EP3638827A1 - Procédé et installation pour la préparation d'un produit gazeux contenant du monoxyde de carbone - Google Patents

Procédé et installation pour la préparation d'un produit gazeux contenant du monoxyde de carbone

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Publication number
EP3638827A1
EP3638827A1 EP18729866.6A EP18729866A EP3638827A1 EP 3638827 A1 EP3638827 A1 EP 3638827A1 EP 18729866 A EP18729866 A EP 18729866A EP 3638827 A1 EP3638827 A1 EP 3638827A1
Authority
EP
European Patent Office
Prior art keywords
electrolysis
mixture
carbon monoxide
gas
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.)
Withdrawn
Application number
EP18729866.6A
Other languages
German (de)
English (en)
Inventor
Werner Leitmayr
Clara DELHOMME-NEUDECKER
Andreas Peschel
Benjamin HENTSCHEL
Anette Franz
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 EP3638827A1 publication Critical patent/EP3638827A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • B01D53/22—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)
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40007—Controlling pressure or 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
    • B01D53/22—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
    • B01D53/225—Multiple stage diffusion
    • B01D53/226—Multiple stage diffusion in serial connexion

Definitions

  • the present invention relates to a method and apparatus for producing a gas product containing at least carbon monoxide according to the respective ones
  • Carbon monoxide can be prepared by a variety of different methods, for example, along with hydrogen by steam reforming of
  • the present invention relates in addition to the production of carbon monoxide or
  • a membrane is used, through which the positive charge carriers (M + ) required according to reaction equation 2 or formed according to reaction equation 3 migrate from the anode to the cathode side.
  • the transport of the positive charge carriers takes place here not in the form of oxygen ions but, for example, in the form of positive ions of the electrolyte salt used (of a metal hydroxide, MOH).
  • An example of a corresponding electrolyte salt may be potassium hydroxide.
  • the positive charge carriers are potassium ions.
  • Other embodiments NT electrolysis include, for example, the use of
  • PEM Proton exchange membranes
  • AEM anion exchange membranes
  • additional value-added products can also be formed in the NT co-electrolysis.
  • an NT co-electrolysis can be carried out to form different amounts of hydrogen.
  • the present invention therefore has as its object to show concepts for the separation of corresponding gas mixtures, in addition to carbon monoxide and
  • Carbon dioxide can also contain hydrogen.
  • the present invention proposes a method for
  • Membrane process or a membrane separation upstream of the formation of said gas product from the crude gas of a carbon dioxide electrolysis or co-electrolysis by adsorption for example pressure swing adsorption (PSA) or temperature swing adsorption (TSA), ie the use of a Pre-separation by a membrane process upstream of the adsorption.
  • PSA pressure swing adsorption
  • TSA temperature swing adsorption
  • the carbon dioxide electrolysis or co-electrolysis can in the context of the present invention in the form of HT electrolysis using one or more solid oxide electrolysis cells or as NT co-electrolysis, for example using a proton exchange membrane and an electrolyte salt in aqueous solution, in particular a metal hydroxide , respectively.
  • the NT co-electrolysis can be carried out using different liquid electrolytes, for example on an aqueous basis, in particular with electrolyte salts, on a polymer basis or in other embodiments.
  • Hydrogen is formed, in addition to water.
  • NT co-electrolysis due to the presence of water, there will always be some, but depending on the particular specific embodiment of the process variable, formation of hydrogen.
  • Gas product is to be formed, to an undesirable contamination of the
  • Carbon monoxide and at the same time does not lead to an accumulation of hydrogen in a cycle formed by the return of carbon dioxide.
  • part of the carbon dioxide in the raw gas is already separated upstream of the adsorption, so that it can be dimensioned much smaller.
  • the advantages of using a membrane process are, in particular, that some of the hydrogen is separated from the raw gas with part of the carbon dioxide and can be recycled with the carbon dioxide.
  • the adsorption can be smaller.
  • the recycling of hydrogen is due to its reducing
  • the present invention proposes a method for producing a gas product containing at least carbon monoxide, in which at least
  • Carbon dioxide to obtain an at least carbon monoxide and carbon dioxide-containing raw gas is subjected to electrolysis.
  • electrolysis process reference is made to the above explanations.
  • the present invention is described below in particular with reference to the NT co-electrolysis of carbon dioxide and water, but also an HT electrolysis is readily usable, in which also hydrogen can be in the raw gas, especially if in this case additionally subjected to electrolysis of water or when hydrogen is mixed as corrosion protection in the Elektrolyserohoch. Therefore, if it is mentioned here that "at least carbon dioxide” is subjected to electrolysis, this does not exclude the possibility that other components of a feed mixture used in the context of the present invention and supplied to the electrolysis can also be subjected to electrolysis. As explained above, this may in particular be water, which can be converted to hydrogen and oxygen. In this way, a the typical components of synthesis gas exhibiting gas mixture are obtained, as also previously explained.
  • raw gas Language usage referred to as "raw gas”.
  • crude gas for example, even oxygen or unreacted inert
  • electrolysis carried out in the context of the present invention can be carried out using one or more electrolysis cells, one or more electrolyzers each having one or more electrolysis cells or one or more others for electrolysis
  • Electrolysis be recycled.
  • carbon dioxide is recycled to the electrolysis, this does not exclude that other components, intentionally or unintentionally, for electrolysis can be attributed, for example by, as also below explains, a partial direct recycling of raw gas without separation of certain components is made.
  • a corresponding recycling can optionally take place in the process according to the invention, but is not
  • the crude gas is partially or completely subjected to membrane separation to obtain a retentate mixture and a permeate mixture enriched in carbon dioxide with respect to the crude gas.
  • the retentate mixture can be enriched in particular with respect to the crude gas to carbon monoxide and depleted of carbon dioxide.
  • Retentate mixture is further depleted of carbon dioxide especially against the raw gas.
  • the retentate mixture in the membrane separation can also be depleted of hydrogen relative to the raw gas or the permeate mixture also be enriched in hydrogen to the raw gas when hydrogen is present in the raw gas in a higher content than is desired in the gas product, for example, when carbon monoxide is to be formed as a gas product.
  • the term “rich” being for a content of at least 50%, 60%, 75%, 80%, 90%, 95%, 98%, 99%, 99.5%, 99.9% or 99.99% and the statement “poor” for a maximum content of 50%, 40%, 25%, 20%, 10%, 5%, 2 %, 1%, 0.5%, 0, 1% or 0.01% may be on a molar, weight or volume basis.
  • the term “rich” or “poor” refers to the sum of all components. If, for example, "carbon monoxide” is mentioned here, it can be a pure gas or a mixture rich in carbon monoxide. A gas mixture containing "predominantly" one or more components is particularly rich in this or this in the sense explained.
  • Material streams, gas mixtures, etc. may also be “enriched” or “depleted” in one or more components as used herein, which terms refer to a content in a starting mixture. They are “enriched” if they are at least 1, 1, 1, 5, 2, 5, 10, 100 or 1000 times “depleted,” if they are at most 0.9-fold, 0.75-fold, 0.5-fold, 0, 1-fold, 0.01-fold or 0.001-fold content of one or more components, based on the
  • membrane separation upstream and in addition to separation by adsorption makes it possible to prevent hydrogen from passing into a carbon monoxide-rich gas product of the process. If hydrogen is present in an adsorption reaction, it typically passes into the gas product together with carbon monoxide and subsequently is difficult to separate from carbon monoxide.
  • a "permeate mixture” is understood as meaning a mixture which predominantly or exclusively comprises components which are not or predominantly components of a membrane used in a membrane separation are not retained, so pass through the membrane (substantially or at least preferably) unhindered.
  • a membrane is used, preferably a passage of hydrogen (if present) and
  • a membrane is, for example, commercial polymer membranes which are used industrially for the separation of carbon dioxide and / or hydrogen.
  • a "retentate mixture" is a mixture which predominantly has components which differ from those described in US Pat
  • Membrane membrane used completely or at least predominantly retained. However, as explained below, too
  • the retentate mixture is enriched in carbon monoxide and enriched with respect to the retentate mixture
  • Carbon dioxide depleted gas product in particular one in the above sense of carbon monoxide rich gas product or synthesis gas, which contains at most small amounts of minor components, and one of the retentate depleted of carbon monoxide and carbon dioxide enriched residual mixture partially or completely subjected to adsorption.
  • the permeate mixture and / or the residual mixture are partly or completely recycled to the electrolysis.
  • One or more appropriately recycled material streams are also referred to in this application as "recycle streams".
  • a recycle stream may be a collection stream formed from the permeate mixture and the remainder mixture or portions thereof.
  • the electrolysis can be carried out at a pressure level corresponding to a pressure level at which the crude gas is fed to the membrane separation (ie not deviating by more than 1 bar, for example), the recycle stream or streams using one or more compressors , so-called recycle compressor, are compressed to the pressure level of the electrolysis.
  • the raw gas does not have to be compressed in such a case.
  • the electrolysis may also be carried out at a pressure level which is lower (for example at least 1, 2, 3, 4, 5, 10, 20, 40 or 80 bar lower) than a pressure level at which the crude gas is fed to the membrane separation becomes.
  • the raw gas is compressed to the pressure level of the membrane separation using one or more compressors, so-called crude gas compressor.
  • larger quantities of gas must be compressed in this alternative, but the electrolysis can be carried out at lower pressure, and thus possibly easier.
  • the membrane separation can advantageously be carried out in such a way that the retentate mixture is depleted of hydrogen relative to the crude gas and the permeate mixture is enriched in hydrogen relative to the crude gas. This is especially true in the event that a carbon monoxide or a
  • carbon monoxide-rich gas mixture is to be formed as a product, not or less, however, in the event that synthesis gas is to be formed as a product.
  • a carbon dioxide-selective membrane is particularly useful in Lin, H. et al. (2014) J. Membr. Be. 457 (1), 149-161, DOI: 10.1016 / j.memsci.2014.01.020.
  • carbon dioxide-selective membrane are used to obtain the carbon monoxide formed in the electrolysis and the hydrogen as a retentate mixture.
  • Carbon dioxide permeable membrane to obtain a hydrogen-containing Recycled flow, and a carbon dioxide permeable membrane, to obtain a carbon dioxide recycle stream, be applied.
  • Permeate mixture contained hydrogen is discharged from the process, if carbon monoxide or a carbon monoxide-rich gas mixture is to be formed as a product. In the production of synthesis gas is a corresponding
  • Discharge usually not required.
  • a portion of the hydrogen is discharged from the process, also includes that in addition to the hydrogen, other components are discharged.
  • a substream in the form of a so-called purge is merely branched off from a stream fed back for electrolysis, but hydrogen is not selectively removed or removed.
  • the hydrogen contained in a corresponding purge is discharged from the process, but at the same time other contained components are removed from the process.
  • an especially targeted i.
  • Gain gas products if desired. It is understood that this also applies in particular when carbon monoxide or a carbon monoxide-rich gas mixture is to be formed as a product.
  • the hydrogen removal can be carried out in particular in the form of a catalytic and / or a non-catalytic oxidation. In the case of catalytic oxidation, this may be particularly selective. As also explained in more detail with reference to the accompanying drawings, the catalytic oxidation can be carried out using oxygen, which is also formed in the electrolysis.
  • a non-catalytic oxidation may in particular include a thermal oxidation (combustion), which in particular also using a
  • Internal combustion engine in particular a gas turbine, can be made. Again, this can be advantageously carried out using oxygen, which is formed in the electrolysis. In this way, the total energy efficiency of the proposed method according to the invention can be further improved.
  • a first portion of the permeate mixture and / or the residual mixture is combined in the form of or the recycle streams with the crude gas and subjected to the membrane separation, whereas a second portion of the permeate mixture and / or the residual mixture a fresh use combined and returned to the electrolysis.
  • Carbon monoxide in the input stream of the electrolysis are reduced. As mentioned there, depending on the particular design of the electrolysis, this can be advantageous for the performance and / or lifetime of the technical equipment used in the electrolysis. Since, in the membrane process used, the membrane selectively separates hydrogen and carbon dioxide from carbon monoxide, the partial recycling has no influence on the subsequent adsorption, as long as the membrane surface is suitably adapted.
  • Crude gas a low-cost blower can be used.
  • the method according to the invention comprises
  • Membrane separation at least two membrane separation steps, wherein the permeate mixture in each case in the at least two membrane separation steps formed permeate parts.
  • the membrane separation comprises at least two membrane separation steps and that the permeate mixture of a downstream membrane separation step for increasing the carbon monoxide yield with pressure increase by means of a
  • Compressor is returned to an upstream membrane separation step.
  • the membrane separation comprises at least two membrane separation steps, and that the permeate mixture of an upstream membrane separation step Pressure increase is supplied by means of a compressor to a downstream membrane separation step.
  • a retentate mixture is obtained, which is recycled to increase the carbon monoxide yield to an upstream membrane separation step is subjected.
  • the contents of hydrogen, carbon monoxide and carbon dioxide depend on the electrolysis process carried out (HT electrolysis, HT co-electrolysis, NT co-electrolysis) and the desired gas product (carbon monoxide or synthesis gas). According to a first embodiment of the present invention is thereby
  • gas product containing 90 to 100%, in particular 95 to 100%, for example 98 to 100%, carbon monoxide. It is then a
  • Carbon monoxide product In this case, the raw gas 10 to 95%, in particular 20 to 90%, advantageously 30 to 70%, carbon monoxide, 0 to 20%, in particular 1 to 15%, advantageously 1 to 10%, hydrogen and 5 to 90%, in particular 20 to 80%, advantageously 30 to 70%, containing carbon dioxide.
  • retentate mixture (RG) and permeate mixture (PG) can have, in particular, the contents of carbon monoxide (CO), hydrogen (H 2 ) and carbon dioxide (CQ 2 ) indicated in the table below.
  • a carbon monoxide and hydrogen-containing gas mixture ie a synthesis gas product
  • a ratio of hydrogen to carbon monoxide of about 1 to 4 or with a stoichiometry of 0.8 to 2.1
  • the gas product in total from 90 to 100%, in particular 95 to 100%, advantageously 99 to 100%, carbon monoxide and hydrogen.
  • the stoichiometric number SN is calculated from the mole fractions x of hydrogen, carbon dioxide and
  • Carbon monoxide to SN (x H 2 -x CO 2 ) / (x CO + x CO 2 ).
  • Typical fields of use for synthesis gas, as known in the art, may be different depending on the ratio of hydrogen to carbon monoxide.
  • retentate mixture (RG) and permeate mixture (PG) for the ratios of hydrogen to carbon monoxide (H 2 / CO) given in each case, in particular the contents of carbon monoxide (CO), hydrogen (H 2 ) and carbon dioxide indicated in the table below (CO2).
  • the present invention also extends to a plant for producing a carbon monoxide-containing gas product according to the corresponding independent claim.
  • a plant for producing a carbon monoxide-containing gas product according to the corresponding independent claim.
  • FIG. 1 illustrates a method according to an embodiment of the invention.
  • FIG. 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.
  • FIG. 5 illustrates a method according to an embodiment of the invention.
  • each other is functional and / or constructive or constructive
  • Embodiments of the invention configured systems in the same way. If, therefore, method steps are explained below, these explanations apply to
  • FIG. 1 a method according to an embodiment of the invention is illustrated schematically and designated 100 as a whole.
  • an electrolysis 10 is provided, which in particular in the form of a high-temperature electrolysis using one or more solid oxide electrolysis cells and / or a
  • Electrolysis techniques can be used within the scope of the present invention.
  • the electrolysis 10 may in particular be carried out using one or more electrolysis cells, groups of electrolysis cells and the like.
  • An insert in the form of a stream H fed to the electrolysis 10 will be explained below. This comprises at least carbon dioxide, which is partially converted in the electrolysis 10 to carbon monoxide.
  • a crude gas A is obtained, which has a composition which is determined by the electrolysis 10 supplied inserts and the
  • the raw gas A contains hydrogen, carbon monoxide and carbon dioxide.
  • the carbon monoxide contained in the crude gas A is one of the target products of the process 00.
  • the carbon dioxide contained in the raw gas A is that carbon dioxide which was supplied to the electrolysis 10 but was not converted there.
  • non-negligible proportions of hydrogen are contained in a corresponding raw gas A, since formation of hydrogen in the electrolysis 10 may or may not be completely avoided.
  • the present invention particularly aims to ensure that such hydrogen does not transfer to a carbon monoxide rich gas product D of process 100.
  • the crude gas A contains in the illustrated example, for example, about 2.5% hydrogen, 34% carbon monoxide and 63% carbon dioxide. It is formed in the example shown, for example, in an amount of 478 standard cubic meters per hour and completely fed to a membrane separation 20.
  • the raw gas A lies here
  • the electrolysis 10 is carried out in the example shown, for example, at a temperature of 30 ° C.
  • the temperatures used in a corresponding NT electrolysis 10 are for example in a range of about 20 to 80 ° C. To a good one
  • the crude gas A to give a comparison with the raw gas A enriched in carbon monoxide and depleted in carbon dioxide and hydrogen retentate mixture B and one with respect to the raw gas A.
  • Carbon monoxide depleted and enriched in carbon dioxide and hydrogen permeate C processed As mentioned, it will be through the use of
  • Membrane separation possible, in a subsequent, here denoted by 40 adsorption to obtain a substantially hydrogen-free and rich in carbon monoxide product. This will be explained below. While the
  • Hydrogen removal substantially affects the purity of the carbon monoxide product D, the reduced carbon dioxide content in the retentate C leads to a significant reduction of the adsorbent material and thus a cost savings, since less carbon dioxide must be adsorbed.
  • a heat exchange can be carried out upstream and / or downstream of the electrolysis 10. It is also possible to use a so-called Feed Effluent Heat Exchanger, in which, for example, the stream H is warmed for electrolysis 10 and the crude gas A is cooled in countercurrent thereto, for example. This is not illustrated in FIG. Likewise, a water separation is not illustrated, in the context of which condenses contained in the raw gas A water vapor and optionally can be returned to the electrolysis 10. After such a water separation, so that the temperature level of the raw gas A is above the dew point, upstream of the membrane separation 20, a renewed heating, typically by about 5 to 20 ° C, made.
  • Removal of oxygen and a catalytic de-oxo reactor in the stream of raw gas A can be installed.
  • suitable catalysts for example, the oxidation of hydrogen to water from 70 ° C and from
  • the retentate mixture B which is formed as a retentate of the membrane separation 20, contains in the illustrated example, for example, about 0.2% hydrogen, 70%
  • Carbon monoxide and 30% carbon dioxide It will be in the example shown
  • a membrane area in the membrane separation 20 is preferably designed such that a correspondingly lower water content fraction is contained in the retentate mixture B.
  • the permeate mixture C which is formed as permeate of the membrane separation 20, in the illustrated example, for example, at a pressure level of about 1, 2 bar before. It is formed in the example shown, for example, in an amount of 277 standard cubic meters per hour and has a hydrogen content of about 4%, a
  • a permeate stream designated H2 is separated off from the permeate mixture C, for example in an amount of about 20 standard cubic meters per hour, and discharged from the process 100.
  • This can be a
  • Enrichment of hydrogen can be avoided in a cycle formed in the process 100 by the return of corresponding gas mixtures. In other words, therefore, part of the hydrogen contained in the permeate C mixture is discharged from the process here, wherein in a simple branching and
  • Components are removed in appropriate proportions. A portion of the permeate mixture C remaining after the separation is returned to the electrolysis 0, as also explained below.
  • the retentate mixture B is in the example shown the already mentioned
  • Retentate mixture B enriched in carbon monoxide and carbon dioxide
  • Carbon monoxide depleted and enriched in carbon dioxide residual mixture E are formed.
  • the gas product D represents a typical product of the process 100, which in the example shown, for example, in an amount of 100 standard cubic meters per hour, a hydrogen content of about 0.3%, a carbon monoxide content of about 99.7% and a carbon dioxide content of about 100 ppm is formed.
  • the residual mixture E is in the example shown, for example, in an amount of 01
  • a part of the permeate mixture C remaining after the branching of the portion denoted by H 2 and the residual mixture E are combined prior to recirculation to the electrolysis 10 to obtain a collecting mixture forming a recycle stream F, and suitably using a compressor 30 pressurized.
  • the extent of the pressurization depends on the electrolysis conditions in the electrolysis 10. As mentioned, a pressure of about 20 bar can be used in the electrolysis 10, so that the
  • the collection mixture or the recycle stream F is formed, for example, in an amount of about 358 standard cubic meters per hour, a hydrogen content of about 3%, a carbon monoxide content of about 17% and a carbon dioxide content of about 80%.
  • Electrolysis 10 are also operated at a lower pressure level than the inlet pressure of the membrane separation 20.
  • a corresponding crude gas compressor is used for the compression of the raw gas A. It is possible in such a case to dispense with the compressor 30 and to supply the collecting mixture or the recycle stream F of the electrolysis 10 at a correspondingly lower pressure level. This variant is usually associated with higher compressor costs, since a larger gas flow must be compressed.
  • the collecting mixture or the recycle stream F is combined with a gaseous fresh feed G, which is provided in the illustrated example, for example, in an amount of 1 19 standard cubic meters per hour.
  • the fresh application G has, for example, a carbon dioxide content of about 99.9975%.
  • the electrolysis 10 is a using the
  • Fresh inserts G are used with typical purities. Especially
  • Impurities of hydrogen, carbon monoxide and water are typically not harmful in use of NT electrolysis and can be tolerated. Other impurities such as saturated hydrocarbons, nitrogen, argon and oxygen can be tolerated in use up to certain limits. In HT electrolysis, water could be removed from the feed if carbon monoxide is to be generated as a gas product.
  • FIG. 2 a method according to a further embodiment of the invention is illustrated schematically and designated overall by 200.
  • the method 200 illustrated in FIG. 2 differs, in particular, from the method 100 illustrated in FIG. 1, in that a part of the collection mixture, as illustrated here in the form of a stream K, does not take the form of the recycle stream F to the electrolysis 10 but to the membrane separation 20 is returned.
  • a part of the collection mixture as illustrated here in the form of a stream K, does not take the form of the recycle stream F to the electrolysis 10 but to the membrane separation 20 is returned.
  • here is a first portion of the
  • the proportion of carbon monoxide in the electrolysis 10 supplied stream H can be reduced.
  • such a reduction may be beneficial to the performance and / or life of the devices used herein.
  • the membrane used in the membrane separation 20 preferably selectively separates hydrogen and carbon dioxide from carbon monoxide, the partial recirculation hardly has an influence on the downstream pressure swing adsorption 40, if the
  • FIG. 3 a method according to a further embodiment of the invention is illustrated schematically and designated overall by 300.
  • the method 300 illustrated in FIG. 3 differs in particular from the methods 100 and 200 explained above and illustrated in FIGS. 1 and 2 in that here a portion of the raw gas A, such as in the form of a
  • Material stream L illustrates, directly, d. H. bypassing the membrane separation 20, 10 for electrolysis is returned.
  • a compressor 50 can be used.
  • a first portion of the raw gas A is combined with the collecting mixture or the recycle stream F and returned to the electrolysis 10 and a second portion of the raw gas A to obtain the
  • FIG. 4 schematically illustrates a method according to a further embodiment of the invention, designated overall by 400.
  • a hydrogen removal 60 is made from the recycle stream F returned to the electrolysis 10.
  • a partial or complete removal of hydrogen can take place.
  • some of the carbon monoxide can be removed by oxidation to carbon dioxide.
  • first hydrogen can be removed by oxidation to water from about 70 ° C and at higher temperatures from about 150 ° C and carbon monoxide by oxidation to carbon dioxide at least partially.
  • second Oxdiationstemperatur in particular a remainder of oxygen can be removed.
  • Operability of the electrolysis is advantageous. Such a procedure is particularly advantageous in those cases in which a particularly pure carbon monoxide product in the form of the gas product D is desired or a particularly high carbon efficiency of a corresponding method is to be achieved. In this way, an enrichment of hydrogen in the raw gas A can be further avoided. Such selective removal of
  • Hydrogen can be made, for example, by catalytic oxidation with the addition of the oxygen by-product from the cathode side of the electrolysis 10.
  • the catalytic oxidation water is formed, which can be easily returned to the electrolysis 10 and downstream of this can be separated.
  • thermal removal by addition of oxygen in a combustion chamber by partial oxidation is alternatively possible.
  • a corresponding thermal conversion can also be carried out in a gas turbine, for example, in order to achieve a better energy efficiency of the method.
  • the methods 200 and 300 in FIGS. 2 and 3 can also be used
  • FIG. 5 a method according to a further embodiment of the invention is illustrated schematically and designated overall by 500.
  • the membrane separation 20 comprises at least two membrane separation steps 21, 22, wherein the permeate mixture C respectively comprises permeate portions C1, C2 formed in the at least two membrane separation steps 21, 22.
  • the measures illustrated in FIGS. 2 and 3 for the methods 200 and 300 can also be used in the method 500 illustrated in FIG. 5 or vice versa.

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

Abstract

L'invention concerne un procédé (100-500) pour la préparation d'un produit gazeux contenant au moins du monoxyde de carbone, dans lequel au moins le dioxyde de carbone est soumis à une électrolyse (10) avec obtention d'un gaz brut (A) contenant au moins du monoxyde de carbone et du dioxyde de carbone et dans lequel le dioxyde de carbone contenu dans le gaz brut (A) est recyclé partiellement ou complètement vers l'électrolyse (10). Selon l'invention, le gaz brut (A) est soumis partiellement ou complètement à une séparation membranaire (20) avec obtention d'un mélange de rétentat (B) et d'un mélange de perméat (C) enrichi en dioxyde de carbone par rapport au gaz brut (A) et le mélange de rétentat (B) est soumis partiellement ou complètement à une absorption à pression modulée (40) avec obtention du produit gazeux (D) enrichi en monoxyde de carbone et appauvri en dioxyde de carbone par rapport au mélange de rétentat (B) et d'un mélange résiduel (E) appauvri en monoxyde de carbone et enrichi en dioxyde de carbone par rapport au mélange de rétentat. La présente invention concerne également une installation correspondante.
EP18729866.6A 2017-06-14 2018-05-30 Procédé et installation pour la préparation d'un produit gazeux contenant du monoxyde de carbone Withdrawn EP3638827A1 (fr)

Applications Claiming Priority (2)

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DE102017005680.3A DE102017005680A1 (de) 2017-06-14 2017-06-14 Verfahren und Anlage zur Herstellung eines Kohlenmonoxid enthaltenden Gasprodukts
PCT/EP2018/000278 WO2018228716A1 (fr) 2017-06-14 2018-05-30 Procédé et installation pour la préparation d'un produit gazeux contenant du monoxyde de carbone

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EP3638827A1 true EP3638827A1 (fr) 2020-04-22

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US (1) US20200131647A1 (fr)
EP (1) EP3638827A1 (fr)
JP (1) JP2020524212A (fr)
CN (1) CN110770369A (fr)
CA (1) CA3065571A1 (fr)
DE (1) DE102017005680A1 (fr)
WO (1) WO2018228716A1 (fr)

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CN110408446B (zh) * 2019-08-01 2021-03-16 兰文旭 膜分离与变温吸附组合的液化天然气预处理设备和方法
DE102019007142A1 (de) * 2019-10-14 2021-04-15 Linde Gmbh Verfahren und Anlage zur Herstellung eines Produktgasstroms, der zumindest Kohlenstoffmonoxid enthält
DE102019007265A1 (de) * 2019-10-18 2021-04-22 Linde Gmbh Verfahren und Anlage zur Herstellung eines an Kohlenstoffmonoxid reichen Gasprodukts
WO2022118849A1 (fr) * 2020-12-02 2022-06-09 東レ株式会社 Système de séparation de gaz, et procédé pour produire du gaz
US20240035169A1 (en) 2020-12-22 2024-02-01 Topsoe A/S An improved method for operation of a solid oxide electrolysis cell in carbon dioxide electrolysis
US11717785B2 (en) * 2021-10-15 2023-08-08 Frito-Lay North America, Inc. Hybrid nitrogen gas generation system

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JPH1121118A (ja) * 1997-07-02 1999-01-26 Mitsubishi Kakoki Kaisha Ltd 高純度一酸化炭素の製造方法
CN1465523A (zh) * 2002-07-02 2004-01-07 鹰 杨 从至少含有一氧化碳、二氧化碳、氮和氢的混合气中提纯一氧化碳的方法
US20070051238A1 (en) * 2005-09-07 2007-03-08 Ravi Jain Process for gas purification
TWI500820B (zh) 2012-03-05 2015-09-21 製造高純度一氧化碳之設備
WO2014154253A1 (fr) 2013-03-26 2014-10-02 Haldor Topsøe A/S Procédé de production de co à partir de co2 dans une cellule d'électrolyse à oxyde solide
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
US9452385B1 (en) * 2015-03-04 2016-09-27 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Hybrid membrane and adsorption-based system and process for recovering CO2 from flue gas and using combustion air for adsorbent regeneration

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DE102017005680A1 (de) 2018-12-20
US20200131647A1 (en) 2020-04-30
CA3065571A1 (fr) 2018-12-20
CN110770369A (zh) 2020-02-07
JP2020524212A (ja) 2020-08-13
WO2018228716A1 (fr) 2018-12-20

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