WO2024076233A1 - Membrane composite à film mince pour électrolyse de co2 - Google Patents

Membrane composite à film mince pour électrolyse de co2 Download PDF

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WO2024076233A1
WO2024076233A1 PCT/NL2023/050506 NL2023050506W WO2024076233A1 WO 2024076233 A1 WO2024076233 A1 WO 2024076233A1 NL 2023050506 W NL2023050506 W NL 2023050506W WO 2024076233 A1 WO2024076233 A1 WO 2024076233A1
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thin film
substrate
membrane
composite membrane
film composite
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Kostadin Veselinov PETROV
David Arie VERMAAS
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Technische Universiteit Delft
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/02—Diaphragms; Spacing elements characterised by shape or form
    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/03—Acyclic or carbocyclic hydrocarbons
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • 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
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/42—Ion-exchange membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08J2300/106—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids

Definitions

  • the present invention is in the field of processes of separation using semi-permeable membranes, e.g. dialysis, osmosis, ultrafiltration, and an apparatus specially adapted therefor. It may also be considered to relate to a climate change mitigation technology in that carbon dioxide is converted by electrolysis to carbon comprising molecules, as well as to a technology for transfer of charged chemical species.
  • Electrolysis is a method using a direct electric current (DC) to drive an otherwise non-sponta- neous chemical reaction, converting first chemical species into further chemical species. Electrolysis may be used in the separation of elements, such as from naturally occurring sources using an electrolytic cell. The voltage providing the direct electric current, needed for electrolysis to occur, is referred to as the decomposition potential. The word “electrolysis” finds its origin in the Greek language.
  • the main components involved in electrolysis are an electrolyte, a positive and a negative electrode, and an external power source providing the voltage and direct electric current.
  • a separator is present, such as an ion-exchange membrane, to prevent diffusion of species to the vicinity of the opposite electrode.
  • the electrolyte is a chemical substance which contains free ions, and carries the electric current. Ions typically are mobile, in order for electrolysis to occur.
  • a liquid electrolyte may be produced by solvation, by reaction of an ionic compound with a solvent, and by melting of an ionic compound. When immersed, in an example the electrodes are separated by a distance, such that a current flows between them through the electrolyte.
  • Electrodes are connected to the external power source, which therewith completes the electrical circuit.
  • Materials of which electrodes are formed are typically a metal, graphite, and a semiconductor material. Suitable electrodes may be selected in view of chemical reactivity between the electrode and electrolyte, and manufacturing cost. Historically, graphite and platinum were often chosen.
  • a membrane is a selective barrier, allowing certain (chemical) species to pass through and preventing others from passing through.
  • Membranes can be classified into synthetic membranes and biological membranes; the present invention relates to synthetic membranes.
  • a first large scale use of membranes was in microfiltration and ultrafiltration technologies.
  • a degree of selectivity of a membrane depends amongst others on the membrane pore size. Depending on the pore size, they can be classified as microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), and reverse osmosis (RO) membranes.
  • the present invention is in the field of NF and/or RO.
  • Membranes can also be of various thickness, with homogeneous or heterogeneous structure. Membranes can be neutral or charged, and particle transport can be active or passive.
  • a thin film is a layer of material with a thickness ranging from a monolayer to several micrometers. Thin films are typically deposited, such as on a substrate, typically under well-controlled conditions. Upon deposition a controlled synthesis of materials forming the thin film occurs. A stack of thin films is called a multilayer. Deposition may take place using chemical [vapor] deposition, physical [vapor] deposition, epitaxial growth mechanisms, atomic layer deposition, and so on. Thin films find application in many fields of technology, ranging from batteries, to small apparatuses, such as acoustic wave resonators, to coatings, and so on.
  • a research trend relates to the conversion of CO2.
  • the electrochemical reduction or electrocatalytic conversion of CO2 can produce value-added chemicals, such small alkanes as methane, small alkenes, such as ethylene, small alcohols as ethanol, etc.
  • the electrolysis of carbon dioxide can result in formate (COOH ) or carbon monoxide, but sometimes more elaborate organic compounds such as ethylene.
  • the technology is under research as a carbon-neutral route to organic compounds.
  • Typical examples of prior art membranes may be found in the following documents.
  • Petrov et al. DOI: 10. 1039/d2se00858k
  • CO2R carbon dioxide
  • MEA Membrane-electrode assembly
  • a device architecture is presented incorporating an anion-exchange membrane (AEM) with internal water channels to mitigate MEA dehydration and demonstrated.
  • a macroscale, two-dimensional continuum model is used to assess water fluxes and local water content within the modified MEA, as well as to determine the optimal channel geometry and composition.
  • the modified AEMs are then fabricated and tested experimentally, demonstrating that the internal channels can both reduce K+ cation crossover as well as improve AEM conductivity and therefore overall cell performance. This work demonstrates the promise of these materials, and operando water-management strategies in general, in handling some of the major hurdles in the development of MEA devices for CO2R. Yan et al.
  • the local pH was measured and controlled within an ⁇ 50-nm -thick weak-acid layer.
  • the weak-acid layer suppressed the competing hydrogen evolution reaction without affecting CO2 reduction.
  • US 4 954 388 A recites an abrasion-resistant, tear-resistant, multilayer composite membrane, useful in electrolysis, is provided comprising a continuous perfluoro ion exchange polymer fdm attached to a reinforcing fabric by means of a porous, expanded polytetrafluoroethylene (EPTFE) interlayer.
  • the fabric and EPTFE are rendered hydrophilic and non-gas-locking by coating the interior and exterior surfaces thereof with a perfluoro ion exchange resin of equivalent weight less than 1000.
  • the composite preferably is treated with an ionic perfluoro surfactant.
  • AU 2020 393 869 Al recites membrane electrode assemblies (MEAs) for CO X reduction.
  • the MEAs are configured to address challenges particular to CO X including managing water in the MEA.
  • Bipolar and anion exchange membrane (AEM)-only MEAs are described along with components thereof and related methods of fabrication. Delacourt et al. (DOI: 10.
  • 1149/1.2801871 recites an electrolysis-cell design for simultaneous electrochemical reduction of CO2 and H2O to make syngas (CO+H2) at room temperature (25 C) was developed, based on a technology very close to that of proton-exchange-membrane fuel cells (PEMFC), i.e., based on the use of gas-diffusion electrodes so as to achieve high current densities.
  • PEMFC proton-exchange-membrane fuel cells
  • the present invention relates to an improved CO2 conversion, which overcomes one or more of the above disadvantages, without jeopardizing functionality and advantages.
  • the present invention relates in a first aspect to a thin film composite membrane (TFCM) for CO2 electrolysis (100), comprising a substrate, in particular a semipermeable membrane substrate, more in particular an ion exchange membrane substrate, preferably a high strength mem- brane, wherein the substrate is selected form an anion-exchange membrane substrate, a cation-ex- change membrane, and a bipolar membrane substrate, and on at least one side of the substrate, at least one polymeric fdm, being a dense polymeric fdm, with a size exclusion of ⁇ 1 nm as determined with size exclusion chromatography (Shimadzu LC-2010AHT, ISO 16014-1:2019), in particular with a size exclusion of ⁇ 0.5 nm, for example with a size exclusion of ⁇ 0.35 nm, in particular at least one first polymeric film on a first side of the substrate and at least one second polymeric film on a second side of the substrate.
  • TFCM thin film composite
  • a film with such a size exclusion characteristics is considered to relate to a dense film.
  • formic acid may be formed in an electrolytic cell, wherein the cell operates at a current density of about 140 mA/cm 2 at a cell voltage of 3.5 V. Power consumption is in the order of 4.5 kWh/kg of product.
  • the present composite membrane comprises a substrate, and at least one, typically one, thin film.
  • the present thin film prevents carbonate (CO3 2 ) and bicarbonate (HCO3 ) from passing the membrane.
  • the present membranes typically comprise a homogeneous structure, that is, with little or substantially no variation in composition and structure.
  • the present membrane composite is typically charged, though a net surface charge may still be substantially 0, that is, it comprises substantially the same amount of positive charge and negative charge.
  • Chemical species transport over the composite membrane is typically active, that is requiring a driving force, such as a pressure, a concentration difference, a voltage, or the like.
  • the present TFCM may be considered as a bi-fimc- tional membrane.
  • the added polymeric (polyamide) layer is responsible for the size exclusion; by coating an ion-exchange membrane with this polymeric layer the bifimctional composite membrane is obtained, typically having two functions being the ion-exchange and the size exclusion. It can be applied to solve critical problems with CO2 electrolysis. It is noted that in prior art CO2 electrolysis more than 50% of the CO2 input is lost, as CO2 dissolves typically as bicarbonate.
  • the present TFCM reduces losses of CO2 well below 50%, typically below 40%, such as to 1-30%, e.g. 5-20%, depending on the precise conditions. Therewith an alkaline anolyte medium, having a relatively high pH is now possible. In addition, the use of rather expensive catalysts, such as Ir, is also no longer required.
  • the present invention relates to a system for electrolysis comprising at least one first electrode of a first polarity, at least one second electrode of a second polarity, the second polarity being opposite of the first polarity, at least one first chamber comprising a first electrolyte, at least one second chamber comprising at least one second electrolyte, and at least one thin film composite membrane according to the invention, the membrane physically separating the first and second chamber, in particular wherein a volume of the respective at least one first chamber and the at least one second chamber each individually is from 1-2500 cm 3 , such as 10-1000 cm 3 .
  • the present invention relates to a method of forming the thin fdm composite membrane according to the invention, comprising providing a substrate, in particular a membrane substrate, wherein the substrate is selected form an anion-exchange membrane substrate, and a bipolar membrane substrate, and providing at least one polymeric film on at least one side of the substrate by interfacial polymerization, in particular a dense polymeric film, more in particular with a size exclusion of ⁇ 10 nm.
  • the present invention also relates to a use of a thin film composite membrane according to the invention or a system according to the invention, for transfer of charged chemical species, in particular charged chemical species selected from cations and anions, in particular for electrochemical separation, for electrolysis, and for combinations thereof.
  • Electrolysis may be performed in a fluid, such as a gas, in an aqueous environment, such as an aqueous electrolyte, in relatively pure conditions, such as an mainly aqueous electrolyte, or in more complex electrolytes, such as salty electrolytes, e.g. NaCl comprising electrolyte.
  • the present invention relates in a first aspect to the thin film composite membrane according to claim 1 .
  • the polymeric film has a thickness of 10-500 nm, in particular 50-300 nm, more in particular 100-200 nm..
  • the substrate is resistant to alkaline substances, in particular to OH’, more in particular resistant up to a temperature of 70 °C at a molar concentration of 1 mole/1 during 24 hours.
  • the substrate is selective for bicarbonate, in particular wherein the substrate has a selectivity for OH’ of >70%, in particular > 85%, more in particular > 95% (at 0 °C and 100 kPa, versus H2).
  • the polymeric film comprises surface charges, in particular with a surface charge density of > 11 * 1 O’ 15 C/mm 2
  • a surface charge is selected from an anion, a cation, and combinations thereof.
  • a surface charge is selected from an anion, a cation, a localized charge, a partial charge, and combinations thereof.
  • the substrate is at least partly formed of a chemical compound comprising at least one nitrogen atom, in particular at least two nitrogen atoms, wherein the chemical compound is selected from saturated and unsaturated organic molecules.
  • the chemical compound is selected from 5 -ring and 6-ring comprising molecules.
  • the 5 -ring and 6-ring comprising molecules comprise at least one nitrogen, in particular at least two nitrogens, such as imidazole.
  • the substrate has a thickness of 1-500 pm, in particular 4-240 pm, more in particular 12-120 pm, even more in particular 20-60 pm, such as 25-35 pm.
  • the polymeric film is selected from a polyamide film, a polypropylene (PP) film, a Polyvinylidene fluoride (PVDF) film, a cellulose acetate film, in particular a Cellulose di(or tri)acetate film, a Piperazine film, a graphene film, a Graphene oxide film, and a PTFE film.
  • PP polypropylene
  • PVDF Polyvinylidene fluoride
  • cellulose acetate film in particular a Cellulose di(or tri)acetate film
  • Piperazine film a graphene film
  • Graphene oxide film a Graphene oxide film
  • PTFE film a PTFE film
  • a surface area of the thin film composite membrane is 1-10 5 cm 2 , in particular 2-10 4 cm 2 , more in particular 10-10 3 cm 2
  • a ratio in permeance of OH’ versus the permeance of carbonate ions of the thin film composite membrane is larger than 5, in particular larger than 20.
  • a ratio in permeance of H + versus the permeance of Na + ions of the thin film composite membrane is larger than 5, in particular larger than 20 [under which conditions measured by applying a current for a period of time, measuring a concentration change, e.g. via pH/titration, and ion chromatography.
  • the present system comprises a catalyst, in particular an Ag catalyst, or a Cu catalyst, more in particular wherein the catalyst is provided on the thin film composite membrane and in electrical and physical contact with the thin film composite membrane, such as by pressing.
  • the system is selected from a system wherein the first and second electrode are physically attached to the thin film composite membrane, and a system wherein the first and second electrode are physically separated from the thin film composite membrane.
  • a ratio of the combined first chamber and second chamber volume: the surface area of the thin film composite membrane is 10" 2 - 10 cm 3 :cm 2 , in particular 10" 2 -2 cm 3 :cm 2 , more in particular 10" 1 - 1 cm 3 :cm 2 , even more in particular 2* 10 -1 -0.5 cm 3 : cm 2 .
  • the pH of the at least one first chamber comprising an anolyte is 7.5-12, in particular 9-11, and/or wherein in operation the pH of the at least one second chamber comprising a catholyte is 4-7, in particular 5-6.
  • the pH of the at least one first chamber comprising an anolyte is 7.5-14, in particular 10-13.5, more in particular 11-12.
  • an Ag catalyst, or a Cu catalyst is used.
  • conversion of CO2 is provided at an operation energy of ⁇ 3 kWh/kg of product, in particular ⁇ 1 kWh/kg product, [current of ⁇ 300 mA and voltage of 3 V]
  • the substrate is an anion exchange membrane, and wherein the at least one polymeric film is a polyamide, and wherein the polymerization is by reacting m-phenylenediamine with 1,3,4- benzenetricarbonyl trichloride.
  • the reaction is carried out during 1-60 minutes, at a temperature of 20-80 °C, at a pressure of 90-110 kPa, at a concentration of 0.01-1 mol m-phenylenediamine, at a concentration of 0.01-1 mol 1,3,4-benzenetricarbonyl trichloride, and at a ratio of m-phenylenediamine : 1,3,4-ben- zenetricarbonyl trichloride of 0.5-2.
  • the present invention further relates to a use of a thin film composite membrane according to the invention, for transfer of charged chemical species, in particular selected from cations and anions, in particular for electrochemical separation, such as wherein the use is in acid-base production, in a flow battery, or in electrolysis.
  • Figure la shows principles of a prior art redox flow battery.
  • Fig. lb, 2 and 3a, b, and 4 show schematics of a present flow cell; figs. 5 and 6 show experimental results.
  • Figure la shows principles of a prior art redox flow battery.
  • the cell comprises a membrane 10, and contacts 13 (current collector).
  • a catholyte tank 11 and an anolyte tank 12 is shown.
  • Two pumps 14 are provided for driving a flow; a first electrolyte flow 31 and a second electrolyte flow 32 is shown.
  • an electrical current 15 flows.
  • first and second chambers 16,17 are shown.
  • Figure lb shows a similar layout as fig. la, only the current flows from membrane 10 to a contact 13.
  • fig. 2 shows schematically the functioning of the present flow cell, comprising two catholyte tanks, and an extra chamber 18, parallel to chamber 16. Such may be in particular relevant if a first tank 11 comprises a liquid, and a second tank 11 comprises a gas.
  • the separator 13 may be a gas diffusion electrode.
  • a contact 13 and a membrane 10 are physically separated by a respective first chamber 16 and second chamber 17, whereas in fig. 3b the contacts 13 are in physical contact with membrane 10, and first chamber 16 and second chamber 17 are on opposite sides of the con- tact/membrane/contact stack.
  • Fig. 4 shows a membrane with a thin film, forming the present thin film composite membrane.
  • FIG. 5 Transport numbers of OH- and CO32- under a stable current.
  • M Base is the bare AEM and M1-M4 are different tested TFCMs.
  • Figs. 7 and 8 show the diffusion coefficient (m 2 /s) and reduction of mobility (relative) as a function of hydrated radius (A), respectively.
  • Figs. 9a, b show comparison of CO2 crossover.
  • Figure 5 shows the result of the cross-over experiments of hydroxide vs carbonate, before optimization of the coating process.
  • transport number of OH has a clear increase for the modified membranes. Since CO3 2 ’ carries twice the charge of OH’, it is concluded that at least 85 % of the ions crossing over the modified membranes were OH’ in this experiment.
  • the ionic resistance of a non-coated AEM and that of a TFCM were measured in 0.1 M KOH and K2CO3.
  • the table shows that the coating gives a very low increase in terms of resistance towards OH’ but the resistance in carbonate has increased at least 22-fold.
  • Table 1 Ionic resistance measured in a 6 compartment setup with 4 electrode configuration.
  • the resistance of the membrane can be further optimized by changing the polyamide film density.
  • RO membranes have been optimized to work for quite a wide range of feeding solutions.
  • materials which can be used for different applications, so it is a matter of finding the correct material, among the already available ones.
  • Typical prior art ion exchange membranes have an immobilized [volumetric] charge density between 0.1 and 7 M (mol fixed charge/L sorbed in membrane), with the majority being between 0.5 and 3 M. So the substrate, an anion-exchange or bipolar-exchange membrane will have an immobilized charge density between 0.1 and 7 M.
  • the present thin film composite membrane layer comprising the at least one polymeric (e.g. polyamide) layer, has a much denser polymer and lower pore size.
  • the charge density typically depends on the polymer used in the at least one polymeric layer, on the pH, and on electrolyte concentration, but is typically much, three orders of magnitude, lower (5-30 mM):for example, between pH 5 and 9, the charge density is between 9 and 20 mM.
  • the present charge density is between 28 and 30 mM, depending on the salt.
  • the present charge density is between 0 and 4.5 mM, sometimes referred to as surface charge. Most modeling works take between 10 and 30 mM.
  • the diffusion coefficients for OH’ and CO3 2 ’ are 1.18* IO’ 10 and 4.10* 10 -11 m 2 /s.
  • the diffusion coefficient for OH’ is between 8.41* 10’ 12 and 2.10* 10’ 11 m 2 /s; and the diffusion coefficient for CO3 2 ’ is between 4.10* 10’ 11 and 7.78* 10’ 13 m 2 /s.
  • the diffusion coefficient for OH’ is reduced in the modified membrane by 6 to 14 times, and the CO3 2 ’ coefficient is reduced by 21 to 53 times.
  • the figure 7 shows the diffusion coefficients plotted against the hydrated radius of the ions (OH’ on the left and CO3 2 ’ ions displayed on the right of the graph). Since the polyamide layer has a low charge density, this larger reduction of CO3 2 ’ mobility compared to OH’ mobility can only be explained by the (partial) size-exclusion.
  • the cut-off size is likely between 3.1 and 3.8A (in line with literature, htps, .nature .com/aiticles/s41467-020-15771 -2 ), but naturally there will be a pore size distribution in the polyamide layer, causing a less sharp cut-off.
  • the thin film composite membrane has an increased selectivity for ions below this size (higher selectivity than the substrate).
  • the present TFCM reduces the diffusion of larger species, i.e. CO3 2 ’ ions, to almost zero, and therewith excludes larger ions from passing trhogh the present TFCMs
  • Figs. 7 and 8 show the diffusion coefficient (m 2 /s) and reduction of mobility (relative) as a function of hydrated radius (A), respectively, for a non-modified membrane, and two modified membranes (TFCM1 and TFCM 2 respectively).
  • TFCM 1 is made with a 2% w/v MPD (m-phe- nylene diamine) aqueous solution and 0.05% TMC (trimesoyl chloride) cyclohexane solution.
  • TFCM 2 is made with a 3% MPD aqueous solution and 0.15% TMC cyclohexane solution.

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Abstract

La présente invention concerne le domaine des procédés de séparation utilisant des membranes semi-perméables, par exemple, la dialyse, l'osmose, l'ultrafiltration, et un appareil spécialement adapté à ceux-ci. L'invention peut également se rapporter à une technologie d'atténuation de changement climatique caractérisée en ce que le dioxyde de carbone est lié par électrolyse à des molécules comprenant du carbone, ainsi qu'à une technologie pour le transfert d'espèces chimiques chargées.
PCT/NL2023/050506 2022-10-03 2023-09-28 Membrane composite à film mince pour électrolyse de co2 WO2024076233A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4954388A (en) 1988-11-30 1990-09-04 Mallouk Robert S Fabric reinforced composite membrane
AU2020393869A1 (en) 2019-11-25 2022-06-09 Twelve Benefit Corporation Membrane electrode assembly for COx reduction

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4954388A (en) 1988-11-30 1990-09-04 Mallouk Robert S Fabric reinforced composite membrane
AU2020393869A1 (en) 2019-11-25 2022-06-09 Twelve Benefit Corporation Membrane electrode assembly for COx reduction

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHARLES DELACOURT ET AL: "Design of an Electrochemical Cell Making Syngas (CO+H2) from CO2 and H2O Reduction at Room Temperature", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 155, no. 1, 1 January 2008 (2008-01-01), pages B42, XP055124598, ISSN: 0013-4651, DOI: 10.1149/1.2801871 *
PETROV KOSTADIN V. ET AL: "Anion-exchange membranes with internal microchannels for water control in CO2 electrolysis", SUSTAINABLE ENERGY FUELS, no. 6, 28 September 2022 (2022-09-28), pages 5077 - 5088, XP093050250 *
YAN ZHIFEI ET AL: "Improving the efficiency of CO2 electrolysis by using a bipolar membrane with a weak-acid cation exchange layer", NATURE CHEMISTRY, vol. 13, no. 1, January 2021 (2021-01-01), pages 33 - 40, XP037320731, ISSN: 1755-4330, DOI: 10.1038/S41557-020-00602-0 *

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