EP0972855A1 - Method and apparatus for ammonia synthesis at atmospheric pressure - Google Patents

Method and apparatus for ammonia synthesis at atmospheric pressure Download PDF

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Publication number
EP0972855A1
EP0972855A1 EP99600008A EP99600008A EP0972855A1 EP 0972855 A1 EP0972855 A1 EP 0972855A1 EP 99600008 A EP99600008 A EP 99600008A EP 99600008 A EP99600008 A EP 99600008A EP 0972855 A1 EP0972855 A1 EP 0972855A1
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Prior art keywords
catalyst
solid electrolyte
ammonia
nitrogen
hydrogen
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EP99600008A
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German (de)
French (fr)
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EP0972855B1 (en
Inventor
Michalis Idrima Tehnologias ke erevnas Stoukidis
Georgos Idrima Tehnologias ke erevnas Marnellos
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Centre for Research and Technology Hellas
Marnellos Georgos Centre For Research And Techn
Stoukides Michael Centre For Research And Techn
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CENTRE FOR RESEARCH AND TECHNOLOGY HELLAS
FOUNDATION FOR RESEARCH AND TE
Foundation for Research and Technology Hellas Chemical Process Engineering Research Institute
Marnellos Georgos Foundation for Research and Technology-Hellas
Stoukides Michael Foundation for Research and Technology-Hellas
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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

Definitions

  • the present invention relates to a method for synthesizing ammonia from its elements (H 2 and N 2 ) at atmospheric pressure. This was achieved in a prototype solid state proton (H + ) conducting cell-reactor.
  • the reaction is exothermic (109 kJ/mol at 500°C) and therefore conversion increases with decreasing temperature. In order to achieve however, industrially acceptable reaction rates, the reaction temperature must be high.
  • the trade-off solution is to operate at temperatures in the range of 430 - 480°C, at which the equilibrium conversion is of the order of 10 -15% [1].
  • the present method refers on an alternative route to ammonia synthesis at atmospheric pressure via the use of solid state proton (H + ) conductors by which the requirement for operation at high pressures is eliminated.
  • Solid electrolyte cells have been used so far in heterogeneous catalysis in order to a) study the mechanism of catalytic reactions [2, 3], b) electrochemically alter reaction rates [4, 5] and c) cogenerate electricity and useful chemicals [6].
  • the solid electrolytes used in most of the above applications were oxygen ion conductors.
  • a vessel 1 has been divided into a hydrogenation reaction chamber 2 and into a chamber containing a hydrogen atmosphere 3, using a proton conducting solid electrolyte (SrCeo 0.95 Yb 0.05 O 3 ) 4.
  • a proton conducting solid electrolyte (SrCeo 0.95 Yb 0.05 O 3 ) 4.
  • Two porous polycrystalline palladium (Pd) films have been deposited inside and outside the solid eletrolyte.
  • the working electrode 5 was deposited in chamber 2 and served also as catalyst for the reaction of ammonia synthesis.
  • the counter electrode 6 was deposited in the other side of the solid electrolyte, i.e. in chamber 3. These two electrodes are connected with Au wires 7 in a galvanostat - potentiostat 8.
  • the cathode (chamber 2) was exposed to a gaseous stream containing nitrogen diluted in helium while the anode (chamber 3) was exposed to a hydrogen stream.
  • the gaseous H 2 passing over the anode of the proton-conducting cell-reactor, will be converted to H + : 3H 2 ---> 6H + + 6e -
  • the protons (H + ) are transported through the solid electrolyte to the cathode where the half-cell reaction: N 2 + 6H + + 6e - ---> 2 NH 3 takes place.
  • reaction [1] is again the overall reaction.
  • a reaction vessel 1 contains a proton conducting solid electrolyte (SrCe 0.95 Yb 0.05 O 3 ) 2.
  • Two porous polycrystalline palladium (Pd) films have been deposited on the two sides of the solid eletrolyte.
  • the working electrode 3 was deposited in the one side of solid electrolyte and served also as catalyst for the reaction of ammonia synthesis.
  • the counter electrode 4 was deposited in the other side of the solid electrolyte. These two electrodes are connected with Au wires 5 in a galvanostat - potentiostat 6. In the following a gaseous mixture containing nitrogen and hydrogen diluted in helium are fed to the reaction vessel 1.
  • this single chamber configuration is simpler than the double chamber configuration because of the fact that the complexity of the separation of the two chambers ia avoided.
  • the ceramic material was a strontia-ceria-ytterbia (SCY) perovskite of the form: SrCe 0.95 Yb 0.05 O 3 .
  • SCY strontia-ceria-ytterbia
  • This perovskite is a solid with good mechanical strength and with high protonic conductivity [9].
  • the electrode preparation and characterization procedure has been described in detail elsewhere [10].
  • Figure 3 shows the dependence of the rate of NH 3 formation in a double chamber cell on I/2F, where I is the imposed current and F is Faraday's constant.
  • I/2F the ratio I/2F is equal to the electrochemical molar flux of hydrogen through the solid electrolyte.
  • the cell was kept at 570°C.
  • a mixture of 1.8% N 2 in He was passing over the cathode at a volumetric flowrate of 8.3x10 -8 m 3 /s and atmospheric total pressure.
  • a flow of 5.0xi0 -7 m 3 /s of 100% H 2 at atmospheric pressure was maintained over the anode.
  • NH 3 appeared at the cathode and after a transient period of 2-6 minutes, a steady state rate of NH 3 formation was established
  • the data points in Figure 3 represent steady state rates.
  • the two dotted lines of Figure 3 are based on thermodynamic calculations and are represented for comparizon of the present results with those that would have been obtained in a conventional catalytic reactor (CCR) in which gaseous H 2 rather than electrochemical H + were used
  • CCR catalytic reactor
  • the curve denoted as CCR represents the maximum rate of NH 3 formation attained in a CCR that operates at 570°C and at atmospheric pressure and in which the same amounts of N 2 and H 2 as in the present experiments, are introduced. It can be seen that the NH 3 rates attained experimentally exceed the CCR rates by at least three orders of magnitude.
  • the curve denoted as PCCR pressure in a conventional catalytic reactor
  • Figure 4 shows the dependence of the rate of NH 3 formation in a single chamber cell on I/2F, where I is the imposed current and F is Faraday's constant.
  • the cell was kept at 600°C.
  • a gas mixture of N 2 (0.5%), H 2 (10%) and He was fed on the reaction vessel at a volumetric flowrate of 3.3x10 -7 m 3 /s and atmospheric total pressure.
  • NH 3 appeared at the cathode and after a transient period of 2-6 minutes, a steady state rate of NH 3 formation were established.
  • the data points in Figure 4 represent steady state rates.
  • the two dotted lines of Figure 4 are based on thermodynamic calculations and are presented for comparizon of the present results with those that would have been obtained in a conventional catalytic reactor (CCR) in which gaseous H 2 rather than electrochemical H + were used.
  • CCR catalytic reactor
  • the curve denoted as CCR represents the maximum rate of NH 3 formation attained in a CCR that operates at 600°C and at atmospheric pressure and in which the same amounts of N 2 and H 2 as in the present experiments, are introduced. It can be seen that the NH 3 rates attained experimentally exceed the CCR rates by at least two orders of magnitude.
  • the curve denoted as PCCR pressure in a conventional catalytic reactor

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

Prototype reactor and method for the ammonia synthesis at atmospheric pressure. This invention relates to the ammonia production from its elements (N2 and H2) at atmospheric pressure. This was achieved in a solid state proton (H+) conducting cell - reactor. Hydrogen was flowing over the anode (6) and was converted into protons that were transported through the solid electrolyte (4) and reached the cathode (5)(Pd) over which nitrogen was passing.

Description

  • The present invention relates to a method for synthesizing ammonia from its elements (H2 and N2) at atmospheric pressure. This was achieved in a prototype solid state proton (H+) conducting cell-reactor.
  • The development of a successful process for ammonia synthesis from its elements: N2 + 3 H2 <----> 2 NH3 is considered a landmark in heterogeneous catalysis. The Haber process which involves reaction of gaseous nitrogen and hydrogen on a Fe-based catalyst at high pressures (15 - 30 MPa), was developed at the beginning of the twentieth century after an extensive search for an active catalyst [1].
  • Even from early studies, it was realized that the conversion is limited by thermodynamics. The gas volume decreases with reaction. Hence, very high pressures have to be used in order to push equilibrium to the right according to the Le Chatelier principle.
  • The reaction is exothermic (109 kJ/mol at 500°C) and therefore conversion increases with decreasing temperature. In order to achieve however, industrially acceptable reaction rates, the reaction temperature must be high. The trade-off solution is to operate at temperatures in the range of 430 - 480°C, at which the equilibrium conversion is of the order of 10 -15% [1].
  • The present method refers on an alternative route to ammonia synthesis at atmospheric pressure via the use of solid state proton (H+) conductors by which the requirement for operation at high pressures is eliminated.
  • Solid electrolyte cells have been used so far in heterogeneous catalysis in order to a) study the mechanism of catalytic reactions [2, 3], b) electrochemically alter reaction rates [4, 5] and c) cogenerate electricity and useful chemicals [6]. The solid electrolytes used in most of the above applications were oxygen ion conductors.
  • In the last decade however, materials that exhibit protonic conductivity in the solid state have been introduced into catalysis research [7]. These H+ conductors are particularly useful because they can operate at temperatures in which many industrial hydro- and dehydrogenation reactions take place. Furthermore, in contrast to oxidation reactions, a number of industrial hydrogenations (ammonia, methanol production) are equilibrium limited at the operating conditions.
  • A model process using solid state proton conductors to obtain conversions higher than those predicted by the reaction equilibrium, has been proposed in the past [8]. It is possible to use two configrations. The double and the single chamber configuration.
  • In the double chamber configuration (Figure 1) a vessel 1 has been divided into a hydrogenation reaction chamber 2 and into a chamber containing a hydrogen atmosphere 3, using a proton conducting solid electrolyte (SrCeo0.95Yb0.05O3) 4. Two porous polycrystalline palladium (Pd) films have been deposited inside and outside the solid eletrolyte. The working electrode 5 was deposited in chamber 2 and served also as catalyst for the reaction of ammonia synthesis. The counter electrode 6 was deposited in the other side of the solid electrolyte, i.e. in chamber 3. These two electrodes are connected with Au wires 7 in a galvanostat - potentiostat 8. The cathode (chamber 2) was exposed to a gaseous stream containing nitrogen diluted in helium while the anode (chamber 3) was exposed to a hydrogen stream. The gaseous H2 passing over the anode of the proton-conducting cell-reactor, will be converted to H+: 3H2 ---> 6H+ + 6e- The protons (H+) are transported through the solid electrolyte to the cathode where the half-cell reaction: N2 + 6H+ + 6e- ---> 2 NH3 takes place. Thus, reaction [1] is again the overall reaction.
  • In the single chamber configuration (Figure 2) a reaction vessel 1 contains a proton conducting solid electrolyte (SrCe0.95Yb0.05O3) 2. Two porous polycrystalline palladium (Pd) films have been deposited on the two sides of the solid eletrolyte. The working electrode 3 was deposited in the one side of solid electrolyte and served also as catalyst for the reaction of ammonia synthesis. The counter electrode 4 was deposited in the other side of the solid electrolyte. These two electrodes are connected with Au wires 5 in a galvanostat - potentiostat 6. In the following a gaseous mixture containing nitrogen and hydrogen diluted in helium are fed to the reaction vessel 1. The gaseous H2 passing over the anode of the proton-conducting cell-reactor, will be converted to H+: 3H2 ----> 6H+ + 6e- The protons (H+) are transported through the solid electrolyte to the cathode where the half-cell reaction: N2 + 6H+ + 6e- ---> 2 NH3 takes place.
  • Specifically, this single chamber configuration is simpler than the double chamber configuration because of the fact that the complexity of the separation of the two chambers ia avoided.
  • The ceramic material was a strontia-ceria-ytterbia (SCY) perovskite of the form: SrCe0.95Yb0.05O3. This perovskite is a solid with good mechanical strength and with high protonic conductivity [9]. The electrode preparation and characterization procedure has been described in detail elsewhere [10].
  • Figure 3 shows the dependence of the rate of NH3 formation in a double chamber cell on I/2F, where I is the imposed current and F is Faraday's constant. Assuming that the SCY is solely a proton conductor, the ratio I/2F is equal to the electrochemical molar flux of hydrogen through the solid electrolyte. The cell was kept at 570°C. A mixture of 1.8% N2 in He was passing over the cathode at a volumetric flowrate of 8.3x10-8 m3/s and atmospheric total pressure. A flow of 5.0xi0-7 m3/s of 100% H2 at atmospheric pressure was maintained over the anode. At I=0, no products were formed. Upon imposing a current through the cell, NH3 appeared at the cathode and after a transient period of 2-6 minutes, a steady state rate of NH3 formation was established
  • The data points in Figure 3 represent steady state rates. The two dotted lines of Figure 3 are based on thermodynamic calculations and are represented for comparizon of the present results with those that would have been obtained in a conventional catalytic reactor (CCR) in which gaseous H2 rather than electrochemical H+ were used Specifically, the curve denoted as CCR represents the maximum rate of NH3 formation attained in a CCR that operates at 570°C and at atmospheric pressure and in which the same amounts of N2 and H2 as in the present experiments, are introduced. It can be seen that the NH3 rates attained experimentally exceed the CCR rates by at least three orders of magnitude. Similarly, the curve denoted as PCCR (pressure in a conventional catalytic reactor) represents the total pressure at which a CCR should operate in order for the NH3 conversion to be as high as that reported here.
  • Figure 4 shows the dependence of the rate of NH3 formation in a single chamber cell on I/2F, where I is the imposed current and F is Faraday's constant. The cell was kept at 600°C. A gas mixture of N2 (0.5%), H2 (10%) and He was fed on the reaction vessel at a volumetric flowrate of 3.3x10-7 m3/s and atmospheric total pressure. At I=0, no products were formed. Upon imposing a current through the cell, NH3 appeared at the cathode and after a transient period of 2-6 minutes, a steady state rate of NH3 formation were established.
  • The data points in Figure 4 represent steady state rates. The two dotted lines of Figure 4 are based on thermodynamic calculations and are presented for comparizon of the present results with those that would have been obtained in a conventional catalytic reactor (CCR) in which gaseous H2 rather than electrochemical H+ were used. Specifically, the curve denoted as CCR represents the maximum rate of NH3 formation attained in a CCR that operates at 600°C and at atmospheric pressure and in which the same amounts of N2 and H2 as in the present experiments, are introduced. It can be seen that the NH3 rates attained experimentally exceed the CCR rates by at least two orders of magnitude. Similarly, the curve denoted as PCCR (pressure in a conventional catalytic reactor) represents the total pressure at which a CCR should operate in order for the NH3 conversion to be as high as that reported here.
  • 1. C.N. Satterfield, Heterogeneous Catalysis in Practice, (McGraw-Hill, New York, 1980), pp. 301-308.
  • 2. M. Stoukides, Ind Eng. Chem. Res., 27, 1745 (1988).
  • 3. C. G. Vayenas, M.M. Jaksic, S.I. Bebelis and S.G. Neophytides, in Modern Aspects in Electrochemistry, J.O'.M Bockris, B. E. Conway and W.R.E. White, Eds. (Plenum, New York, 1996) vol. 29, 57 (1996).
  • 4. T. M. Gür and R. A. Huggins, Science, 219 , 967 (1983).
  • 5. Y. Jiang, I. V. Yentekakis and C.G. Vayenas, Science, 264 , 1563 (1994).
  • 6. C.G. Vayenas and R.D. Fart, Science, 208, 593 (1980).
  • 7. H. Iwahara, Sol. St. Tonics, 86-88, 9 (1996).
  • 8. E. Panagos, I. Voudouris and M. Stoukides, Chem. Eng. Sci., 51, 3175 (1996).
  • 9. H. Iwahara, T. Esaka, H. Uchida and N. Maeda, Sol. St. Tonics, 3/4, 359 (1981).
  • 10. C. Athanasiou, G. Marnellos, P. Tsiakaras and M. Stoukides, Tonics, 2, 353 (1996).

Claims (10)

  1. The process for synthesing ammonia at atmospheric pressure which comprises passing a nitrogen -containing feed gas in contact with a first catalyst (cathodic electrode) deposited on a first surface of a proton conducting solid electrolyte and passing a hydrogen -containing gas such as diatomic hydrogen (H2), water (steam) or any hydrogen -containing compound in contact with a second catalyst (anodic electrode) deposited on a second surface of said solid electrolyte, said first catalyst being capable of promoting the hydrogenation of nitrogen to ammonia, said second catalyst being capable of dissociating hydrogen gas to form protons (H+) to contact said nitrogen to form ammonia and applying a voltage between said first and second catalysts through said solid electrolyte.
  2. The process of claim 1, wherein said solid electrolyte comprises strontia, ceria and ytterbia (SrCe0.95Yb0.05O3).
  3. The process of any one of claims 1 and 2, wherein said first catalyst (cathodic electrode) comprises palladium-containing metal composition.
  4. The process of any one of claims 1 and 2, wherein said second catalyst (anodic electrode) comprises a palladium-containing metal composition.
  5. The process of claim 1, wherein said solid electrolyte comprises any material exhibiting protonic conductivity in the solid state.
  6. The process of claim 5, wherein said first catalyst (cathodic electrode) comprises of palladium-containing metal composition.
  7. The process of claim 5, wherein said second catalyst (anodic electrode) comprises of palladium-containing metal composition.
  8. The process of claims 1, 3 and 6, wherein said first catalyst (cathodic electrode) comprises an iron -containing, platinum -containing, ruthenium -containing, cobalt -containing or any metal composition that effectively catalyses ammonia synthesis.
  9. The process of claims 1 and 5, wherein both said first and second surfaces of the solid electrolyte are exposed to the same gaseous mixture that contains both said nitrogen -containing and hydrogen -containing gases.
  10. The process of claims 1 or 9 wherein instead of a nitrogen -containing, a carbon and oxygen -containing compound is passing over the said first surface of claim 1 or both surfaces of claim 9 and wherein methanol is produced instead of ammonia.
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003076687A3 (en) * 2002-03-04 2004-09-23 Lynntech Inc Electrochemical synthesis of ammonia
US7314544B2 (en) 2004-09-07 2008-01-01 Lynntech, Inc. Electrochemical synthesis of ammonia
WO2008079586A1 (en) * 2006-12-21 2008-07-03 Arizona Board Of Regents For And On Behalf Arizona State University Method and apparatus for ammonia (nh3) generation
WO2008097644A1 (en) * 2007-02-10 2008-08-14 Nhthree, Llc Method and apparatus for anhydrous ammonia production
US20110120880A1 (en) * 2007-08-31 2011-05-26 Junhua Jiang Electrochemical process for the preparation of nitrogen fertilizers
US20120234689A1 (en) * 2007-08-31 2012-09-20 Energy & Environmental Research Center Foundation Electrochemical Process for the Preparation of Nitrogen Fertilizers
KR101460988B1 (en) * 2013-05-22 2014-11-17 한국에너지기술연구원 Module for Ammonia Synthesis Using Gas Separation Membrane, Fabrication Method thereof and Ammonia Synthesis Method using the same
NL2011188C2 (en) * 2013-07-18 2015-01-21 Univ Delft Tech Electrolytic cell for the production of ammonia.
JP2016014176A (en) * 2014-07-02 2016-01-28 アイ’エムセップ株式会社 Ammonia electrosynthesis system
KR101695622B1 (en) 2015-11-10 2017-01-13 한국에너지기술연구원 Method for electrochemical ammonia synthesis using alcohol-based electrolyte
US10017866B2 (en) 2014-11-17 2018-07-10 Korea Institute Of Energy Research Apparatus for synthesizing ammonia
CN108350584A (en) * 2015-11-16 2018-07-31 西门子股份公司 Electrochemical cell and technique
KR20200078844A (en) 2018-12-24 2020-07-02 한국에너지기술연구원 Electrochemical Ammonia Synthesis Method Using Recycling Process
JP2021059747A (en) * 2019-10-04 2021-04-15 国立大学法人 東京大学 Electrolyte-electrode joint body for use in electrolytic synthesis of ammonia
CN115896818A (en) * 2022-11-09 2023-04-04 中国科学院长春应用化学研究所 A method and system for thermoelectric synergistic synthesis of ammonia
US12240755B2 (en) 2020-07-06 2025-03-04 Saudi Arabian Oil Company Method for producing compressed hydrogen using electrochemical systems
US12244044B2 (en) 2020-07-06 2025-03-04 Saudi Arabian Oil Company Direct ammonia-fed solid oxide fuel cell and methods for making the same

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WO2015103391A1 (en) * 2013-12-31 2015-07-09 Mcalister Technologies, Llc Processes and apparatus for production and use of fuels sourced from organic wastes

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WO2003076687A3 (en) * 2002-03-04 2004-09-23 Lynntech Inc Electrochemical synthesis of ammonia
US7314544B2 (en) 2004-09-07 2008-01-01 Lynntech, Inc. Electrochemical synthesis of ammonia
US8282809B2 (en) 2006-12-21 2012-10-09 Arizona Board Of Regents For And On Behalf Of Arizona State University Method and apparatus for ammonia (NH3) generation
WO2008079586A1 (en) * 2006-12-21 2008-07-03 Arizona Board Of Regents For And On Behalf Arizona State University Method and apparatus for ammonia (nh3) generation
US8075757B2 (en) 2006-12-21 2011-12-13 Arizona Board Of Regents For And On Behalf Of Arizona State University Method and apparatus for ammonia (NH3) generation
CN101589176B (en) * 2006-12-21 2012-02-15 代理并代表亚利桑那州立大学的亚利桑那董事会 Method and apparatus for ammonia (NH3) generation
WO2008097644A1 (en) * 2007-02-10 2008-08-14 Nhthree, Llc Method and apparatus for anhydrous ammonia production
US7811442B2 (en) * 2007-02-10 2010-10-12 N H Three LLC Method and apparatus for anhydrous ammonia production
US9005422B2 (en) 2007-08-31 2015-04-14 Energy & Environmental Research Center Foundation Electrochemical process for the preparation of nitrogen fertilizers
US8398842B2 (en) 2007-08-31 2013-03-19 Energy & Environmental Research Center Foundation Electrochemical process for the preparation of nitrogen fertilizers
US20110120880A1 (en) * 2007-08-31 2011-05-26 Junhua Jiang Electrochemical process for the preparation of nitrogen fertilizers
US20120234689A1 (en) * 2007-08-31 2012-09-20 Energy & Environmental Research Center Foundation Electrochemical Process for the Preparation of Nitrogen Fertilizers
KR101460988B1 (en) * 2013-05-22 2014-11-17 한국에너지기술연구원 Module for Ammonia Synthesis Using Gas Separation Membrane, Fabrication Method thereof and Ammonia Synthesis Method using the same
AU2014290913B2 (en) * 2013-07-18 2019-02-21 Battolyser Holding B.V. Electrolytic cell for the production of ammonia
NL2011188C2 (en) * 2013-07-18 2015-01-21 Univ Delft Tech Electrolytic cell for the production of ammonia.
WO2015009155A1 (en) * 2013-07-18 2015-01-22 Technische Universiteit Delft Electrolytic cell for the production of ammonia
US10309020B2 (en) 2013-07-18 2019-06-04 Technische Universiteit Delft Electrolytic cell for the production of ammonia
JP2016014176A (en) * 2014-07-02 2016-01-28 アイ’エムセップ株式会社 Ammonia electrosynthesis system
US10017866B2 (en) 2014-11-17 2018-07-10 Korea Institute Of Energy Research Apparatus for synthesizing ammonia
EP3567134A1 (en) 2014-11-17 2019-11-13 Korea Institute of Energy Research Ammonia synthesis apparatus
KR101695622B1 (en) 2015-11-10 2017-01-13 한국에너지기술연구원 Method for electrochemical ammonia synthesis using alcohol-based electrolyte
CN108350584A (en) * 2015-11-16 2018-07-31 西门子股份公司 Electrochemical cell and technique
CN108350584B (en) * 2015-11-16 2020-07-07 西门子股份公司 Electrochemical cell and process
KR20200078844A (en) 2018-12-24 2020-07-02 한국에너지기술연구원 Electrochemical Ammonia Synthesis Method Using Recycling Process
JP2021059747A (en) * 2019-10-04 2021-04-15 国立大学法人 東京大学 Electrolyte-electrode joint body for use in electrolytic synthesis of ammonia
US12240755B2 (en) 2020-07-06 2025-03-04 Saudi Arabian Oil Company Method for producing compressed hydrogen using electrochemical systems
US12244044B2 (en) 2020-07-06 2025-03-04 Saudi Arabian Oil Company Direct ammonia-fed solid oxide fuel cell and methods for making the same
CN115896818A (en) * 2022-11-09 2023-04-04 中国科学院长春应用化学研究所 A method and system for thermoelectric synergistic synthesis of ammonia

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DE69904990D1 (en) 2003-02-27
GR1003196B (en) 1999-09-01
EP0972855B1 (en) 2003-01-22

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