EP3260578A1 - Herstellung von wasserstoffperoxid - Google Patents

Herstellung von wasserstoffperoxid Download PDF

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Publication number
EP3260578A1
EP3260578A1 EP16176252.1A EP16176252A EP3260578A1 EP 3260578 A1 EP3260578 A1 EP 3260578A1 EP 16176252 A EP16176252 A EP 16176252A EP 3260578 A1 EP3260578 A1 EP 3260578A1
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EP
European Patent Office
Prior art keywords
compartment
hydrogen peroxide
exchange membrane
ion
cathode
Prior art date
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EP16176252.1A
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English (en)
French (fr)
Inventor
Roel Johannes Martinus Bisselink
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Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
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Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
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Application filed by Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO filed Critical Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
Priority to EP16176252.1A priority Critical patent/EP3260578A1/de
Priority to PCT/NL2017/050421 priority patent/WO2017222382A1/en
Priority to EP17737903.9A priority patent/EP3475468A1/de
Priority to US16/312,522 priority patent/US11091846B2/en
Publication of EP3260578A1 publication Critical patent/EP3260578A1/de
Withdrawn legal-status Critical Current

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    • 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
    • C25B1/28—Per-compounds
    • C25B1/30—Peroxides
    • 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
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded

Definitions

  • the invention relates to the electrochemical production of hydrogen peroxide, in particular from oxygen and water or hydrogen.
  • the electrochemical production of hydrogen peroxide is particularly desirable for the decentralized on site production of hydrogen peroxide solutions.
  • These solutions can for example be used for disinfection and/or water treatment, such as in swimming pools.
  • Other applications include bleaching of pulp, paper and textiles and production of chemicals.
  • On site production i.e. at the site of use, mitigates the need for transport of the hydrogen peroxide solution and on demand or just in time production avoids the need for storage. This would for instance be especially advantageous for use in swimming pools.
  • the produced hydrogen peroxide can be used in combination with UV radiation to break down organic compounds (through advanced oxidation), for example to remove drugs, drug residues, and pesticides from aqueous streams, such as in waste water streams in agriculture.
  • a method for the electrochemical production of hydrogen peroxide is described in EP 2845927 .
  • This document describes a process for the electrochemical production of hydrogen peroxide, comprising producing protons at an anode, transporting produced protons through a cation exchange membrane (CEM) into catholyte, producing HO 2 - anions in a cathode membrane assembly comprising a gas diffusion electrode and an anion exchange membrane (AEM) adjoined to said gas diffusion electrode and in contact with said catholyte.
  • CEM cation exchange membrane
  • AEM anion exchange membrane
  • the catholyte or solution in the compartment wherein hydrogen peroxide is formed comprises an electrolyte, in particular a dissolved salt (e.g. 0.5 M K 2 SO 4 ) in order to ensure conductivity in the electrochemical cell.
  • the obtained H 2 O 2 solution contains an electrolyte.
  • US 4357217 which describes a method for producing hydrogen peroxide comprising producing HO 2 - ions within basic aqueous catholyte, producing hydrogen ions (H + ) within acidic aqueous anolyte, wherein the hydrogen ions (H + ) to move through a cation membrane from the acidic aqueous anolyte to the aqueous solution and the HO 2 - ions move through the anion membrane from the basic aqueous catholyte to the aqueous solution whereupon said hydrogen ions (H + ) react with the HO 2 - ions to produce hydrogen peroxide within said aqueous solution.
  • the aqueous solution is an electrolyte. Exemplified is 100 ml of 0.1-1 M sulfuric acid solution circulating through the central compartment.
  • the invention pertains in a first aspect to a process for the electrochemical production of hydrogen peroxide, the process comprising producing H + cations at an anode, producing HO 2 - anions at a cathode, transporting said H + cations through a cation exchange membrane into a compartment, transporting said HO 2 - anions through an anion exchange membrane into said compartment, wherein hydrogen peroxide is formed in said compartment, and withdrawing a hydrogen peroxide solution from said compartment, wherein said compartment comprises a solid ion-conductive material.
  • the invention pertains to a reactor comprising an electrochemical cell comprising an anode, a cathode comprising a gas diffusion electrode, a cation exchange membrane and an anion exchange membrane, preferably wherein said anion exchange membrane is adjoined to said cathode or defines a catholyte compartment with said cathode, and a compartment between said cation exchange membrane and said anion exchange membrane, wherein said compartment between said membranes comprises an outlet for formed hydrogen peroxide solution and a solid ion-conductive material comprising an ion exchange material and channels allowing for flow of liquid through said solid ion-conductive material to said outlet.
  • the compartment comprises a solid ion-conductive material.
  • the compartment comprises a fixed packed bed comprising cation exchange resin beads, optionally together with anion exchange resin beads.
  • the anion exchange resin beads and the cation exchange resin beads are preferably mixed with each other. They can for example also be applied in layers.
  • the packed bed of resin beads generally stays in the compartment.
  • the bed is a packed bed but contains a void fraction, which in operation allows for outflow of hydrogen peroxide solution to an outlet of the compartment.
  • Alternative solid ion-conductive materials include, for example, ion exchange spacers and structured ion exchange membranes.
  • the solid ion-conductive material may facilitate transport of ionic species in the material.
  • the solid ion-conductive material may comprise ionic or ionogenic groups.
  • formed H + cations which permeate through the CEM may further migrate through the solid ion-conductive material by hopping by virtue of anionic groups in the material.
  • formed HO 2 - anions may also migrate through solid ion-conductive material by hopping by virtue of cationic groups in the solid material.
  • Protons may recombine with HO 2 - anions for instance at the surface of the solid material, such as particles or beads at the interface with a liquid, (with either ion in solution), or for example at an interface between an anion and a cation exchange solid material, to form hydrogen peroxide.
  • the hydrogen peroxide is released into a liquid phase flowing through the material.
  • the hydrogen peroxide may also form in solution.
  • a further advantage of the solid material is that immobilized ionic species are provided in said compartment.
  • the solution is salinated by virtue of the solid material.
  • a solution with a concentration of at least 10 g H 2 O 2 /l or at least 50 g H 2 O 2 /l or at least 70 g H 2 O 2 /l or at least 100 g H 2 O 2 /l is obtained (based on total weight of solution withdrawn from the compartment).
  • the solution obtained at an outlet of the compartment comprises at least 99 wt.%, or at least 99.9 wt.%, or at least 99.99 wt.% water and hydrogen peroxide together, preferably with at least 70 g H 2 O 2 /l or at least 100 g H 2 O 2 / 1.
  • the solution has a conductivity of less than 50 mS/cm, more preferably less than 10 mS/cm, even more preferably less than 5 mS/cm or less than 1.0 mS/cm or less than 500 ⁇ S/cm, or less than 100 ⁇ S/cm or even less than 10 ⁇ S/cm, or less than 2 ⁇ S/cm.
  • the compartment may comprise one or more types of solid ion-conductive material.
  • ion-conductive material is used as including, preferably, any material which is permeable to at least one kind of ions, more preferably is selectively permeable to either anions or cations.
  • said material is permeable for anions and not for cations, or is permeable for cations and not for anions.
  • the solid material is usually an insulator for electrons.
  • the solid material is a polymer electrolyte material.
  • the material is polymeric.
  • the material is an ion exchange material, such as a cation and/or anion exchange material, more preferably an ion exchange resin.
  • the compartment comprises a cation exchange material.
  • the compartment comprises an anion exchange material.
  • the material is a solid polymer electrolyte.
  • Solid polymer electrolytes as used in e.g. fuel cells generally do not have channels for flow of solution to an outlet.
  • Ion permeable membranes are generally used to separate charged species from uncharged species. Accordingly, the solid ion-conductive material is used in a rather different way in the present invention.
  • the material comprises an ionomer.
  • An ionomer is for example a polymer that comprises constitutional units (monomer residues) comprising ionisable and/or ionic moieties, preferably as pendant group moieties, preferably for less than 20 mole percent based on total number of constitutional units.
  • said cation exchange material comprises sulfonic acid or carboxylic acid functional groups attached to or incorporated in a resin matrix, including their salt forms.
  • said cation exchange material comprises a polymer comprising constitutional units having pendant carboxylic acid and/or carboxylate groups and/or pendant sulfonic acid and/or sulfonate groups.
  • the anion exchange material comprises a polymer comprising quaternary primary, secondary, and/or tertiary amino groups, preferably as pendent groups.
  • the material comprises a polymer comprising constitutional units comprising said groups, more preferably quaternary amino groups.
  • quaternary ammonium groups and sulfonic acid groups are preferred as ion exchange groups.
  • the solid material preferably comprises a water-insoluble cross-linked polymer, such as a cross-linked styrene copolymer, in particular crosslinked styrene divinyl benzene polymeric resins, having said groups.
  • a cross-linked styrene copolymer in particular crosslinked styrene divinyl benzene polymeric resins, having said groups.
  • Acrylic and methacrylic resins may also be used, as well as polyalkylamine, polyolefins, and phenolic resins.
  • perfluorinated polymers in particular with sulfonyl-containing comonomers.
  • Nafion® PFSA Superacid Resins NR-40 and NR-50 can be used. These are a bead-form, strongly acidic resin. It is a copolymer of tetrafluoroethylene and perfluoro-3,6-dioxa-4-methyl-7-octenesul
  • the compartment comprises one or more outlets for hydrogen peroxide solution.
  • the outlet is for example provided in the casing at a side including top or bottom of the compartment, between the cation exchange membrane and the anion exchange membrane.
  • the solid material in the compartment is preferably configured for flow of liquid from throughout the compartment to the outlet or to at least one of the outlets, wherein said flow is by convective flow, e.g. by gravity or a pressure difference.
  • the solid material is a flow-through ion exchange material configured for flow of a liquid through the material.
  • the solid material comprises passageways or channels allowing for flow of a liquid through them.
  • the channels are essentially open spaces and may include, for example, pores, ducts and voids. Examples of channels include macropores of a foam, interstitial voids in a particle bed, ducts in a monolith and open space in a spacer.
  • said channels comprise channels extending in a direction parallel to the membranes.
  • the channels more preferably extend in the vertical direction.
  • the solid material allows for flow of liquid in the vertical direction in such case. More preferably, the material allows for flow of a liquid stream from said outlet throughout the compartment and throughout the solid material.
  • at least 50% or at least 90% of the surface of a side of the solid material facing a membrane is in fluid connection with an outlet of the compartment for hydrogen peroxide solution through said solid material.
  • a packed bed of particles can be used, having a void fraction between the particles of at least 5 vol.%,or at least 10 vol.%, or at least 20 vol.%, preferably provided by interstitial voids between particles.
  • the packed bed preferably essentially consists of particles, such as beads, having a particle size of 100 ⁇ m or more, or at least 0.5 mm, or at least 1.0 mm.
  • the outlet has a screen for filtering the particles.
  • the solid ion-conductive material may be provided into the compartment for example by a slurry of ion exchange resin particles introduced into pre-formed compartments.
  • ion exchange resin may be adhered to a spacer sheet.
  • resin beads can be provided within a spacer envelope positioned between the membranes as the compartment is formed.
  • a bed comprising cation exchange resin beads is used, wherein optionally the bed further comprises anion exchange resin beads.
  • the resin beads can be mixed or are for example applied as horizontal layers in the bed.
  • the bed is fixed and immobile during operation.
  • beads of the same type are in communication in series with each other so as to promote ion transfer. Also possible are beads comprising both anion and cation exchange resin in a single bead.
  • this material is preferably provided with channels, preferably throughout the solid material, and preferably having a channel diameter of at least 0.10 mm or at least 1 mm.
  • ion exchange gels can be shaped by molding.
  • vertical channels may be provided in a molded monolithic ion exchange material structure, preferably with interconnected channels.
  • Spacers typically comprise a woven or non-woven fabric, including a mesh, web, net or screen.
  • the spacer can for example comprise, in particular be made of, fibers having ion exchange functionality, such as fibers comprising or consisting of ion exchange resin.
  • the fibers can be combined with or without binder into a spacer.
  • the binder optionally forms a matrix.
  • a polyolefin spacer is provided with ion-conduction functionality by radiation-induced graft polymerization to introduce ion exchange groups. Coated fibers with ion exchange coatings could also be used.
  • a cation exchange resin spacer is in close contact with the CEM and preferably an anion exchange resin spacer is in close contact with the AEM, such that ions can smoothly transfer from membrane into spacer.
  • ions can smoothly transfer from membrane into spacer.
  • other materials such as beads.
  • ribs or strips of ion exchange membranes can be arranged, such as woven, to provide for a multilayer spacer.
  • structured ion exchange membranes as solid ion-conductive material, for example membranes provided with ribbons and/or grooves or channels, typically parallel rather than through the membrane.
  • an ion exchange foam preferably with an open cell structure.
  • a polyurethane foam with open cell structure may be grafted with styrene and sulfonated.
  • Ion exchange groups may be introduced onto phenol-formaldehyde polymers, styrene-grafted polyurethane and polyethylene foams by for example sulfonation, chloromehtylation and amination.
  • the compartment may for instance comprise one or two or more selected from the group consisting of beads, spacers, foams, monolithic material and structured membranes comprising ion exchange material.
  • At least one of said anion and cation exchange membrane is in contact with said solid ion-conductive material, preferably both, more preferably with a packed bed of the one or more solid materials or a spacer, more in particular in contact with a packed bed of ion exchange resin beads.
  • solid ion-conductive materials are for instance those used in electro deionization in the feed channel for capturing ions from a feed stream.
  • the process is carried out in a reactor comprising an electrochemical cell comprising two electrodes and a casing, for example a container, and a CEM and an AEM, and a compartment between the CEM and AEM comprising solid ion-conductive material.
  • the compartment between AEM and CEM is usually further defined, in particular at the edges, by a part of the casing.
  • the reactor further comprises an external power supply and electrical lines for connecting the electrodes to the external power supply.
  • a reactor may comprise multiple cells, wherein the reactor can be constructed for monopolar or bipolar operation. For monopolar operation, each electrode is separately connected to a power supply. For bipolar operation, only the two outer electrodes are connected to the power supply.
  • the inner cathodes and anodes are connected with each other forming one electrode which operates at one side as cathode and at the other side as anode.
  • the invention also pertains in an aspect to such reactor.
  • the reactor comprises between an anode and a cathode not more than one AEM and not more than one CEM. Between the CEM and the cathode, the AEM is positioned. Between the AEM and the anode, the CEM is positioned. A CEM is provided adjacent to the anode or defines a compartment with the anode. An AEM is provided adjacent to the cathode or defines a compartment with the cathode. This arrangement is different from that used for electro deionization.
  • the anode, cathode and membranes may for example be provided in a planar arrangement, such as in an essentially parallel plate arrangement, or in a concentric arrangement, such as in a circular configuration, or in a spirally wound configuration.
  • the AEM and CEM are preferably spaced from each other, preferably by at least 0.50 mm, or at least 1 mm, or at least 2 mm, or at least 5 mm, or at least 10 mm, and/or less than 5 cm or less than 10 mm or less than 5 mm. This provides a dimension of the compartment. Such separation is advantageous in order to enclose the solid material and also to enable liquid flow with small pressure drop.
  • the anode is for example a dimensionally stable anode, such as an anode comprising an iridium oxide coating, ruthenium oxide coating or platinum oxide coating, for example on a titanium (oxide) substrate element.
  • Suitable forms for the anode and/or cathode are for example plate, mesh, rod, wire and ribbon.
  • the electrodes and membranes, including the gas diffusion electrode (GDE), AEM, and/or CEM preferably have a relatively small thickness compared to their length and width and preferably have a sheet-like or plate-like shape which can be for example flat, curved, rolled or tubular.
  • the process uses an AEM and CEM as selective ion-permeable membranes.
  • the membranes are generally polymeric.
  • the AEM typically comprises fixed cationic groups and allows for passage of anions and blocks cations.
  • the CEM typically comprises fixed anionic groups and allows for passage of cations while blocking anions.
  • the CEM for example comprises a polymer with fixed negatively charged groups, for example but not restricted to SO 3 - , COO - , PO 3 - or HPO 3 - , salts and acids thereof.
  • Such a cation exchange membrane selectively permits the transfer of positively charged cations, such as protons, such as from anolyte into an adjacent compartment.
  • Suitable cation exchange membranes include for example membranes based on perfluorosulfonic acid, in particular comprising perfluorosulfonic acid / PTFE copolymer in acid form.
  • Preferred are polymers comprising perfluorovinyl ether groups terminated with sulfonate groups incorporated onto a tetrafluoroethylene backbone, for example the various Nafion® membranes available from DuPont (sulfonated tetrafluoroethylene based fluoropolymer-copolymer membranes), such as N112, N115 and N117.
  • Other suitable membranes are for example CM1, CM2, CMB, CMS, CMX and CMXSB available from Eurodia and/or Astom Corporation.
  • the anionic exchange membrane comprises a polymeric membrane comprising fixed positively charged groups, such as for example RH 2 N + , R 2 HN + , R 3 N + , R 3 P + , R 2 S + . These groups can be covalently bonded to a polymer backbone.
  • the anionic exchange membrane is preferably base resistant. Suitable exchange groups include tetraalkyl ammonium groups with a polyolefin backbone chain.
  • Suitable anion exchange membranes include for example the Tokuyama Neosepta, AHA, ACM, ACS, AFX, AM1, AM3, AMX membranes, also available from Astom Corporation, Japan and Eurodia, France) and the FAA, FAB, FAD, FAS and FTAM membranes available from Fumatech.
  • the anion exchange membrane has a selectivity of 0.9 or more, more preferably 0.95 or more, even more preferably 0.98 or more.
  • Anion exchange membranes with such selectivity are commercially available, for example the AHA membrane available from Eurodia and Astom.
  • the membranes are for example less than 1 mm thick or less than 0.50 mm, and are for example provided with fiber reinforcement.
  • the cathode is typically a gas diffusion electrode (GDE).
  • GDE gas diffusion electrode
  • the reactor preferably comprises a compartment at the gas side of the GDE.
  • the reactor comprises an inlet for supplying oxygen-containing gas to a GDE cathode.
  • a GDE is porous, permeable for gases such as air, and electrically conductive.
  • the GDE preferably provides a conjunction of a solid, liquid and gaseous phase.
  • the GDE is in liquid contact with electrolyte in the process.
  • the GDE preferably comprises carbon, a hydrophobic binder and a catalyst.
  • a suitable hydrophobic binder is for example PTFE (polytetrafluoroethylene).
  • Suitable catalyst materials for the cathode include, for example, metals, metal alloys, metal oxides, metal complexes, and organic compounds, such as tin-nickel, cerium oxide, cobalt (II) phthalocyanine, cobalt, several carbon compounds, platinum, platinum alloys, alkyl-anthraquinone, catechol-modified chitosan, vanadium, gold, gold alloys or iron (II) phthalocyanine.
  • organic compounds such as tin-nickel, cerium oxide, cobalt (II) phthalocyanine, cobalt, several carbon compounds, platinum, platinum alloys, alkyl-anthraquinone, catechol-modified chitosan, vanadium, gold, gold alloys or iron (II) phthalocyanine.
  • the catalyst is preferably in the form of small particles, for example with volume average particle size smaller than 5 ⁇ m.
  • the cathode is preferably configured for two electron reduction of O 2 .
  • the GDE preferably comprises a current collector such as a metal mesh, for example nickel, gold-plated nickel wire mesh or stainless steel wire mesh, or carbon paper or carbon fleece.
  • the current collector preferably is positioned at the oxygen gas stream side of the gas diffusion electrode cathode.
  • Other types of electrodes suitable for hydrogen peroxide production include carbon plates, optionally with an anion exchange membrane placed onto it, reticulated vitreous carbon (RVC), carbon particles and carbon cloth.
  • the AEM and cathode are spaced apart and a catholyte compartment is provided between them such that the AEM is in liquid contact with the cathode.
  • a catholyte compartment comprises an inlet and/or outlet for liquids.
  • the catholyte compartment does not contain an outlet, and optionally neither an inlet, for a liquid stream.
  • the AEM and cathode, in particular GDE can be adjoined to each other and form a Membrane Electrode Assembly (MEA).
  • the anode is a gas diffusion electrode, allowing for withdrawal of formed oxygen from the oxidation of water to the gas side, or for using hydrogen at the gas side.
  • the reactor comprises a compartment at the gas side of the anode GDE with an inlet and/or outlet for supply of H 2 or withdrawal of O 2 .
  • the CEM and GDE anode form a Membrane Electrode Assembly.
  • the GDE and CEM or AEM are adjoined to each other.
  • they are attached face-to-face to each other, more preferably adjoined.
  • the GDE and membrane preferably both have a sheet-like or plate-like shape.
  • GDE and membrane are adjoined at a side surface of each, as opposed to at an edge.
  • the GDE and membrane are in contact, preferably in touching contact, with each other over at least 90 % by area of a side of each, more preferably over 95 % or more. This contact between GDE and membrane provides the advantage that the assembly can act as a single structural unit of the reactor.
  • the assembly accordingly preferably forms an integrated structure.
  • the GDE and membrane are preferably stacked on each other to form a multilayer structure of generally parallel layers, one layer comprising or formed by a gas diffusion electrode and a next layer comprising or formed by the ion exchange membrane.
  • the membrane preferably covers at least one surface of the GDE completely, such as 95-100 % by area.
  • the GDE and membrane can for example be clamped, pressed, adhered and/or glued to each other.
  • the membrane can also be directly formed on the GDE, for example by casting of the membrane on the GDE or by incorporating ion exchange particles into a top layer of a GDE which faces electrolyte.
  • the GDE can also be formed on the membrane.
  • the assembly may comprise one or more elements that attach the membrane and the GDE to each other, such as one or more clamps and/or adhesive. Another way of assuring good contact between the membrane and the GDE is by applying a higher pressure at the electrolyte side thus pressing the membrane onto the GDE, e.g. in operation.
  • the assembly can optionally comprise a very thin liquid layer at the interface of the GDE and the membrane, having a thickness of less than 0.1 mm, more preferably less than 50 ⁇ m, even more preferably less than ⁇ m.
  • the optional very thin liquid layer can also be absent.
  • Figure 1 schematically depicts a non-limiting example of the invention.
  • the electrochemical cell reactor comprises an anode (1), a gas diffusion electrode (GDE) as cathode (2), a cation exchange membrane (3) and an anion exchange membrane (4) defining a compartment (5) between them.
  • the compartment (5) comprises a solid ion-conductive material (6) and an outlet (7) for formed hydrogen peroxide solution.
  • the reactor further comprises a casing shown in part as bottom (10) wherein outlet (7) for hydrogen peroxide solution of compartment (5) is provided.
  • a anolyte compartment (8) is provided between the anode (1) and CEM (3).
  • the AEM (4) and the cathode (2) define a catholyte compartment (9) between them.
  • the solid ion-conductive material (6) is provided as a resin beads (12), more in particular as a packed bed of resin particles.
  • the reactor further comprises a compartment (11) at the gas side of the cathode (2) for supply of oxygen containing gas such as air.
  • compartment (5) also comprises an inlet for a liquid (not shown), usually in the casing at a side opposite of outlet (7).
  • the pH in the anolyte compartment (8) is typically lower than 5 or lower than 3.
  • the pH in compartment 5 is for instance lower than 8 or lower than 7, for example in the range of 3 to 8 or 4 to 7.
  • the liquid in compartment 5 can have a pH of lower than 8 or lower than 7, for example in the range of 3 to 8 or 4 to 7.
  • the pH in the catholyte compartment (9) is preferably higher than 8, more preferably higher than 10, for example the catholyte has a pH between 12 and 14.
  • FIG. 1 is schematic, in practice the compartments (5, 8, 9) could be defined by frames between membranes.
  • said anolyte compartment (8) and/or catholyte compartment (9) are also provided with solid ion-conductive material.
  • the solid ion-conductive material (6) is provided as a spacer (13) of cation-ion exchange material which spaces the CEM (3) and AEM (4) form each other.
  • anode (1) is a gas diffusion electrode.
  • AEM (4) is adjoined to cathode (2) to form a MEA.
  • AEM (4) and cathode (2) are in touching contact (for the purpose of clarity of the drawing, a small gap is shown in the figure).
  • anode (1) is adjoined to CEM (3) to form a GDE - Membrane Assembly.
  • the reactor comprises a compartment (14) for withdrawal of oxygen gas or for supply of H 2 (not shown). This embodiment could be stackable if a bipolar electrode configuration is used.
  • the pH in compartment 5 is lower than 8 or lower than 7, for example in the range of 3 to 8 or 4 to 7.
  • compartments than the compartment between CEM and AEM may comprise solid ion-conductive material as well, such as the anolyte and/or catholyte compartments.
  • the process can be a batch process or a continuous process.
  • the electrochemical process preferably comprises applying a direct electric current (DC) to the electrodes to drive chemical reactions by externally applying a voltage.
  • the process comprises applying electric current (DC) at 100 A/m 2 or more, more preferably 250 A/m 2 , even more preferably 500 A/m 2 or more, typically less than 4000 A/m 2 .
  • the process is for instance carried out at about ambient pressure, or for instance at a pressure in the range of 1.1 to 3 bar.
  • the method comprises as active step applying an electric current to the electrodes such that H + ions are produced at the anode and migrate to the cathode, thereby permeating through the CEM, and HO 2 - anions are produced at the cathode and migrate to the anode, thereby permeating through the AEM, and the H + and HO 2 - ions combine to form H 2 O 2 in the compartment between AEM and CEM.
  • HO 2 - anions are produced at the cathode by the two-electron reduction of oxygen at basic pH. Water molecules migrate with H + ions and/or HO 2 - ions through the AEM and/or CEM, for example due to electro osmosis drag.
  • oxygen is for example produced.
  • Compounds other than oxygen (and H + ions) can be produced as well.
  • the reaction at the anode may for instance involve oxidation to yield peroxy acids, ions and/or salts thereof, such as oxidation of sulphate to persulphate.
  • the process comprising supplying an oxygen-containing gas, such as air, oxygen-enriched air (22 to 50 vol.% oxygen) or oxygen (e.g. more than 90 or more than 99 vol.% oxygen) to the gas side of a GDE cathode.
  • an oxygen-containing gas such as air, oxygen-enriched air (22 to 50 vol.% oxygen) or oxygen (e.g. more than 90 or more than 99 vol.% oxygen)
  • makeup water is supplied into the cell because of water transport to the middle compartment.
  • a limited amount of base and/or acid is added to account for the non-ideal nature of membranes, e.g. less than 10 mmol or less than 1 mmol or less than 10 ⁇ mol acid and/or base per mol hydrogen peroxide formed.
  • the hydroperoxide anions (HO 2 - ) and protons (H + ) combine in the compartment to form hydrogen peroxide (H 2 O 2 ).
  • a solution with high concentration of hydrogen peroxide can be formed in the compartment between the membranes. Because the formed hydrogen peroxide is isolated and separated from the anode and from the cathode, a greater concentration of hydrogen peroxide is possible, such as 70 g/l or more.
  • the invention also relates to use of a solid ion-conductive material in an electrochemical process for the production of hydrogen peroxide for facilitating combination of H + cations and HO 2 - anions, preferably having the mentioned features.
  • the invention also relates to an electrochemical cell reactor comprising an anode and cathode and AEM and/or CEM, wherein at least one compartment comprises an ion-conductive solid material, preferably having the described features, and to a process for the electrochemical production of hydrogen peroxide using such reactor.
  • the formed hydrogen peroxide is for example used for disinfection, for instance of an object, surface, or liquid.
  • the hydrogen peroxide is used for treatment of swimming pool water.
  • the outlet of the reactor is in liquid connection with a liquid stream or liquid to be treated, such as swimming pool water.
  • the outlet is hence preferably provided with a liquid flow connection for dispensing the solution in a swimming pool.
  • the invention also relates to a swimming pool system comprising a swimming pool containing water and the reactor, wherein the outlet of the reactor is in liquid communication with the swimming pool.
  • the hydrogen peroxide solution is optionally dispensed into a liquid stream or liquid to be treated, for instance comprising a contamination, directly or through a liquid connection line.
  • the hydrogen peroxide is used in a method of treating liquids, such as sprays, aerosols, solutions, suspensions, foams and emulsions.
  • the liquid is a liquid to which humans, animals, plants and/or living material such as cultured cells and tissues are contacted or exposed.
  • the hydrogen peroxide is used as bleaching agent for the paper, pulp and textile.
  • the hydrogen peroxide is used as chemical reagent for the synthesis of chemical compounds.
  • the hydrogen peroxide is used for disinfection of swimming pool water and water for showers, baths, toilets, whirlpools and saunas.
  • the disinfection may comprise deactivating and/or killing microorganisms and pathogens, and preferably comprises reducing or inhibiting micro-organism growth, for example bacterial growth.
  • the process may further comprise a step of a treatment of water, a fluid, an object or a surface, comprising reducing the concentration of contaminants in the water, fluid, or on the object or the surface, such as by oxidising the contaminants with the formed hydrogen peroxide.
  • a treatment of water, a fluid, an object or a surface comprising reducing the concentration of contaminants in the water, fluid, or on the object or the surface, such as by oxidising the contaminants with the formed hydrogen peroxide.
  • halogenated compounds as contaminants are oxidized.
  • the process comprises treating a waste water stream with the hydrogen peroxide, for instance to oxidize such contaminants, in particular hydrofluorocarbon compounds.
  • the hydrogen peroxide is formed and used on site, for example in the same plant or building, or for example in a range of 5 km or less or 1 km or less or 100 m or less.
  • the hydrogen peroxide is preferably used and consumed in the same plant or building or at such distance from the electrochemical reactor wherein it is produced according to the invention.
  • the formed hydrogen peroxide is used in less than 3 days after the production, or in less than 1 day, or within 1 hour, or within 10 minutes.
  • the reactor comprises less than 10 L, or less than 1 L, or less than 100 mL of hydrogen peroxide containing solution.
  • the rate of the production is continuously, or at regular intervals, adjusted by adjusting the electric current, depending on the demand for hydrogen peroxide.
  • a liquid stream to be treated such as swimming pool water, is passed through a compartment comprising the solid ion-conductive material.
  • the compartment does not have an inlet for liquid and no liquid is introduced into it. All water may be supplied into the compartment through the membranes.
  • the method can further comprise UV-light exposure and/or activation of the hydrogen peroxide by a catalyst e.g. a transition metal catalyst.
  • a catalyst e.g. a transition metal catalyst. UV-light exposure is preferred in view of avoiding contamination.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
EP16176252.1A 2016-06-24 2016-06-24 Herstellung von wasserstoffperoxid Withdrawn EP3260578A1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP16176252.1A EP3260578A1 (de) 2016-06-24 2016-06-24 Herstellung von wasserstoffperoxid
PCT/NL2017/050421 WO2017222382A1 (en) 2016-06-24 2017-06-23 Electrochemical process and reactor
EP17737903.9A EP3475468A1 (de) 2016-06-24 2017-06-23 Elektrochemisches verfahren und reaktor
US16/312,522 US11091846B2 (en) 2016-06-24 2017-06-23 Electrochemical process and reactor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP16176252.1A EP3260578A1 (de) 2016-06-24 2016-06-24 Herstellung von wasserstoffperoxid

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EP3260578A1 true EP3260578A1 (de) 2017-12-27

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DE102017208610A1 (de) * 2017-05-22 2018-11-22 Siemens Aktiengesellschaft Zwei-Membran-Aufbau zur elektrochemischen Reduktion von CO2
DE102017211930A1 (de) * 2017-07-12 2019-01-17 Siemens Aktiengesellschaft Membran gekoppelte Kathode zur Reduktion von Kohlendioxid in säurebasierten Elektrolyten ohne mobile Kationen
DE102017223521A1 (de) * 2017-12-21 2019-06-27 Siemens Aktiengesellschaft Durchströmbare Anionentauscher-Füllungen für Elektrolytspalte in der CO2-Elektrolyse zur besseren räumlichen Verteilung der Gasentwicklung
WO2020036274A1 (ko) * 2018-08-17 2020-02-20 오씨아이 주식회사 과산화수소의 정제 방법
CN113789538A (zh) * 2021-11-15 2021-12-14 广东工业大学 一种带悬浮催化层的气体扩散阴极及电化学反应器

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102017208610A1 (de) * 2017-05-22 2018-11-22 Siemens Aktiengesellschaft Zwei-Membran-Aufbau zur elektrochemischen Reduktion von CO2
US11932954B2 (en) 2017-05-22 2024-03-19 Siemens Energy Global GmbH & Co. KG Two-membrane construction for electrochemically reducing CO2
DE102017211930A1 (de) * 2017-07-12 2019-01-17 Siemens Aktiengesellschaft Membran gekoppelte Kathode zur Reduktion von Kohlendioxid in säurebasierten Elektrolyten ohne mobile Kationen
DE102017223521A1 (de) * 2017-12-21 2019-06-27 Siemens Aktiengesellschaft Durchströmbare Anionentauscher-Füllungen für Elektrolytspalte in der CO2-Elektrolyse zur besseren räumlichen Verteilung der Gasentwicklung
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CN113789538A (zh) * 2021-11-15 2021-12-14 广东工业大学 一种带悬浮催化层的气体扩散阴极及电化学反应器

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