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WO2024256205A1 - Procédé et système de synthèse de méthanol - Google Patents

Procédé et système de synthèse de méthanol Download PDF

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Publication number
WO2024256205A1
WO2024256205A1 PCT/EP2024/065221 EP2024065221W WO2024256205A1 WO 2024256205 A1 WO2024256205 A1 WO 2024256205A1 EP 2024065221 W EP2024065221 W EP 2024065221W WO 2024256205 A1 WO2024256205 A1 WO 2024256205A1
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Prior art keywords
stream
reactor
hydrogen
methanol
arrangement
Prior art date
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PCT/EP2024/065221
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German (de)
English (en)
Inventor
Alexander Schulz
Beata Banik
Jonas Moritz AMBROSY
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
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Filing date
Publication date
Priority claimed from DE102023115491.5A external-priority patent/DE102023115491A1/de
Priority claimed from LU103148A external-priority patent/LU103148B1/de
Application filed by ThyssenKrupp AG, ThyssenKrupp Uhde GmbH filed Critical ThyssenKrupp AG
Publication of WO2024256205A1 publication Critical patent/WO2024256205A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C01B2203/1264—Catalytic pre-treatment of the feed
    • C01B2203/127—Catalytic desulfurisation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas

Definitions

  • the invention relates to a process for the synthesis of methanol according to the preamble of claim 1 and a plant for the synthesis of methanol according to the preamble of claim 21.
  • Methanol is an important basic chemical that is used for the synthesis of higher or functionalized hydrocarbon compounds and as a solvent. Methanol is used, for example, as a starting material for the production of formaldehyde, formic acid and acetic acid.
  • Methanol is usually produced in a reactor arrangement in a plant for the synthesis of methanol (methanol reactor arrangement), to which a synthesis gas stream containing hydrogen and carbon oxides is fed and in which an (exothermic) chemical reaction takes place to produce methanol.
  • Synthesis gas can be produced in a synthesis gas reactor arrangement that is upstream of the methanol reactor arrangement.
  • Carbon-containing gases i.e. carbon-containing energy sources
  • Such carbon-containing energy sources often contain methane.
  • the synthesis gas reactor arrangement and the methanol reactor arrangement can together form a plant for the synthesis of methanol.
  • the synthesis gas reactor arrangement mentioned can be based on the principle of autothermal reforming or partial oxidation and can comprise corresponding reactors (e.g. a reforming reactor or oxidation reactor).
  • the synthesis gas reactor arrangement can also comprise a steam reformer.
  • the use of a steam reformer can be advantageous when adding CO2 or using a CO2-rich carbon-containing energy source such as biogas. This is generally known from the prior art.
  • the proportion of hydrogen in the synthesis gas stream obtained can be lower than is actually desired.
  • the proportion of hydrogen can be substoichiometric.
  • Such a hydrogen-rich stream returned to the reactor arrangement can compensate to a certain extent for the hydrogen deficiency mentioned and caused by the substoichiometry.
  • a hydrogen deficit during the synthesis of methanol can be (at least partially) compensated by adding external hydrogen.
  • the external hydrogen can come from fossil sources or be generated renewably and added to the synthesis gas stream.
  • purge gas is produced, which must be removed from the synthesis or recovery circuit in order to avoid excessive accumulation of inert components such as nitrogen and methane.
  • Such purge gas is usually burned off as fuel gas. To ensure a satisfactory ecological balance of such synthesis plants, it is desirable to keep the amount of purge or fuel gas produced as low as possible.
  • the invention is based on the object of providing a method and a plant for the synthesis of methanol, with which on the one hand a substoichiometric presence of hydrogen can be compensated and on the other hand the proportion of purge or fuel gas produced can be reduced.
  • a particular object of the invention is therefore on the one hand to increase the efficiency or yield in methanol synthesis and on the other hand to improve the environmental friendliness or ecological balance. This object is achieved by a method having the features of claim 1 and a system having the features of claim 21.
  • the invention relates to a process for the synthesis of methanol, wherein a carbon-containing energy carrier stream is fed to a synthesis gas reactor arrangement for obtaining a synthesis gas stream containing hydrogen and carbon oxides.
  • the synthesis gas stream can be fed to a synthesis gas compressor for increasing the pressure.
  • the synthesis gas stream is fed at least partially to a first reactor stage of a methanol reactor arrangement for at least partial conversion into methanol, wherein optionally unreacted residual gas from the first reactor stage is then fed to a second reactor stage of the methanol reactor arrangement for at least partial conversion into methanol, wherein a residual gas stream with unreacted carbon oxides is obtained from the methanol reactor arrangement, which residual gas stream is fed to a recycle compressor for increasing the pressure of the residual gas stream, wherein the pressure-increased residual gas stream is fed to the methanol reactor arrangement for at least partial conversion into methanol, wherein optionally a recovery stream comprising unreacted residual gas from the first and/or second reactor stage is fed to a hydrogen recovery arrangement for obtaining an H recycle stream, which H recycle stream contains unreacted hydrogen from the unreacted residual gas from the first reactor stage and/or from the unreacted residual gas from the second reactor stage wherein the unreacted hydrogen of the H recycle
  • the method is characterized in that a hydrogen stream with external hydrogen is fed to one of the streams upstream or downstream of the synthesis gas reactor arrangement, and that part of the residual gas stream, and/or the optional recovery stream, and/or a stream downstream of the hydrogen recovery arrangement is branched off and fed to the synthesis gas reactor arrangement as a recycle stream.
  • An embodiment may be preferred in which the water stream with external hydrogen is fed to the synthesis gas stream (downstream of the synthesis gas reactor arrangement).
  • the proposed process is used to synthesize methanol.
  • a carbon-containing energy carrier stream is fed to a synthesis gas reactor arrangement to obtain a synthesis gas stream with hydrogen and carbon oxides.
  • the synthesis gas stream therefore contains hydrogen, carbon monoxide and carbon dioxide and can also contain other components such as nitrogen and noble gases.
  • the synthesis gas stream can also be referred to as a fresh gas stream.
  • the synthesis gas stream can be fed to a synthesis gas compressor to increase the pressure.
  • the synthesis gas compressor referred to can be designed with one or more stages.
  • the (optionally pressure-increased) synthesis gas stream is at least partially fed to a first reactor stage of a methanol reactor arrangement for at least partial conversion into methanol. It is preferred that the (optionally pressure-increased) synthesis gas stream is fed essentially completely to the first reactor stage. However, it is also possible for part of the synthesis gas stream to be branched off beforehand.
  • the feature of "at least partial conversion into methanol" is based on the fact that an unreacted residue of reactants escapes from the methanol reactor arrangement and therefore the conversion cannot take place completely.
  • the methanol reactor arrangement can have several (in particular two, but also more than two) reactor stages or only a single reactor stage. If the methanol reactor arrangement does not have several reactor stages, the first reactor stage is the only reactor stage of the methanol reactor arrangement.
  • the first reactor stage of the methanol reactor arrangement is the reactor stage of the methanol reactor arrangement to which the synthesis gas stream is at least partially fed before it or a remaining residual gas stream is fed to another, e.g. a second, reactor stage.
  • the first reactor stage is in this respect the first reactor stage of the methanol reactor arrangement in terms of process technology. This circumstance corresponds to the possible designation of the synthesis gas stream as a fresh gas stream.
  • Each individual reactor stage of the methanol reactor arrangement can have several individual reactors for methanol synthesis that are connected in parallel to one another in terms of process technology.
  • a residual gas stream containing unreacted carbon oxides is obtained from the methanol reactor arrangement, which residual gas stream is fed to a recycle compressor to increase the pressure of the residual gas stream.
  • the residual gas stream can also contain unreacted hydrogen or even methane (which was not previously converted to synthesis gas).
  • the residual gas stream can also contain inert components such as nitrogen or noble gases. If the methanol reactor arrangement has more than one reactor stage (e.g. two reactor stages), this residual gas stream can be obtained after any reactor stage.
  • a residual gas stream can also be present between the first reactor stage and the second reactor stage.
  • An unreacted substance/constituent or an unreacted component is understood here and below to mean a substance (in the gaseous state) which was fed as a reactant for the methanol synthesis to a reactor stage of the methanol reactor arrangement, in particular the first reactor stage, and then left the reactor stage without having taken part in a reaction to synthesize methanol.
  • An unreacted substance can also be a substance fed to the synthesis gas reactor arrangement but not converted there.
  • the recycle compressor is used to circulate the majority of the unreacted residual gas through the methanol reactor arrangement.
  • the process also provides that the pressure-increased residual gas flow is fed to the methanol reactor arrangement for partial conversion into methanol. This is therefore a return of the now pressure-increased residual gas flow to the methanol reactor arrangement from which the residual gas flow was obtained.
  • unreacted residual gas from the first and/or second reactor stage can be fed in the form of a recovery stream to a hydrogen recovery arrangement for obtaining an H recycle stream, which H recycle stream comprises unreacted hydrogen from the unreacted residual gas from the first reactor stage and/or from the unreacted residual gas from the second reactor stage, wherein the unreacted hydrogen from the H recycle stream is fed again to the first reactor stage for at least partial conversion into methanol.
  • a partial stream of the unreacted residual gas e.g. from the first and/or second reactor stage
  • the recovery stream can be obtained from the unreacted residual gas from the first and/or second reactor stage, for example by branching off.
  • the H recycle stream comprises unreacted hydrogen from the unreacted residual gas (of the first and/or second reactor stage), which unreacted hydrogen of the H recycle stream is fed again to the first reactor stage for at least partial conversion into methanol. It may be that the unreacted hydrogen of the H recycle stream is only a part of the total unreacted hydrogen of the first and/or second reactor stage and/or only a part of the total unreacted hydrogen of the unreacted residual gas.
  • the unreacted hydrogen of the H recycle stream can be fed again to the first reactor stage both directly and indirectly. In the case of indirect feeding, the unreacted hydrogen is initially fed to other devices.
  • the proposed method is characterized in that a hydrogen stream with external hydrogen is fed to one of the streams upstream or downstream of the synthesis gas reactor arrangement, and that part of the residual gas stream and/or the optional recovery stream is branched off and fed to the synthesis gas reactor arrangement as a recycle stream.
  • a preferred embodiment may be one in which the water stream with external hydrogen is fed to the synthesis gas stream (downstream of the synthesis gas reactor arrangement).
  • the external hydrogen does not necessarily have to be fed to the synthesis gas stream (i.e. downstream of the synthesis gas reactor arrangement); it may also be provided that the external hydrogen is fed into the system before the synthesis gas is generated.
  • the hydrogen recovery arrangement mentioned can be reduced in size or even eliminated completely. This is because, compared to a process without the addition of external hydrogen, a smaller amount or no internal hydrogen needs to be produced by a hydrogen recovery arrangement when external hydrogen is supplied.
  • the proposed invention provides for a portion of the residual gas flow and/or the optional recovery flow and/or a flow downstream of the hydrogen recovery arrangement to be diverted and fed to the synthesis gas reactor arrangement as a recycle flow.
  • This has the effect that the residual gas flow fed to the recycle compressor and then again to the methanol reactor arrangement is reduced (i.e. less unreacted residual gas circulates in the methanol reactor arrangement).
  • Unreacted residual gas from the first reactor stage and/or unreacted residual gas from the optional second reactor stage is thus fed back to the methanol reactor arrangement (i.e. the reactor stages) in a smaller proportion.
  • the proportion of residual gas remaining or circulating in the methanol reactor arrangement is thus reduced.
  • Those components that were not converted to synthesis gas during synthesis gas production e.g. methane
  • methane that entered the synthesis gas stream
  • the total amount of fuel gas produced is reduced by the recirculation, which - since fuel gas is usually burned off - has a positive effect on the ecological balance of methanol synthesis.
  • the residual gas can contain a certain amount of methane. If this is fed back into the synthesis gas reactor arrangement as fuel gas instead of being burned off, it can be converted - at least to a certain extent - into synthesis gas and ultimately into methanol.
  • the aforementioned effects can be achieved if only a portion of the residual gas stream is diverted and fed to the synthesis gas reactor arrangement as a recirculation stream, but also if only a portion of the recovery stream (this can be optionally provided if a hydrogen recovery arrangement is used) is fed back. Since both the recovery stream and the residual gas stream contain unreacted residual gas, the effects described above can be achieved with both recirculation variants.
  • a combined recirculation of a branched-off part of the residual gas stream and a branched-off part of the recovery stream can also be provided and advantageous.
  • a "branch” does not necessarily mean a branch in the pipeline, but can also be understood as a "feed to" or "line to” (e.g. to the synthesis gas reactor arrangement).
  • the synthesis gas stream is fed to a heat recovery device for recovering heat from the synthesis gas stream and then to the synthesis gas compressor. It is conceivable that the synthesis gas stream is fed to another device or several other devices between the heat recovery device and the synthesis gas compressor. It should also be noted that the heat recovery device usually represents only one stage of a heat recovery arrangement with several heat recovery devices. In other words, it can be that the synthesis gas stream is fed to only one heat recovery device of several interconnected heat recovery devices.
  • the unreacted hydrogen of the H-recycle stream can be pressure-increased at least partially from the first reactor stage until it is fed back to the first reactor stage by the recycle compressor with the unreacted carbon oxides.
  • a pressure increase can be carried out by the recycle compressor. Since the recycle compressor - as already described - increases the pressure of the residual gas flow with unreacted carbon oxides, the pressure increase of the unreacted hydrogen can take place by the recycle compressor together with the unreacted carbon oxides.
  • the unreacted hydrogen of the H recycle stream can essentially be completely pressure increased from the first reactor stage to the refeed to the first reactor stage by the recycle compressor with the unreacted carbon oxides.
  • the synthesis gas reactor arrangement, the synthesis gas compressor, the methanol reactor arrangement, the heat recovery device, the recycle compressor and the hydrogen recovery arrangement can be included in a plant for the synthesis of methanol.
  • the residual gas stream fed to the recycle compressor can have any composition, as long as the residual gas stream comprises unreacted carbon oxides in basically any proportion and optionally unreacted hydrogen from the recovery stream.
  • the hydrogen stream for example from a hydrogen recovery device, is fed to the synthesis gas stream after it has left the heat recovery device.
  • the supply of the hydrogen stream to the synthesis gas stream does not impair the heat recovery from the synthesis gas stream, which is advantageous for ecological balance reasons (e.g. due to a possible temperature reduction after the hydrogen stream has been supplied).
  • the hydrogen stream is fed to the synthesis gas stream before it is fed into the synthesis gas compressor. This can ensure that a substoichiometric hydrogen content in the synthesis gas stream can be at least partially compensated before the synthesis gas enters the first reactor stage of the methanol reactor arrangement.
  • the hydrogen stream, as well as the external hydrogen can in principle be fed to the system at any point, including before the recycle compressor, after the first reactor stage, before the synthesis gas reactor arrangement, etc.
  • unreacted hydrogen from the H recycling stream can be added to the (external) hydrogen stream.
  • the hydrogen stream is made up of external hydrogen and hydrogen recycled from the recovery stream in the recovery arrangement. Whether hydrogen recovery is required depends largely on the respective plant design and the amount of hydrogen (or the hydrogen content) present in the synthesis gas stream. Furthermore, the need for hydrogen recovery can depend on the feed gas used and the amount of hydrogen available.
  • additional hydrogen can be added to the synthesis gas stream in addition to the external hydrogen via the hydrogen stream mentioned (which can compensate for any hydrogen deficit).
  • the hydrogen stream can be pressure-increased using a hydrogen compressor before being fed into the methanol reactor arrangement, in particular into the synthesis gas stream. This is advantageous in order to raise the hydrogen stream to the pressure level of the synthesis gas stream if necessary or to set a desired pressure level. Transporting a pressurized hydrogen stream can be advantageous because this can be done in smaller lines compared to transporting a non-pressurized hydrogen stream. It can be advantageous to compress the pressure of the hydrogen stream spatially (i.e. to increase the pressure) only shortly before it is fed to the methanol reactor arrangement or to the synthesis gas stream. This is because, from a plant engineering perspective, transporting hydrogen over short distances is advantageous.
  • the hydrogen compressor can have one or more compressor units.
  • the unreacted hydrogen from the H recycle stream is fed to the hydrogen stream via the hydrogen compressor, in particular that the unreacted hydrogen and the external hydrogen are jointly pressure-increased by means of the hydrogen compressor.
  • a joint pressure increase in the hydrogen compressor can have cost advantages.
  • the external hydrogen is supplied to the hydrogen stream from an electrolysis hydrogen stream which is produced from an electrolysis arrangement to split water into external hydrogen and oxygen.
  • the electrolysis arrangement can be arranged externally to the proposed plant for the synthesis of methanol, but can also be integrated into this plant (i.e. be part of it).
  • the electrolysis hydrogen stream preferably essentially comprises hydrogen.
  • the electrolysis referred to is therefore an electrolysis of water (water electrolysis).
  • water (H2O) is split into the components hydrogen (H2) and oxygen (O2) using electrical current. It is particularly advantageous if the electrical current used is generated from renewable energy sources (e.g. wind, sun, biomass, etc.).
  • the oxygen produced during water electrolysis can be used simultaneously in the reforming reactor (if autothermal reforming is used) or in the oxidation reactor (if partial oxidation is used) to generate the synthesis gas.
  • the methanol reactor arrangement preferably comprises a first methanol separation device for recovering the unreacted residual gas from the first reactor stage and a first crude methanol stream from the first reactor stage.
  • the first methanol separation device can comprise a first condensation device for recovering the unreacted residual gas from the first reactor stage and the first crude methanol stream from the first reactor stage by condensation.
  • the methanol reactor arrangement can comprise a second methanol separation device for recovering the unreacted residual gas from the second reactor stage and a second crude methanol stream from the second reactor stage, wherein in particular the second methanol separation device comprises a second condensation device for recovering the unreacted residual gas from the second reactor stage and the second crude methanol stream from the second reactor stage by condensation.
  • the first and/or second methanol separation device can be designed in any desired manner. As mentioned, it can be advantageous for the first and/or second methanol separation device to comprise a first or second condensation device.
  • the methanol reactor arrangement comprises only a single (first) methanol reactor stage.
  • the methanol reactor arrangement can also comprise a plurality of process-related reactor stages connected in series for methanol synthesis, for example a first reactor stage and a second reactor stage connected downstream of the first reactor stage.
  • Each individual reactor stage can have one or more reactors.
  • the reactors of a reactor stage can in particular be arranged in parallel with one another in terms of process technology.
  • a methanol separation device can be used to recover a respective unreacted residual gas from each of the large number of reactor stages.
  • Each reactor stage can be assigned a separate methanol separation device.
  • a common methanol separation device can also be assigned to several or all of the reactor stages, with the reactor stages in this case being connected in parallel.
  • reactor stage is not to be understood as meaning “stages” of reactors connected in series in terms of process technology, but rather “reactors” connected in parallel.
  • first and second reactor stages are connected in series in terms of process technology (the second reactor stage is connected downstream of the first reactor stage) means that residual gas from a reactor stage - unless it is the last reactor stage in a series of several reactor stages - is fed directly or indirectly to the reactor stage connected after it.
  • first and second reactor stage residual gas from the first reactor stage is fed directly or indirectly to the second reactor stage.
  • the above recycle compressor can be arranged in any way with respect to the plurality of reactor stages.
  • the recycle compressor is arranged between two reactor stages in terms of process technology, for example in the case of two reactor stages between the first and second reactor stages. This means that at least part of the unreacted residual gas from a reactor stage is fed to the recycle compressor as a residual gas stream and the pressure-increased residual gas stream is then fed to the reactor stage downstream of this reactor stage.
  • the H recycle stream mentioned can be conducted in any way as long as at least part of its hydrogen is converted into methanol.
  • the H recycle stream is fed to the unreacted residual gas of a reactor stage that is downstream of the first reactor stage (e.g. second).
  • the unreacted hydrogen from the H recycle stream can be fed into the unreacted residual gas of the second reactor stage.
  • the unreacted hydrogen of the H recycle stream is treated after feeding together with at least part of the unreacted residual gas of a reactor stage other than the first reactor stage.
  • the H recycle stream "skips" one or more reactor stages after the first reactor stage.
  • the advantage of such an approach is that the pressure loss of the H recycle stream due to hydrogen recovery essentially occurs parallel to the pressure loss of the unreacted residual gas of the downstream (e.g. second) reactor stage in this reactor stage.
  • the respective pressure of this unreacted residual gas and the H recycle stream are closer to each other, which in turn reduces a pressure loss that occurs when they are combined by adjusting to the lower pressure level.
  • the H recycle stream can be fed to the recycle compressor with the residual gas stream to increase the pressure.
  • the residual gas stream is obtained from a reactor stage that is downstream of the first reactor stage in terms of process technology, in particular the second reactor stage.
  • the residual gas stream fed to the recycle compressor does not come from the first reactor stage - i.e. the reactor stage to which the synthesis gas stream is at least partially fed directly - but from a downstream reactor stage.
  • the recycle compressor feeds the pressure-increased residual gas stream to the first reactor stage.
  • the pressure-increased residual gas stream can also be fed to another reactor stage of the plurality of reactor stages.
  • the pressure-increased residual gas stream is split up and fed to several reactor stages of the plurality of reactor stages.
  • the residual gas stream is obtained from a reactor stage that is the last in the process of the plurality of reactor stages.
  • the second reactor stage is the last reactor stage.
  • the recovery stream can be obtained at any point and from any origin within the methanol reactor arrangement.
  • the recovery stream contains unreacted hydrogen from an unreacted residual gas from the first reactor stage and/or the second reactor stage.
  • One variant provides that the recovery stream is at least partially branched off from the unreacted residual gas from the first reactor stage.
  • the recovery stream (if two reactor stages are provided) can be branched off from the unreacted residual gas from the second reactor stage. It is also conceivable that the recovery stream is branched off from both the unreacted residual gas from the first reactor stage and from the unreacted residual gas from the second reactor stage. It is therefore possible that the recovery stream is at least partially branched off upstream of the recycle compressor in terms of process technology.
  • the hydrogen content in the first reactor stage can be increased and thus the stoichiometry for methanol synthesis can be improved.
  • the synthesis gas reactor arrangement can comprise a reforming reactor or an oxidation reactor.
  • an oxygen-containing stream can be fed to the synthesis gas reactor arrangement to obtain the synthesis gas stream.
  • the synthesis gas stream is obtained from the carbon-containing energy carrier stream by an autothermal reforming in the reforming reactor or a partial oxidation in the oxidation reactor.
  • the synthesis gas reactor arrangement can have further devices.
  • the synthesis gas reactor arrangement can have a device for desulfurizing the carbon-containing energy carrier stream, a saturation stage for saturating the carbon-containing energy carrier stream with water, a pre-reforming reactor (pre-reformer) for pre-reforming the carbon-containing energy carrier stream and/or a device for heating the carbon-containing energy carrier stream, which is installed upstream of the reactor in terms of process technology.
  • pre-reformer pre-reforming reactor
  • the synthesis gas stream can be obtained from the energy carrier stream in any way. It is preferred that an oxygen-containing stream is fed to the synthesis gas reactor arrangement to obtain the synthesis gas stream.
  • the oxygen-containing stream can contain other components in addition to oxygen.
  • the oxygen-containing stream can also be ambient air.
  • the synthesis gas stream can be obtained by steam reforming (using a steam reformer as a reforming reactor) the carbon-containing energy carrier stream.
  • a steam reformer can be useful when adding CO2 or using a CO2-rich carbon-containing energy carrier stream (such as biogas).
  • a further preferred embodiment of the method is characterized in that in the synthesis gas reactor arrangement the synthesis gas stream is obtained from the carbon-containing energy carrier stream by autothermal reforming, namely in the reforming reactor mentioned.
  • autothermal reforming a catalytic partial oxidation provides the heat required for the endothermic reforming reactions.
  • autothermal reforming offers the advantage that the synthesis gas stream can be provided at a higher pressure.
  • the synthesis gas stream can be obtained from the carbon-containing energy carrier stream by partial oxidation in the synthesis gas reactor arrangement, namely in the oxidation reactor mentioned.
  • autothermal reforming can also be carried out with ambient air.
  • the oxygen comprised in the oxygen-containing stream is obtained from an air separation device for obtaining an oxygen stream from ambient air.
  • the air separation device can also be set up to obtain a nitrogen stream.
  • the oxygen-containing stream can then essentially comprise oxygen. In this way, the proportion of inert gases in the methanol synthesis is reduced, so that various devices in the plant can be made smaller.
  • the plant for synthesizing methanol comprises the air separation device.
  • the oxygen contained in the oxygen-containing stream can be obtained from the electrolysis arrangement.
  • oxygen is also produced due to the chemical reaction underlying this process.
  • synthesis gas autothermal reforming or partial oxidation
  • the recycle stream of the synthesis gas reactor arrangement is fed upstream of the reforming reactor or the oxidation reactor.
  • This enables the recycle stream and the components contained therein to pass through the reforming reactor (e.g. an autothermal reforming reactor or steam reformer) or the oxidation reactor (for partial oxidation) again.
  • the components contained in the recycle stream, in particular methane can then pass through the (chemical) processes taking place in the synthesis gas reactor arrangement again and be converted into synthesis gas. If catalysts are used, this allows the components of the recycle stream to come into contact again with the catalysts used to produce synthesis gas.
  • a pre-reformer reactor can be arranged upstream of the reforming reactor, with the recycle stream being fed to the synthesis gas reactor arrangement between the pre-reforming reactor and the reforming reactor. Since the components of the recycle stream have already passed through the pre-reforming reactor in a previous run, it may not be necessary to pass it through the pre-reforming reactor again. Further processing in the sense of pre-reforming can therefore be omitted.
  • the H recycle stream can have any composition, provided it contains the unreacted hydrogen from the unreacted residual gas of the first reactor stage.
  • the H recycle stream has a higher molar proportion of hydrogen than the recovery stream. This refers not only to the unreacted hydrogen from the unreacted residual gas of the first reactor stage, but to the hydrogen in the H recycle stream as a whole. In other words, the hydrogen in the H recycle stream is enriched compared to the recovery stream. It is also preferred that the H recycle stream has a higher molar proportion of hydrogen than the purge stream.
  • the hydrogen recovery arrangement can function according to any principle, for example based on a membrane arrangement or a refrigeration device.
  • the hydrogen recovery arrangement can have a pressure swing adsorption device (PSA) for recovering the H recycle stream from the recovery stream.
  • PSA pressure swing adsorption device
  • the pressure losses in such a pressure swing adsorption device are also acceptable.
  • a high hydrogen purity is not required in this case, it can still be achieved. It is therefore possible that the H recycle stream essentially contains hydrogen.
  • the hydrogen recovery arrangement outputs a purge stream and/or that a purge stream is branched off from the recycle stream and/or that a purge stream is branched off from the recovery stream, and/or that a purge stream is branched off from the residual gas stream.
  • the purge stream is preferably fed to a combustion facility or to a flare.
  • a ratio of a first mass flow formed by a sum of carbon-containing compounds present in the purge stream relative to a second mass flow formed by a sum of carbon-containing compounds present in the synthesis gas stream can assume a value of 10' 5 to 0.4, and preferably assume a value of 0.0001 to 0.3, and more preferably assume a value of 0.0005 to 0.21.
  • the first and/or second mass flow can in particular comprise CO, CO2, CPU and/or methanol as carbon-containing compounds.
  • said ratio can assume a value of approximately 0.0005, 0.05 or 0.22, preferably of exactly 0.0005, 0.015 or 0.22.
  • the object underlying the invention is also achieved by a plant for the synthesis of methanol.
  • a plant for the synthesis of methanol is proposed with a synthesis gas reactor arrangement for obtaining a synthesis gas stream with hydrogen and carbon oxides from a carbon-containing energy carrier stream fed to the synthesis gas reactor arrangement, optionally with a synthesis gas compressor for increasing the pressure of the synthesis gas stream, with a methanol reactor arrangement which has a first reactor stage and optionally a second reactor stage, with a recycle compressor, and optionally with a hydrogen recovery arrangement.
  • the plant also comprises a device for at least partially feeding the (optionally pressure-increased) synthesis gas stream into the first reactor stage for at least partial conversion into methanol.
  • the "device” can be a physical device which is used for at least partial for feeding the (optionally pressurized) synthesis gas stream into the first reactor stage. Such a “device” can be, for example, a line.
  • the “device” can include general valve systems, control and regulation systems.
  • the plant may further comprise an optional device for supplying unreacted residual gas from the first reactor stage to the optional second reactor stage for at least partial conversion into methanol.
  • the “device” may be a physical device configured to supply unreacted residual gas from the first reactor stage to the optional second reactor stage. Such a “device” may be, for example, a line.
  • the “device” may include general valve systems, pump systems, control and regulation systems.
  • the plant further comprises a device for recovering a residual gas stream from the methanol reactor arrangement with unreacted carbon oxides.
  • This "device” is understood to mean a physical device that is designed to recover a residual gas stream from the methanol reactor arrangement with unreacted carbon oxides.
  • this can be a methanol separation device including the associated piping system.
  • the system further comprises a device for feeding the residual gas flow into the recycle compressor to increase the pressure of the residual gas flow.
  • the “device” can be a physical device that is designed to feed the residual gas flow into the recycle compressor. Such a “device” can be a line, for example.
  • the “device” can include general valve systems, pump systems, control and regulating systems.
  • the system also includes a device for feeding the pressure-increased residual gas stream into the methanol reactor arrangement for at least partial conversion into methanol.
  • the "device” can be a physical device that is set up to feed the pressure-increased residual gas stream into the methanol reactor arrangement. Such a “device” can be a line, for example.
  • the “device” can include general valve systems, control and regulation systems.
  • the system can optionally comprise a device for feeding a recovery stream comprising unreacted residual gas from the first and/or second reactor stage into the hydrogen recovery arrangement to obtain an H recycle stream, wherein the H recycle stream comprises unreacted hydrogen from the unreacted residual gas from the first reactor stage and/or from the unreacted residual gas from the second reactor stage.
  • the “device” can be a physical device which is set up to feed a recovery stream comprising unreacted residual gas from the first and/or second reactor stage into the hydrogen recovery arrangement.
  • a “device” can be, for example, a line.
  • the “device” can include general valve systems, pump systems, control and regulating systems.
  • the plant can optionally have a device for re-feeding the unreacted hydrogen of the H recycle stream into the first reactor stage for at least partial conversion into methanol.
  • the “device” can be a physical device that is designed to re-feed the unreacted hydrogen of the H recycle stream into the first reactor stage.
  • Such a “device” can be a line, for example.
  • the “device” can include general valve systems, control and regulating systems.
  • the system is characterized by a device for supplying a hydrogen stream with external hydrogen to one of the streams upstream or downstream of the synthesis gas reactor arrangement. It can be advantageous to supply the hydrogen stream with external hydrogen into the synthesis gas stream.
  • the “device” can be a physical device that is designed to supply a hydrogen stream with external hydrogen into the synthesis gas stream. This “device” can be a line, for example.
  • the “device” can include general valve systems, control and regulating systems.
  • the “device” can also include a hydrogen compressor.
  • the plant is further characterized by one or more devices for branching off and feeding a portion of the residual gas stream, and/or the optional recovery stream, and/or a stream downstream of the hydrogen recovery arrangement into the synthesis gas reactor arrangement as a recycle stream.
  • the said “device(s)” may be physical devices for branching off and feeding a portion of the residual gas stream, and/or the optional recovery stream, and/or one of the hydrogen recovery arrangement downstream stream into the synthesis gas reactor arrangement as a recycle stream.
  • This "device” can be, for example, a line.
  • the “device” can include general valve systems, control and regulation systems.
  • the characteristics, advantages and properties of the proposed plant correspond to the characteristics, advantages and properties of the proposed process and vice versa.
  • Fig. 1 shows a schematic flow diagram of a plant known from the prior art for the synthesis of methanol
  • FIG. 2 schematically shows the flow diagram of the plant for the synthesis of methanol according to Figure 1, but with further specifications known from the prior art,
  • FIG. 3 schematically shows the flow diagram of a plant for carrying out the proposed method according to a first embodiment
  • Fig. 4 shows a schematic flow diagram of a plant for carrying out the proposed method according to a second embodiment
  • Fig. 5 shows a schematic flow diagram of a plant for carrying out the proposed method according to a third embodiment
  • Fig. 6 shows a schematic flow diagram of a plant for carrying out the proposed method according to a fourth embodiment
  • Fig. 7 schematically shows the flow diagram of a plant for carrying out the proposed method according to a fifth embodiment
  • Fig. 8 shows a schematic flow diagram of a plant for carrying out the proposed process, whereby the external hydrogen is produced on the basis of water electrolysis
  • Fig. 9 schematically shows the flow diagram of a plant for carrying out the proposed method according to a further embodiment
  • Fig. 10 shows a schematic flow diagram of a plant for carrying out the proposed method according to a further embodiment.
  • Figure 1 shows the supply of an energy carrier stream 11, formed from natural gas or biogas, for example, and thus containing carbon, into a synthesis gas reactor arrangement 13.
  • a synthesis gas stream 2 comprising hydrogen, carbon monoxide and carbon dioxide is produced from the energy carrier stream 11.
  • the synthesis gas reactor arrangement 13 can have a reforming reactor 30 or an oxidation reactor 31.
  • an autothermal reforming takes place in the synthesis gas reactor arrangement 13 to obtain the synthesis gas stream 2.
  • an oxygen-containing stream 22 is supplied, which was obtained here from an air separation device 23 and essentially comprises oxygen.
  • the Air separation device 23 is designed to obtain an oxygen stream - in this case the oxygen-containing stream 22 - from the ambient air.
  • the synthesis gas stream 2 is first fed to a heat recovery device 10 in which the synthesis gas stream 2 is cooled and in this way a portion of the heat generated during the autothermal reforming is recovered.
  • the synthesis gas stream 2 is then fed to a synthesis gas compressor 3 of the system for further pressure increase.
  • the synthesis gas stream 2 of the first reactor stage 21a is then fed to a methanol reactor arrangement 4, in which first reactor stage 21a methanol synthesis takes place and at least part of the synthesis gas stream 2 is converted into methanol 1.
  • Unreacted residual gas 16a of the first reactor stage 21a is then fed to a second reactor stage 21b of the methanol reactor arrangement 4 for at least partial conversion into methanol 1.
  • a residual gas stream 15 with unreacted carbon oxides is then obtained from the methanol reactor arrangement 4 and fed to a recycling compressor.
  • the plant has a hydrogen recovery arrangement 5 designed as a pressure swing adsorption plant 24 - which can also be referred to as PSA - which recovers an H recycle stream 7 from a recovery stream 6, which H recycle stream 7 essentially comprises hydrogen.
  • the recovery stream 6 is branched off from unreacted residual gas 16a of the first reactor stage in accordance with the plant concept shown in Figure 1.
  • the remaining gas is also output from the hydrogen recovery arrangement 5 as a purge stream 8 and then burned in a fired heating device of the plant (not shown here).
  • the H recycle stream 7 is fed to the residual gas stream 15.
  • the plant has a recycle compressor 14, which compresses the residual gas stream 15.
  • the residual gas stream 15 has unreacted residual gas 16b from the second reactor stage 21b, which in turn essentially contains those components of the synthesis gas which were not converted into methanol 1 in the methanol reactor arrangement 4. Accordingly, the Residual gas stream 15 contains, in particular, unreacted carbon oxides.
  • the residual gas stream 15, which has thus increased its pressure, is firstly fed back to the methanol reactor arrangement 4, namely the first reactor stage.
  • the unreacted residual gas 16a, b is obtained from a first methanol separation device 17a and a second methanol separation device 17b of the methanol reactor arrangement 4.
  • the unreacted residual gas 16a, b on the one hand and a respective first and second raw methanol stream 19a, b on the other hand are obtained in these by condensation.
  • the raw methanol streams 19a, b are then fed to a distillation 20 of the system so that the methanol 1 can be obtained from the raw methanol streams 19a, b.
  • the first methanol separation device 17a is connected downstream of the first reactor stage 21a in terms of process technology.
  • the second methanol separation device 17b is connected downstream of the second reactor stage 21b in terms of process technology.
  • the methanol reactor arrangement 4 - as mentioned - has two reactor stages 21a, b connected in series for methanol synthesis.
  • the first reactor stage 21a has two isothermal reactors arranged parallel to one another and the second reactor stage 21b has a single isothermal reactor.
  • the product stream from one reactor stage 21a, b is fed to each of the two methanol separation devices 17a, 17b.
  • the reactor stage 21a to which the synthesis gas stream 2 is fed directly is referred to as the first reactor stage 21a.
  • the reactor stage 21b is then downstream of this in the sense that the unreacted residual gas 16a from the first reactor stage 21a is fed to it for conversion into methanol 1.
  • the residual gas stream 15 also contains unreacted hydrogen from the first reactor stage 21a. Any unreacted hydrogen from the residual gas 16a of the first reactor stage 21a is fed to the second reactor stage 21b. Since the hydrogen does not react completely in the second reactor stage 21b either, the unreacted residual gas 16b of the second reactor stage 21b also contains unreacted hydrogen from the first reactor stage 21a.
  • a ratio of a first mass flow formed by a sum of carbon-containing compounds present in the purge stream 8 relative to a second mass flow formed by a sum of carbon-containing compounds present in the synthesis gas stream 2 assumes a value of approximately or exactly 0.22.
  • the plant shown in Figure 2 comprises all components of the plant already shown in Figure 1. Nevertheless, Figure 2 specifies the type of synthesis gas production based on autothermal reforming in a reforming reactor 30.
  • the energy carrier stream 11 Before entering the reforming reactor 30, the energy carrier stream 11 is passed through a pre-reforming reactor 29. After adding steam 33, the pre-reformed energy carrier stream 11 enters the reforming reactor 30. A generated synthesis gas stream 2 then enters a heat recovery device 10.
  • FIG 3 shows a first embodiment of a system according to the invention.
  • the synthesis gas is produced in a reforming reactor 30 (see the previous explanations for Figure 2).
  • the reforming reactor 30 thus provides the synthesis gas reactor arrangement 13 or part of the synthesis gas reactor arrangement 13.
  • a hydrogen stream 35 with external hydrogen is fed to the synthesis gas stream 2 between the heat recovery device 10 and the inlet to the synthesis gas compressor 3.
  • the hydrogen stream 35 is pressure-increased by means of a hydrogen compressor 45 before being fed into the synthesis gas stream 2.
  • a portion of the recovery stream 6 (alternatively from the residual gas 16a) is branched off and fed to the synthesis gas reactor arrangement 13 as a recycle stream 40, namely directly between the pre-reforming reactor 29 and the reforming reactor 30.
  • a recycle stream 40 can be branched off from a stream 71 downstream of the hydrogen recovery arrangement 5 (here, for example, a pressure swing adsorption device 24), as indicated in dashed lines.
  • the recycle stream 40 is fed to the synthesis gas reactor arrangement 13 as a recycle stream 40, namely directly between the pre-reforming reactor 29 and the reforming reactor 30.
  • the second embodiment of the proposed system differs from the embodiment of Fig. 3 in that the Recovery stream 6 is branched off from the residual gas stream 15 or the residual gas 16b (downstream of the second reactor stage 21b).
  • the H recycle stream 7 is fed to the residual gas 16b of the second reactor stage 21b downstream of the first reactor stage 21a.
  • the H recycle stream 7 can be fed to the synthesis gas stream upstream of the synthesis gas compressor 3. Specifically, this supply takes place before the pressure is increased by the recycle compressor 14.
  • the hydrogen in the H recycle stream 7 corresponding to the unreacted hydrogen from the residual gas 16a of the first reactor stage 21a in the recovery stream 6 thus receives a pressure increase from the recycle compressor 14 with the other unreacted residual gas 16b of the second reactor stage 21b and in particular with unreacted carbon oxides. This pressure increase takes place before this unreacted hydrogen is fed again to the first reactor stage 21a.
  • a recycle stream 40 can be branched off from a stream 71 downstream of the hydrogen recovery arrangement 5 (here, for example, a pressure swing adsorption device 24).
  • the recycle stream 40 is fed to the synthesis gas reactor arrangement 13 as recycle stream 40, namely directly between the pre-reforming reactor 29 and the reforming reactor 30.
  • a portion of the recovery stream 6 can also be branched off and fed to the synthesis gas reactor arrangement 13 as recycle stream.
  • the third embodiment of the proposed system differs from the embodiment in Fig. 4 in that the hydrogen recovery arrangement 5 is a membrane arrangement 25.
  • An H recycle stream 7 obtained in the membrane arrangement 25 is fed to the hydrogen stream 35 via the hydrogen compressor 45 before being fed into the synthesis gas stream 2, where the pressure is increased.
  • a portion of the recovery stream 6 (here branched off from the residual gas 16b or residual gas stream 15) is fed to the synthesis gas reactor arrangement 13 as a recycle stream 40 after passing through the membrane arrangement 25. This can also be understood as a "branch" from a stream 71 downstream of the hydrogen recovery arrangement 5.
  • a "branch” does not necessarily mean a branch in terms of pipework, but can also be referred to as a "feed to” or “line to” (e.g. B. to the synthesis gas reactor arrangement 13).
  • the supply takes place upstream of the reforming reactor 30.
  • a purge stream 8 is branched off from the recycle stream 40 and burned off.
  • the H recycle stream 7 is not returned to the residual gas 16b or residual gas stream 15, but via the hydrogen compressor 45 back into the synthesis loop.
  • FIG. 6 differs from the embodiment according to Fig. 5 in that the purge stream 8 is not branched off from the recycle stream 40 (Fig. 5), but directly from the recovery stream 6.
  • the stream 71 downstream of the hydrogen recovery arrangement 5 is returned directly as recycle stream 40 to the synthesis gas reactor arrangement 13 or upstream of the reforming reactor 30.
  • a "branch" in the sense of the line technology does not take place, but an immediate return in the sense of the terminology used here can also be understood as a "branch".
  • a recycle stream 40 is branched off from the residual gas stream 15 and fed to the synthesis gas reactor arrangement 13, namely between the pre-reforming reactor 29 and the reforming reactor 30.
  • a purge stream 8 is branched off from the recovery stream 40 and burned off.
  • a ratio of a first mass flow formed by a sum of carbon-containing compounds present in the purge stream 8 relative to a second mass flow formed by a sum of carbon-containing compounds present in the synthesis gas stream 2 assumes a value of approximately or exactly 0.0008.
  • Figure 8 shows a section of a proposed system in which the oxygen-containing stream 22 fed to the reforming reactor 30 is not obtained from an air separation device 23, but from an electrolysis arrangement 60.
  • the oxygen-containing stream 22 can be supplemented with oxygen from another source, e.g. an air separation device 23.
  • Oxygen (O2) and hydrogen (H2) are produced, the pressure of the oxygen being/can be increased before the oxygen-containing stream 22 is formed.
  • the hydrogen produced during the electrolysis can also be used, namely by supplying an electrolysis hydrogen stream 50 to the synthesis gas stream 2 as a hydrogen stream 35 after the pressure has been increased by the hydrogen compressor 45. Accordingly, the external hydrogen supplied to the synthesis gas stream 2 can come from the electrolysis arrangement 60.
  • a recirculation stream 40 can be branched off from the residual gas stream 15 and returned to the reforming reactor 30.
  • a purge stream 8 can also be branched off from the residual gas stream 15 and burned off.
  • the carbon-containing energy carrier stream 11 can in particular be biogas or another CO2-rich gas, for example natural gas mixed with CO2. It should be noted that when biogas is used as a carbon-containing energy source stream 11, the pre-reformer 29 can be omitted, since biogas hardly contains any higher hydrocarbons.
  • Fig. 9 shows an embodiment of the proposed system, in which, in contrast to the embodiment according to Fig. 7, a synthesis gas compressor 3 is dispensed with.
  • a recycle stream 40 is branched off from the residual gas stream 15 and fed to the synthesis gas reactor arrangement 13, namely between the pre-reforming reactor 29 and the reforming reactor 30.
  • the recycle stream can also be branched off before the pressure increase, compressed in a separate compressor and fed to the synthesis gas reactor arrangement 13. From the A purge stream 8 is branched off from the residual gas stream 15 and burned off.
  • a ratio of a first mass flow formed by a sum of carbon-containing compounds present in the purge stream 8 relative to a second mass flow formed by a sum of carbon-containing compounds present in the synthesis gas stream 2 assumes a value of approximately or exactly 0.005.
  • Fig. 10 shows a further embodiment of the proposed system, wherein the reforming reactor 30 is designed as a steam reformer.
  • a carbon-containing energy carrier stream 11 is first fed to a preparation stage 71 and then fed to the reforming reactor 30 designed as a steam reformer with the addition of water vapor 72 and CO2.
  • Only one methanol reactor arrangement 4 with a single reactor stage (the first reactor stage 21a) is provided. Accordingly, only one first methanol separation device 17a downstream of the reactor stage 21 is provided.
  • a recirculation stream 40 is branched off from the residual gas stream 15 and fed back upstream of the reforming reactor 30.
  • the carbon-containing energy carrier stream 11 can be the same energy carrier as in the embodiments according to Figs. 1 to 7, but also biogas.
  • a ratio of a first mass flow formed by a sum of carbon-containing compounds present in the purge stream 8 relative to a second mass flow formed by a sum of carbon-containing compounds present in the synthesis gas stream 2 assumes a value of approximately or exactly 0.015 or even values ⁇ 0.015.

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Abstract

L'invention concerne un procédé et un système de synthèse de méthanol (1) : un flux d'hydrogène (35) comprenant de l'hydrogène externe étant fourni à un flux de gaz de synthèse (2) ; une partie d'un flux de gaz restant (15) évacué d'un ensemble réacteur de méthanol (4), et/ou d'un flux de récupération (6) éventuellement fourni à un ensemble de récupération d'hydrogène (5), et/ou d'un flux (71) en aval de l'ensemble de récupération d'hydrogène (5) étant ramifiée et étant fournie à un ensemble réacteur de gaz de synthèse (13) en tant que flux de retour (40). Ce concept permet d'augmenter significativement l'efficacité de la production de méthanol. En outre, des émissions indésirables peuvent être réduites et ainsi l'éclat du procédé ou du système est amélioré.
PCT/EP2024/065221 2023-06-14 2024-06-03 Procédé et système de synthèse de méthanol Pending WO2024256205A1 (fr)

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LULU103148 2023-06-14
DE102023115491.5 2023-06-14
DE102023115491.5A DE102023115491A1 (de) 2023-06-14 2023-06-14 Verfahren und Anlage zur Synthese von Methanol
LU103148A LU103148B1 (de) 2023-06-14 2023-06-14 Verfahren und Anlage zur Synthese von Methanol

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007108014A1 (fr) 2006-03-20 2007-09-27 Cri Ehf Procédé de production de carburant liquide à partir de dioxyde de carbone et d'eau
WO2013144041A1 (fr) 2012-03-28 2013-10-03 Akzo Nobel Chemicals International B.V. Procédé de préparation continue de méthanol par hydrogénation de dioxyde de carbone
DE102016213668A1 (de) 2016-07-26 2018-02-01 Thyssenkrupp Ag Verfahren und Anlage zur Herstellung von Alkoholen oder Kohlenwasserstoffen
US20190185887A1 (en) 2014-07-22 2019-06-20 Iogen Corporation Process for using biogenic carbon dioxide derived from non-fossil organic material
WO2020048809A1 (fr) 2018-09-04 2020-03-12 Basf Se Procédé de production de méthanol à partir de gaz de synthèse sans émission de dioxyde de carbone
WO2020058859A1 (fr) 2018-09-19 2020-03-26 Eni S.P.A. Procédé de production de méthanol à partir d'hydrocarbures gazeux
WO2020239754A1 (fr) * 2019-05-28 2020-12-03 Gascontec Gmbh Procédé et installation de synthèse du méthanol
WO2020249923A1 (fr) 2019-06-12 2020-12-17 Johnson Matthey Davy Technologies Limited Procédé de synthèse de méthanol
DE102019124078A1 (de) 2019-09-09 2021-03-11 Thyssenkrupp Ag Verfahren zur Synthese eines Stoffs
WO2022238671A1 (fr) * 2021-05-11 2022-11-17 Johnson Matthey Davy Technologies Limited Procédé de synthèse de méthanol

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007108014A1 (fr) 2006-03-20 2007-09-27 Cri Ehf Procédé de production de carburant liquide à partir de dioxyde de carbone et d'eau
WO2013144041A1 (fr) 2012-03-28 2013-10-03 Akzo Nobel Chemicals International B.V. Procédé de préparation continue de méthanol par hydrogénation de dioxyde de carbone
US20190185887A1 (en) 2014-07-22 2019-06-20 Iogen Corporation Process for using biogenic carbon dioxide derived from non-fossil organic material
DE102016213668A1 (de) 2016-07-26 2018-02-01 Thyssenkrupp Ag Verfahren und Anlage zur Herstellung von Alkoholen oder Kohlenwasserstoffen
WO2020048809A1 (fr) 2018-09-04 2020-03-12 Basf Se Procédé de production de méthanol à partir de gaz de synthèse sans émission de dioxyde de carbone
WO2020058859A1 (fr) 2018-09-19 2020-03-26 Eni S.P.A. Procédé de production de méthanol à partir d'hydrocarbures gazeux
WO2020239754A1 (fr) * 2019-05-28 2020-12-03 Gascontec Gmbh Procédé et installation de synthèse du méthanol
WO2020249923A1 (fr) 2019-06-12 2020-12-17 Johnson Matthey Davy Technologies Limited Procédé de synthèse de méthanol
DE102019124078A1 (de) 2019-09-09 2021-03-11 Thyssenkrupp Ag Verfahren zur Synthese eines Stoffs
WO2022238671A1 (fr) * 2021-05-11 2022-11-17 Johnson Matthey Davy Technologies Limited Procédé de synthèse de méthanol

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