EP0972855A1 - Procédé et dispositif de synthèse d'ammoniac à pression atmosphérique - Google Patents

Procédé et dispositif de synthèse d'ammoniac à pression atmosphérique 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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EP
European Patent Office
Prior art keywords
catalyst
solid electrolyte
ammonia
nitrogen
hydrogen
Prior art date
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EP99600008A
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German (de)
English (en)
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EP0972855B1 (fr
Inventor
Michalis Idrima Tehnologias ke erevnas Stoukidis
Georgos Idrima Tehnologias ke erevnas Marnellos
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre for Research and Technology Hellas
Marnellos Georgos Centre For Research And Techn
Stoukides Michael Centre For Research And Techn
Original Assignee
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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Application filed by 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 filed Critical CENTRE FOR RESEARCH AND TECHNOLOGY HELLAS
Publication of EP0972855A1 publication Critical patent/EP0972855A1/fr
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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)
  • Catalysts (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP19990600008 1998-07-03 1999-07-01 Procédé et dispositif de synthèse d'ammoniac à pression atmosphérique Expired - Lifetime EP0972855B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GR98100255 1998-07-03
GR98100255 1998-07-03

Publications (2)

Publication Number Publication Date
EP0972855A1 true EP0972855A1 (fr) 2000-01-19
EP0972855B1 EP0972855B1 (fr) 2003-01-22

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EP19990600008 Expired - Lifetime EP0972855B1 (fr) 1998-07-03 1999-07-01 Procédé et dispositif de synthèse d'ammoniac à pression atmosphérique

Country Status (3)

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EP (1) EP0972855B1 (fr)
DE (1) DE69904990D1 (fr)
GR (1) GR1003196B (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003076687A2 (fr) * 2002-03-04 2003-09-18 Lynntech, Inc. Synthese electrochimique de l'ammoniac
US7314544B2 (en) 2004-09-07 2008-01-01 Lynntech, Inc. Electrochemical synthesis of ammonia
WO2008079586A1 (fr) * 2006-12-21 2008-07-03 Arizona Board Of Regents For And On Behalf Arizona State University Procédé et appareil de production d'ammoniac (nh3)
WO2008097644A1 (fr) * 2007-02-10 2008-08-14 Nhthree, Llc Procédé et appareil pour la production d'ammoniac
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 (ko) * 2013-05-22 2014-11-17 한국에너지기술연구원 분리막을 이용한 암모니아 합성 모듈, 그 제조방법 및 그를 이용한 암모니아 합성방법
NL2011188C2 (en) * 2013-07-18 2015-01-21 Univ Delft Tech Electrolytic cell for the production of ammonia.
JP2016014176A (ja) * 2014-07-02 2016-01-28 アイ’エムセップ株式会社 アンモニア電解合成装置
KR101695622B1 (ko) 2015-11-10 2017-01-13 한국에너지기술연구원 알코올 기반의 전해질을 이용한 전기화학적 암모니아 합성방법
US10017866B2 (en) 2014-11-17 2018-07-10 Korea Institute Of Energy Research Apparatus for synthesizing ammonia
CN108350584A (zh) * 2015-11-16 2018-07-31 西门子股份公司 电化学电池和工艺
KR20200078844A (ko) 2018-12-24 2020-07-02 한국에너지기술연구원 재순환 과정을 이용한 전기화학적 암모니아 합성방법
CN115896818A (zh) * 2022-11-09 2023-04-04 中国科学院长春应用化学研究所 一种热电协同合成氨的方法及系统

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015103391A1 (fr) * 2013-12-31 2015-07-09 Mcalister Technologies, Llc Procédés et appareil utilisables en vue de la production et de l'utilisation de combustibles issus de déchets organiques

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62278287A (ja) * 1986-05-26 1987-12-03 Mitsubishi Heavy Ind Ltd 一酸化炭素シフト反応方法
EP0480116A1 (fr) * 1990-10-10 1992-04-15 Constantin G. Vayenas Utilisé de Catalyseurs métal-électrolytes solides
JPH08246177A (ja) * 1995-03-08 1996-09-24 Agency Of Ind Science & Technol 水素の輸送、貯蔵のための水素化物の製造方法及びその装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62278287A (ja) * 1986-05-26 1987-12-03 Mitsubishi Heavy Ind Ltd 一酸化炭素シフト反応方法
EP0480116A1 (fr) * 1990-10-10 1992-04-15 Constantin G. Vayenas Utilisé de Catalyseurs métal-électrolytes solides
JPH08246177A (ja) * 1995-03-08 1996-09-24 Agency Of Ind Science & Technol 水素の輸送、貯蔵のための水素化物の製造方法及びその装置

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEM. ENG. SCI. (1996), 51(11), 3175-3180 CODEN: CESCAC;ISSN: 0009-2509, 1996 *
CHEMICAL ABSTRACTS, vol. 124, no. 26, 24 June 1996, Columbus, Ohio, US; abstract no. 347240, PANAGOS, E. ET AL: "Modeling of equilibrium limited hydrogenation reactions carried out in H+ conducting solid oxide membrane reactors" XP002091039 *
DATABASE WPI Section Ch Week 8803, Derwent World Patents Index; Class E36, AN 88-017141, XP002091040 *
PATENT ABSTRACTS OF JAPAN vol. 097, no. 001 31 January 1997 (1997-01-31) *

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003076687A3 (fr) * 2002-03-04 2004-09-23 Lynntech Inc Synthese electrochimique de l'ammoniac
WO2003076687A2 (fr) * 2002-03-04 2003-09-18 Lynntech, Inc. Synthese electrochimique de l'ammoniac
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 (fr) * 2006-12-21 2008-07-03 Arizona Board Of Regents For And On Behalf Arizona State University Procédé et appareil de production d'ammoniac (nh3)
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 (zh) * 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 生成氨(nh3)的方法和装置
WO2008097644A1 (fr) * 2007-02-10 2008-08-14 Nhthree, Llc Procédé et appareil pour la production d'ammoniac
US7811442B2 (en) * 2007-02-10 2010-10-12 N H Three 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
US8398842B2 (en) 2007-08-31 2013-03-19 Energy & Environmental Research Center Foundation Electrochemical process for the preparation of nitrogen fertilizers
US9005422B2 (en) 2007-08-31 2015-04-14 Energy & Environmental Research Center Foundation Electrochemical process for the preparation of nitrogen fertilizers
KR101460988B1 (ko) * 2013-05-22 2014-11-17 한국에너지기술연구원 분리막을 이용한 암모니아 합성 모듈, 그 제조방법 및 그를 이용한 암모니아 합성방법
WO2015009155A1 (fr) * 2013-07-18 2015-01-22 Technische Universiteit Delft Cellule électrolytique pour la production d'ammoniac
NL2011188C2 (en) * 2013-07-18 2015-01-21 Univ Delft Tech Electrolytic cell for the production of ammonia.
AU2014290913B2 (en) * 2013-07-18 2019-02-21 Battolyser Holding B.V. 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 (ja) * 2014-07-02 2016-01-28 アイ’エムセップ株式会社 アンモニア電解合成装置
US10017866B2 (en) 2014-11-17 2018-07-10 Korea Institute Of Energy Research Apparatus for synthesizing ammonia
EP3567134A1 (fr) 2014-11-17 2019-11-13 Korea Institute of Energy Research Appareil de synthèse d'ammoniac
KR101695622B1 (ko) 2015-11-10 2017-01-13 한국에너지기술연구원 알코올 기반의 전해질을 이용한 전기화학적 암모니아 합성방법
CN108350584A (zh) * 2015-11-16 2018-07-31 西门子股份公司 电化学电池和工艺
CN108350584B (zh) * 2015-11-16 2020-07-07 西门子股份公司 电化学电池和工艺
KR20200078844A (ko) 2018-12-24 2020-07-02 한국에너지기술연구원 재순환 과정을 이용한 전기화학적 암모니아 합성방법
CN115896818A (zh) * 2022-11-09 2023-04-04 中国科学院长春应用化学研究所 一种热电协同合成氨的方法及系统

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EP0972855B1 (fr) 2003-01-22
GR1003196B (el) 1999-09-01
DE69904990D1 (de) 2003-02-27

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