EP4045172A1 - Procédé et installation pour la fabrication d'un produit gazeux riche en monoxyde de carbone - Google Patents

Procédé et installation pour la fabrication d'un produit gazeux riche en monoxyde de carbone

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Publication number
EP4045172A1
EP4045172A1 EP20786449.7A EP20786449A EP4045172A1 EP 4045172 A1 EP4045172 A1 EP 4045172A1 EP 20786449 A EP20786449 A EP 20786449A EP 4045172 A1 EP4045172 A1 EP 4045172A1
Authority
EP
European Patent Office
Prior art keywords
gas
electrolysis
adsorption
carbon monoxide
carbon dioxide
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
EP20786449.7A
Other languages
German (de)
English (en)
Inventor
Andreas Peschel
Benjamin HENTSCHEL
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.)
Linde GmbH
Original Assignee
Linde 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
Application filed by Linde GmbH filed Critical Linde GmbH
Publication of EP4045172A1 publication Critical patent/EP4045172A1/fr
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0407—Constructional details of adsorbing systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0462—Temperature swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • B01D53/0476—Vacuum pressure swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • 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
    • C25B1/23—Carbon monoxide or syngas
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/083—Separating products
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/085—Removing impurities
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/087—Recycling of electrolyte to electrochemical cell
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/20—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the invention relates to a method and a plant for the production of a carbon monoxide-rich gas product according to the respective preambles of the independent claims.
  • Carbon monoxide can be produced using a number of different processes, for example together with hydrogen by steam reforming natural gas and subsequent purification from the synthesis gas formed, or by gasifying feedstocks such as coal, natural gas, crude oil or biomass and subsequent purification from the synthesis gas formed.
  • a membrane is used through which the positive charge carriers (M + ) required according to reaction equation 2 or formed according to reaction equation 3 diffuse from the anode to the cathode side.
  • the positive charge carriers are not transported in the form of oxygen ions but, for example, in the form of positive ions of the electrolyte salt used (a metal hydroxide, MOH).
  • An example of a corresponding electrolyte salt can be potassium hydroxide.
  • the positive charge carriers are potassium ions.
  • Further embodiments of the low-temperature electrolysis include, for example, the use of proton exchange membranes through which protons migrate or of so-called anion exchange membranes. Different variants of corresponding processes are described, for example, in Delacourt et al., J. Electrochem. Soc. 2008, 155, B42-B49, DOI: 10.1149 / 1.2801871.
  • a low-temperature electrolysis can be carried out with the formation of different amounts of hydrogen.
  • Corresponding methods and devices are described, for example, in WO 2016/124300 A1 and WO 2016/128323 A1.
  • the oxygen ions are essentially selectively conducted from the cathode to the anode via a ceramic membrane.
  • reaction equation 5 It has not been fully clarified whether the reaction according to reaction equation 5 takes place in the manner shown. It is also possible that only hydrogen is formed electrochemically and carbon monoxide is formed in the presence of carbon dioxide according to the reverse water-gas shift reaction: C0 2 + H 2 ⁇ H 2 0 + CO (8)
  • the gas mixture formed in the high-temperature co-electrolysis is in the water-gas shift equilibrium (or close to it).
  • the specific manner in which the carbon monoxide is formed has no influence on the present invention.
  • the separation process disclosed in the already mentioned DE 102017005681 A1 for separating the crude gas formed during the electrolysis comprises only a separation of the unconverted carbon dioxide, the electrolysis products pass together into the gas product. With this process, the production of carbon monoxide is only possible with impurities in a non-negligible amount.
  • the present invention therefore sets itself the task of improving the purity of a gas product rich in carbon monoxide in a corresponding separation and at the same time improving the yield in relation to the amount of raw material used.
  • the present invention proposes a method for producing a gas product rich in carbon monoxide and a corresponding plant having the features of the respective independent claims.
  • Preferred configurations are the subject matter of the dependent claims and the description below.
  • a “gas product rich in carbon monoxide” is understood here in particular to mean carbon monoxide of different purities which is formed by means of the method according to the invention. Accordingly, in addition to carbon monoxide, other gas components can also be contained, but which have a volume fraction of less than 40%, 30%, 20%, 10%, 5%, 3%, 2%, 1%,
  • Such other gas components can in particular be carbon dioxide and / or hydrogen.
  • raw gas any gas mixture provided using electrolysis to which (among other things or exclusively) is subjected to carbon dioxide is referred to as “raw gas” in the language used here.
  • the raw gas can also contain, for example, oxygen or unconverted inert components, with “inert” in the language used here being understood as “not converted in the electrolysis” and is not limited to classic inert gases.
  • the electrolysis carried out in the context of the present invention can be carried out using one or more electrolysis cells, one or more electrolysers each with one or more electrolysis cells or one or more other structural units suitable for electrolysis. This is or are set up in the context of the present invention in particular to carry out a low-temperature electrolysis with aqueous electrolytes, as was explained at the beginning.
  • high-temperature electrolysis can also be provided.
  • the one or more electrolysis cell (s) are also set up for such a method.
  • no aqueous electrolytes are provided, but solid electrolytes, for example of a ceramic type and / or based on transition metal oxides.
  • substance flows, gas mixtures, etc. in the language used here can be “enriched” or “depleted” in one or more components, whereby these terms each refer to a corresponding content in a starting mixture. They are “enriched” if they are at least 1.1 times, 1.5 times, 2 times, 5 times, 10 times, 100 times or 1000 times the salary, “depleted” if they are at most contain 0.9 times, 0.75 times, 0, 5 times, 0.1 times, 0.01 times or 0.001 times the content of one or more components, based on the starting mixture.
  • material flows, gas mixtures, etc. can also be “rich” or “poor” in one or more components, with the indication “rich” for a content of at least 50%, 60%, 75%, 90%, 99 %, 99.9% or 99.99% and the indication “poor” for a content of at most 50%, 40%, 25%,
  • a “permeate” is understood here and below to mean a gas mixture obtained in a membrane separation which predominantly or exclusively comprises components that are not or not completely retained by the membrane used in the membrane separation, that is to say at least partially pass through the membrane
  • membranes are used that preferentially retain carbon monoxide and preferentially allow other components to pass through. In this way, these other components are enriched in the permeate.
  • Such membranes can, for example, be commercial polymer membranes which are used on an industrial scale for the separation of hydrogen and / or carbon dioxide
  • a “retentate” in the sense of this disclosure is a mixture which consists predominantly or exclusively of components which are at least partially retained by the membranes used in the membrane separation will be. A passage of the respective components can be adjusted by the appropriate choice of the membrane.
  • the present invention proposes a method for producing a carbon monoxide-rich gas product in the sense explained above, in which at least carbon dioxide is subjected to electrolysis to obtain a raw gas containing at least carbon monoxide and carbon dioxide.
  • At least carbon dioxide is subjected to electrolysis, this does not exclude that further components of a feed mixture, in particular, for example, water, can also be fed to and subjected to electrolysis.
  • a feed mixture in particular, for example, water
  • the supply of hydrogen and carbon monoxide to the electrolysis can have a positive effect on the service life of the electrolysis cell (s) due to the resulting setting of reducing conditions.
  • electrolysis can take place in the form of high-temperature electrolysis using one or more solid oxide electrolysis cells or as low-temperature electrolysis, for example using a proton exchange membrane and an electrolyte salt in aqueous solution, in particular a metal hydroxide.
  • the low-temperature electrolysis can be carried out using different liquid electrolytes, for example on an aqueous basis, in particular with electrolyte salts, on a polymer basis, on an organic solvent basis, on the basis of ionic liquids or in other configurations.
  • Cooling devices are used.
  • Corresponding heat exchangers can particularly advantageously be designed in such a way that a mixture that leaves a process step transfers its thermal energy to a mixture that is fed to the process step (“feed-effluent heat exchanger”).
  • the raw gas formed in the electrolysis can have a content of 0% to 20% hydrogen, 10% to 90% carbon monoxide and 10% to 90% carbon dioxide, especially in the non-aqueous portion (ie "dry"). Its water content depends on the temperature and the pressure and can be, for example, 10% to 60% at 80 ° C. and 100 kPa. Here and below, percentages relate to the volume or molar fraction.
  • the raw gas partially or completely adsorbs the raw gas while receiving a recycling stream enriched in carbon dioxide and depleted in carbon monoxide and other components compared to the raw gas and an intermediate product depleted in carbon dioxide and enriched in carbon monoxide and other components compared to the raw gas is subjected.
  • the intermediate product is furthermore partially or completely a membrane separation as a permeate, while obtaining a gas product enriched in carbon monoxide and depleted in hydrogen and other components, rich in carbon monoxide as retentate and a residual gas depleted in carbon monoxide and enriched in hydrogen and other components compared to the intermediate product subjected, wherein the recycling stream and thus the carbon dioxide contained therein is at least partially returned to the electrolysis and the residual gas is at least partially returned together with the raw gas for adsorption.
  • An essential aspect of the present invention is therefore to use a raw gas from electrolysis, which due to the electrolysis conditions used contains at least carbon monoxide and carbon dioxide, but can also contain significant proportions of hydrogen, initially using adsorption, in particular pressure swing adsorption, vacuum pressure swing adsorption and / or a temperature swing adsorption, before a membrane separation is carried out.
  • the water contained in the raw gas is advantageously partially or completely removed from the raw gas before it is fed to the adsorption.
  • the separated water can be partially or completely returned to the electrolysis.
  • the inventive arrangement of the adsorption upstream of the membrane separation results in several advantages which have a positive effect on the separation performance. In this way, water is removed from the raw gas before the membrane is separated, which saves energy in the process.
  • the (almost) quantitative separation of the carbon dioxide contained in the raw gas by adsorption results in a lower volumetric load on the membrane in the downstream membrane separation, whereby a higher resistance and better separation performance can be achieved there. Because a larger amount of by-products, such as hydrogen, can be discharged in the residual gas, the yield of carbon monoxide is also increased in relation to the amount of carbon dioxide used.
  • an intermediate product is formed in adsorption, as is a gas mixture referred to here as the "recycling stream".
  • the former is particularly heavily depleted in carbon dioxide, since this adsorbs to the adsorbent used in adsorption.
  • Carbon monoxide is distributed in particular between the intermediate product and the recycling stream The proportions can be influenced by choosing appropriate adsorption conditions.
  • the intermediate product is therefore low in or free of carbon dioxide and can consist predominantly or exclusively of carbon monoxide and possibly hydrogen consist.
  • the intermediate contains less than 5%, 4%, 3%,
  • the carbon monoxide-rich gas product is formed as retentate as well as a gas mixture, referred to here as residual gas, which is formed using permeate fractions.
  • the carbon monoxide-rich gas product hydrogen and carbon dioxide are depleted and carbon monoxide is enriched compared to the intermediate product.
  • carbon dioxide is hardly contained in any significant amount.
  • the gas product contains, for example, 90% to 100% carbon monoxide, 0% o to 1% o carbon dioxide,
  • the residual gas contains the majority of the hydrogen contained in the intermediate product and is otherwise essentially composed of carbon monoxide and carbon dioxide. However, since the latter has already been removed for the most part in the adsorption, the residual gas is low in carbon dioxide.
  • Another essential aspect of the present invention is to recycle portions of the recycling stream (together with fresh input) into the electrolysis and / or recycle portions of the residual gas (together with the raw gas) for adsorption.
  • advantageous conditions can be set for the process steps by adapting the composition of the respective insert.
  • carbon dioxide for electrolysis and carbon monoxide can be returned to the separation process in a targeted or targeted manner. This is advantageous because, depending on the design, the electrolysis of Carbon dioxide is favored to carbon monoxide when there is an excess of carbon dioxide.
  • carbon dioxide contained in the raw gas can be used to improve the yield of a corresponding process by partially or completely returning it to the electrolysis.
  • this does not exclude the possibility that other components, intentionally or unintentionally, can also be returned to the electrolysis.
  • the return of the carbon monoxide contained in the residual gas to the adsorption increases the product yield, since this can ultimately be converted into the gas product in this way and is not lost via the residual gas.
  • the admixture of residual gas to the raw gas reduces the concentration of carbon dioxide before entering the adsorption, which has an advantageous effect on the process management, in particular with regard to the pressure setting.
  • a fresh feed containing at least predominantly carbon dioxide can also be fed to the electrolysis.
  • This fresh use can for example have a content of more than 90%, 95%, 99%, 99.9% or 99.99% of carbon dioxide.
  • the higher this proportion the fewer by-products there are in the electrolysis formed and the lower the proportion of non-product components that have to be separated from the raw gas.
  • the use of a suitable membrane separation downstream of the adsorption can prevent undesirably high amounts of by-products from getting into the carbon monoxide-rich gas product.
  • the separation performance and the service life of the membrane can be improved.
  • the membrane separation comprises at least a first and a second membrane separation step, the permeate being formed using permeate fractions from the first and / or second separation step.
  • the membrane separation comprises a first and a second membrane separation step and that the permeate of one of the membrane separation steps is fed to the input mixture of another of the membrane separation steps to increase the yield and / or purity while increasing the pressure by means of a compressor.
  • At least part of the residual gas (which is otherwise returned to the process) is discharged from the process.
  • a partial flow is branched off from the residual gas in the form of a so-called purge.
  • the components contained in a corresponding purge are removed from the process and thus removed from the process.
  • the membrane separation comprises a first and a second membrane separation step, wherein in one of the two membrane separation steps a membrane is used that generates a permeate that is particularly rich in by-products, in particular hydrogen and / or inert components.
  • a membrane is used that generates a permeate that is particularly rich in by-products, in particular hydrogen and / or inert components.
  • the electrolysis is carried out on an electrolysis pressure level, the adsorption on an adsorption pressure level and the membrane separation on a membrane pressure level.
  • the adsorption pressure level and the membrane pressure level are each the entry pressures in the respective process steps.
  • a first pressure level is “at” a second pressure level if the two pressure levels do not differ from one another by more than 0.1 MPa, 0.2 MPa, 0.3 MPa or 0.5 MPa.
  • a first pressure level is “above” a second pressure level if it is in particular more than 0.5 MPa and up to 3 MPa above the first pressure level.
  • the electrolysis can be operated at the (entry or upper) pressure level of the adsorption (which in the case of pressure swing adsorption is, for example, 1 MPa to 8 MPa, preferably 1 MPa to 4 MPa), or at a lower pressure level.
  • the raw gas does not have to be compressed, or only to a small extent.
  • the recycling stream has to be compressed to the electrolysis pressure level, since it leaves the adsorption at a desorption pressure level which, in the case of pressure swing adsorption, is significantly below the adsorption pressure level.
  • the raw gas or its adsorption portion has to be compressed to the adsorption pressure level, whereby it may be possible to dispense with compressing the recycling stream before it is fed to the electrolysis.
  • the adsorption can take the form of vacuum pressure swing adsorption be executed.
  • the adsorption pressure level is then at the electrolysis pressure level (for example 100 kPa to 1000 kPa, preferably 100 to 500 kPa) and the desorption pressure level (for example 20 kPa to 90 kPa, preferably 30 kPa to 70 kPa) is below the electrolysis pressure level.
  • the electrolysis pressure level for example 100 kPa to 1000 kPa, preferably 100 to 500 kPa
  • the desorption pressure level for example 20 kPa to 90 kPa, preferably 30 kPa to 70 kPa
  • the permeate from the membrane separation can be returned to the electrolysis via the same compressor as the recycling stream from the adsorption. This means that a compressor can be saved.
  • a raw gas is advantageously formed which has a content of 10% to 95% carbon monoxide, 0% to 10% hydrogen and 5% to 90% carbon dioxide.
  • the present invention also extends to a plant for the production of a carbon monoxide-rich gas product according to the corresponding independent claim.
  • FIG. 1 illustrates a method according to an embodiment of the invention.
  • Figure 2 illustrates a method according to an embodiment of the invention.
  • FIG. 3 illustrates a method according to an embodiment of the invention.
  • FIG. 4 illustrates a method according to an embodiment of the invention.
  • An electrolysis E which can be carried out as explained at the beginning, is provided as an essential process step of the process.
  • a carbon dioxide-rich electrolysis insert 2 fed to the electrolysis contains carbon dioxide. This is partially converted in the electrolysis E to carbon monoxide, which passes from the cathode side of the electrolysis unit (s) into the raw gas 3, which, depending on the electrolysis conditions and the components of the electrolysis insert 2, may also contain other components.
  • the oxygen produced on the anode side is not shown in the figures and is removed from the process.
  • the addition, separation and discharge or recycling of water are also not shown any heat exchangers and / or external heat sources that can be used as described above.
  • the raw gas contains, for example, approximately 1% hydrogen, 34% carbon monoxide and 65% carbon dioxide, based on the dry raw gas. It is formed, for example, in an amount of approx. 500 Nm 3 / h and is present at the electrolysis pressure level of approx. 0 kPa to 100 kPa above atmospheric pressure, for example approx. 150 kPa absolute. After compression to the adsorption pressure level (for example 2 MPa), it is completely fed to an adsorption A as part of an adsorption insert 4 explained below according to the present embodiment according to the invention.
  • the temperatures used in an electrolysis are, for example, in a range from 20 ° C to 80 ° C, for example approx. 60 ° C. Complete conversion of the carbon dioxide used is generally not desired in order to protect the electrolysis material or is not possible in terms of reaction kinetics, which is why the raw gas also contains carbon dioxide.
  • the adsorption insert 4 which contains, for example, approx. 3% hydrogen, 38% carbon monoxide and 58% carbon dioxide and is provided, for example, in a mass flow of approx. 550 Nm 3 / h, is processed.
  • the recycling stream 7 is from the desorption pressure level, which is, for example, approx.
  • 120 kPa is compressed to the electrolysis pressure level by means of a compressor and with a fresh insert 1, which comprises, for example, approx. 110 Nm 3 / h of pure carbon dioxide, to the electrolysis insert 2, which contains approx. 0.2% hydrogen,
  • the intermediate product 5 is according to the embodiment of the invention illustrated here downstream of the adsorption A without adjusting the pressure of a Membrane separation M supplied.
  • the membrane pressure level is accordingly at the adsorption pressure level, as explained above.
  • a carbon monoxide gas product 6 with a composition of, for example, approx. 0.1% hydrogen, 99.9% carbon monoxide and 100 ppm carbon dioxide and approx. 60 Nm 3 / h of a residual gas 8 and 9, which is composed, for example, of approx. 22% hydrogen, 78% carbon monoxide and 0.2% carbon dioxide.
  • a portion of the residual gas for example approx. 10 Nm 3 / h, is withdrawn as a purge 9 with the same composition as the residual gas from the process.
  • the remaining portion of the residual gas 8 is mixed and compressed downstream of the electrolysis E with the raw gas 3 while retaining the adsorption insert 4.
  • the method illustrated in FIG. 2 differs from the method illustrated in FIG. 1 in particular by the multi-stage execution of the membrane separation.
  • the intermediate product 5 is accordingly processed in a first membrane separation step M1 to obtain a first retentate 12 and a first permeate 14.
  • the first membrane separation step M1 is carried out, for example, in such a way that a high concentration of hydrogen in the first permeate 14, for example a proportion of more than 25%, is achieved.
  • the first retentate is processed in a second membrane separation step M2 to obtain a second retentate 13 and the carbon monoxide gas product 6.
  • the residual gas 8, which is formed using the permeates 13 and 14, is mixed and compressed downstream of the electrolysis E together with the raw gas 3 to the adsorption insert 4.
  • the removal of the purge 9 to be removed from the process can in this embodiment of the process take place with particular advantage from the first permeate 14, since in this way the loss of carbon monoxide and carbon dioxide, as already described, can be minimized.
  • FIG 3 an embodiment of the method according to the invention is illustrated in which the adsorption is carried out in the form of a vacuum pressure swing adsorption VA.
  • the raw gas 3 is subjected to vacuum pressure swing adsorption VA, and compression of the adsorption insert can be dispensed with.
  • the electrolysis pressure level essentially corresponds to the adsorption pressure level of approximately 150 kPa, for example.
  • the residual gas 8 formed in the membrane separation M is compressed together with the intermediate product 5 to the membrane pressure level of, for example, approximately 2 MPa and returned to the membrane separation M.
  • FIG. 4 illustrates an embodiment within the scope of the present invention in which the electrolysis E is carried out in the form of high pressure electrolysis at an electrolysis pressure level of, for example, approximately 2 MPa. Compression of the raw gas to form the adsorption insert 4 can also be dispensed with in this embodiment.
  • the adsorption A is carried out at the electrolysis pressure level.
  • the residual gas 8 from the membrane separation M is compressed together with the recycling stream 7 to form a recycling insert 10, which is returned to the electrolysis E together with the fresh insert 1 as an electrolysis insert 2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Automation & Control Theory (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Separation Of Gases By Adsorption (AREA)

Abstract

L'invention concerne un procédé de production d'un produit gazeux riche en monoxyde de carbone (6), dans lequel au moins du dioxyde de carbone est soumis à une électrolyse (E), de manière à obtenir un gaz non traité (3) comprenant au moins du monoxyde de carbone et du dioxyde de carbone, et dans lequel procédé le gaz non traité (3) est soumis à un processus de séparation qui comprend une adsorption (A) et la séparation membranaire (M), de manière à obtenir un flux de recyclage (7), qui comprend la majeure partie du dioxyde de carbone contenu dans le gaz non traité (3), un gaz résiduel (8), et le produit gazeux riche en monoxyde de carbone (6), le flux de recyclage (7) est partiellement ou entièrement recirculé vers l'électrolyse (E), le gaz non traité (3) est partiellement ou entièrement soumis à l'adsorption (A) de façon à obtenir le flux de recyclage (7) et un flux de produit intermédiaire (5) qui est enrichi en monoxyde de carbone et appauvri en dioxyde de carbone par rapport au gaz non traité (3), et le flux de produit intermédiaire (5) est partiellement ou entièrement soumis à la séparation membranaire (M) de manière à obtenir le produit gazeux (6) et le gaz résiduel (8), le gaz résiduel (8) étant partiellement ou entièrement remis en circulation vers l'adsorption (A). L'invention concerne également une installation permettant de réaliser un tel procédé.
EP20786449.7A 2019-10-18 2020-09-22 Procédé et installation pour la fabrication d'un produit gazeux riche en monoxyde de carbone Pending EP4045172A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102019007265.0A DE102019007265A1 (de) 2019-10-18 2019-10-18 Verfahren und Anlage zur Herstellung eines an Kohlenstoffmonoxid reichen Gasprodukts
PCT/EP2020/025430 WO2021073769A1 (fr) 2019-10-18 2020-09-22 Procédé et installation pour la fabrication d'un produit gazeux riche en monoxyde de carbone

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EP4045172A1 true EP4045172A1 (fr) 2022-08-24

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US (1) US20220235478A1 (fr)
EP (1) EP4045172A1 (fr)
JP (1) JP2022552039A (fr)
KR (1) KR20220079511A (fr)
CN (1) CN113939612A (fr)
CA (1) CA3143870A1 (fr)
DE (1) DE102019007265A1 (fr)
TW (1) TW202116674A (fr)
WO (1) WO2021073769A1 (fr)

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Publication number Priority date Publication date Assignee Title
FR2788051B1 (fr) * 1999-01-05 2001-02-09 Air Liquide Procede et installation de production de monoxyde de carbone ou d'un melange co/h2
TWI500820B (zh) 2012-03-05 2015-09-21 製造高純度一氧化碳之設備
ES2820347T3 (es) 2013-03-26 2021-04-20 Haldor Topsoe As Un proceso para producir CO a partir de CO2 en una célula de electrolisis de óxido sólido
ES2583903T3 (es) 2013-07-30 2016-09-22 Haldor Topso¿E A/S Procedimiento para producir CO de alta pureza mediante purificación con membrana de CO producido mediante SOEC
EP2940773A1 (fr) 2014-04-29 2015-11-04 Haldor Topsøe A/S Éjecteur pour système d'empilement de cellule d'électrolyse d'oxyde solide
DE102015202117A1 (de) 2015-02-06 2016-08-11 Siemens Aktiengesellschaft Verfahren und Elektrolysesystem zur Kohlenstoffdioxid-Verwertung
DE102015202258A1 (de) 2015-02-09 2016-08-25 Siemens Aktiengesellschaft Reduktionsverfahren und Elektrolysesystem zur elektrochemischen Kohlenstoffdioxid-Verwertung
EP3368193A4 (fr) * 2015-10-26 2019-06-26 Uop Llc Procédé pour maximiser la récupération d'hydrogène
DE102017005681A1 (de) 2017-06-14 2018-12-20 Linde Aktiengesellschaft Verfahren und Anlage zur Herstellung eines Kohlenmonoxid enthaltenden Gasprodukts
DE102017005678A1 (de) 2017-06-14 2018-12-20 Linde Aktiengesellschaft Verfahren und Anlage zur Herstellung eines Kohlenmonoxid enthaltenden Gasprodukts
DE102017005680A1 (de) * 2017-06-14 2018-12-20 Linde Aktiengesellschaft Verfahren und Anlage zur Herstellung eines Kohlenmonoxid enthaltenden Gasprodukts

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TW202116674A (zh) 2021-05-01
WO2021073769A1 (fr) 2021-04-22
KR20220079511A (ko) 2022-06-13
US20220235478A1 (en) 2022-07-28
CA3143870A1 (fr) 2021-04-22
JP2022552039A (ja) 2022-12-15
CN113939612A (zh) 2022-01-14
DE102019007265A1 (de) 2021-04-22

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