DE1057582B - Process for the production of copper chromite catalysts - Google Patents

Process for the production of copper chromite catalysts

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Publication number
DE1057582B
DE1057582B DEL24986A DEL0024986A DE1057582B DE 1057582 B DE1057582 B DE 1057582B DE L24986 A DEL24986 A DE L24986A DE L0024986 A DEL0024986 A DE L0024986A DE 1057582 B DE1057582 B DE 1057582B
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DE
Germany
Prior art keywords
solution
copper chromite
copper
ammoniacal
production
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
DEL24986A
Other languages
German (de)
Inventor
Dr-Ing Rolf K Ladisch
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.)
ROLF K LADISCH DR ING
Original Assignee
ROLF K LADISCH DR ING
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 ROLF K LADISCH DR ING filed Critical ROLF K LADISCH DR ING
Priority to DEL24986A priority Critical patent/DE1057582B/en
Publication of DE1057582B publication Critical patent/DE1057582B/en
Pending legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/86Chromium
    • B01J23/868Chromium copper and chromium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027Powdering
    • B01J37/0045Drying a slurry, e.g. spray drying

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Verfahren zur Herstellung von Kupferchromit-Katalys atoren Kupferchromitverbindungen enthaltende Katalysatoren wurden bisher beispielsweise durch thermisches Zersetzen des Doppelsalzes (NH4)2 [Cu(CrO4)2. 2NH3] oder durch Tränken von Aktivkohle mit einer ammoniakalischen Lösung von Kupfer- und Chromhydroxyd und darauffolgende thermische Behandlung der getränkten Aktivkohle hergestellt. Die katalytische Wirksamkeit der so dargestellten Katalysatoren ist erfahrungsgemäß stark von den bei der Zersetzung auftretenden Temperaturen abhängig. Länger einwirkende Temperaturen von bereits 200 bis 2500 C bringen die Kupferchromitverbindungen zur Teilkristallisation mit einer damit verbundenen Minderung der katalytischen Wirksamkeit. Höhere Temperaturen können zum Zerfall der Kupferchromitverbindungen in die katalytisch minderwertigen Metalloxyde führen. Process for the production of copper chromite catalysts copper chromite compounds Catalysts containing have hitherto been used, for example, by thermal decomposition of the double salt (NH4) 2 [Cu (CrO4) 2. 2NH3] or by soaking activated carbon with an ammoniacal solution of copper and chromium hydroxide and subsequent thermal Treatment of the soaked activated carbon. The catalytic effectiveness of the Experience has shown that the catalysts shown in this way differ greatly from those during decomposition occurring temperatures dependent. Long-term temperatures from already 200 to 2500 C bring the copper chromite compounds with them to partial crystallization an associated reduction in the catalytic effectiveness. Higher temperatures can cause the copper chromite compounds to break down into the catalytically inferior ones Lead metal oxides.

Die Zersetzung der ammoniakalischen Kupferchromitverbindungen wird durch Erwärmen eingeleitet und erfolgt dann exotherm. In keinem der bekannten Verfahren ist es möglich, die hierbei frei werdenden Wärmemengen schnellstens abzuleiten und damit eine Teilkristallisation und/oder einen Zerfall der Katalysatoren in Metalloxyde völlig zu vermeiden. Erfahrungsgemäß tritt auch bei strengster Betriebskontrolle bisweilen ein Verglimmen der Katalysatormasse zu den katalytisch minderwertigen Oxyden ein. The decomposition of the ammoniacal copper chromite compounds will initiated by heating and then takes place exothermic. In none of the known processes it is possible to dissipate the released heat as quickly as possible and thus partial crystallization and / or disintegration of the catalysts into metal oxides to be avoided entirely. Experience has shown that this occurs even with the strictest operational controls Sometimes the catalyst mass fades to the catalytically inferior ones Oxides a.

Die vorliegende Erfindung bezieht sich auf ein Verfahren zur Herstellung von Kupferchromit4&atalysatoren, die infolge schonendster Temperaturbehandlung bei der Zersetzung amorph und daher katalytisch höchst wirksam ausfallen. Die Erfindung bezweckt weiterhin, Kupferchromit-Katalysatoren in einfachster Weise, daher mit geringen Kosten, herzustellen und zugleich einen laufenden Herstellungsgang zur Herstellung großer Mengen zu ermöglichen und ein möglichst gleichmäßiges Erzeugnis zu gewinnen. The present invention relates to a method of manufacture of copper chromite analyzers, which as a result of the most gentle temperature treatment amorphous upon decomposition and therefore highly catalytically effective. The invention further aims to use copper chromite catalysts in the simplest possible way, therefore with low cost to produce and at the same time an ongoing production process for To enable the production of large quantities and a product that is as uniform as possible to win.

Das Verfahren besteht darin, daß eine Kupfer und Chrom enthaltende, ammoniakalische Lösung, beispielsweise eine ammoniakalische wäßrige Lösung des Doppelsalzes (NH4)2 [Cu(CrO4)2. NH3], oder in einfacherer Weise eine ammoniakalische wäßrige Lösung aus Kupferhydroxyd und Chromhydroxyd, in einen Warmluftstrom zerstäubt wird. Den obigen Lösungen kann vor dem Zerstäuben pulverförmige Aktivkohle als Trägersubstanz für den Katalysator durch gutes Vermischen mit den Lösungen zugesetzt werden. The method consists in that a copper and chromium containing, ammoniacal solution, for example an ammoniacal aqueous solution of the double salt (NH4) 2 [Cu (CrO4) 2. NH3], or, more simply, an ammoniacal aqueous solution Solution of copper hydroxide and chromium hydroxide, is atomized in a stream of warm air. The above solutions can be powdered activated carbon as a carrier substance before atomization for the catalyst can be added by mixing well with the solutions.

Für die Zerstäubung der Lösung in einen Warmluftstrom hat sich die Verwendung eines gewöhnlichen Zerstäubungstrockners als durchaus zufriedenstellend erwiesen. Nach dem Einstäuben der Lösung in den Warmluftstrom verdampft das überschüssige Wasser. For the atomization of the solution in a stream of warm air, the Use of an ordinary spray dryer is quite satisfactory proven. After dusting the solution in the stream of warm air, the excess evaporates Water.

Die zurückbleibende, aus den Kupfer- und Chromverbindungen bestehende, feinverteilte Festsubstanz zersetzt sich in dem Warmluftstrom in einen praktisch amorphen, hochwirksamen Katalysator. Der gesamte Vorgang des Auftrocknens und Zersetzens der Lösung dauert nur einen Bruchteil einer Sekunde bis zu höchstens wenigen Sekunden. Hierdurch und wegen der in dem großflächigen Sprühnebel schnellstens verlaufenden Ableitung der bei der Zersetzung entstehenden exothermen Wärme verläuft die Bildung des Katalysators äußerst schonend.The remaining, consisting of the copper and chromium compounds, finely divided solid matter decomposes in the stream of warm air into a practically amorphous, highly effective catalyst. The whole process of drying up and decomposing the solution only takes a fraction of a second to a few seconds at most. Because of this and because of the fastest running in the large spray mist The formation proceeds by dissipating the exothermic heat generated during the decomposition extremely gentle on the catalytic converter.

Die Konzentration der in der zu zerstäubenden Lösung enthaltenen Festsubstanz, die Abmessungen des zur Zersetzung der Lösung verwendeten Apparates, die Durchsatzleistung, das Verhältnis von Warmluftmenge zu der Menge des zerstäubten Gutes und andere allgemein im Zerstäubungstrockenwesen bekannte Faktoren bestimmen die Höhe der Temperatur des Warmluftstromes, bei der wirksame Katalysatoren erhalten werden. Ausgezeichnete Katalysatoren wurden beispielsweise bei der Versprühung einer ammoniakalischen Lösung des Doppelsalzes (NH4)2 [Cu (Cr 04)2 2NH3] mit einer Zweistoffdüse der in den deutschen Patentschriften 411 948 und 413 679 beschriebenen Art in einem Gleichstromzerstäubungstrockner bei Warmlufttemperaturen zwischen 450 und 5500 C erzeugt. Ähnlich gute Katalysatoren wurden bei der Versprühung einer die obige ammoniakalische Kupferchromitverbindung enthaltenden wäßrigen Paste aus Aktivkohlepulver in einen Warmluftstrom von 6000 C erhalten. The concentration of the contained in the solution to be atomized Solid matter, the dimensions of the apparatus used to decompose the solution, the throughput, the ratio of the amount of hot air to the amount of atomized air Determine goodness and other factors commonly known in atomization drying the level of the temperature of the hot air flow at which effective catalysts are obtained will. Excellent catalysts have been used, for example, in the spraying of a ammoniacal solution of the double salt (NH4) 2 [Cu (Cr 04) 2 2NH3] with a two-fluid nozzle of the type described in German patents 411 948 and 413 679 in one Co-current atomization dryer with hot air temperatures between 450 and 5500 C generated. Similar good catalysts were found in the spraying process one the above aqueous paste containing ammoniacal copper chromite compound Get activated carbon powder in a warm air stream of 6000 C.

Zweckmäßig werden die zu zerstäubendenAusgangslösungen in der Weise hergestellt, daß auf 1 Mol Kupfer 2 Mol Chrom kommen. Davon abweichende Mischungsverhältnisse von Cu : Cr ergeben jedoch ebenfalls brauchbare Kupferchromit-Katalysatoren. The starting solutions to be atomized are expedient in the manner manufactured so that there are 2 moles of chromium for every mole of copper. Mixing ratios deviating from this however, Cu: Cr also make useful copper chromite catalysts.

PATENTANSPR8CHE: 1. Verfahren zur Herstellung von Kupferchromit-Katalysatoren durch thermische Zersetzung einer ammoniakalischen Kupfer und Chrom enthaltenden Lösung, dadurch gekennzeichnet, daß die Lösung in einen Warmluftstrom zerstäubt wird. PATENT CLAIMS: 1. Process for the production of copper chromite catalysts by thermal decomposition of an ammoniacal containing copper and chromium Solution, characterized in that the solution is atomized into a stream of warm air will.

Claims (1)

2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als ammoniakalische, Kupfer und Chrom enthaltende Lösung eine ammoniakalische Lösung des Doppelsalzes (NH4)2 [Cu (CrO4)2 2 NH3] verwendet wird. 2. The method according to claim 1, characterized in that as ammoniacal, Copper and Chromium-containing solution is an ammoniacal solution of the double salt (NH4) 2 [Cu (CrO4) 2 2 NH3] is used. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Lösung vor dem Zerstäuben Aktivkohle zugesetzt wird. 3. The method according to claim 1 or 2, characterized in that activated charcoal is added to the solution before atomization. In Betracht gezogene Druckschriften: USA.-Patentschrift Nr. 2031475; deutsche Auslegeschrift St 6847 IVal 12g (bekanntgemacht am 12. 4. 1956); Gmelin-Krauts Handbuch der anorganischen Chemie, 7. Auflage, Bd. V, Abt. 1, Heidelberg, 1909, S. 1187, 1194; Ullmanns Enzyklopädie der technischen Chemie, 3. Auflage, Bd. 1, 1951, S. 602 und 603. References considered: U.S. Patent No. 2031475; German Auslegeschrift St 6847 IVal 12g (published on April 12, 1956); Gmelin Krauts Handbook of Inorganic Chemistry, 7th Edition, Vol. V, Dept. 1, Heidelberg, 1909, Pp. 1187, 1194; Ullmann's Encyclopedia of Technical Chemistry, 3rd Edition, Vol. 1, 1951, pp. 602 and 603.
DEL24986A 1956-06-01 1956-06-01 Process for the production of copper chromite catalysts Pending DE1057582B (en)

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Application Number Priority Date Filing Date Title
DEL24986A DE1057582B (en) 1956-06-01 1956-06-01 Process for the production of copper chromite catalysts

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1230403B (en) * 1962-04-24 1966-12-15 Japan Gas Chemical Company Inc Process for the production of a Cu-Cr-Zn catalyst
FR2449478A1 (en) * 1979-02-26 1980-09-19 Ashland Oil Inc COPPER CHROMITE CATALYST AND ITS USE IN THE PREPARATION OF FURFURYL ALCOHOLS FROM FURFURAL BY A DISCONTINUOUS OR LIQUID PHASE PROCESS

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2031475A (en) * 1931-06-25 1936-02-18 Joseph C W Frazer Oxidizing catalysts

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2031475A (en) * 1931-06-25 1936-02-18 Joseph C W Frazer Oxidizing catalysts

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1230403B (en) * 1962-04-24 1966-12-15 Japan Gas Chemical Company Inc Process for the production of a Cu-Cr-Zn catalyst
FR2449478A1 (en) * 1979-02-26 1980-09-19 Ashland Oil Inc COPPER CHROMITE CATALYST AND ITS USE IN THE PREPARATION OF FURFURYL ALCOHOLS FROM FURFURAL BY A DISCONTINUOUS OR LIQUID PHASE PROCESS

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