DE1230963B - Process for the vapor phase splitting of hydrocarbons with water vapor to form hydrogen-containing gases - Google Patents

Process for the vapor phase splitting of hydrocarbons with water vapor to form hydrogen-containing gases

Info

Publication number
DE1230963B
DE1230963B DEG42868A DEG0042868A DE1230963B DE 1230963 B DE1230963 B DE 1230963B DE G42868 A DEG42868 A DE G42868A DE G0042868 A DEG0042868 A DE G0042868A DE 1230963 B DE1230963 B DE 1230963B
Authority
DE
Germany
Prior art keywords
hydrocarbons
water vapor
phase splitting
containing gases
vapor phase
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
DEG42868A
Other languages
German (de)
Inventor
Dipl-Chem Dr Karl Hein Kanzler
Dipl-Chem Dr Philipp Guenther
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.)
GIRDLER SUEDCHEMIE KATALYSATOR
Original Assignee
GIRDLER SUEDCHEMIE KATALYSATOR
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 GIRDLER SUEDCHEMIE KATALYSATOR filed Critical GIRDLER SUEDCHEMIE KATALYSATOR
Priority to DEG42868A priority Critical patent/DE1230963B/en
Publication of DE1230963B publication Critical patent/DE1230963B/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
    • 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
    • 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
    • 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

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  • 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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Description

Verfahren zur Dampfphasenspaltung von Kohlenwasserstoffen mit Wasserdampf auf wasserstoffhaltige Gase Gegenstand des Patentes 1200 466 ist ein Verfahren zur Dampfphasenspaltung von Kohlenwasserstoffen im Benzinsiedebereich mit Wasserdampf auf wasserstoffhaltige Gase mit Nickelkatalysatoren, das dadurch gekennzeichnet ist, daß in Gegenwart eines bis 25 °/o Nickeloxyd, höchstens etwa 0,5 °/o Alkalioxyd, berechnet als K20, und einen hochgebrannten, von sauren Funktionen. freien Träger enthaltenden Katalysators und eines diesem Katalysator vorgeschalteten 3 bis 7 °/o Nickeloxyd auf hochgebrannten Trägern bestehenden Katalysators gearbeitet wird. Hierbei wird die Menge des vorgeschalteten Katalysators auf 10 bis 50 Volumprozent, vorzugsweise etwa 20 Volumprozent, des Gesamtkatalysatorvolumens bemessen.Process for the vapor phase splitting of hydrocarbons with water vapor on hydrogen-containing gases The subject of patent 1200 466 is a method for Vapor phase splitting of hydrocarbons in the gasoline boiling range with water vapor on hydrogen-containing gases with nickel catalysts, which is characterized is that in the presence of up to 25% nickel oxide, at most about 0.5% alkali oxide, calculated as K20, and a highly burned one, of acidic functions. free carrier containing catalyst and a 3 to 7% upstream of this catalyst Nickel oxide is worked on high-fired supports existing catalyst. Here, the amount of the upstream catalyst is reduced to 10 to 50 percent by volume, preferably about 20 percent by volume of the total catalyst volume.

Es wurde nun überraschenderweise gefunden, daß man dieses Verfahren nicht nur zum Spalten von. Kohlenwasserstoffen im Benzinsiedebereich, sondern auch zum Spalten von Kohlenwasserstoffen mit 1 bis 5 Kohlenstoffatomen anwenden kann.It has now surprisingly been found that this process can be used not just for splitting. Hydrocarbons in the gasoline boiling range, but also can be used to split hydrocarbons with 1 to 5 carbon atoms.

In Frage kommende Kohlenwasserstoffe sind gesättigte und ungesättigte Kohlenwasserstoffe, wie Methan, Äthan, Propan, Butan, Pentan, Äthylen, Propen, Buten, Penten, Butadien, Pentadien, Acetylen, Acetylene mit bis zu 5 Kohlenstoffatomen. Die Acetylene sollen jedoch nur in kleinen Mengen im Gasstrom enthalten sein. Es können sowohl geradkettige als auch verzweigtkettige Kohlenwasserstoff'e verwendet werden.The hydrocarbons in question are saturated and unsaturated Hydrocarbons such as methane, ethane, propane, butane, pentane, ethylene, propene, butene, Pentene, butadiene, pentadiene, acetylene, acetylenes with up to 5 carbon atoms. However, the acetylenes should only be contained in the gas stream in small amounts. It Both straight-chain and branched-chain hydrocarbons can be used will.

Diese Kohlenwasserstoffe werden mit Wasserdampf in einem solchen Verhältnis umgesetzt, daß je Grammatom Kohlenstoff in den Kohlenwasserstoffen etwa 2,5 bis 10 Mol Wasserdampf entfallen. Vorzugsweise wendet man Wasserdampf im Überschuß über die für die Reaktionen C..H2n+2 -I- n 11,0 -, n CO + 2 n + 1 HZ und CnH2n+2 -I- 2 n H20 :r-=t n COZ -I- 3 n -f- 1 HZ benötigte Menge an. Jedoch wird aus Kostengründen angestrebt, das Verhältnis Wasserdampf zu Kohlenwasserstoff so niedrig wie möglich zu halten, ohne den Spaltbetrieb durch Rußbildung zu beeinträchtigen. Es ist bekannt, daß der erforderliche Dampfüberschuß für rußfreie Spaltung mit der mittleren C-Zahl des Einsatzkohlenwasserstoffes stark ansteigt und bei Gegenwart von Olefinen oder schwefelhaltigen Verunreinigungen noch weiter erhöht werden muß. Beispiel Das nachstehende Beispiel veranschaulicht die Spaltung eines Flüssiggasgemisches aus Propan und Butan über einer Katalysatorkombination aus einem Katalysator mit 5,001, Nickel auf einem gebrannten Sinterkorundträger und einem darunter angeordneten Katalysator mit etwa 13,00/, Nickel und 0,5 Gewichtsprozent K20. Versuchsbedingungen: Katalysatorvolumen . . . . . . . . . . 50 cm3 Davon Katalysator mit 5 °/o Nickel . . . . . . . . . . . . . . . . . . . . 10 cm3 Katalysator mit 13 °/o Nickel und 0,5 Gewichtsprozent K20 40 cm3 Flüssiggaseinsatz ............ 23 Nl/Std. (Gemisch aus etwa 500/, Propan und etwa 50 °/o Butan) Dampfeinsatz . . . . . . . . . . . . . . . 370 Nl/Std. Dampf-Gas-Verhältnis ....... 16:1 H20/C-Verhältnis ............ etwa 4,5 Raumgeschwindigkeit . . . . . . . . 7860 Nl/1/Std. Reaktortemperatur . .. . . . . . . . . 730 bis 760°C Die Zusammensetzung des Spaltgases blieb während der ganzen Versuchsdauer konstant. Laufzeit CO@ I CO I CH, Volumprozent 1 Stunde . ... ....... 12,2 14,7 0,8 3 Stunden . . . . . . . . . . . 12,7 13,9 0,6 27 Stunden . . . . . . . . . . . 12,9 14,1 0,7 51 Stunden . . . . . . . . . . . 12,3 14,3 0,7 Der Rest bestand in allen Fällen aus Wasserstofft Nach dem 51stündigen Versuch waren beide Katalysatoren unverändert. Insbesbiielere konnten weder Ruß noch Erosionsspuren festgestellt werden.These hydrocarbons are reacted with water vapor in such a ratio that about 2.5 to 10 mol of water vapor are used per gram atom of carbon in the hydrocarbons. Preference is given to using steam in excess over that required for the reactions C..H2n + 2 -I- n 11.0 -, n CO + 2 n + 1 HZ and CnH2n + 2 -I- 2 n H20: r- = t n COZ -I- 3 n -f- 1 HZ required amount of. However, for reasons of cost, the aim is to keep the ratio of water vapor to hydrocarbon as low as possible without impairing the cracking operation through soot formation. It is known that the excess steam required for soot-free cleavage increases sharply with the average carbon number of the hydrocarbon feed and must be increased even further in the presence of olefins or sulfur-containing impurities. Example The following example illustrates the cleavage of a liquefied gas mixture of propane and butane over a catalyst combination of a catalyst with 5.001, nickel on a burnt sintered corundum support and a catalyst arranged below with about 13.00 /, nickel and 0.5 weight percent K20. Test conditions: Catalyst volume. . . . . . . . . . 50 cm3 5 ° / o of which was catalyst Nickel. . . . . . . . . . . . . . . . . . . . 10 cm3 Catalyst with 13% nickel and 0.5 percent by weight K20 40 cm3 Liquid gas use ............ 23 Nl / h. (Mixture of about 500 /, propane and about 50% butane) Use of steam. . . . . . . . . . . . . . . 370 Nl / h Steam-gas ratio ....... 16: 1 H20 / C ratio ............ about 4.5 Space velocity. . . . . . . . 7860 Nl / 1 / hour Reactor temperature. ... . . . . . . . 730 to 760 ° C The composition of the cracked gas remained constant during the entire duration of the experiment. Duration CO @ I CO I CH, Volume percentage 1 hour . ... ....... 12.2 14.7 0.8 3 hours . . . . . . . . . . . 12.7 13.9 0.6 27 hours. . . . . . . . . . . 12.9 14.1 0.7 51 hours. . . . . . . . . . . 12.3 14.3 0.7 The remainder consisted of hydrogen in all cases. After the 51 hour test, both catalysts were unchanged. In particular, neither soot nor traces of erosion could be found.

Claims (1)

Patentanspruch: Abänderung .des Verfahrens zur: Dampfphasenspaltung von, -Kohlenwasserstoffen im Benzinsiedebereich mit Wässerdämpf äuf wasserstoffhaltige -Gase in Gegenwart eines :bis 25,°/o Nickeloxyd, höchstens etwa 0;5."/,y@Alkalioxyd, berechnet als K.,0, und einen hochgebrannten, von sauren Funktionen freien Träger enthaltenden Katalysators, nach Patent 1200'466, d a d u r c h g ek e n n z e i c h n e t, däß an- Stelle von Kohlehwasserstoffen im BenzinsiedebereichKohlenwasserstoffe mit 1 bis 5 Kohlenstoffatomen verwendet werden.Claim: Modification of the process for: vapor phase splitting of, -hydrocarbons in the gasoline boiling range with Wässerdämpf äuf hydrogen-containing -Gases in the presence of: up to 25,% nickel oxide, at most about 0; 5. "/, Y @ alkali oxide, calculated as K., 0, and a highly burned carrier free of acidic functions containing catalyst, according to patent 1200'466, d a d u r c h g ek e n n z e i n e t, that instead of hydrocarbons in the gasoline boiling range, hydrocarbons with 1 to 5 carbon atoms can be used.
DEG42868A 1965-02-16 1965-02-16 Process for the vapor phase splitting of hydrocarbons with water vapor to form hydrogen-containing gases Pending DE1230963B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEG42868A DE1230963B (en) 1965-02-16 1965-02-16 Process for the vapor phase splitting of hydrocarbons with water vapor to form hydrogen-containing gases

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEG42868A DE1230963B (en) 1965-02-16 1965-02-16 Process for the vapor phase splitting of hydrocarbons with water vapor to form hydrogen-containing gases

Publications (1)

Publication Number Publication Date
DE1230963B true DE1230963B (en) 1966-12-22

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
DEG42868A Pending DE1230963B (en) 1965-02-16 1965-02-16 Process for the vapor phase splitting of hydrocarbons with water vapor to form hydrogen-containing gases

Country Status (1)

Country Link
DE (1) DE1230963B (en)

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