is interrupted, so that in step (d) in at least one of the NH 3 -Synthesis units NH 3 is synthesized.
  • Sentence 50 The process according to sentence 48 or 49, wherein during the first time interval the reactant gas stream as such or as a partial stream thereof is introduced into the second NH 3 -synthesis unit is introduced, so that in step (d) in the second NH 3 -Synthesis unit NH 3 is synthesized.
  • Sentence 51 The process according to sentence 49 or 49, wherein during the first time interval the reactant gas stream for the second NH3 synthesis unit is interrupted, so that in step (d) no NH3 is synthesized in the second NH3 synthesis unit.
  • Sentence 52 The process according to one of sentences 48 to 51, wherein during the first time interval the reactant gas stream as such or as a partial stream thereof is fed into the third NH 3 -synthesis unit is initiated, so that in step (d) in the third NH 3 -Synthesis unit NH 3 is synthesized.
  • Sentence 53 The method according to any one of sentences 48 to 51, wherein during the first time interval the reactant gas flow for the third NH3 synthesis unit is interrupted, so that in step (d) no NH3 is synthesized in the third NH3 synthesis unit.
  • Sentence 54 The method according to any one of sentences 48 to 53, wherein during the second time interval the reactant gas flow as such or as a partial flow thereof is introduced into the first NH3 synthesis unit, so that in step (d) NH3 is synthesized in the first NH3 synthesis unit.
  • Sentence 55 The method according to any one of sentences 48 to 53, wherein during the second time interval the reactant gas flow for the first NH3 synthesis unit is interrupted, so that in step (d) no NH3 is synthesized in the first NH3 synthesis unit.
  • Sentence 56 The process according to any one of sentences 48 to 55, wherein during the second time interval the reactant gas stream is introduced as such or as a partial stream thereof into the third NH3 synthesis unit, so that NH3 is synthesized in the third NH3 synthesis unit in step (d).
  • Sentence 57 The process according to any one of sentences 48 to 55, wherein during the second time interval the reactant gas stream for the third NH3 synthesis unit is interrupted, so that no NH3 is synthesized in the third NH3 synthesis unit in step (d).
  • Sentence 58 The process according to any one of sentences 48 to 57, wherein during the third time interval the reactant gas stream is introduced as such or as a partial stream thereof into the first NH3 synthesis unit, so that NH3 is synthesized in the first NH3 synthesis unit in step (d).
  • Sentence 59 The process according to any one of Sentences 48 to 57, wherein during the third time interval the reactant gas flow for the first NH3 synthesis unit is interrupted, so that in step (d) no NH3 is synthesized in the first NH3 synthesis unit.
  • Sentence 60 The process according to any one of Sentences 48 to 59, wherein during the third time interval the reactant gas flow as such or as a partial flow thereof is fed into the second NH 3 -synthesis unit is introduced, so that in step (d) in the second NH 3 -Synthesis unit NH 3 is synthesized.
  • Sentence 61 The process according to any one of sentences 48 to 59, wherein during the third time interval the reactant gas flow for the second NH 3 -synthesis unit is interrupted, so that in step (d) in the second NH 3 -Synthesis unit no NH 3 is synthesized.
  • Sentence 62 The process according to one of sentences 48 to 61, wherein - during the first time interval, the reactant gas flow for the first NH3 synthesis unit and for the second NH3 synthesis unit is interrupted in each case, so that in step (d) in the first NH3 synthesis unit and in the second NH3 synthesis unit no NH 3 is synthesized; and wherein the reactant gas stream as such is introduced into the third NH 3 - synthesis unit is initiated, so that in the third NH 3 -Synthesis unit NH 3 is synthesized; - during the second time interval, the reactant gas flow for the second NH 3 -synthesis unit and for the third NH 3 -synthesis unit is interrupted in each case, so that in step (d) in the second NH 3 -synthesis unit and in the third NH3 synthesis unit, no NH3 is synthesized; and wherein the reactant gas stream as such is introduced into the first NH3 synthesis unit, so that NH3 is synthesized in the first NH
  • Sentence 63 The method according to sentence 62, wherein - during the first time interval, the throughput of the reactant gas stream, which is introduced as such into the third NH3 synthesis unit, is reduced compared to the maximum possible throughput for the third NH3 synthesis unit, so that NH3 is synthesized in the third NH3 synthesis unit with a reduced throughput (partial load operation); and/or - during the second time interval, the throughput of the reactant gas stream, which is introduced as such into the first NH3 synthesis unit, is reduced compared to the maximum possible throughput for the first NH3 synthesis unit, so that NH3 is synthesized in the first NH3 synthesis unit with a reduced throughput (partial load operation); and/or - during the third time interval, the throughput of the reactant gas stream, which is introduced as such into the second NH3 synthesis unit, is reduced compared to the maximum possible throughput for the second NH3 synthesis unit, so that NH3 is synthesized in the second NH
  • Clause 64 The method according to clause 62 or 63, wherein - during the first time interval, the first NH3 synthesis unit and the second NH 3 -synthesis unit; the first time interval ends and the second time interval begins as soon as the temperature of the first NH 3 -synthesis unit falls below a specified threshold; - during the second time interval, the reactant gas stream as such or as a partial stream thereof into the first NH 3 -synthesis unit is introduced, so that in step (d) in the first NH 3 -Synthesis unit NH 3 is synthesized and the temperature of the first NH 3 -synthesis unit increases again; during the second time interval the second NH 3 -synthesis unit and the third NH 3 -synthesis unit; and wherein the second time interval ends and the third time interval begins as soon as the temperature of the second NH 3 -synthesis unit falls below a specified threshold; and - during the third time interval, the reactant gas stream as such or as a partial stream thereof into the second NH 3 -synthesis unit is introduced, so that in
  • Sentence 65 A plant for the synthesis of NH 3 at variable throughput, the plant comprising: - a device configured to provide H 2 by electrolysis of H 2 O with electrical power from renewable energy; - a device configured to provide a reactant gas stream comprising the H2; - a plurality of NH3 synthesis units connected in parallel, configured to synthesize NH3 from H2 and N2; and - a device configured to introduce the reactant gas stream, depending on the currently available amount of H2, - as such into a single one of the NH3 synthesis units; or - divided into independent partial streams into several of the NH3 synthesis units or into all of the NH3 synthesis units.
  • Sentence 66 The plant according to sentence 65, which comprises three NH3 synthesis units connected in parallel.
  • Sentence 67 The plant according to sentence 65 or 66, wherein the NH3 synthesis units have essentially the same structure.
  • Sentence 68 The plant according to one of sentences 65 to 67, wherein each of the NH3 synthesis units is arranged separately in its own pressure vessel.
  • Sentence 69 The plant according to one of sentences 65 to 68, wherein the NH3 synthesis units are arranged in a common pressure vessel.
  • Sentence 70 The plant according to one of sentences 65 to 69, wherein the NH3 synthesis units are in heat exchange with one another.
  • Sentence 71 The plant according to one of sentences 65 to 70, wherein each of the NH3 synthesis units contains at least one catalyst bed; preferably wherein the reactant gas stream can flow axially against the catalyst bed.
  • Sentence 72 The plant according to one of sentences 65 to 71, wherein each of the NH3 synthesis units contains only a single catalyst bed; preferably wherein the reactant gas stream can flow axially against the catalyst bed.
  • Sentence 73 The installation according to one of the sentences 65 to 72, where several NH 3 -synthesis units, preferably exactly two NH 3 -synthesis units, preferably exactly three NH 3 -synthesis units, arranged in a common pressure vessel; preferably the plurality of NH 3 -Synthesis units exchange heat with each other.
  • Sentence 74 The system according to sentence 73, wherein the common pressure vessel has a substantially circular cross-sectional area and thus a substantially cylindrical shape.
  • Sentence 75 The system according to sentence 73 or 74, wherein the reactant gas flow can be introduced into the pressure vessel in the axial direction; preferably, wherein targeted introduction into a single, several, or all of the NH3 synthesis units is possible.
  • Sentence 76 The system according to one of sentences 73 to 75, wherein the interior of the common pressure vessel is divided into several cylinder sectors, which preferably have substantially the same shape and size.
  • Sentence 77 The system according to sentence 76, wherein in each of the cylinder sectors, one of the NH 3 -synthesis units; preferably wherein the number of cylinder sectors corresponds to the number of NH 3 -synthesis units in the common pressure vessel.
  • Sentence 78 The system according to sentence 76 or 77, wherein the cylinder sectors are delimited by walls which separate the NH3 synthesis units from one another.
  • Sentence 79 The system according to sentence 78, wherein the walls are essentially gas-tight.
  • Sentence 80 The system according to sentence 78 or 79, wherein heat can flow through the walls from one NH3 synthesis unit into an adjacent NH3 synthesis unit.
  • Sentence 81 The system according to one of sentences 65 to 80, which is configured to carry out the method according to one of sentences 1 to 64.
  • Preferred embodiments are explained in more detail below with reference to Figures 1, 2 and 3. However, these explanations are not to be interpreted as restrictive.
  • Figure 1 schematically shows a preferred embodiment of a plant according to the invention with a device (1) which is configured to introduce the reactant gas stream (H2 + N2) depending on the currently available amount of H2.
  • the reactant gas stream can be introduced as such or as a partial stream thereof via a first line (2) into a first NH3 synthesis unit (3), in which, in the case of such introduction, the synthesis of NH3 from H2 and N2 takes place on a suitable catalyst.
  • the reactant gas stream can be introduced as such or as a partial stream thereof alternatively or additionally via a second line (4) into a second NH3 synthesis unit (5), in which, in the case of such introduction, the synthesis of NH3 from H2 and N2 takes place on a suitable catalyst.
  • Figure 2 schematically shows a preferred development of the embodiment according to Figure 1, wherein the first NH 3 -synthesis unit (3), the second NH 3 -synthesis unit (5) and the third NH 3 -synthesis unit (7) are also connected in parallel, but unlike Figure 1, are arranged in a common pressure vessel.
  • Figure 2A shows a perspective view
  • Figure 2B a top view.
  • the first NH3 synthesis unit (3), the second NH3 synthesis unit (5) and the third NH3 synthesis unit (7) are preferably in heat exchange with each other.
  • FIG. 3 schematically shows another preferred embodiment of a plant according to the invention with a first NH3 synthesis unit (3), a second NH3 synthesis unit (5) and a third NH3 synthesis unit (7), which are connected in parallel.
  • the reactant gas stream is introduced as such into the NH3 synthesis unit (5).
  • the heat generated in the NH3 synthesis unit (5) can be used to heat the other two NH3 synthesis units (3) and (7), which would otherwise cool down.
  • the gas mixture leaving the NH3 synthesis unit (5) can be recirculated, optionally as a partial stream, via the valves (13a-c) and (14a-c) into the NH3 synthesis units (3) and (7), to which no reactant gas stream is currently being supplied.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
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  • Metallurgy (AREA)
  • Automation & Control Theory (AREA)
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Abstract

L'invention concerne un procédé de synthèse de NH3 à débit variable sur un système présentant plusieurs unités de synthèse connectées en parallèle. Un flux de gaz réactif comprend du H2 qui est fourni par électrolyse de l'eau avec un courant électrique à partir d'une énergie renouvelable. La quantité actuellement disponible de H2 varie sur la base de la quantité actuellement disponible d'énergie renouvelable. Sur la base de la quantité actuellement disponible de H2 en tant que telle, le flux de gaz réactif est introduit dans une unité de synthèse individuelle des unités de synthèse ou dans une pluralité d'unités de synthèse ou dans toutes les unités de synthèse de manière divisée dans des sous-flux indépendants, NH3 étant ensuite synthétisé à partir de H2 et N2 dans ladite ou lesdites unités de synthèse. L'invention concerne en outre un système qui est configuré pour mettre en œuvre ledit procédé.
PCT/EP2024/077390 2023-10-04 2024-09-27 Synthèse d'ammoniac vert à débit variable Pending WO2025073609A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102023126893.7 2023-10-04
LULU103199 2023-10-04
DE102023126893.7A DE102023126893A1 (de) 2023-10-04 2023-10-04 Synthese von grünem Ammoniak bei variablem Durchsatz
LU103199A LU103199B1 (de) 2023-10-04 2023-10-04 Synthese von grünem Ammoniak bei variablem Durchsatz

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7892511B2 (en) 2004-07-02 2011-02-22 Kellogg Brown & Root Llc Pseudoisothermal ammonia process
EP2589574A1 (fr) 2011-11-02 2013-05-08 Ammonia Casale S.A. Procédé pour la régulation de charge d'une installation de fabrication d'ammoniac
WO2017153304A1 (fr) 2016-03-08 2017-09-14 Thyssenkrupp Industrial Solutions Ag Procédé et installation pour la production d'un produit gazeux sous des conditions de charge variables
WO2021060985A1 (fr) 2019-09-26 2021-04-01 Technische Universiteit Delft Production périodique d'ammoniac
EP3819261A1 (fr) * 2019-11-08 2021-05-12 Casale Sa Contrôle d'une boucle de synthèse d'ammoniac à charge partielle
WO2021151672A1 (fr) 2020-01-27 2021-08-05 Thyssenkrupp Industrial Solutions Ag Procédé de synthèse d'ammoniac et installation pour préparation d'ammoniac
WO2022173794A1 (fr) 2021-02-10 2022-08-18 Icarus Technology Llc Production d'ammoniac renouvelable
US20220388855A1 (en) * 2021-06-07 2022-12-08 FuelPositive Corporation Modular, transportable clean hydrogen-ammonia maker
WO2023006291A1 (fr) 2021-07-30 2023-02-02 Casale Sa Procédé intégré pour la synthèse d'ammoniac et d'acide nitrique
EP4148020A1 (fr) * 2021-09-13 2023-03-15 Casale Sa Procédé de commande d'une installation de production d'ammoniac

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7892511B2 (en) 2004-07-02 2011-02-22 Kellogg Brown & Root Llc Pseudoisothermal ammonia process
EP2589574A1 (fr) 2011-11-02 2013-05-08 Ammonia Casale S.A. Procédé pour la régulation de charge d'une installation de fabrication d'ammoniac
WO2017153304A1 (fr) 2016-03-08 2017-09-14 Thyssenkrupp Industrial Solutions Ag Procédé et installation pour la production d'un produit gazeux sous des conditions de charge variables
WO2021060985A1 (fr) 2019-09-26 2021-04-01 Technische Universiteit Delft Production périodique d'ammoniac
EP3819261A1 (fr) * 2019-11-08 2021-05-12 Casale Sa Contrôle d'une boucle de synthèse d'ammoniac à charge partielle
WO2021089276A1 (fr) 2019-11-08 2021-05-14 Casale Sa Contrôle d'une boucle de synthèse d'ammoniac à charge partielle
WO2021151672A1 (fr) 2020-01-27 2021-08-05 Thyssenkrupp Industrial Solutions Ag Procédé de synthèse d'ammoniac et installation pour préparation d'ammoniac
WO2022173794A1 (fr) 2021-02-10 2022-08-18 Icarus Technology Llc Production d'ammoniac renouvelable
US20220388855A1 (en) * 2021-06-07 2022-12-08 FuelPositive Corporation Modular, transportable clean hydrogen-ammonia maker
WO2022256907A1 (fr) 2021-06-07 2022-12-15 FuelPositive Corporation Dispositif de fabrication d'hydrogène-ammoniac modulaire, transportable et propre
WO2023006291A1 (fr) 2021-07-30 2023-02-02 Casale Sa Procédé intégré pour la synthèse d'ammoniac et d'acide nitrique
EP4148020A1 (fr) * 2021-09-13 2023-03-15 Casale Sa Procédé de commande d'une installation de production d'ammoniac
WO2023036560A1 (fr) 2021-09-13 2023-03-16 Casale Sa Méthode de contrôle d'une installation d'ammoniac

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