DE2006347A1 - Catalyst for the synthesis of ammonia - Google Patents

Catalyst for the synthesis of ammonia

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Publication number
DE2006347A1
DE2006347A1 DE19702006347 DE2006347A DE2006347A1 DE 2006347 A1 DE2006347 A1 DE 2006347A1 DE 19702006347 DE19702006347 DE 19702006347 DE 2006347 A DE2006347 A DE 2006347A DE 2006347 A1 DE2006347 A1 DE 2006347A1
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catalyst
alkali metal
porphyrin
graphite
ammonia
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DE2006347C3 (en
DE2006347B2 (en
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Kenji Kamakura; Ohnishi Takaharu Yokohama; Soma Mitsuyuki; Sudo Mizuo; Tokio; Ichikawa Masaru Tokorozawa; Tamaru (Japan). P 8329
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Kato, Ichiro, Tokio
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01CAMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00Ammonia; Compounds thereof
    • C01C1/02Preparation, purification or separation of ammonia
    • C01C1/04Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0411Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/11Lithium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/12Sodium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/13Potassium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46Titanium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/66Tungsten
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82Metals of the platinum group
    • B01J2531/821Ruthenium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84Metals of the iron group
    • B01J2531/842Iron
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84Metals of the iron group
    • B01J2531/845Cobalt
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
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  • Analytical Chemistry (AREA)
  • Catalysts (AREA)

Description

Katalysator für die AmmoniaksyntheseCatalyst for the synthesis of ammonia

BAD ORIGINALBATH ORIGINAL

Die Erfindung betrifft einen Katalysator für eine direkte Ämmoniaksynthese aus gasförmigem Wasserstoff und Stickstoff. ' : ■ The invention relates to a catalyst for direct ammonia synthesis from gaseous hydrogen and nitrogen. ': ■

Die bisher benutzten industriellen Verfahren zur Aimnoniaksynthese sind dasHaber-Bosch-Verfahren, das Claude-Verfahren und das Mont-Cenis-Verfahren. Als wichtigster Katalysator wird bei den ersten beiden Verfahren ein Eisenoxid-Katalysator und bei dem letztgenannten Verfahren ein Cyanoferrat-Komplexsalz benutzt. Allen diesen Katalysatoren ist gerneinsam,- dass sie im wesentlichen aus Eisenverbindungen als katalytisch aktiver Komponente und gegebenenfalls aus Aktivatoren bestehen und dass sie erstr nach einer Reduktionsbehandlung eingesetzt werden sollten.The industrial processes used to date for the synthesis of Aimnoniaks are the Haber-Bosch process, the Claude process and the Mont Cenis method. As the main catalyst an iron oxide catalyst is used in the first two processes and a cyanoferrate complex salt in the latter process used. What all these catalysts have in common is that they are essentially composed of iron compounds as a catalytically active component and optionally off Activators exist and that they only take effect after a reduction treatment should be used.

Spuren von Sauerstoff oder Kohlenmonoxid wirken darüber "· hinaus auf diese Katalysatoren als Katalysatorgifte und führen zu einem Nachlassen der katalytischen Wirksamkeit,Traces of oxygen or carbon monoxide also act on these catalysts as catalyst poisons and lead to a decrease in the catalytic effectiveness,

■Die-Katalysatoren gemä-ss der Erfindung, die in ihrer Art vollkommen neu sind und eine von den bisher gebräuchlichen■ Die-catalysts according to the invention, which in their kind are completely new and one of the previously used

009832/1735009832/1735

Katalysatoren vollkommen abweichende Zusammensetzung aufweisen, üind dadurch gekennzeichnet, dass sie Komplexverbindungen mindestens eines der Alkalimetalle mit nindestens einem der Übergangsnietallphthalocy.anine, mindestens einem der Übergangsmetallporphyrine oder mit Graphit enthalten.Catalysts have completely different compositions, characterized in that they are complex compounds at least one of the alkali metals with at least one of the transition nietallphthalocy.anine, at least one contain the transition metal porphyrins or with graphite.

Diese Komplexverbindungen gehören zu. der Gruppe der Elektronen-Donator-Akzeptor-Komplexe bzw. charge-tränsfer-Komplexe, in denen die tfbergajagsmetallplithalocyanine, die übergangöinetallporphyrine und Graphit die Elektronen-Akzeptoren und die Alkalimetalle die Elektronen-Donatoren sind.These complex compounds belong to. the group of electron donor acceptor complexes or charge transfer complexes, in which the tfbergajagsmetallplithalocyanine, the transition metal porphyrins and graphite are the electron acceptors and the alkali metals are the electron donors.

Der Begriff Alkalimetalle schliesst die folgenden rietalle ein: Lithium, Natrium, Kalium, Rubidium und Cäsium.The term alkali metals includes the following rietalle a: lithium, sodium, potassium, rubidium and cesium.

Die Übrrgangsmetal!phthalocyanine sind z.B. die Phthalocyanine von Eisen, Nickel, Kobalt, Wolfram, Platin, Titan, Mangan, Chrom, Zirkon, Hafnium, Vanadin, Molybdän, Osmium, Palladium, Ruthenium, Rhodium und Iridium.The remaining metal phthalocyanines are, for example, the phthalocyanines of iron, nickel, cobalt, tungsten, platinum, titanium, manganese, chromium, zirconium, hafnium, vanadium, molybdenum, osmium, Palladium, ruthenium, rhodium and iridium.

Diese Übergangsmetallporphyrine sind z.B. Porphyrine von Eisen, Nickel, Kobalt, Wolfram, Platin, Iridium, Osmium, Titan, Mangan, Chrom, Zirkon, Hafnium, Vanadin, Molybdän, Wk Palladium, Ruthenium und Rhodium.These transition metal porphyrins are, for example, porphyrins of iron, nickel, cobalt, tungsten, platinum, iridium, osmium, titanium, manganese, chromium, zirconium, hafnium, vanadium, molybdenum, Wk palladium, ruthenium and rhodium.

Die Katalysatoren gemäss der Erfindung absorbieren eine beträchtliche Menge von gasförmigem Wasserstoff und Stickstoff und setzen eine Mischung von gasförmigem Wasserstoff und Stickstoff katalytisch in Ammoniak um. Eine Animonialfcbildung findet dagegen nicht statt, wenn das Gasgemisch nur über Alkalimetalle, nur übor Übergangsmetallphthalocyanine, nur über Übergangsmetallporphyrine oder nur über Graphit geleitet wird. Darüber hinaus wird an den Katalysatoren gemäss der Erfindung ebenso wie an den vorbekannten Katalysatoren der Prozess der Ainmoniakzersetzung umgekehrt. Die höchste Ammoniakausbeute wird daher bei tiefen Temperaturen und hohen Drücken, also auf der Seite hoher Gleichgewichtskonzentration an Ammoniak erzielt, The catalysts according to the invention absorb a considerable amount of gaseous hydrogen and nitrogen and put a mixture of gaseous hydrogen and nitrogen catalytically into ammonia. An animonial education does not take place, however, if the gas mixture only via alkali metals, only via transition metal phthalocyanines, is passed only over transition metal porphyrins or only over graphite. In addition, the catalysts according to of the invention as well as the process of ammonia decomposition in the previously known catalysts is reversed. the The highest ammonia yield is therefore achieved at low temperatures and high pressures, i.e. on the side with a high equilibrium concentration of ammonia,

009832/1735 bad original009832/1735 bad original

Die Katalysatoren gemass der Erfindung können "beispielsweise durch eines de?? folgenden Verfahren Iiergestellt werden:The catalysts according to the invention can "for example by one de ?? the following procedures can be established:

Ein überschuss mindestens eines der Alkalimetalle wird mit mindestens einem der Übergangsrietallphthalocyanine, mindestens einem der ÜbergangsiGetallporphyrine oder mit Graphit "bei einer Temperatur gemischt, die über dem Schmelzpunkt des Alkalimetalle^ "bzw. der Alkalimetalle liegt·An excess of at least one of the alkali metals is used at least one of the transition metal phthalocyanines, at least one of the transition metal porphyrins or with graphite "in one Mixed temperature that is above the melting point of the alkali metals ^ "or the alkali metals is ·

Bei Verwendung von Übergangsmetallphthalocynineri oder'" Über— gangSDietallporphyrinen werden das Alkalimetall "bzw· die i When using transition metal phthalocyanines or "transition dietal porphyrins, the alkali metal" or the i

Alkalimetalle und die Übergangsmetallphthalocyanine oder Übergangsmetallporphyrine auf einem Träger mit grosser Oberfläche niedergeschlagen und die so erhaltene Masse wird bei einer Temperatur oberhalb des Schmelzpunktes des Alkalimetalles bzw. der Alkalimetalle wärmebehandelt.Alkali metals and the transition metal phthalocyanines or Transition metal porphyrins deposited on a carrier with a large surface and the mass thus obtained is at a temperature above the melting point of the Alkali metal or the alkali metals heat-treated.

Die Erwähnung dieser Verfahren schliesst die Anwendung anderer Verfahren zur Herstellung von Katalysatoren gemäss der Erfindung nicht aus.The mention of these procedures concludes the application other process for the preparation of catalysts according to the invention does not stop.

Die erfindungsgemässen Katalysatoren bestehen aus komplexen Verbindungen zwischen den Alkalimetallen und den Übergangsmet allphthal ο cya Hin en, den Übergangsmetallporphyrinen oder Graphit und sind nach einem der vorgenannten Verfahren herstellbar.The catalysts according to the invention consist of complexes Compounds between the alkali metals and the transition metal allphthal ο cya Hin en, the transition metal porphyrins or graphite and are according to one of the aforementioned methods manufacturable.

Zur Aktivierung der erfindungsgemässen Katalysatoren bedarf es weder des Zusatzes von Aktivatoren noch einer reduzierenden Behandlung mit Wasserstoff. Darüber hinaus nimmt <lie katalytisch© Wirksamkeit der Katalysatoren gemäss der Erfindung in Gegenwart von gasförmigem Sauerstoff nicht ab.To activate the catalysts according to the invention, neither the addition of activators nor a reducing treatment with hydrogen. Furthermore increases the efficiency of the catalytic converters according to of the invention in the presence of gaseous oxygen does not depend.

Die im folgenden mitgeteilten Ausführungsbeispiele dienen zur Verdeutlichung deE Erfindung und sind nicht begrenzend zu versieben. 009832/1735 The exemplary embodiments reported below serve to illustrate the invention and should not be sifted in a limiting manner. 009832/1735

Beispiel 1example 1

0,5 g iyctallirch.es Natrium wurden an der Innenwand ein ο ρ gläserner, als Heaktionsgefäse dien tu den U-Rohres nierlorgesclilager, ur ^ auf diese Schicht wurden dann o,1 g Eitonphthalocyanin aufgedampft. Diese niedergeschlagenen Substanzen wurden anschliessend bei 20O0C im Vakuuir getempert, wobei sicli ein tiefgefärbter Komplex von Eisenphthalocynin-Natrium bildete. In das Reaktionsgefäss mit dem so geb?lde ten Komplex wurde eine Ki ;;·.:■ lau. g von gasförmigem Ua.jcc.rstoff und Stickstoff eingeleitet und mit einer GeßcLvrindigkeit von 12,2 ml/min umgewälzt. Dac Volumen des "ΰι,:-:'ά1ζ-systems betrug ca. 140 ml. Die nech dem BET-Veνfahreη bestimmte Oberfläche des komplexen Katalysetoz-c betixi^ ca. 1 m /g'der in einer Kühlfalle gesammelte Ammoniak mirde quantitativ mit Hilfe der Gasiiromatograpliie und Infrarotspektrometrio analysiert. Die Ergebnisse sind in Tabelle I zusammengestellt. Wenn der so erhaltene Katalysator 10 bis 20 cmllg Sauerstoff oder Kohlenmonoxid ausgesetzt wurdo, so wurde dadurch seine katalytisch^ Aktivität praktir-cli nicht verändert.0.5 g of iyctallirch.es sodium was placed on the inner wall of a glass, the U-tubes serve as heating vessels; 0.1 g of ion phthalocyanine was then evaporated onto this layer. These precipitated substances were then tempered in a vacuum at 20O 0 C, whereby a deeply colored complex of iron phthalocyanine sodium formed. A Ki ;; ·.: ■ lukewarm. g of gaseous fuel and nitrogen were introduced and circulated at a speed of 12.2 ml / min. Dac volume of the "ΰι,: -:. 'Ά1ζ- system was approximately 140 ml The nech the BET specific surface Ve ν fahreη the complex Katalysetoz-c ^ betixi about 1 m / g'der in a cold trap collected ammonia mirde Analyzed quantitatively with the aid of gas chromatography and infrared spectrometry, the results are summarized in Table I. If the catalyst obtained in this way was exposed to 10 to 20 cm / 1 g of oxygen or carbon monoxide, its catalytic activity was practically unchanged.

H2 H 2 (cmllg)(cmllg) TabelleTabel 110110 II. NIINII 3/N23 / N 2 3030th 170170 3030th ReaktionstemReaction stem ?40? 40 Amm ο η i a ka u s—Amm ο η i a ka u s— Partialdruck desPartial pressure of 3030th peraturtemperature 260260 beule nachbump after eingeleiteteninitiated 3030th 0C 0 C 240240 20 Stunden20 hours 00 ,02, 02 GasesGas 1010 (ml unter Nor(ml under Nor 00 ,07, 07 N2 N 2 malbedingungen )painting conditions) 00 ,27, 27 0,260.26 00 ,36, 36 1010 0,920.92 00 ,05, 05 1010 3,643.64 1010 4,604.60 1010 1,801.80 3030th

009.832/1735009.832 / 1735

BAD ORIGINAL BATH ORIGINAL

Beispiel 2 . " . - Example 2 . ". -

Die Katalysatoren wurden in der gleichen Weise wie in Beispiel 1 hergestellt, wobei 0,5 g der verschiedenen Alkalimetalle mit 0,2 g der verschiedenen tJbergangsmetallphbhalocyanine in der aus Tabelle II ersichtlichen Zusammenstellung umgesetzt wurden* Ebenfalls aus Tabelle II sind die Ergebnisse der unter Verwendung der entsprechenden .Katalysatoren durchgeführten Ammoniaksyfchese zu entnehmen, wobei die Oberfläche der Katalysatoren wiederkam $e ca. 1 m /g. betrug. .The catalysts were prepared in the same manner as in Example 1, 0.5 g of the various alkali metals being reacted with 0.2 g of the various transition metal phbhalocyanines in the compilation shown in Table II refer corresponding .Katalysatoren performed Ammoniaksyfchese, wherein the surface of the catalysts returned $ e about 1 m / g. fraud. .

Partial-Partial desof G-aseiG-asei (CmHg)(CmHg) 1010 3030th Oabelle IIOabelle II 33 240240 Ammoniak—Ammonia- NN H /NH / N druckpressure eingeleiinitiated UpUp 1010 4545 200\200 \ ausbeuteyield 3 23 2 Katalysatorcatalyst tetenkilled 1515th 4545 Eeaktions-Reaction 240240 nach 20after 20 N2 N 2 1010 4545 temperaturtemperature 240240 Stundenhours 1010 4545 0G 0 G 240 .240. (ml unter(ml under 1010 4545 -■ 240- ■ 240 NormalbeNormal OO ,24, 24 dingungen)conditions) OO ,36, 36 3,23.2 OO ,42, 42 1010 OO ,19, 19th K-FePc*K-FePc * 1818th OO ,07, 07 Na-CoPc**Na-CoPc ** 5,85.8 OO ,17, 17th Na-GoPc**Na-GoPc ** 2,12.1 Na-WPc**Na-WPc ** 5,2.5.2. Na-PtPc**Na-PtPc ** Na-ClTiPc**Na-ClTiPc **

Pc » Phthalocyanin ·.Pc »phthalocyanine ·.

* ■ Das Volumen des Heaktionssystems beträgt ca· 100 ml ** » Das Volumen des Reaktionssystems beträgt ca. 210 ml* ■ The volume of the heating system is approx. 100 ml ** »The volume of the reaction system is approx. 210 ml

009832/1735 .*" °HIGINAL 009832/1735. * "° HIGINAL

Beispiel 5Example 5

0,5 g metallisches Matrium und 0,2 g Eiseuphfclialocyaniri wurden auf 0,1 g Aktivkohle mit einer Oberfläche von ca. 600 Hi4Vg niedergeschlagen und zum Katalysator umgesetzt. Die Ergebnisse der mit diesem Katalysator durchgeführten Ammoniaksyntbese sind in Tabelle IET dargestellt. Das Volumen des Reaktionssystems betrug ca. 140 ml.0.5 g metallic matrium and 0.2 g Eiseuphfclialocyaniri were deposited on 0.1 g activated charcoal with a surface of about 600 Hi 4 µg and converted to the catalyst. The results of the ammonia synthesis carried out with this catalyst are shown in Table IET. The volume of the reaction system was about 140 ml.

(cmllg)(cmllg) 1010 desof Tabelle IIITable III 2525th Ammon ialcau s—Ammon ialcau s— mm /IT/ IT 22 1515th 5050 beute nachprey after PartialdruckPartial pressure Eeaktionstem-Reaction tem- 20 Stunden20 hours eingeleiteteninitiated H2 H 2 peraturtemperature (ml unter Kor—(ml under Kor- GasesGas o.O. malbedingun- .malbeding-. 015015 N2 N 2 CC. gen)gene) o,O, 0606 4545 0*30 * 3 o,O, 4545 1*21 * 2

Beispiel 4Example 4

Die Katalysatoren wux'den in der gleichen Weise wie in Beispiel 1 beschrieben dargestellt, wobei 0,5 g metallisches Natrium und 0,2 g Übergangsmetall-Tetraphenylporphin in der aus Tabelle IV ersichtlichen Zusammensetzung umgesetzt wurden. Die Ergebnisse der mit den so dargestellten Katalysatoren durchgeführten Ammoniaksynthese sind in Tabelle IV zusammengestellt· Das Volumen des Reaktionssystems betrug ca. 140 ml .The catalysts wux'den in the same way as in example 1, with 0.5 g of metallic sodium and 0.2 g of transition metal tetraphenylporphine in the from Table IV apparent composition were implemented. The results of the catalysts shown in this way ammonia synthesis carried out are shown in Table IV. The volume of the reaction system was approx. 140 ml.

BAD ORIGINALBATH ORIGINAL

009832/1735009832/1735

--

Tabelle IVTable IV

Katalysator Partial— drucit desCatalyst partial pressure des

' eingeleiteten Gases ' introduced gas

-(cmtQg)- (cmtQg)

Reaktionstemperatur Reaction temperature

Or·Or

Ammoniak ausbeute nach 20Ammonia yield after 20

tundenhours

:(mT unter ITormalbedingungen) : (mT under ITormal conditions)

Na-OlFe (Hl)-tetraphenyl- porphinNa-OlFe (Hl) -tetraphenyl- porphine

Na-Oirin (IIT)-tetraplienyl— porphinNa-Oirin (IIT) -tetraplienyl- porphine

1010

JOJO

3030th

110 240110 240

240240

0,20.2

8,28.2

0,80.8

0,01 0,410.01 0.41

0,040.04

Beispielexample

Ein Graphit-Alkalimetall-Komplex-Katalysator wurde durch tTir-retzen von ca. 2 g Graphitpulver mit ca. 2 g AlkalimetallA graphite alkali metal complex catalyst was made by tTir-retting of approx. 2 g of graphite powder with approx. 2 g of alkali metal

im Vakuum "beiin a vacuum "

O/O/

einem gläsernen U-Rohr erhalten.a glass U-tube.

In dem auf einer bestimmten Temperatur gehaltenen Eeaktionsgefäss wird ein Wasserstoff-Stickstoff-Gemisch mit einer Geschwindigkeit von Ί2 ml/min umgewälzt. Das Volumen des TJmwäl ζ systems "beträgt; ca. 114- ml. Die Oberfläche des Komplexes, die mit Hilfe der BET-Methode unter Verwendung von Stickstoff bestimmt wrde, betrug ca. 5OO m /g.In the reaction vessel kept at a certain temperature a hydrogen-nitrogen mixture is circulated at a rate of Ί2 ml / min. The volume of the TJmwäl ζ systems "is approx. 114 ml. The surface of the complex, which is determined with the aid of the BET method using Nitrogen was determined, was approx. 500 m / g.

009832/17009832/17

BAD ORIGINALBATH ORIGINAL

Das Reaktionsprodukte, der Ammoniak, wurde in eine.n al;; K'*:.lfalle dienenden und im 'Jmwälasystem eingebauten glHserner! U-Rohr, das mit flüssigem Stickstoff gekühlt wurde, aufgefangen, und anschliessend mit Hilfe der Infrarot spektrometrie und der Gar.chromatographie analysiert. Die Ergebnisse sind in Tobelle Y wiedergegeben.The reaction product, the ammonia, was converted into a.n al ;; K '*: lfalle serving and in the' Jmwälasystem built in glass! U-tube, which has been cooled with liquid nitrogen, is collected and then analyzed with the aid of infrared spectrometry and Garchromatographie. The results are given in Tobelle Y.

Durch die Gegenwart vcn Sauerstoff und Kohlenmonoxid vrurdr? die Aktivität· des Komplexes praktisch kaum verändert.Due to the presence of oxygen and carbon monoxide the activity of the complex hardly changed at all.

Tabelle VTable V

Katalysator Tartialdruck des eingeleiteten Catalyst partial pressure des initiated

GasesGas

( cmllg )(cmllg)

Reaktionstemperatur Reaction temperature

ο,ο,

Ammoniakausbeute nach 12 S bun den (ml unler Normalbodingungen) Ammonia yield after 12 buns (ml unler Normal conditions)

K-GraphitK graphite 5,5, 88th 9,9, 22 3OC3OC 11 ,9, 9 o,O, PAPA Na-GraphitNa graphite 5,5, 88th OO
-',- ',
?? 300300 o,O,

Beispiel 6Example 6

5 beschriebenen Weise wurde5 was described

In der gleichen wie in Beispiel
der Katalysator aus einem Gramm eim: π Alkalinictalles und zwei Gramm Graphit hergestellt. Die Ergebnisse der mit diesen •Katalysatoren durchgeführten Amineninksynth.esο sind ih Tabelle VI zusammengestellt. Die Oberfläche des Katalysators betrug ca. 20 m /g und das Volumcr. dos Reaktionssycteir.n betrug ca. 510 ml.
In the same as in example
The catalyst is made from one gram of eim : π Alkalinictalles and two grams of graphite. The results of the Amineninksynth.esο carried out with these catalysts are summarized in Table VI. The surface of the catalyst was approx. 20 m / g and the volume. dos reaction sycteir.n was approx. 510 ml.

009832/1735009832/1735

ORIGINALORIGINAL

Tabelle VITable VI Reaktions-Reaction .Ammoniak- -.Ammonia- - NH /N
3 2
NH / N
3 2
Partial-Partial bemperaturtemperature ausbeute,yield, Katalysatorcatalyst "druck des"print of 0C 0 C nach 20after 20 eingeleiinitiated Stundenhours tetenkilled .(ml unter. (ml under 0,0020.002 GasesGas !•Tonnalbe-! • Tonnal 0,004'0.004 ' IT2 H2 IT 2 H 2 dingungen )conditions) 0,0080.008 (cmllg)(cmllg) 306306 0,060.06 0,0080.008 8; 248th; 24 325325 0,110.11 K-GraphitK graphite 8 248 24 350350 0,230.23 8 24-8 24- 300 '300 ' 0,390.39 12 3812 38 Eb-GraphitEb graphite

Pat en t an st>rüclie;Pat en t an st> rüclie;

BAD ORIGJNÄLBAD ORIGJNÄL

00 9832/17 3500 9832/17 35

Claims (1)

: P a t e η b a η ε χ> r ü c h >j : P ate η ba η ε χ> r ü ch > j 1. Katalysator für die Aiumoniaksynthese, dadurch gekennzeichnet, da£ er Komplexverbindungen mindestens eines der Alkalimetalle mit mindestens einem der Über^angsmetallphthalocyanine, mindestens einem der ÜLez-gangsmetall porphyrine oder mit Graphit enthält.1. Catalyst for the Aiumoniaksynthese, characterized in that £ he complex compounds with at least one of the alkali metals at least one of the Über ^ angsmetallphthalocyanine, at least one of the ÜLez-gang metal contains porphyrine or graphite. 2. Katalysator nach Anspruch 1, dadurch gekennzeichnet, daß das2. Catalyst according to claim 1, characterized in that the :'■· Alkalimetall Lithium, Natrium, Kalium, Rubidium, oder Cäsium ist.: '■ · the alkali metal is lithium, sodium, potassium, rubidium, or cesium. Λ . J. Katalysator nach Anspruch Ί, dadurch gekennzeichnet, dass das L^ergangsmetallphthalocyariin ein Phthalocyanin des Eisens, .Nikkeis, Kobalts, Wolframs, Platins, Titans, Kangans, Chroms, Zirkon ε, Hafniums, Vanadins, Ilolybdäns, Osmiums, Palladiums, Rutheniums, 'Rhodiums oder Iridiums ist. Λ . J. Catalyst according to claim Ί, characterized in that the L ^ ergangsmetallphthalocyariin a phthalocyanine of iron, .Nikkeis, cobalt, tungsten, platinum, titanium, kangan, chromium, zircon ε, hafnium, vanadium, ilolybdenum, osmium, palladium, ruthenium, 'Is Rhodiums or Iridiums. 4. Katalysator nach Anspruch 1, dadurch gekennzeichnet, daß das Übergangsmetallporphyrin ein Porphyrin des Eisens, Nickels, Kobalts, Wolframs, Platins, Iridiums, Osmiums, Titans, Mangans, Chroms, Zirkons, Hafniums, Vanadins, Molybdäns, Palladiums, Rutheniums oder Rhodiums ist.4. Catalyst according to claim 1, characterized in that the transition metal porphyrin is a porphyrin of iron, nickel, cobalt, Tungsten, platinum, iridium, osmium, titanium, manganese, chromium, zirconium, hafnium, vanadium, molybdenum, palladium, Is ruthenium or rhodium. ^ 5· Verfahren zum Herstellen von Katn"i^-r,n boren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Alkalimetall auf einem Träger niedergeschlagen wird, dass das Phthalocyanin oder das Porphyrin dos Übergangsuietails auf diese niedergeschlagene Schicht aufgedampft wird und dass die Umsetzung sum Katalysator durch eine anschliessende Temperung im Vakuum bei geeigneter Temperatur vorgenommen wird.^ 5 · Method for producing Katn "i ^ -r, n boren according to one of the claims 1 to 4, characterized in that the alkali metal is deposited on a support that the phthalocyanine or the porphyrin dos transition uietails deposited on this Layer is evaporated and that the reaction sum catalyst is carried out by subsequent heat treatment in vacuo at a suitable temperature. 6. Verfahren zum Herstellen von Katalysatoren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass gleiche Mengen Alkalimetall und Graphitpulver gemischt und im Vakuum bei Temperaturen oberhalb der Schmelztemperatur des Alkalimetalls zur { - Reaktion gebracht werden.6. A process for preparing catalysts according to any one of claims 1 to 4, characterized in that equal amounts of alkali metal and graphite powder were mixed and in a vacuum at temperatures above the melting temperature of the alkali metal to {- are brought reaction. Dr.Qjfefe/Ur - 22 239 D oBtGWAUDr.Qjfefe / Ur - 22 239 D oB tGWAU 009832/173S009832 / 173S
DE2006347A 1969-02-06 1970-02-04 Process for the preparation of a catalyst Expired DE2006347C3 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0066103A1 (en) * 1981-05-29 1982-12-08 Eckert, Heiner, dr. Process for the reduction of reducible groups, and its application
US4800188A (en) * 1987-03-20 1989-01-24 Hoechst Celanese Corp. Method for supporting metalloporphyrins on polybenzimidazole porous articles

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8827123D0 (en) * 1988-11-21 1988-12-29 Atomic Energy Authority Uk Supported oxidation catalyst

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0066103A1 (en) * 1981-05-29 1982-12-08 Eckert, Heiner, dr. Process for the reduction of reducible groups, and its application
US4800188A (en) * 1987-03-20 1989-01-24 Hoechst Celanese Corp. Method for supporting metalloporphyrins on polybenzimidazole porous articles

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DE2006347B2 (en) 1973-09-20
BE745624A (en) 1970-07-16

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