EP4339326A1 - Verfahren zur paarweisen elektrosynthese zur (co)herstellung von hydroxylamin und ammoniak - Google Patents

Verfahren zur paarweisen elektrosynthese zur (co)herstellung von hydroxylamin und ammoniak Download PDF

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Publication number
EP4339326A1
EP4339326A1 EP22195550.3A EP22195550A EP4339326A1 EP 4339326 A1 EP4339326 A1 EP 4339326A1 EP 22195550 A EP22195550 A EP 22195550A EP 4339326 A1 EP4339326 A1 EP 4339326A1
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EP
European Patent Office
Prior art keywords
compartment
electrolyte
based catalysts
anode
cathode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22195550.3A
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English (en)
French (fr)
Inventor
Jan Vaes
Yuvray Y. BIRDJA
Jason SONG
Metin BULUT
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Vito NV
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Vito NV
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Priority to EP22195550.3A priority Critical patent/EP4339326A1/de
Priority to PCT/EP2023/075120 priority patent/WO2024056718A2/en
Publication of EP4339326A1 publication Critical patent/EP4339326A1/de
Pending 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
    • 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
    • C25B1/27—Ammonia
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C25B11/032—Gas diffusion electrodes
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • 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
    • C25B9/13—Single electrolytic cells with circulation of an electrolyte
    • C25B9/15—Flow-through cells
    • 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

Definitions

  • the present invention is directed to a paired electrosynthesis process for the (co)production of hydroxylamine (HA) and/or ammonia out of N 2 or air and water. It further provides an electrolyzer developed for said purpose comprising both a porous cathode and anode with an effective catalyst layer and based on a continuous flow process.
  • the process and electrolyzer of the present invention are particularly useful to efficiently convert reactants such as NO 3 -, NO 2 -, NO x and N 2 at both, the cathode and anode.
  • the electrosynthesis of nitrogen species such as ammonia and HA are promising in view of renewable energy storage and electrification of the chemical industry.
  • the current production of ammonia leads to large CO 2 emissions due to the fossil fuel based Haber Bosch process.
  • Electrochemical reduction of dinitrogen/NO 3 - is a sustainable process for ammonia synthesis without CO 2 emissions when renewable electricity is used.
  • the production of HA is important for the production of caprolactam, a precursor of nylon-6.
  • waste water streams can be utilized since they contain nitrates and nitrites.
  • the present invention provides an electrochemical flow reactor configured for paired electrosynthesis of NH 3 and/or Hydroxylamine (HA), said reactor comprising metal electrocatalyst based porous gas diffusion electrodes (GDEs) as cathode and anode.
  • GDEs metal electrocatalyst based porous gas diffusion electrodes
  • the electrochemical flow cell reactor is characterized in that the metal electrocatalysts are selected from Bismuth/Molybdate based catalysts, Copper based catalysts, Ruthenium based catalysts, Platinum based catalysts, Cobalt based catalysts, Nickel based catalysts, Palladium based catalysts, Cobalt/Iron/Zinc/Oxide alloy based catalysts, Iron/Tin alloy based catalysts and combinations thereof.
  • the metal electrocatalysts of the cathode and the metal electrocatalysts of the anode are different.
  • the metal electrocatalysts of the cathode are selected from Bismuth/Molybdate based catalysts, Copper based catalysts, Ruthenium based catalysts, Platinum based catalysts, Cobalt based catalysts, Nickel based catalysts, Palladium based catalysts, and combinations thereof; and the metal electrocatalysts of the anode is selected from Ruthenium based catalysts, Platinum based catalysts, Palladium based catalysts, Cobalt/Iron/Zinc/Oxide alloy based catalysts, Iron/Tin alloy based catalysts and combinations thereof.
  • the metal electrocatalysts of the cathode is selected from a Bismuth/Molybdate alloy, Copper, a Platinum/Ruthenium alloy, a Platinum/Tin alloy, Cobalt, Nickel, and Palladium; more in particular the metal electrocatalysts of the cathode is selected from Bismuth/Molybdate alloy, Copper, a Platinum/Ruthenium alloy, a Platinum/Tin alloy, Cobalt, and Nickel,
  • the metal electrocatalysts of the anode is selected from Platinum, a Ruthenium/Titanium alloy, Palladium, a Cobalt/Iron/Zinc/Oxide alloy, an Iron/Tin alloy, and a Palladium/Ruthenium alloy; more in particular the metal electrocatalysts of the anode is selected from Platinum, a Ruthenium/Titanium alloy, a Cobalt/Iron/Zinc/Oxide alloy, an Iron/Tin alloy, and a Palladium/Ruthenium alloy.
  • the electrochemical flow cell reactor will typically comprise an anode and a cathode compartment separated by an ion exchange membrane or a one-compartment system where the cathode and anode are not separated from each other.
  • the person skilled in the art is aware of the ion exchange membrane separators used in electrochemical flow cell reactors, including cation exchange membranes, anion exchange membranes and bipolar membranes.
  • said anode and cathode compartment each preferably comprise an electrolyte compartment and a gas compartment separated from one another by means of the metal electrocatalyst based porous GDEs, configured for gas from the gas compartment to reach the metal electrocatalyst from the GDEs, wherein the metal electrocatalyst is configured to be in contact with the electrolyte from the electrolyte compartment.
  • the electrolyte compartment of the anode compartment and the electrolyte compartment of the cathode compartment comprise a common electrolyte (either an alkaline or acidic electrolyte; in particular alkaline), wherein the outlet of the electrolyte compartment of the anode compartment is fluidly connected to the inlet of the electrolyte compartment of the cathode compartment.
  • a common electrolyte either an alkaline or acidic electrolyte; in particular alkaline
  • the gas compartment of the anode compartment and the gas compartment of the cathode compartment comprise a gas inlet for a Nitrogen containing gas (such as N 2 , NO, NO 2 , N 2 O and mixtures thereof), in particular dinitrogen (N 2 ) gas.
  • a Nitrogen containing gas such as N 2 , NO, NO 2 , N 2 O and mixtures thereof
  • N 2 dinitrogen
  • the present invention provides an electrochemical flow cell reactor for paired electrosynthesis of NH 3 and/or Hydroxylamine (HA) from a Nitrogen containing gas, wherein the dinitrogen (N 2 ) from the Nitrogen containing gas from a gas compartment of the anode compartment is oxidized at the anode with the formation of NOx, Nitrate (NO 3 - ) and/or Nitrite (NO 2 - ) in the electrolyte of the anode compartment, wherein the thus obtained Nitrate (NO 3 - ) containing electrolyte is fed into to electrolyte compartment of the cathode compartment, to be reduced at the cathode together with the Nitrogen (N 2 ) from the Nitrogen containing gas from the gas compartment of the cathode compartment with the formation of Ammonia (NH 3 ) and/or hydroxylamine (HA) in the electrolyte of the cathode compartment, and removing the thus obtained Ammonia (NH 3 ) and/or hydroxy
  • the electrochemical flow cell reactor further comprising a separator to retrieve the Ammonia (NH 3 ) and/or hydroxylamine (HA) from the Ammonia (NH 3 ) and/or hydroxylamine (HA) containing electrolyte, and recycling the electrolyte into the electrolyte compartment of the anode compartment.
  • a separator to retrieve the Ammonia (NH 3 ) and/or hydroxylamine (HA) from the Ammonia (NH 3 ) and/or hydroxylamine (HA) containing electrolyte, and recycling the electrolyte into the electrolyte compartment of the anode compartment.
  • the present invention provides a method of paired electrosynthesis of NH 3 and/or Hydroxylamine (HA) in an electrochemical flow cell reactor comprising an anode and a cathode compartment separated by an ion exchange membrane, said method comprising;
  • the method of paired electrosynthesis of NH 3 and/or Hydroxylamine (HA) is characterized in that the metal electrocatalysts of the cathode is selected from Bismuth/Molybdate based catalysts, Copper based catalysts, Ruthenium based catalysts, Platinum based catalysts, Cobalt based catalysts, Nickel based catalysts, Palladium based catalysts, and combinations thereof; and wherein the metal electrocatalysts of the anode is selected from Ruthenium based catalysts, Platinum based catalysts, Palladium based catalysts, Cobalt/Iron/Zinc/Oxide alloy based catalysts, Iron/Tin alloy based catalysts and combinations thereof.
  • Figure 1 herein also referred to as Fig. 1 , provides a schematic diagram of the paired electrosynthesis process for NH 3 / HA production.
  • the present invention is in particular directed to a paired electrosynthesis process for the (co)production of hydroxylamine (HA) and/or ammonia out of N 2 or air and water. It provides thereto a continuous flow process and a continuous electrochemical flow reactor with porous electrodes at both the anode and the cathode, wherein each of said porous electrodes comprise a metal electrocatalyst layer.
  • such continuous electrochemical flow reactor consists of a membrane or diaphragm, separating the anode and the cathode compartment and at either side a metal electrocatalyst layer incorporated in a gas diffusion electrode (GDE) to enhance mass transport and increase the electrochemical active surface area.
  • GDE gas diffusion electrode
  • Nitrate (NO 3 - ) source is hard to get (waste water can be used, however, the concentration of nitrates and nitrites herein are typically too low to produce large amounts of ammonia and / or HA) the technical realization of an electrochemical process for HA and/or ammonia synthesis has thus far been hindered by;
  • the invention also benefits from a synergistic effect by co-reduction of N 2 and NO 3 - or NO 2 - at the cathode which can be controlled by the potential window. Compared to the existing technologies, this results in high product yields of HA and/or ammonia.
  • the present invention utilizes the anode reaction products in a paired electrosynthesis concept for the production of HA and ammonia.
  • electrodes reported for NRR to ammonia there are no indications in the literature to co-produce with 100% selectivity only ammonia or HA.
  • Nitrogen oxidation has not been carried out electrochemically in a continuous flow cell which is the key of our anode reaction. It is accordingly an object of the present invention to provide the use of Nitrogen oxidation, i.e.
  • Electrochemical Nitrogen Oxidation Reaction in the electrochemical synthesis of ammonia and/or hydroxylamine, more in particular the use of NOR in a continuous flow cell configuration, in the electrochemical synthesis of ammonia and/or hydroxylamine.
  • the present invention accordingly provides for the use of the products obtained from the anodic oxidation of Nitrogen as reactant for a cathodic reaction to produce NH 3 and/or HA.
  • the present invention accordingly provides for the use of the products obtained from the anodic oxidation of Nitrogen in a continuous flow cell, as reactant for a cathodic reaction to produce NH 3 and/or HA, more in particular as reactant for a cathodic reaction to produce NH 3 and/or HA in a continuous flow cell.
  • Fig. 1 provides a schematic diagram for the paired electrosynthesis of ammonia and/or HA in a continuous electrochemical flow cell reactor (1) using the anodic reaction products as reactant for the cathodic reduction.
  • the electrochemical flow cell reactor comprises an anode compartment (2) and a cathode compartment (3) separated from one another by an ion exchange membrane (4).
  • Both the anode compartment and the cathode compartment are configured as a continuous flow cell, and accordingly comprise an electrolyte compartment (5, 6) comprising a common electrolyte (20) (in the present example an alkaline electrolyte) and a gas compartment (7, 8) separated from one another by means of a metal electrocatalyst based porous GDE (9, 10).
  • the GDE of the anode compartment (9) is configured for N 2 containing gas (13) from the gas compartment (7) to reach the metal electrocatalyst layer (11) of the anode which is in contact with the alkaline electrolyte (20) of the anode electrolyte compartment (5).
  • Nitrogen is oxidized with the formation of Nitrate (NO 3 - )/Nitrite (NO 2 - ) in the alkaline electrolyte.
  • Nitrate (NO 3 - ) containing alkaline electrolyte (21) is fed by means of a fluid connection (19) into the electrolyte compartment of the cathode cell (6).
  • another GDE (10) is present and configured for N 2 containing gas (14) from the gas compartment (8) the reach the metal electrocatalyst layer (12) of the cathode which is in contact with the Nitrate (NO 3 - ) containing alkaline electrolyte (21) of the cathode electrolyte compartment (6).
  • the double arrow symbolises a separator to separate Ammonia (NH 3 ) and/or Hydroxylamine (HA) from the Ammonia (NH 3 ) and/or Hydroxylamine (HA) containing alkaline electrolyte (22), with possible recycling of the alkaline electrolyte (20) into the electrolyte compartment of the anode (5).
  • the recycling of the alkaline electrolyte (20) is an optional step in the method as disclosed.
  • the separator as used is simply to indicate any possible means and procedures to obtain the reaction products Ammonia (NH 3 ) and/or Hydroxylamine (HA), from the Ammonia (NH 3 ) and/or Hydroxylamine (HA) containing alkaline electrolyte (22).
  • the alkaline electrolyte is an aqueous alkaline electrolyte
  • the electrochemical flow cell reactor may also act as an electrolyzer with the formation of Oxygen (O 2 ) gas at the anode and Hydrogen (H 2 ) gas at the cathode.
  • O 2 Oxygen
  • H 2 Hydrogen

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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)
  • Catalysts (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP22195550.3A 2022-09-14 2022-09-14 Verfahren zur paarweisen elektrosynthese zur (co)herstellung von hydroxylamin und ammoniak Pending EP4339326A1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP22195550.3A EP4339326A1 (de) 2022-09-14 2022-09-14 Verfahren zur paarweisen elektrosynthese zur (co)herstellung von hydroxylamin und ammoniak
PCT/EP2023/075120 WO2024056718A2 (en) 2022-09-14 2023-09-13 Paired electrosynthesis process for (co)production hydroxylamine and ammonia

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Application Number Priority Date Filing Date Title
EP22195550.3A EP4339326A1 (de) 2022-09-14 2022-09-14 Verfahren zur paarweisen elektrosynthese zur (co)herstellung von hydroxylamin und ammoniak

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EP4339326A1 true EP4339326A1 (de) 2024-03-20

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WO (1) WO2024056718A2 (de)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5447610A (en) * 1994-06-23 1995-09-05 Sachem, Inc. Electrolytic conversion of nitrogen oxides to hydroxylamine and hydroxylammonium salts
WO1999009234A2 (en) * 1997-08-15 1999-02-25 Sachem, Inc. Electrosynthesis of hydroxylammonium salts and hydroxylamine using a mediator, a catalytic film, methods of making the catalytic film, and electrosynthesis of compounds using the catalytic film
WO2012051507A2 (en) * 2010-10-15 2012-04-19 Energy & Environmental Research Center Foundation Electrochemical process for the preparation of nitrogen fertilizers
US20210340683A1 (en) * 2020-05-01 2021-11-04 University Of Tennessee Research Foundation Development of ruthenium-copper nano-sponge electrodes for ambient electrochemical reduction of nitrogen to ammonia
WO2022060920A2 (en) * 2020-09-16 2022-03-24 The Board Of Trustees Of The University Of Illinois Device and methods for production of ammonia and nitrates under ambient conditions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5447610A (en) * 1994-06-23 1995-09-05 Sachem, Inc. Electrolytic conversion of nitrogen oxides to hydroxylamine and hydroxylammonium salts
WO1999009234A2 (en) * 1997-08-15 1999-02-25 Sachem, Inc. Electrosynthesis of hydroxylammonium salts and hydroxylamine using a mediator, a catalytic film, methods of making the catalytic film, and electrosynthesis of compounds using the catalytic film
WO2012051507A2 (en) * 2010-10-15 2012-04-19 Energy & Environmental Research Center Foundation Electrochemical process for the preparation of nitrogen fertilizers
US20210340683A1 (en) * 2020-05-01 2021-11-04 University Of Tennessee Research Foundation Development of ruthenium-copper nano-sponge electrodes for ambient electrochemical reduction of nitrogen to ammonia
WO2022060920A2 (en) * 2020-09-16 2022-03-24 The Board Of Trustees Of The University Of Illinois Device and methods for production of ammonia and nitrates under ambient conditions

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WO2024056718A3 (en) 2024-05-16
WO2024056718A2 (en) 2024-03-21

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