WO1996004201A1 - Catalyst for methane steam reforming and/or methane oxidation - Google Patents

Catalyst for methane steam reforming and/or methane oxidation Download PDF

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Publication number
WO1996004201A1
WO1996004201A1 PCT/EP1995/003101 EP9503101W WO9604201A1 WO 1996004201 A1 WO1996004201 A1 WO 1996004201A1 EP 9503101 W EP9503101 W EP 9503101W WO 9604201 A1 WO9604201 A1 WO 9604201A1
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catalyst
methane
nickel
cerium
steam reforming
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PCT/EP1995/003101
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German (de)
French (fr)
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Jürgen Ladebeck
Karl Kochloefl
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Süd-Chemie AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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    • 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
    • C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
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    • 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
    • C01B3/386—Catalytic partial combustion
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    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • 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
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
    • 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
    • C01B2203/1064—Platinum group metal catalysts
    • C01B2203/107—Platinum 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
    • C01B2203/1082—Composition of support materials
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a catalyst for methane vapor reforming and / or methane oxidation, containing platinum on an aluminum oxide support.
  • the production of various synthesis gases or of hydrogen from methane is one of the most important processes in chemical technology as the basis for the synthesis of methanol, Fischer-Tropsch hydrocarbons, oxo alcohols and ammonia.
  • the technically preferred production process is methane steam reforming according to equations 1 and 2.
  • the first reaction is endothermic and the heat required for this must be supplied to the reaction system.
  • the basic information on methane steam reforming is contained in numerous references (see, for example, "Catalytic Steam Reforming” in “Catalysis” Science and Technology, Vol. 5, Springer Verlag, Berlin, 1985 or “Catalysis” Vol. 3, Specialist Periodical Reports , London 1980, The Chemical Society).
  • a technically important variant is the autothermal methane steam reforming, in which the required heat is not supplied from the outside, but is generated directly in the reformer reactor. This is achieved by adding oxygen to a mixture of methane and water vapor.
  • Partial methane oxidation is a technically important alternative for synthesis gas production.
  • a mechanical destruction of the shaped catalyst articles and the loss of activity, in particular the upper catalyst layer in the reformer, are mostly caused by a strong mechanical-thermal load.
  • the result is a reduced ignitability of the catalyst, which should initiate the catalytic combustion of the methane component, and thereby an increased risk of explosion.
  • noble metal catalysts Pt, Pd, Rh on aluminum oxide
  • Ru, Pd, Rh on aluminum oxide are known which are used to initiate methane oxidation (equation 3) in the upper part of a reformer, the lower part of the reactor being coated with a commercial nickel -Reforming catalyst is filled.
  • these noble metal catalysts initiate methane oxidation, they have the disadvantage that the heat of reaction builds up in the first catalyst zone before it is removed by the subsequent reforming reaction (equation 1). The The consequence of this is overheating of the precious metal catalyst and its damage, or a significantly shortened service life.
  • the invention was based on the object of developing a catalyst which, in addition to the high methane oxidation activity, also has a corresponding steam reforming activity.
  • a catalyst for methane steam reforming and / or methane oxidation which contains platinum on an aluminum oxide support and which is characterized in that the support 2 to 12 wt .-%, preferably 5 to 8 wt .-% nickel and 1 to 10 wt .-%, preferably 3 to 6 wt .-% cerium (each calculated as metals and based on the total catalyst).
  • the catalyst according to the invention is surprisingly mechanically and catalytically very stable at temperatures above 850 ° C. and enables a reliable mode of operation in the case of autothermal methane vapor reforming, its oxidation activity (ignitability) remaining constant over longer periods of time.
  • the catalyst according to the invention initiates methane oxidation, and the heat of reaction developed in this way (equation 3) is simultaneously consumed by the reforming reaction taking place on the catalyst (equation 1).
  • the catalyst according to the invention without acting as a reforming catalyst, can be used as a catalyst for partial methane oxidation (equation 5).
  • the nickel is preferably present as nickel oxide or partly as nickel aluminate and cerium as cerium dioxide in an X or O_-Al 2 O 3 matrix.
  • the catalyst according to the invention generally contains about 0.01 to 1.0% by weight, preferably about 0.03 to 0.8% by weight. Platinum.
  • the carrier is preferably in the form of tablets, spheres, in particular rings or multi-hole tablets or wagon wheels. It can also be used in differently shaped articles.
  • the hollow bodies which are preferably used have a lower gas flow resistance than the solid molded bodies.
  • the catalyst according to the invention is preferably prepared by impregnating support bodies made of (- or ⁇ -Al 03 with aqueous nickel and cerium salt solution and thermally decomposing these salts to nickel oxide and cerium dioxide, whereupon an impregnation is carried out with an aqueous platinum salt solution.
  • Aqueous nickel and cerium salts Ce 3+ and Ni 2+ nitrate are preferably used, and H PtClg as the platinum salt.
  • the support impregnated with the nickel and cerium salt solutions is dried at about 100 to 180 ° C., in particular at about 130 ° C., and then calcined at about 400 to 1300 ° C., preferably at about 450 to 1200 ° C.
  • the aqueous hexachloroplatinic acid (H 2 PtClg) solution drying at about 100 to 180 ° C., in particular at about 130 ° C., and a final calcination at about 400 to 500 ° C., in particular at about 450 ° C.
  • the invention furthermore relates to the use of the catalyst indicated above in the autothermal methane reforming to initiate the methane oxidation and to the methane steam reforming which takes place in parallel therewith.
  • Another use of the catalyst comprises the initiation of methane oxidation in the upper part of a reformer reactor which is filled with a nickel-supported catalyst known per se is.
  • a third use of the catalyst involves partial methane oxidation to produce synthesis gas (Equation 5).
  • 500 g of a shaped ⁇ -Al 2 03 carrier are dissolved in 200 ml of deionized in 200 ml of aqueous cerium and nickel nitrate solution (75 g of Ce (NO3) 3 -6H 2 0 and 160 g of Ni ( ⁇ 3) 2 -6H 2 0 Water and made up to a volume of 200 ml) at 45 ° C.
  • the Al 2 ⁇ 3 support impregnated with cerium and nickel is first dried at 130 ° C. for 12 hours and then calcined at 450 ° C. for 3 hours.
  • Example 2 570 g of the cerium- and nickel-containing catalyst precursor from Example 2 are immersed in 200 ml of aqueous hexachloroplatinic acid solution (6 g of 10% H 2 PtClg, dissolved in deionized water and made up to a volume of 200 ml) at 25 ° C. Further processing is carried out as in Example 2.
  • aqueous hexachloroplatinic acid solution (6 g of 10% H 2 PtClg, dissolved in deionized water and made up to a volume of 200 ml
  • the "ignition temperature” was determined as a measure of the catalyst activity;
  • the composition of the reaction products was as Selekti ⁇ vticianshackstab by gas chromatography at temperatures Zvi ⁇ rule 300 and 700 ° C.
  • the test gas was composed of 2 6 V ol -% CH 4, 8 V ol .-% 0 2 and 66 vol .-% N 2 together.
  • the space ⁇ speed of the test gas was 10000 "l.
  • the catalyst temperature was a b 250 ° C at a rate of l ° C / min. increased to determine the ignition temperature.
  • the other catalysts according to the invention such as K-2, K-3 and K-4, also showed practically identical behavior in the methane oxidation and gave similar compositions of the reaction products.
  • the dry test gas had the following composition:

Abstract

Described is a catalyst for methane steam reforming and/or methane oxidation, containing platinum on an aluminum oxide substrate, characterized in that the substrate contains 2 to 12 wt %, preferably 5 to 8 wt %, nickel and 1 to 10 wt %, preferably 3 to 6 wt %, cerium (each percentage being calculated as metal and related to the overall catalyst).

Description

PATENTANMELDUNG PATENT APPLICATION
Katalysator für die Methandampfreformierung und/oder MethanoxidationCatalyst for methane steam reforming and / or methane oxidation
Beschreibungdescription
Die Erfindung betrifft einen Katalysator für die Methandampf- reformierung und/oder Methanoxidation, enthaltend Platin auf einem Aluminiumoxidträger.The invention relates to a catalyst for methane vapor reforming and / or methane oxidation, containing platinum on an aluminum oxide support.
Die Produktion von diversen Synthesegasen oder von Wasser¬ stoff aus Methan gehört zu den wichtigsten Prozessen der che¬ mischen Technologie als Basis für die Synthesen von Methanol, Fischer-Tropsch-Kohlenwasserstoffen, Oxo-Alkoholen und von Ammoniak. Das technisch bevorzugte Produktionsverfahren ist die Methan¬ dampfreformierung gemäß den Gleichungen 1 und 2.The production of various synthesis gases or of hydrogen from methane is one of the most important processes in chemical technology as the basis for the synthesis of methanol, Fischer-Tropsch hydrocarbons, oxo alcohols and ammonia. The technically preferred production process is methane steam reforming according to equations 1 and 2.
CH4 + H20 — ■> CO + 3H2; Δ H = + 49,2 kcal/mol (1) CO + H20 -→- C02 + H2 ΔH - - 9,8 kcal/mol (2)CH 4 + H 2 0 - ■> CO + 3H 2; Δ H = + 49.2 kcal / mol (1) CO + H 2 0 - → - C0 2 + H 2 ΔH - - 9.8 kcal / mol (2)
Die erste Reaktion ist endotherm, und die dazu benötigte Wärme muß dem Reaktionssystem zugeführt werden. Die Grundinforma¬ tionen über die Methandampfreformierung sind in zahlreichen Literaturstellen enthalten (vergl. z.B. "Catalytic Steam Reforming" in "Catalysis" Science and Technology, Vol. 5, Springer Verlag, Berlin, 1985 oder "Catalysis" Vol. 3, Specialist Periodical Reports, London 1980, The Chemical Society) .The first reaction is endothermic and the heat required for this must be supplied to the reaction system. The basic information on methane steam reforming is contained in numerous references (see, for example, "Catalytic Steam Reforming" in "Catalysis" Science and Technology, Vol. 5, Springer Verlag, Berlin, 1985 or "Catalysis" Vol. 3, Specialist Periodical Reports , London 1980, The Chemical Society).
Eine technisch wichtige Variante ist die autotherme Methan¬ dampfreformierung, bei welcher die benötigte Wärme nicht von außen zugeführt, sondern direkt im Reformerreaktor erzeugt wird. Dies wird durch die Zugabe von Sauerstoff zu einem Ge¬ misch von Methan und Wasserdampf erreicht.A technically important variant is the autothermal methane steam reforming, in which the required heat is not supplied from the outside, but is generated directly in the reformer reactor. This is achieved by adding oxygen to a mixture of methane and water vapor.
Wie aus Gleichung 3 ersichtlich, ist die Methanoxidation stark exotherm.As can be seen from Equation 3, methane oxidation is highly exothermic.
CH4 + 202 —■> C02 + 2 H20; ^H = -191,8 kcal/mol (3)CH 4 + 20 2 - ■> C0 2 + 2 H 2 0; ^ H = -191.8 kcal / mol (3)
Es genügt, nur ein Viertel des zur Dampfreformierung anstehen¬ den Methans zu oxidieren und dadurch die entsprechende Wärme zu erzeugen.It is sufficient to oxidize only a quarter of the methane pending for steam reforming and thereby to generate the corresponding heat.
CH4 + 0,22 H20 + 0,52 02 — ■> 0,74 CO + 0,26 C02 + 2,22 H2; Λ H = 0 (4)CH 4 + 0.22 H 2 0 + 0.52 0 2 - ■> 0.74 CO + 0.26 C0 2 + 2.22 H 2 ; Λ H = 0 (4)
Die autotherme Dampfreformierung von Kohlenwasserstoffen wurde in dem Beitrag von M. Flytazani-Stephanopoulos and G.E. Voecks zu dem "90th National Meeting of American Institute of Chemi- cal Engineers", Houston, Texas 1981, ausführlich beschrieben.Autothermal steam reforming of hydrocarbons was discussed in the contribution by M. Flytazani-Stephanopoulos and GE Voecks to the "90th National Meeting of American Institute of Chemical cal Engineers ", Houston, Texas 1981, described in detail.
Ein weiteres Verfahren zur Herstellung von Synthesegas ist die partielle Methanoxidation entsprechend der GleichungAnother method of producing synthesis gas is partial methane oxidation according to the equation
CH4 + 0,5 02 —> CO + 2 H2;^ H - 8,5 kcal/mol (5).CH 4 + 0.5 0 2 -> CO + 2 H 2 ; ^ H - 8.5 kcal / mol (5).
Die partielle Methanoxidation stellt eine technische wichtige Alternative der Synthesegasherstellung dar.Partial methane oxidation is a technically important alternative for synthesis gas production.
Kommerzielle Nickelkatalysatoren für die autotherme Methan¬ dampfreformierung sind beispielsweise in Catalysis Science and Technology J.R. Andersen and M. Boudart, Vol. 5 Springer-Ver¬ lag, Berlin 1984 beschrieben.Commercial nickel catalysts for autothermal methane steam reforming are described, for example, in Catalysis Science and Technology J.R. Andersen and M. Boudart, Vol. 5 Springer-Ver¬ lag, Berlin 1984.
Da die autotherme Methandampfreformierung bei Temperaturen na¬ he 1000°C abläuft, werden an die kommerziellen Nickelträgerka¬ talysatoren sehr hohe Ansprüche gestellt.Since the autothermal methane steam reforming takes place at temperatures close to 1000 ° C., very high demands are placed on the commercial nickel carrier catalysts.
Eine mechanische Zerstörung der Katalysatorformlinge und der Aktivitätsverlust, insbesondere der oberen Katalysatorschicht im Reformer, werden meistens durch eine starke mechanisch¬ thermische Belastung verursacht. Die Folge ist eine herabge¬ setzte Zündfähigkeit des Katalysators, der die katalytische Verbrennung des Methananteils einleiten sollte, und dadurch eine erhöhte Explosionsgefahr.A mechanical destruction of the shaped catalyst articles and the loss of activity, in particular the upper catalyst layer in the reformer, are mostly caused by a strong mechanical-thermal load. The result is a reduced ignitability of the catalyst, which should initiate the catalytic combustion of the methane component, and thereby an increased risk of explosion.
Ferner sind aus der US-A-4 522 894 Edelmetallkatalysatoren (Pt, Pd, Rh auf Aluminiumoxid) bekannt, die zur Einleitung der Methandoxidation (Gleichung 3) im oberen Teil eines Reformers eingesetzt werden, wobei der untere Teil des Reaktors mit einem kommerziellen Nickel-Reformierkatalysator befüllt wird. Diese Edelmetallkatalysatoren leiten zwar die Methanoxidation ein, haben aber den Nachteil, daß sich die Reaktionswärme in der ersten Katalysatorzone staut, bevor sie durch sie nachfol¬ gende Reformierreaktion (Gleichung 1) abgeführt wird. Die Folge davon ist eine Überhitzung des Edelmettallkatalysators und seine Schädigung, bzw. eine deutlich verkürzte Lebensdauer.Furthermore, from US-A-4 522 894 noble metal catalysts (Pt, Pd, Rh on aluminum oxide) are known which are used to initiate methane oxidation (equation 3) in the upper part of a reformer, the lower part of the reactor being coated with a commercial nickel -Reforming catalyst is filled. Although these noble metal catalysts initiate methane oxidation, they have the disadvantage that the heat of reaction builds up in the first catalyst zone before it is removed by the subsequent reforming reaction (equation 1). The The consequence of this is overheating of the precious metal catalyst and its damage, or a significantly shortened service life.
Der Erfindung lag die Aufgabe zugrunde, einen Katalysator zu entwickeln, der neben der hohen Methanoxidationsaktivität auch eine entsprechende Dampfreformierungsaktivität zeigt.The invention was based on the object of developing a catalyst which, in addition to the high methane oxidation activity, also has a corresponding steam reforming activity.
Diese Aufgabe wird erfindungsgemäß durch einen Katalysator für die Methandampfreformierung und/oder Methanoxidation gelöst, der Platin auf einem Aluminiumoxidträger enthält und der da¬ durch gekennzeichnet ist, daß der Träger 2 bis 12 Gew.-%, vorzugsweise 5 bis 8 Gew.-% Nickel und 1 bis 10 Gew.-%, vor¬ zugsweise 3 bis 6 Gew.-% Cer (jeweils berechnet als Metalle und bezogen auf den gesamten Katalysator), enthält.This object is achieved according to the invention by a catalyst for methane steam reforming and / or methane oxidation which contains platinum on an aluminum oxide support and which is characterized in that the support 2 to 12 wt .-%, preferably 5 to 8 wt .-% nickel and 1 to 10 wt .-%, preferably 3 to 6 wt .-% cerium (each calculated as metals and based on the total catalyst).
Der erfindungsgemäße Katalysator ist überraschenderweise bei Temperaturen über 850°C mechanisch und katalytisch sehr stabil und ermöglicht eine zuverlässige Fahrweise bei der autothermen Methandamp reformierung, wobei seine Oxidationεaktivität (Zündfähigkeit) über längere Zeiträume konstant bleibt. Bei der Verwendung als Vorschaltkatalysator vor kommerziellen Nickel-Reformierkatalysatoren leitet der erfindungsgemäße Katalysator die Methanoxidation ein, und die hierbei ent¬ wickelte Reaktionswärme (Gleichung 3) wird gleichzeitig durch die am Katalysator ablaufende Reformierreaktion (Gleichung 1) verbraucht. Ferner kann der erfindungsgemäße Katalysator, ohne daß er als Reformierkatalysator wirkt, als Katalysator für die partielle Methanoxidation (Gleichung 5) eingesetzt werden.The catalyst according to the invention is surprisingly mechanically and catalytically very stable at temperatures above 850 ° C. and enables a reliable mode of operation in the case of autothermal methane vapor reforming, its oxidation activity (ignitability) remaining constant over longer periods of time. When used as a primary catalyst upstream of commercial nickel reforming catalysts, the catalyst according to the invention initiates methane oxidation, and the heat of reaction developed in this way (equation 3) is simultaneously consumed by the reforming reaction taking place on the catalyst (equation 1). Furthermore, the catalyst according to the invention, without acting as a reforming catalyst, can be used as a catalyst for partial methane oxidation (equation 5).
In dem erfindungsgemäßen Katalysator liegt das Nickel vorzugs¬ weise als Nickeloxid oder teilweise als Nickelaluminat und Cer als Cerdioxid in einer X - bzw. o_-Al2θ3-Matrix vorliegen.In the catalyst according to the invention, the nickel is preferably present as nickel oxide or partly as nickel aluminate and cerium as cerium dioxide in an X or O_-Al 2 O 3 matrix.
Der erfindungsgemäße Katalysator enthält im allgemeinen etwa 0,01 bis 1,0 Gew.-%, vorzugsweise etwa 0,03 bis 0,8 Gew.-% Platin.The catalyst according to the invention generally contains about 0.01 to 1.0% by weight, preferably about 0.03 to 0.8% by weight. Platinum.
Vorzugsweise liegt der Träger in Form von Tabletten, Kugeln, insbesondere von Ringen bzw. Mehrlochtabletten oder Wagen¬ rädern vor. Er kann auch in anders geformten Formkörpern eingesetzt werden. Die vorzugsweise verwendeten Hohlkörper haben einen geringeren Gasdurchflußwiderstand als die Vollformkörper.The carrier is preferably in the form of tablets, spheres, in particular rings or multi-hole tablets or wagon wheels. It can also be used in differently shaped articles. The hollow bodies which are preferably used have a lower gas flow resistance than the solid molded bodies.
Der erfindungsgemäße Katalysator wird vorzugsweise dadurch hergestellt, daß Trägerformkörper aus ( - oder α-Al 03 mit wäßriger Nickel- und Cersalzlösung imprägniert und diese Salze thermisch zu Nickeloxid und Cerdioxid zersetzt werden, worauf eine Imprägnierung mit einer wäßrigen Platinsalzlösung vorgenommen wird.The catalyst according to the invention is preferably prepared by impregnating support bodies made of (- or α-Al 03 with aqueous nickel and cerium salt solution and thermally decomposing these salts to nickel oxide and cerium dioxide, whereupon an impregnation is carried out with an aqueous platinum salt solution.
Vorzugsweise verwendet man wäßrige Nickel- und Cersalze Ce3+- und Ni2+-Nitrat und als Platinsalz H PtClg.Aqueous nickel and cerium salts Ce 3+ and Ni 2+ nitrate are preferably used, and H PtClg as the platinum salt.
Im allgemeinen wird der mit den Nickel- und Cersalzlösungen imprägnierte Träger bei etwa 100 bis 180°C, insbesondere bei etwa 130°C, getrocknet und anschließend bei etwa 400 bis 1300°C, vorzugsweise bei etwa 450 bis 1200°C calciniert. Nach der Imprägnierung mit der wäßrigen Hexachloroplatinsäure- (H2PtClg) -Lösung schließt sich eine Trocknung bei etwa 100 bis 180°C, insbesondere bei etwa 130°C, und eine Abschlußcalcinie- rung bei etwa 400 bis 500°C, insbesondere bei etwa 450°C, an.In general, the support impregnated with the nickel and cerium salt solutions is dried at about 100 to 180 ° C., in particular at about 130 ° C., and then calcined at about 400 to 1300 ° C., preferably at about 450 to 1200 ° C. After impregnation with the aqueous hexachloroplatinic acid (H 2 PtClg) solution, drying at about 100 to 180 ° C., in particular at about 130 ° C., and a final calcination at about 400 to 500 ° C., in particular at about 450 ° C.
Gegenstand der Erfindung ist ferner die Verwendung des vor¬ stehend angegebenen Katalysators bei der autothermen Methan- da pfreformierung zur Einleitung der Methanoxidation und zu der parallel dazu ablaufenden Methandampfreformierung.The invention furthermore relates to the use of the catalyst indicated above in the autothermal methane reforming to initiate the methane oxidation and to the methane steam reforming which takes place in parallel therewith.
Eine weitere Verwendung des Katalysators umfaßt die Einleitung der Methanoxidation im oberen Teil eines Reformerreaktors, der mit einem an sich bekannten Nickel-Trägerkatalysator befüllt ist .Another use of the catalyst comprises the initiation of methane oxidation in the upper part of a reformer reactor which is filled with a nickel-supported catalyst known per se is.
Eine dritte Verwendung des Katalysators umfaßt die partielle Methanoxidation zur Erzeugung von Synthesegas (Gleichung 5) .A third use of the catalyst involves partial methane oxidation to produce synthesis gas (Equation 5).
Die Erfindung ist durch die nachstehenden Beispiele erläutertThe invention is illustrated by the examples below
Beispiel 1example 1
560 g eines geformten j£ -Al θ3-Trägers (4,5x4,5 mm Tabletten) (Glühverlust 15 Gew.-% bei 700°C) werden in 200 ml wäßriger Cernitratlösung (70 g Ce(N03)3-6H20, gelöst in entionisiertem Wasser und aufgefüllt auf 200 ml Volumen) bei 45°C getaucht. Der mit Cer imprägnierte A1 03-Träger wird 12 Stunden bei 130°C getrocknet, danach 3 Stunden bei 450°C und schließlich 3 Stunden bei 1200°C in Luft calciniert.560 g of a shaped j £ -Al θ3 carrier (4.5 × 4.5 mm tablets) (loss on ignition 15% by weight at 700 ° C.) are dissolved in 200 ml aqueous cerium nitrate solution (70 g Ce (N0 3 ) 3-6H 2 0, dissolved in deionized water and made up to a volume of 200 ml) immersed at 45 ° C. The A1 0 3 support impregnated with cerium is dried for 12 hours at 130 ° C., then for 3 hours at 450 ° C. and finally for 3 hours at 1200 ° C. in air.
500 g des mit Cer promotierten Al2Ü3-Trägers werden in 200 ml wäßriger Nickelnitratlösung (150 g Ni(NO3) -6H 0, gelöst in entionisertem Wasser und aufgefüllt auf 200 ml) bei 45°C ge¬ taucht. Danach erfolgt eine Trocknung (3 Stunden) bei 130°C und eine Calcinierung (3 Stunden) bei 450°C.500 g of the Al 2 Ü3 carrier promoted with cerium are immersed at 45 ° C. in 200 ml of aqueous nickel nitrate solution (150 g of Ni (NO3) -6H 0, dissolved in deionized water and made up to 200 ml). This is followed by drying (3 hours) at 130 ° C and calcination (3 hours) at 450 ° C.
540 g des cer- und nickelhaltigen Katalysatorvorläufers werden in 200 ml wäßriger Hexachloroplatinsäurelösung (57 g l0%ige H2PtClg, gelöst in entionisiertem Wasser und aufgefüllt auf 200 ml) bei 25°C getaucht. Nach der Trockung (3 Stunden) bei 120°C wird das Material einer Endcalcinierung (3 Stunden) bei 450°C unterworfen. Die chemische Zusammensetzung des auf die¬ ser Weise hergestellten Katalysators (bezeichnet als K-l) ist in Tabelle I angegeben. Beispiel 2540 g of the cerium and nickel-containing catalyst precursor are immersed in 200 ml of aqueous hexachloroplatinic acid solution (57 g of 10% H 2 PtClg, dissolved in deionized water and made up to 200 ml) at 25.degree. After drying (3 hours) at 120 ° C, the material is subjected to final calcination (3 hours) at 450 ° C. The chemical composition of the catalyst prepared in this way (designated as Kl) is given in Table I. Example 2
500 g eines geformten α-Al203-Trägers werden in 200 ml wäßriger Cer- und Nickelnitratlösung (75 g Ce(NO3)3 -6H20 und 160 g Ni( θ3)2 -6H20, gelöst in 200 ml entionisiertem Wasser und aufgefüllt auf 200 ml Volumen) bei 45°C getaucht. Der mit Cer und Nickel imprägnierte Al2θ3-Träger wird zuerst 12 Stunden bei 130°C getrocknet und anschließend 3 Stunden bei 450°C calciniert.500 g of a shaped α-Al 2 03 carrier are dissolved in 200 ml of deionized in 200 ml of aqueous cerium and nickel nitrate solution (75 g of Ce (NO3) 3 -6H 2 0 and 160 g of Ni (θ3) 2 -6H 2 0 Water and made up to a volume of 200 ml) at 45 ° C. The Al 2 θ3 support impregnated with cerium and nickel is first dried at 130 ° C. for 12 hours and then calcined at 450 ° C. for 3 hours.
570 g des cer- und nickelhaltigen Katalysatorvorläufers werden in 200 ml wäßriger Hexachloroplatinsäurelösung (60 g 10%ige H2PtClg, gelöst in entionisiertem Wasser und aufgefüllt auf 200 ml Volumen) bei 25°C getaucht. Nach der Trocknung (3 Stun¬ den bei 130°C) wird das Material einer Endcalcinierung (3 Stunden bei 450°C) unterworfen. Die chemische Zusammensetzung des auf diese Weise hergeteilten Katalysators (bezeichnet als K-2) ist in Tabelle I angegeben. Die weitere Verarbeitung erfolgt wie nach Beispiel 1.570 g of the cerium and nickel-containing catalyst precursor are immersed in 200 ml of aqueous hexachloroplatinic acid solution (60 g of 10% H 2 PtClg, dissolved in deionized water and made up to a volume of 200 ml) at 25 ° C. After drying (3 hours at 130 ° C) the material is subjected to a final calcination (3 hours at 450 ° C). The chemical composition of the catalyst thus prepared (referred to as K-2) is shown in Table I. The further processing is carried out as in Example 1.
Beispiel 3Example 3
570 g des cer- und nickelhaltigen Katalysatorvorläufers von Beispiel 2 werden in 200 ml wäßriger Hexachloroplatinsäurelö¬ sung (6 g 10%ige H2PtClg, gelöst in entionisiertem Wasser und aufgefüllt auf 200 ml Volumen) bei 25°C getaucht. Die weitere Verarbeitung erfolgt wie nach Beispiel 2.570 g of the cerium- and nickel-containing catalyst precursor from Example 2 are immersed in 200 ml of aqueous hexachloroplatinic acid solution (6 g of 10% H 2 PtClg, dissolved in deionized water and made up to a volume of 200 ml) at 25 ° C. Further processing is carried out as in Example 2.
Die chemische Zusammensetzung des auf diese Weise hergestell¬ ten Katalysators (bezeichnet als K-3) ist in Tabelle I ange¬ geben. Beispiel 4The chemical composition of the catalyst produced in this way (designated K-3) is given in Table I. Example 4
560 g des geformten Jf -Al2θ3-Trägers (Glühverlust 15 Gew.-% be 700°C) werden in 200 ml wäßriger Cernitratlösung (140 g Ce(N03)3-6H20, gelöst in entionisiertem Wasser und aufgefüllt auf 200 ml Volumen) bei 45°C getaucht. Die Trocknung und die Calcinierung des mit Cer imprägnierten Al 03-Trägers erfolgt wie nach Beispiel 1.560 g of the shaped Jf -Al 2 θ3 support (loss on ignition 15% by weight at 700 ° C.) are dissolved in 200 ml of aqueous cerium nitrate solution (140 g of Ce (N0 3 ) 3-6H 2 0, dissolved in deionized water and filled up 200 ml volume) immersed at 45 ° C. The Al 03 support impregnated with cerium is dried and calcined as in Example 1.
530 g des mit Cer promotierten Al2θ3-Trägers wurden in 200 ml wäßriger Nickelnitratlösung (155 g Ni(N03) 6.6H 0, gelöst in entionisiertem Wasser und aufgefüllt auf 200 ml Volumen) bei 45°C getaucht. Die Trocknung und die Calcinierung des cer- und nickelhaltigen Materials erfolgt wie nach Beispiel 1.530 g of the Al 2 θ3 carrier promoted with cerium were immersed in 200 ml of aqueous nickel nitrate solution (155 g of Ni (N0 3 ) 6.6H 0, dissolved in deionized water and made up to a volume of 200 ml) at 45 ° C. The drying and calcination of the cerium and nickel-containing material is carried out as in Example 1.
570 g des cer- und nickelhaltigen Katalysatorvorläufers werden in 200 ml wäßriger Hexachloroplatinsäurelösung (60 g 10%ige H PtClς, gelöst in entionisiertem Wasser und aufgefüllt auf 200 ml Volumen) bei 25°C getaucht. Die weitere Verarbeitung erfolgt wie nach Beispiel 1. Die chemische Zusammensetzung des auf dieser Weise hergestellten Katalysators (bezeichnet als K- 4) ist in Tabelle I angegeben. 570 g of the cerium and nickel-containing catalyst precursor are immersed in 200 ml of aqueous hexachloroplatinic acid solution (60 g of 10% H PtClς, dissolved in deionized water and made up to a volume of 200 ml) at 25 ° C. The further processing is carried out as in Example 1. The chemical composition of the catalyst prepared in this way (designated K-4) is given in Table I.
Tabelle ITable I
Chemische Zusammensetzung der hergestellten KatalysatorenChemical composition of the catalysts produced
Katalysator K-l K-2 -3 K-4 Catalyst Kl K-2 -3 K- 4
Trägercarrier
A1203 (Gew.-%) Ce02 (Gew.-%) NiO (Gew.-%) Pt (Gew.-%)
Figure imgf000011_0001
A1 2 0 3 (% by weight) Ce0 2 (% by weight) NiO (% by weight) Pt (% by weight)
Figure imgf000011_0001
Alle hergestellten Katalysatoren wurden bei der Methanoxida¬ tion und bei der autothermen Dampfreformierung in Laborappa¬ raturen geprüft.All catalysts prepared were tested at the Methanoxida ¬ tion and in the autothermal steam reforming in La b orappa ¬ tures.
Bei der Methanoxidation wurde einersetis die "Zündtemperatur" als Maßstab der Katalysatoraktivität ermittelt; andererseits wurde die Zusammensetzung der Reaktionsprodukte als Selekti¬ vitätsmaßstab mittels Gaschromatographie bei Temperaturen zwi¬ schen 300 und 700°C gemessen. Das Testgas setzte sich aus 26 Vol -% CH4, 8 Vol.-% 02 und 66 Vol.-% N2 zusammen. Die Raum¬ geschwindigkeit des Testgases betrug 10000 "l. Der Katalysa¬ tor befand sich in einem elektrisch beheizten Rohr, durch wel¬ ches das Testgas strömte. Die Katalysatortemperatur wurde ab 250°C mit einer Rate von l°C/min. erhöht, um die Zündungstem- peratur zu ermitteln.In the case of methane oxidation, the "ignition temperature" was determined as a measure of the catalyst activity; On the other hand, the composition of the reaction products was as Selekti ¬ vitätsmaßstab by gas chromatography at temperatures Zvi ¬ rule 300 and 700 ° C. The test gas was composed of 2 6 V ol -% CH 4, 8 V ol .-% 0 2 and 66 vol .-% N 2 together. The space ¬ speed of the test gas was 10000 "l. The Katalysa ¬ tor b efand in an electrically heated tube through wel ¬ ches flowing the test gas. The catalyst temperature was a b 250 ° C at a rate of l ° C / min. increased to determine the ignition temperature.
Die Ergebnisse dieser Messungen sind in Tabelle II zusammenge¬ stellt.The results of these measurements are shown in Table II sets together amount ¬.
Wie ersichtlich, zeigte Katalysator K-4 die höchste Methanoxi¬ dationsaktivität (niedrigste Zündtemperatur) , gefolgt von Ka- talysator K-l. Aber auch die Katalysatoren K-2 und K-3 waren noch ausreichend aktiv. Die Vorerhitzung des methanhaltigen Gases auf 400°C wäre noch ausreichend, um die Oxidation auf jedem der erfindungsgemäßen Katalysatoren einzuleiten.As can be seen, showed Catalyst K-4, the highest Methanoxi ¬ dationsaktivität (lowest ignition temperature), followed by Ka Talysator Kl. But the catalysts K-2 and K-3 were still sufficiently active. The preheating of the methane-containing gas to 400 ° C. would still be sufficient to initiate the oxidation on each of the catalysts according to the invention.
Die Zusammensetzung der Reaktionsprodukte auf dem Katalysator K-l bei verschiedenen Temperaturen zeigt die Tabelle III.The composition of the reaction products on the catalyst K-1 at different temperatures is shown in Table III.
Aus dieser Tabelle ergibt sich, daß bei 400°C eine totale Methanoxidation gemäß der folgenden Gleichung erfolgtThis table shows that at 400 ° C total methane oxidation takes place according to the following equation
CH4 + 202 —■> 2H20 + C02,CH 4 + 20 2 - ■> 2H 2 0 + C0 2 ,
bei 700°C dagegen nur eine partielle Oxidation abläuft.at 700 ° C, however, only a partial oxidation takes place.
2CH4 + 02 — ■> 2CO + 4H2 2CH 4 + 0 2 - ■ > 2CO + 4H 2
Wie die Ergebnisse weiter zeigen, laufen bei 550°C beide Reak¬ tionen ab.As the results further show, both reactions take place at 550 ° C.
Auch die anderen erfindungsgemäßen Katalysatoren, wie K-2, K-3 und K-4 zeigten bei der Methanoxidation praktisch identisches Verhalten und ergaben ähnliche Zusammensetzungen der Reak¬ tionsprodukte.The other catalysts according to the invention, such as K-2, K-3 and K-4, also showed practically identical behavior in the methane oxidation and gave similar compositions of the reaction products.
Ferner wurden alle erfindungsgemäßen Katalysatoren einem Dampf reformierungstest unterworfen.Furthermore, all the catalysts according to the invention were subjected to a steam reforming test.
Das trockene Testgas hatte folgende Zusammensetzung:The dry test gas had the following composition:
CH4 33 Vol.-% 02 13 " N2 54 "CH 4 33 vol.% 0 2 13 "N 2 54"
02/CH4 (Mol.Verh.)= 0,39, H20/CH4 (Mol.Verh.) = 2,8; Raumge¬ schwindigkeit (trocken) = 3500 h_1. Mit dem Katalysator K-l wurden folgende Ergebnisse erhalten:0 2 / CH 4 (molar ratio) = 0.39, H 2 0 / CH 4 (molar ratio) = 2.8; Raumge¬ speed (dry) = 3500 h _1 . With the catalyst Kl the following results were obtained:
Austrittstemperatur 750°C, Methanumsatz = 95%. Die Zusammen¬ setzung der Gasprodukte zeigt Tabelle IV.Outlet temperature 750 ° C, methane conversion = 95%. The composition of the gas products is shown in Table IV.
Unter den gleichen Reaktionsbedingungen wurden mit den Kataly¬ satoren K-2, K-3 und K-4 Methanumsätze zwischen 95 und 97% erhalten. Auch die Zusammensetzung der Gasprodukte war etwa die gleiche wie in Tabelle IV.Under the same reaction conditions with the catalysts K-2, K-3 and K-4 methane conversions between 95 and 97% were obtained. The composition of the gas products was also approximately the same as in Table IV.
Tabelle IITable II
Ergebnisse des AktivitätstestesResults of the activity test
Katalysator K-l K-2 K-3 K-4Catalyst K-1 K-2 K-3 K-4
Zündtemperatur o C 328 355 388 310 Ignition temperature o C 328 355 388 310
Tabelle IIITable III
Zusammensetzung der Reaktionsprodukte auf dem Katalysator K-l bei verschiedenen Temperaturen.Composition of the reaction products on the catalyst K-1 at different temperatures.
Gaszusammen- T(°C)Gas total T (° C)
Setzung <Vol.-%) 250* 400 550 700Settlement <% by volume) 250 * 400 550 700
CH4 CH 4
02 N2 C02 0 2 N 2 C0 2
COCO
H
Figure imgf000014_0001
H
Figure imgf000014_0001
Testgas Test gas
Tabelle IVTable IV
Zusammensetzung der Reaktionsprodukte nach der autothermen DampfreformierungComposition of the reaction products after autothermal steam reforming
Gaszusammensetzung Vol.-%Gas composition vol .-%
(trocken)(dry)
CH4 1,2 C02 13,9 CO 13,5CH 4 1.2 CO 2 13.9 CO 13.5
H2 51,2 N2 20,1 H 2 51.2 N 2 20.1

Claims

Patentansprüche claims
1. Katalysator für die Methandampfreformierung und/oder Methanoxidation, enthaltend Platin auf einem Aluminiumoxid- träger, dadurch gekennzeichnet, daß der Träger 2 bis 12 Gew.- %, vorzugsweise 5 bis 8 Gew.-% Nickel und 1 bis 10 Gew.-%, vorzugsweise 3 bis 6 Gew.-% Cer (jeweils berechnet als Metalle und bezogen auf den gesamten Katalysator) , enthält.1. Catalyst for methane steam reforming and / or methane oxidation, containing platinum on an aluminum oxide support, characterized in that the support 2 to 12 wt .-%, preferably 5 to 8 wt .-% nickel and 1 to 10 wt .-% , preferably 3 to 6 wt .-% cerium (in each case calculated as metals and based on the total catalyst).
2. Katalysator nach Anspruch 1, dadurch gekennzeichnet, daß Nickel als Nickeloxid oder teilweise als Nickelaluminat und Cer als Cerdioxid in einer / ' - bzw. α-Al 03-Matrix vorliegen.2. Catalyst according to claim 1, characterized in that nickel is present as nickel oxide or partially as nickel aluminate and cerium as cerium dioxide in a / ' - or α-Al 0 3 matrix.
3. Katalysator nach Anspruch l und 2, dadurch gekennzeichnet, daß er etwa 0,01 bis 1,0 Gew.-%, vorzugsweise etwa 0,03 bis 0,8 Gew.-% Platin enthält.3. Catalyst according to claim 1 and 2, characterized in that it contains about 0.01 to 1.0 wt .-%, preferably about 0.03 to 0.8 wt .-% platinum.
4. Katalysator nach einem der Ansprüche 1 bis 3, dadurch ge¬ kennzeichnet, daß der Träger in Form von Tabletten, Kugeln, insbesondere von Ringen bzw. Mehrlochtabletten oder Wagen¬ rädern vorliegt.4. Catalyst according to one of claims 1 to 3, characterized ge indicates that the carrier is in the form of tablets, balls, in particular rings or multi-hole tablets or Wagen¬ wheels.
5. Verfahren zur Herstellung des Katalysators nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß Trägerform¬ körper ausΛ- oder α-Al203 mit wäßriger Nickel- und Cersalz¬ lösung imprägniert und diese Salze thermisch zu Nickeloxid und Cerdioxid zersetzt werden, worauf eine Imprägnierung mit einer wäßrigen Platinsalzlösung vorgenommen wird.5. A process for the preparation of the catalyst according to one of claims 1 to 4, characterized in that Trägerform¬ body made of Λ- or α-Al 2 03 impregnated with aqueous nickel and cerium salt solution and these salts are thermally decomposed to nickel oxide and cerium dioxide, whereupon an impregnation with an aqueous platinum salt solution is carried out.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß als wäßrige Nickel- und Cersalze Ce3+- und Ni2+-Nitrat und als Platinsalz H PtClg verwendet werden.6. The method according to claim 5, characterized in that Ce 3+ - and Ni 2+ nitrate and as platinum salt H PtClg are used as the aqueous nickel and cerium salts.
7. Verwendung des Katalysators nach einem der Ansprüche 1 bis 4 bei der autothermen Methandampfreformierung zur Einleitung der Methanoxidation und zu der parallel dazu ablaufenden Me¬ thandampfreformierung.7. Use of the catalyst according to one of claims 1 to 4 in the autothermal methane steam reforming for introduction the methane oxidation and the parallel methane steam reforming.
8. Verwendung des Katalysators nach einem der Ansprüche l bis 4 zur Einleitung der Methanoxidation im oberen Teil eines Re¬ formerreaktors, der mit einem an sich bekannten Nickel-Träger¬ katalysator befüllt ist.8. Use of the catalyst according to one of claims 1 to 4 for initiating the methane oxidation in the upper part of a reformer reactor which is filled with a known nickel carrier catalyst.
9. Verwendung des Katalysators nach einem der Ansprüche 1 bis 4 für die partielle Methanoxidation zur Erzeugung von Synthe¬ segas. 9. Use of the catalyst according to one of claims 1 to 4 for the partial methane oxidation to produce Synthe¬ segas.
PCT/EP1995/003101 1994-08-04 1995-08-03 Catalyst for methane steam reforming and/or methane oxidation WO1996004201A1 (en)

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