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DE2322702A1 - Hydrogen prodn. by thermal decompsn of steam - on ferrous chloride bed, with regeneration of the obtd. magnetite - Google Patents

Hydrogen prodn. by thermal decompsn of steam - on ferrous chloride bed, with regeneration of the obtd. magnetite

Info

Publication number
DE2322702A1
DE2322702A1 DE19732322702 DE2322702A DE2322702A1 DE 2322702 A1 DE2322702 A1 DE 2322702A1 DE 19732322702 DE19732322702 DE 19732322702 DE 2322702 A DE2322702 A DE 2322702A DE 2322702 A1 DE2322702 A1 DE 2322702A1
Authority
DE
Germany
Prior art keywords
iron
hydrogen
steam
reaction
obtd
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
DE19732322702
Other languages
German (de)
Inventor
Karl Friedrich Prof Dr Knoche
J Dipl Ing Schubert
Rudolph Prof Dr Rer N Schulten
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.)
KNOCHE KARL FRIEDRICH DR ING
Original Assignee
KNOCHE KARL FRIEDRICH DR ING
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by KNOCHE KARL FRIEDRICH DR ING filed Critical KNOCHE KARL FRIEDRICH DR ING
Priority to DE19732322702 priority Critical patent/DE2322702A1/en
Publication of DE2322702A1 publication Critical patent/DE2322702A1/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/10—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with metals
    • C01B3/105—Cyclic methods
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/061—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of metal oxides with water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/061—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of metal oxides with water
    • C01B3/063—Cyclic methods
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/10—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Compounds Of Iron (AREA)

Abstract

Hydrogen is produced by reacting FeCl2 with water vapour at 1000 degrees C to form FeO and HCl and then reacting FeO with water vapour to form Fe3O4 and H2. Fe3O4 is subsequently regenerated to FeCl2 by reaction with HCl (or its mixt. with Cl2). The reaction is carried out in cycles, pref. in a solid-bed reactor (shaft furnaces, rotary kilns or fluidised bed, reactors can also be used). The process can be economically performed, if a heat source having very high temp. such as a nuclear reactor, is used.

Description

Verfahr en zur Erzeugung von Wasserstoff Es ist bekannt, daß sich Wasser ausschließlich unter Verwendung von Prozeßwärme in seine Komponenten Wasserstoff und Sauerstoff zerlegen läßt /1/. Verfahr s for the production of hydrogen It is known that Water exclusively using process heat in its components hydrogen and decomposes oxygen / 1 /.

Allerdings ist dies nur in sogenannten Mehrstufenverfahren möglich, bei denen die zur Wasserstofferzeugung erforderlichen chemischen Umsetzungen in verschiedenen Prozeßschritten durchgeführt werden müssen.However, this is only possible in so-called multi-stage processes, in which the chemical reactions required for hydrogen production in different process steps have to be carried out.

Aufgabe der Erfindung ist es daher, ein Verfahren zur thermischen Wasserzersetzung zu schaffen, bei welchem die erforderlichen chemischen Umsetzungen in einem einzigen Festbettreaktor durchgeführt werden.The object of the invention is therefore to provide a method for thermal To create water decomposition in which the necessary chemical reactions be carried out in a single fixed bed reactor.

Die der. Erfindung zugrundeliegende Aufgabe wird gelöst durch folgenden Verfahrensablauf: Der Festbettreaktor, der mit feinverteiltem Eisen(ll)-chlorid (FeC12) angefüllt ist, wird von Wasserdampf durchsetzt, welcher bei etwa 10000C mit dem Eisen(ll)-chlorid reagiert gemäß der endothermen Reaktion 3FeCl2 + 3H2O 3FeO+ 6HCI, wobei der gebildete Chlorwasserstoff nach bekanntem Verfahren vom überschüssigen Wasserdampf abgetrennt werden muß und das gebildete Eisen(ll)-oxid eO) sich mit Wasserdampf nach dem bekannten Bamag-Verfahren bei tieferer Temperatur zu Wasserstoff umsetzt: 3FeQ + H20 Fe304 + H2 ; das hierbei gebildete Eisen(ll,lll)-oxid (Fe.OA) wird anschließend wieder zu Eisen(ll)-chlorid umgesetzt, indem der Reaktor mit Chlorwasserstoff durchströmt wird, welcher mit dem Eisenoxid gemäß Fe304 + 6HCI 3FeC12 + 3H20 +.i/202 reagiert Zwar ist bekannt, daß das Gleichgewicht der Reaktion Fe304 + 6HCl = 3FeCl2 + 3H20 + 1/202 stark nach links verschoben ist und außerdem noch andere Reaktionen ablaufen, allerdings kann ein genügend großer Umsatz dadurch erreicht werden, daß Chlorwasserstoff und Eisen(ll,lll)-oxid im Gegenstrom durch den Reaktor geführt werden, wobei der Chlorwasserstoff mit hoher Temperatur dem Reaktor zugeführt wird und das Eisen(ll,ill)-oxid gekühlt wird. Vorteilhaft für die Durchführung dieser Reaktion ist ferner, wenn man anstelle von Chlorwasserstoff ein Chlorwasserstoff-Chlor-Gemisch verwendet.The the. The problem on which the invention is based is achieved by the following process sequence: The fixed-bed reactor, which is filled with finely divided iron (II) chloride (FeC12), is permeated by water vapor, which reacts with the iron (II) chloride at about 10000C according to the endothermic reaction 3FeCl2 + 3H2O 3FeO + 6HCI, whereby the hydrogen chloride formed must be separated from the excess water vapor by a known process and the iron (II) oxide eO) formed is converted to hydrogen with water vapor by the known Bamag process at a lower temperature: 3FeQ + H20 Fe304 + H2; the iron (II, III) oxide (Fe.OA) formed in this way is then converted back into iron (II) chloride by flowing through the reactor with hydrogen chloride, which is mixed with the iron oxide according to Fe304 + 6HCl 3FeC12 + 3H20 + .i / 202 reacts It is known that the equilibrium of the reaction Fe304 + 6HCl = 3FeCl2 + 3H20 + 1/202 is strongly shifted to the left and that other reactions also take place, but a sufficiently large conversion can be achieved that hydrogen chloride and iron (II, III) oxide are passed in countercurrent through the reactor, the hydrogen chloride being fed to the reactor at a high temperature and the iron (II, III) oxide being cooled. It is also advantageous for carrying out this reaction if a mixture of hydrogen chloride and chlorine is used instead of hydrogen chloride.

Die Wirtschaftlichkeit des Verfahren erweist sich insbXesondere dann, wenn die zur Durchführung des Prozesses erforderliche Wärme einen Hochtemperaturreaktor entnommen wird.The economic viability of the process is particularly evident when when the heat required to carry out the process is a high temperature reactor is removed.

Als vorteilhaft hat es sich erwiesen, die genannten Reaktionen in einem Festbett durchzuführen. Selbstverständlich ist es auch möglich, anstelle eines Festbettes einen Schachtofen oder Drehrohrofen bzw. Fließbettreaktoren zu verwenden. It has proven to be advantageous to carry out the reactions mentioned in a fixed bed. Of course, it is also possible instead of one Fixed bed to use a shaft furnace or rotary kiln or fluidized bed reactors.

Patentansprüche: 1) Verfahren zur Erzeugung von Wasserstoff, dadurch gekennzeichnet, daß in einem Reaktor in periodischem Betrieb Eisen(ll)-chlorid mit Wasserdampf zunächst zu Eisen(ll)-oxid und anschließend weiter zu Eisen (ll,lll)oxid umgesetzt werden entsprechend den Reaktionsgleichungen 3FeCl2 + 3H20 3FeO + 6HCI 1) 3FeO + H2O Fe39 + H2 2) wobei die Reaktion nach Gleichung 1) so abläuft, daß Wasserdampf bei eie r Temperatur von etwa 10000C mit festem Eisen(ll)-chlorid in Kontakt gebracht wird und das entstehende Wasserdampf-Chlorwasserstoff-Gemisch nach bekanntem Verfahren getrennt wird, wohingegen das gebildete tisen(ll)-oxid nach Abkühlung mit Wasserdampf weiterreagiert zu Eisen(II,III)-oxid und Wasserstoff, und das dabei entstehende Eisen(ll,lll)-oxid mit Chlorwasserstoff zu Eisen(llk chlorid zurückgebildet wird.Claims: 1) Process for the production of hydrogen, characterized in that in a reactor in periodic operation iron (II) chloride is converted with steam first to iron (II) oxide and then further to iron (II, III) oxide accordingly the reaction equations 3FeCl2 + 3H20 3FeO + 6HCI 1) 3FeO + H2O Fe39 + H2 2) where the reaction according to equation 1) proceeds in such a way that water vapor at a temperature of about 10000C is brought into contact with solid iron (II) chloride and the resulting water vapor-hydrogen chloride mixture is separated according to a known method, whereas the iron (II) oxide formed reacts further to iron (II, III) oxide and hydrogen after cooling with water vapor, and the iron (II, III) oxide that is formed is reformed with hydrogen chloride to iron (IIk chloride).

2) Verfahren nach den Anspruchen 1, dadurch gekennzeichnet, daß zur Ruckbildung des Eisen(ll)-chloricis aus Eisen(II,III)-oxid und Chlorwasserstoff das Eisen(ll,lll)-oxid und der Chlorwasserstoff im Gegenstrom geführt werden.2) Method according to claims 1, characterized in that for Formation of iron (II) chloricis from iron (II, III) oxide and hydrogen chloride the iron (ll, lll) oxide and the hydrogen chloride are conducted in countercurrent.

Claims (1)

3) -Verfahren nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß zur Ruckbildung des Eisen(II)-chlorids aus Eisen(ll,lll)-oxid anstelle von Chlorwasserstoff einGemisch aus Chlorwasserstoff und Chlor verwendet wird.3) method according to claims 1 and 2, characterized in that that for the reformation of iron (II) chloride from iron (ll, lll) oxide instead of hydrogen chloride a mixture of hydrogen chloride and chlorine is used. 4) Verfahren nach den Ansprüchen 1, 2 und 3, dadurch gekennzeichnet, daß4) Method according to claims 1, 2 and 3, characterized in that that die zur Durchführung der angegebenen Verfahrensabläufe erforderliche Wärme einem Kernreaktor entnommen wird.the necessary to carry out the specified procedures Heat is taken from a nuclear reactor. 5) Verfahren nach den Ansprüchen 1, 2 und 3, dadurch gekennzeichnet, daß die angegebenen Verfahrensabldufe in einem Festbett erfolgen, in das die zur Reaktion erforderlichen Gase eingeführt und von dem die bei der Reaktion gebildeten Gase abgezogen werden.5) Method according to claims 1, 2 and 3, characterized in that that the specified procedural steps take place in a fixed bed in which the for Reaction required gases introduced and of which those formed during the reaction Gases are withdrawn.
DE19732322702 1973-05-05 1973-05-05 Hydrogen prodn. by thermal decompsn of steam - on ferrous chloride bed, with regeneration of the obtd. magnetite Pending DE2322702A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19732322702 DE2322702A1 (en) 1973-05-05 1973-05-05 Hydrogen prodn. by thermal decompsn of steam - on ferrous chloride bed, with regeneration of the obtd. magnetite

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19732322702 DE2322702A1 (en) 1973-05-05 1973-05-05 Hydrogen prodn. by thermal decompsn of steam - on ferrous chloride bed, with regeneration of the obtd. magnetite

Publications (1)

Publication Number Publication Date
DE2322702A1 true DE2322702A1 (en) 1974-11-21

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4098875A (en) * 1976-03-16 1978-07-04 Agency Of Industrial Science & Technology Method for thermochemical production of hydrogen from water
WO2009141549A1 (en) * 2008-05-20 2009-11-26 Commissariat A L'energie Atomique System for the autonomous generation of hydrogen for an on-board system

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4098875A (en) * 1976-03-16 1978-07-04 Agency Of Industrial Science & Technology Method for thermochemical production of hydrogen from water
WO2009141549A1 (en) * 2008-05-20 2009-11-26 Commissariat A L'energie Atomique System for the autonomous generation of hydrogen for an on-board system
FR2931471A1 (en) * 2008-05-20 2009-11-27 Commissariat Energie Atomique AUTONOMOUS HYDROGEN PRODUCTION SYSTEM FOR AN ONBOARD SYSTEM
CN102036910A (en) * 2008-05-20 2011-04-27 原子能与替代能源委员会 System for the autonomous generation of hydrogen for an on-board system
CN102036910B (en) * 2008-05-20 2013-12-18 原子能与替代能源委员会 System for autonomous generation of hydrogen for on-board system

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