DE2257375A1 - Hydrogen, carbon monoxide and oxygen generation - by reacting metal oxides with sulphur dioxide and carbon dioxide or steam and decomposing metal sulphates obtd - Google Patents

Hydrogen, carbon monoxide and oxygen generation - by reacting metal oxides with sulphur dioxide and carbon dioxide or steam and decomposing metal sulphates obtd

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Publication number
DE2257375A1
DE2257375A1 DE19722257375 DE2257375A DE2257375A1 DE 2257375 A1 DE2257375 A1 DE 2257375A1 DE 19722257375 DE19722257375 DE 19722257375 DE 2257375 A DE2257375 A DE 2257375A DE 2257375 A1 DE2257375 A1 DE 2257375A1
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DE
Germany
Prior art keywords
hydrogen
dioxide
steam
oxygen
metal oxides
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
DE19722257375
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German (de)
Inventor
Spaeter Genannt Werden Wird
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SCHULTEN R PROF DR RER NAT
Original Assignee
SCHULTEN R PROF DR RER NAT
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 SCHULTEN R PROF DR RER NAT filed Critical SCHULTEN R PROF DR RER NAT
Priority to DE19722257375 priority Critical patent/DE2257375A1/en
Publication of DE2257375A1 publication Critical patent/DE2257375A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0203—Preparation of oxygen from inorganic compounds
    • C01B13/0207—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
    • 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
    • C01B3/068—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 the hydrogen being generated from the water as a result of a cyclus of reactions, not covered by groups C01B3/063 or C01B3/105
    • 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
    • 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

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  • 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)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

Thermal generation of H2 and O2 by reacting metal oxides with SO2 and then with CO2, with formation of metal sulphates and CO, or with steam, with formation of metal sulphates and H2, at 200-400 degrees C, under 30-100 atmos. press. The metal sulphates obtd. are converted back to the metal oxides by thermal decompsn. at 800 degrees C, with simultaneous prodn. of SO2 and O2. Oxides of Fe, Mn, Cu, Pb, Sn, ZN, Al, Cr and/or V are prefd. SO2 and CO2 or steam may be used together in 1st step.

Description

Erzeugung von Wasserstoff und Sauerstoff aus Wasser mit Hilfe von Wärme Im Hinblick auf die zukünftigen Forderungen der Umwelttechnik, ist die Erzeugung von Wasserstoff und Sauerstoff als zukünftiger Brennstoff eine interessante Aufgabe geworden. Gegenstand der vorgelegten Erfindung ist ein Verfahren, das durch eine Kombination von verschiedenen Wärmeprozessen in chemischen Kreisläufen Wasserstoff und Sauerstoff aus Wasser produziert. Zur Erläuterung des Verfahrens dient die beigefügte Abbildung über den Prozeßablauf. Generation of hydrogen and oxygen from water with the help of Warmth With regard to the future demands of environmental technology, is the generation hydrogen and oxygen as future fuels is an interesting task become. The present invention is a method that by a Combination of different heat processes in chemical cycles Hydrogen and produces oxygen from water. The attached document serves to explain the procedure Illustration of the process flow.

Der Prozeß besteht im wesentlichen darin, daß Metalloxyde mit Hilfe von Schwefeldioxyd im Temperaturbereich zwischen 200 und 400 OC in Metallsulfate umgewandelt werden. In dem genannten Temperaturbereich erfolgt dann eine Einwirkung von Wasserdampf oder Kohlendioxyd, wobei im ersten Fall Wasserstoff und im zweiten Fall Kohlenmonoxyd entsteht. Diese Prozesse finden insbesondere dann besonders günstig statt, wenn ein Druck im Bereich von 30 bis 100 at angewendet wird. Das gebildete Metallsulfat wird dann mit Hilfe eines Wärmeträgers, z.B. durch Kohlendioxyd, auf eine Temperatur von ca. 800 OC gebracht, wobei das Sulfat in Schwefeldioxyd und Sauerstoff zerfällt. Diese beiden Gase können aufgrund ihrer thermodynamischen Eigenschaften leicht voneinander getrennt werden, wobei der Sauerstoff als Produktion verwendet wird und das abgetrennte Schwefeldioxyd dem Prozeß wieder zugeführt wird. Für eine Reaktion mit Einwirkung von Kohlendioxyd ist das folgende Beispiel dargestellt: AL203 + AL2(SO3) 3 AL2(S03)3 + 3CQ2 AL2 (504)3 + 3 CO AL2 (S04) 3 AL2O3 + 3SO2 + 3/2 O2 Für die Reaktion, bei der Wasser als Oxydationsmittel verwendet wird, ist der Reaktionsablauf folgendermaßen darzustellen: AL203 + 3502 AL2(503) AL2(SO3)3 + 3H2O AL2(SO4)3 + 3H2 AL2(S04)3 ALO +3SO2 + 2 °2 23 22 Als Metalloxyd können die Oxyde von Eisen, Mangan, Kupfer, Blei, Zinn, Zink,Aluminium, Chrom und Vanadium verwendet werden. Es hat sich gezeigt, daß vor allem Mischungen dieser verschiedenen Metalle günstig sind, da sie gegeneinander eine katalytische Wirkung für die Absorption des Schwefeldioxyds und für die nachfolgende Umsetzung mit Kohlendioxyd bzw. Dampf ausüben. Es ist möglich, die beiden erwähnten Gase, Schwefeldioxyd und Kohlendioxyd, gleichzeitig auf die Metalloxyde einwirken zu lassen. In diesem Fall ergibt sich nur eine schwach exotherme Reaktion.The process essentially consists in converting metal oxides into metal sulphates with the aid of sulfur dioxide in the temperature range between 200 and 400 ° C. In the temperature range mentioned, there is then an action of water vapor or carbon dioxide, hydrogen being produced in the first case and carbon monoxide in the second case. These processes take place particularly favorably when a pressure in the range from 30 to 100 at is used. The metal sulfate formed is then brought to a temperature of approx. 800 ° C. with the aid of a heat carrier, for example carbon dioxide, the sulfate breaking down into sulfur dioxide and oxygen. Due to their thermodynamic properties, these two gases can easily be separated from one another, the oxygen being used as production and the separated sulfur dioxide being fed back into the process. The following example is shown for a reaction with the action of carbon dioxide: AL203 + AL2 (SO3) 3 AL2 (S03) 3 + 3CQ2 AL2 (504) 3 + 3 CO AL2 (S04) 3 AL2O3 + 3SO2 + 3/2 O2 For the reaction in which water is used as an oxidizing agent, the course of the reaction must be shown as follows: AL203 + 3502 AL2 (503) AL2 (SO3) 3 + 3H2O AL2 (SO4) 3 + 3H2 AL2 (S04) 3 ALO + 3SO2 + 2 ° 2 23 22 The oxides of iron, manganese, copper, lead, tin, zinc, aluminum, chromium and vanadium can be used as metal oxides. It has been shown that mixtures of these different metals are particularly beneficial, since they mutually exert a catalytic effect for the absorption of the sulfur dioxide and for the subsequent reaction with carbon dioxide or steam. It is possible to have the two gases mentioned, sulfur dioxide and carbon dioxide, act on the metal oxides at the same time. In this case there is only a weakly exothermic reaction.

Für das vorgeschlagene Verfahren ist die Verwendung einer Regenerativschaltung am besten geeignet. Ein Mischbett der Metalloxyde wird zunächst einmal in den angegebenen Temperaturen zwischen 200 und 400 °C mit Schwefeldioxyd und Kohlendioxyd behandelt. Nach erfolgter Reaktion, wird das Bett wie voraus erwähnt durch heißes Kohlendioxyd auf eine Temperatur von 800 °C gebracht, wobei die Zersetzungsprodukte zusammen mit dem CO2 abgeführt werden. Nach Ablauf dieser Zersetzungsreoktion wird die dann vorhandene Reaktionstemperatur von 800°C ausgenutzt, um die im Bett vorhandene Warmemenge für ein parallel geschaltetes Bett zur Wärmeübertragung zu nutzen. Für die Wärmeübertragung wird zweckmäßigerweise wiederum Kohlendioxyd verwendet. Auf diese Weise können zwei regenerativ parallel geschaltete Reoktionsbetten wechselweise auf die niedrige bzw.For the proposed method is the use of a regenerative circuit most suitable. A mixed bed of the metal oxides is first of all in the specified Treated temperatures between 200 and 400 ° C with sulfur dioxide and carbon dioxide. After the reaction has taken place, the bed is replaced by hot carbon dioxide, as previously mentioned brought to a temperature of 800 ° C, the decomposition products together be removed with the CO2. After this decomposition reaction has elapsed, the existing reaction temperature of 800 ° C exploited to the amount of heat present in the bed to use for a parallel connected bed for heat transfer. For heat transfer carbon dioxide is expediently used again. That way, two can Regeneratively parallel-connected reaction beds alternately on the low or

auf die höhere Temperatur gebracht werden, wobei die fUr den Prozeß erforderliche zusätzliche Wärme durch einen zusätzlichen Strom von erhitztem Kohlendioxyd zugeführt werden kann.be brought to the higher temperature, with the for the process additional heat required from an additional stream of heated carbon dioxide can be fed.

Claims (4)

Paten tansprucheSponsorship claims 1. Verfahren zur Erzeugung von Wasserstoff und Sauerstoff mit Hilfe von wärmetechnischen Prozessen, dadurch gekennzeichnet, daß Metal loxyde zunächst mit Schwefeldioxyd und nachfolgend mit Kohlendioxyd unter Entwicklung voh Kohlenmonoxyd oder nachfolgend mit Wasserdampf unter Entwicklung von Wasserstoff in einem Temperaturbereich zwischen 200 und 400 OC und Drucken zwischen 30 und 100 at zur Reaktion gebracht werden, wobei das bei diesem Prozeß erzeugte Metallsulfat durch Wärmebehandlung bei 800 OC in das Metalloxyd rückverwandelt wird unter gleichzeitiger Abspaltung- von Schwefeldioxyd und Sauerstoff.1. Process for the production of hydrogen and oxygen with the help of thermal processes, characterized in that metal oxides initially with sulfur dioxide and subsequently with carbon dioxide with evolution of carbon monoxide or subsequently with water vapor with evolution of hydrogen in a temperature range brought to reaction between 200 and 400 OC and pressures between 30 and 100 at the metal sulfate produced in this process by heat treatment is converted back into the metal oxide at 800 OC with simultaneous elimination of sulfur dioxide and oxygen. 2. Verfahren nach Anspruch 1, insbesondere unter Verwendung der Oxyde Aluminium, Kupfer, Mangan, Blei, Zinn, Zink, Chrom, Vanadium und Eisen.2. The method according to claim 1, in particular using the oxides Aluminum, copper, manganese, lead, tin, zinc, chromium, vanadium and iron. 3. Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, daß die Wärme-.3. The method according to claim 1 and 2, characterized in that the Warmth-. übertragung, die für die Abspaltung des Sauerstoffs aus dem Sulfat notwendig tst, durch eine Regenerativschaltung übertragen wird. transmission necessary for the splitting off of oxygen from the sulphate necessary, is transmitted through a regenerative circuit. 4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeichn8t, dgl3 im ersten Verfahrensschritt Schwefeldioxyd und Kohlensaure oder Wasserdampf zugleich angewendet werden L e e r s e i t e4. The method according to claims 1 to 3, characterized in that Like3 in the first process step sulfur dioxide and carbonic acid or water vapor can be used at the same time L e r s e i t e
DE19722257375 1972-11-23 1972-11-23 Hydrogen, carbon monoxide and oxygen generation - by reacting metal oxides with sulphur dioxide and carbon dioxide or steam and decomposing metal sulphates obtd Pending DE2257375A1 (en)

Priority Applications (1)

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DE19722257375 DE2257375A1 (en) 1972-11-23 1972-11-23 Hydrogen, carbon monoxide and oxygen generation - by reacting metal oxides with sulphur dioxide and carbon dioxide or steam and decomposing metal sulphates obtd

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DE19722257375 DE2257375A1 (en) 1972-11-23 1972-11-23 Hydrogen, carbon monoxide and oxygen generation - by reacting metal oxides with sulphur dioxide and carbon dioxide or steam and decomposing metal sulphates obtd

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0005622A2 (en) * 1978-05-16 1979-11-28 Westinghouse Electric Corporation Process for the decomposition of water

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0005622A2 (en) * 1978-05-16 1979-11-28 Westinghouse Electric Corporation Process for the decomposition of water
EP0005622A3 (en) * 1978-05-16 1979-12-12 Westinghouse Electric Corporation Process for the decomposition of water

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