DE594395C - Production of hydrogen and hydrogen-containing gases from hydrocarbons - Google Patents

Production of hydrogen and hydrogen-containing gases from hydrocarbons

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Publication number
DE594395C
DE594395C DEI29643D DEI0029643D DE594395C DE 594395 C DE594395 C DE 594395C DE I29643 D DEI29643 D DE I29643D DE I0029643 D DEI0029643 D DE I0029643D DE 594395 C DE594395 C DE 594395C
Authority
DE
Germany
Prior art keywords
hydrogen
hydrocarbons
production
gases
optionally
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.)
Expired
Application number
DEI29643D
Other languages
German (de)
Inventor
Dr Wilhelm Haller
Dr William Hennicke
Dr Gustav Wietzel
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.)
IG Farbenindustrie AG
Original Assignee
IG Farbenindustrie AG
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
Priority claimed from DEI28399D external-priority patent/DE558430C/en
Application filed by IG Farbenindustrie AG filed Critical IG Farbenindustrie AG
Priority to DEI29643D priority Critical patent/DE594395C/en
Application granted granted Critical
Publication of DE594395C publication Critical patent/DE594395C/en
Expired 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
    • 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
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • 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
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • 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
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Description

Herstellung -von Wasserstoff und wasserstoffhaltigen Gasen aus Kohlenwasserstoffen Das Hauptpatent 558 43o betrifft die Herstellung von Wasserstoff oder Wasserstoff enthaltenden Gasgemischen aus Kohlenwasserstoffen oder solche enthaltenden Gemischen. Diese werden mit so viel Sauerstoff oder sauerstoffreicher Luft, evtl. unter Zusatz von Dampf und gegebenenfalls in Gegenwart von Katalysatoren, teilweise verbrannt, so daß das entstandene Gemisch noch einen inerkliohen Gehalt an Kohlenwasserstoffein besitzt, worauf das entstandene Gasgemisch gegebenenfalls nach Zuführung von Wasserdampf über aktivierte Katalysatoren geführt und die gebildete Kohlensäure entfernt wird.Production of hydrogen and gases containing hydrogen from hydrocarbons The main patent 558 43o relates to the production of hydrogen or hydrogen containing gas mixtures of hydrocarbons or mixtures containing them. These are made with as much oxygen or oxygen-rich air, possibly with an addition of steam and possibly in the presence of catalysts, partially burned, so that the resulting mixture still has a moderate content of hydrocarbons possesses, whereupon the gas mixture formed, optionally after the addition of steam passed over activated catalysts and the carbonic acid formed is removed.

Es wurde gefunden, daß es mitunter vorteilhaft ist, die erste Stufe dieses Verfahrens in folgender Weise auszuführen. Die Kohlenwasserstoffe oder solche enthaltende Gemische werden solchen Temperaturen, gegebenenfalls in Gegenwart von Katalysatoren, ausgesetzt, daß sie sich unter Abscheidung von - Kohle thermisch zersetzen und im Endgas sich noch ein merklicher Gehalt an Kohlen-,vasserstoffen befindet. Die Wärmezufuhr kann dabei direkt oder indirekt oder auf beiden Wegen geschehen. Die Kohlenwasserstoffe können z. B. durch von außen erhitzte Rohre geführt und der sich bildende Kohlenstoff in Staubfängern gesammelt werden. Dieser kann als Ruß für andere Zwecke oder auch für die Außenheizung verwendet werden. Das Verfahren kann auch z. B. diskontinuierlich ohne Außenheizung ausgeführt werden, indem das Kohlenwasserstoffgemisch über erhitzte feuerfeste Körper geleitet wird. Nach einiger Zeit wird die Zuführung der Kohlenwasserstoffe abgestellt und heißes Verbrennungsgas oder Luft über die feuerfesten Körper geführt, wobei diese den abgesetzten Kohlenstoff verbrennt und dadurch die feuerfesten Körper wieder aufheizt. In diesem Falle werden zweckmäßig zwei oder mehrere Zersetzungsapparate verwandt, die in verschiedenen Phasen arbeiten. Die Zersetzung kann unter Umständen durch Zuführung anderer Gase und Dämpfe, wie Wasserdampf oder Kohlensäure oder beschränkte Mengen Luft oder Sauerstoff oder- mehrere dieser Mittel, gefördert werden.The first stage has been found to be sometimes beneficial carry out this procedure in the following manner. The hydrocarbons or such Mixtures containing such temperatures, optionally in the presence of Catalysts that are exposed to the deposition of - coal thermally decompose and there is still a noticeable amount of carbon and hydrogen in the end gas is located. The heat supply can be direct or indirect or both ways happen. The hydrocarbons can, for. B. passed through externally heated pipes and the carbon that forms is collected in dust collectors. This can used as soot for other purposes or for external heating. The procedure can also z. B. run discontinuously without external heating by the Hydrocarbon mixture is passed over heated refractory bodies. After some During this time, the supply of hydrocarbons and hot combustion gas are switched off or air is passed over the refractory bodies, which removes the deposited carbon burns and thereby heats up the refractory bodies again. In this case it will be suitably two or more decomposition apparatuses used in different Work phases. The decomposition may be caused by the introduction of other gases and vapors such as water vapor or carbonic acid or limited quantities Air or oxygen or several of these agents can be promoted.

Die erhaltenen Gase werden darauf gegebenenfalls nach Zuführung von Wasserdampf oder Kohlensäure oder von Sauerstoff oder Luft oder mehreren dieser Mittel über aktivierte Katalysatoren geführt, die, falls das Kohlenoxyd mit Wasserdampf zu Wasserstoff und Kohlensäure umgesetzt werden soll, wenigstens in der letzten Schicht diese Umsetzung bewirken.The gases obtained are then optionally after the supply of Water vapor or carbonic acid or oxygen or air or several of these Means passed over activated catalysts, which, if the carbon oxide with water vapor to be converted to hydrogen and carbonic acid, at least in the last Layer effect this implementation.

Es ist zwar bekannt, wasserstoffhaltige Gase dadurch zu erzeugen, daß Methan bei iooo bis i2oo° durch Überleiten über Koks gespalten und dann, nach Überführung etwa gebildeten Kohlenoxyds in Methan und Wasser, die Spaltung bei etwa i2oo° wiederholt wird. Bei diesem Verfahren kommt die Verwendung von Wasserdampf oder Kohlensäure oder Sauerstoff überhaupt nicht in Betracht. Zum Unterschied von dem Verfahren des Hauptpatents wird bei dem vorliegenden Verfahren in der ersten Stufe eine unvollständige thermische Spaltung der Kohlenwas:serstoffe vorgenommen. Auch hier wird die zweite Stufe unter Ausnutzung der fühlbaren Wärme, welche die Gase nach der ersten Stufe enthalten, ohne äußere Wärmezufuhr durchgeführt. Durch die Abänderung der ersten Stufe des Verfahrens des Hauptpatents wird an Sauerstoff gespart. Beispiel Leuchtgas von der Zusammensetzung c02 2,2 010 CmHn 2,4 % C O 7,80/0 H2 51,3 010 CH, 29,61/, N.@ 6,7 010 100,00/0 wird durch ein System von mit Nickel auf Magnesia als Kontakt gefüllten Metallröhren geleitet, die durch Feuergase auf goo° gehalten werden. Es entsteht ein Gasgemisch folgender Zusammensetzung: C02 1,801o C O 6,4 01o H2 78,401, CH4 7,901o N2 5,5 0lo. i00,0110. Dieses Gemisch wird unter Zuführung von 0,3o Teilen hocherhitzten Wasserdampfes pro i Teil des Gemisches über einen erhitzten aktivierten Nickelkontakt geleitet, dem in der letzten Schicht noch ein Eisen- und Chromoxyd enthaltender Katalysator zur Umsetzung des Kohlenoxyds in Wasserstoff beigemischt ist. Das Reaktionsgemisch verläßt mit 6oo° den Kontakt; es enthält C02 9,0010 CO 2,601, H2 83,8 % C H4 0,501, N2 4,1 olo.It is known that hydrogen-containing gases can be generated by splitting methane at 100 to 1200 ° by passing it over coke and then, after converting any carbon oxide formed into methane and water, the splitting is repeated at about 1200 °. In this process, the use of steam or carbon dioxide or oxygen does not come into consideration at all. In contrast to the process of the main patent, an incomplete thermal cracking of the hydrocarbons is carried out in the present process in the first stage. Here, too, the second stage is carried out using the sensible heat contained in the gases after the first stage without external heat input. The modification of the first stage of the main patent process saves oxygen. example Luminous gas of the composition c02 2.2 010 CmHn 2.4% CO 7.80 / 0 H2 51.3 010 CH, 29.61 /. N. @ 6.7 010 100.00 / 0 is passed through a system of metal tubes filled with nickel on magnesia as a contact, which are kept at goo ° by fire gases. The result is a gas mixture with the following composition: C02 1.801o CO 6.4 01o H2 78,401, CH4 7.901o N2 5.5 0lo. i00.0110. This mixture is passed over a heated activated nickel contact with the addition of 0.3o parts of highly heated steam per i part of the mixture, to which an iron and chromium oxide-containing catalyst for converting the carbon oxide into hydrogen is added in the last layer. The reaction mixture leaves the contact at 600 °; it contains C02 9.0010 CO 2.601, H2 83.8% C H4 0.501, N2 4.1 olo.

Claims (1)

PAT1:N'rANSl'1tUC11 Abänderung des Verfahrens des Patents 558 430 zur Gewinnung von Wasserstoff, Wasserstoff-Stickstoff- oder Wasserstoff-Kohlenoxyd-Gemischen, dadurch gekennzeichnet, daß man die Kohlenwasserstoffe oder solche enthaltende Gase, gegebenenfalls unter Zuführung von anderen Gasen oder Dämpfen, solchen höheren Temperaturen, gegebenenfalls in Gegenwart von Katalysatoren, aussetzt, daß eine Spaltung unter Abscheidung von Kohlenstoff erfolgt, das entstandene Gemisch jedoch noch einen merklichen Gehalt an Kohlenwasserstoffen besitzt und das erhaltene Reaktionsgemisch, gegebenenfalls nach Zuführung von Wasserdampf oder Kohlensäure oder Sauerstoff oder Luft oder mehreren dieser Mittel, über aktivierte Kontakte führt.PAT1: N'rANSl'1tUC11 Modification of the procedure of patent 558 430 for the production of hydrogen, hydrogen-nitrogen or hydrogen-carbon oxide mixtures, characterized in that the hydrocarbons or gases containing such, possibly with the addition of other gases or vapors, such higher temperatures, optionally in the presence of catalysts, exposes a cleavage under Carbon is deposited, but the resulting mixture is still noticeable Has content of hydrocarbons and the reaction mixture obtained, optionally after the addition of steam or carbonic acid or oxygen or air or more this means, via activated contacts.
DEI29643D 1926-06-27 1926-11-28 Production of hydrogen and hydrogen-containing gases from hydrocarbons Expired DE594395C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEI29643D DE594395C (en) 1926-06-27 1926-11-28 Production of hydrogen and hydrogen-containing gases from hydrocarbons

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEI28399D DE558430C (en) 1926-06-27 1926-06-27 Process for the production of hydrogen or nitrogen-hydrogen mixtures from hydrocarbons
DEI29643D DE594395C (en) 1926-06-27 1926-11-28 Production of hydrogen and hydrogen-containing gases from hydrocarbons

Publications (1)

Publication Number Publication Date
DE594395C true DE594395C (en) 1934-03-16

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DEI29643D Expired DE594395C (en) 1926-06-27 1926-11-28 Production of hydrogen and hydrogen-containing gases from hydrocarbons

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1145586B (en) * 1955-02-22 1963-03-21 Azote Office Nat Ind Process and device for the cyclical and catalytic conversion of hydrocarbons into hydrogen-containing gases

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1145586B (en) * 1955-02-22 1963-03-21 Azote Office Nat Ind Process and device for the cyclical and catalytic conversion of hydrocarbons into hydrogen-containing gases

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