WO1999001203A1 - Method for producing fine-grained catalysts from natural zeolite - Google Patents

Method for producing fine-grained catalysts from natural zeolite Download PDF

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Publication number
WO1999001203A1
WO1999001203A1 PCT/EP1998/004119 EP9804119W WO9901203A1 WO 1999001203 A1 WO1999001203 A1 WO 1999001203A1 EP 9804119 W EP9804119 W EP 9804119W WO 9901203 A1 WO9901203 A1 WO 9901203A1
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ions
aqueous suspension
cation exchange
naturally occurring
zeolite
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PCT/EP1998/004119
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German (de)
French (fr)
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Gurudas Samant
Hansjörg Herden
Gernot Mayer-Schwinning
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Metallgesellschaft Aktiengesellschaft
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Priority to AU89731/98A priority Critical patent/AU8973198A/en
Publication of WO1999001203A1 publication Critical patent/WO1999001203A1/en

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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst

Definitions

  • the invention relates to a method for producing fine-grained catalysts from naturally occurring zeolite for the catalytic reduction of nitrogen oxides contained in oxygen-containing exhaust gases from combustion devices in a suspension reactor.
  • DE-PS 3 912 596 describes a process for producing a catalyst for exhaust gas purification with a copper-containing synthetic zeolite.
  • the production takes place by an ion exchange in which a refractory support coated with the zeolite is immersed for the ion exchange in a mixed solution of a copper carboxylate and ammonia.
  • Catalyst produced in this way is intended for the use of automobile exhaust gases.
  • the high costs of synthetic zeolites are disadvantageous. Use in large-scale combustion facilities is inefficient.
  • a method for producing a catalyst for the purification of gases and exhaust gases of NO x with ammonia and / or urea as a reducing agent is known using copper-containing synthetic zeolite.
  • the hydrophobic dealuminated Y-type zeolite is treated with an aqueous solution of a copper compound, in particular copper chloride, and the moist zeolite is dried at from 110 to 200 ° C.
  • the copper content is up to 20%.
  • the disadvantage of a catalyst produced in this way is that the copper salt on the surface of the zeolite is rubbed off and discharged from the reaction space.
  • the invention has for its object to provide a process for the production of fine-grained catalysts from naturally occurring zeolite, with which a high denitrification performance can be achieved, in which the catalytic substance remains firmly connected to the zeolite and thus a constant denitrification performance is ensured.
  • the object on which the invention is based is achieved in that the hydrogen ions and / or alkali metal and / or alkaline earth metal ions present as compensation ions in naturally occurring zeolite in the lattice partially or completely by cation exchange in an aqueous suspension by ions of Fe and / or Cu and / or Mn and / or V and / or Cr and / or Ni and / or Co and / or Zn and / or Mo and / or Nb and / or W can be replaced.
  • the metal ions are incorporated into the lattice of the zeolite. It has surprisingly been found that the incorporation of these metal ions by cation exchange in natural zeolite is possible in an advantageous manner, so that the catalysts have a high denitrification performance, particularly in a suspension reactor.
  • the process is simple and, because of the inexpensive, naturally occurring zeolites, can be carried out economically and economically.
  • a preferred embodiment of the invention is that mordenite is used as the naturally occurring zeolite.
  • mordenite enables simple and quick cation exchange of the contaminants present in the lattice due to metal ions.
  • the cation exchange can be realized relatively quickly and completely.
  • the molar ratio of Si0 2 to A1 2 0 3 of the mordenite is in the range from 2 to 10. This measure has an advantageous effect on the denitrification performance of the catalyst.
  • the naturally occurring zeolite consists of 10 to 20% by weight mordenite, 60 to 70% by weight clinoptilolite, 0 to 5% by weight montmorillonite, the rest Si0 2 and iron.
  • Zeolite with these components can be used in a particularly advantageous manner as a denitrification catalyst.
  • the suspension is treated with liquid or gaseous ammonia compounds and / or ammonia before the cation exchange.
  • ammonium chloride or ammonium sulfate are used as ammonia compounds.
  • the pretreatment with ammonia and / or ammonia compounds facilitates the incorporation of the metal ions into the zeolite lattice during the cation exchange.
  • the cation exchange can advantageously take place in a short time.
  • the cation exchange is carried out at a temperature of the aqueous suspension of 10 to 50 ° C., which enables a relatively simple incorporation of the metal ions into the zeolite lattice in a relatively short time.
  • the cation exchange is carried out by stirring in the aqueous suspension for 2 to 24 hours, the metal ions of Fe and / or Cu and / or Mn and / or V and / or Cr and / or Ni and / or Co and / or Zn and / or Mo and / or Nb and / or W and the ions of the ammonia compounds in the form of their chlorides, sulfates, nitrates or other soluble salts.
  • the naturally occurring zeolite catalysts produced by this process have a relatively high denitrification performance.
  • a molar ratio of alkali ions to introduced metal ions of 0.1 to 10 is set in the suspension. By setting this molar ratio, the consumption of the chemicals necessary for the cation exchange can be reduced.
  • a molar ratio of sodium and / or potassium ions to introduced metal ions of 1 to 5 is set in the aqueous suspension. This measure also has an advantageous effect on the consumption of chemicals during cation exchange.
  • an average particle size for the catalyst has become so d ⁇ 0.2 mm, preferably from 5 microns to 50 proved.

Abstract

The method consists in making fine-grained catalysts from natural zeolite, intended to enable catalytic reduction of nitric oxides for slurry bed reactors. According to that method, the hydrogen ions and/or the alkaline metals and/or alkaline-earth metals which are to be found in natural zeolites are partially or totally replaced by means of an ion exchange in an aqueous suspension, by ions from Fe and/or Cu and/or Mn and/or V and/or Cr and/or Ni and/or Co and/or Zn and/or Mo and/or Nb and/or W.

Description

Verfahren zur Herstellung feinkörniger Katalysatoren aus natürlich vorkommendem Zeolith Process for the production of fine-grained catalysts from naturally occurring zeolite
Beschreibungdescription
Die Erfindung bezieht sich auf ein Verfahren zur Herstellung feinkörniger Katalysatoren aus natürlich vorkommendem Zeolith zur katalytischen Reduktion von in sauerstoffhaltigen Abgasen von Verbrennungseinrichtungen enthaltenden Stickoxiden in einem Suspensionsreaktor.The invention relates to a method for producing fine-grained catalysts from naturally occurring zeolite for the catalytic reduction of nitrogen oxides contained in oxygen-containing exhaust gases from combustion devices in a suspension reactor.
Verfahren zur Herstellung feinkörniger Katalysatoren aus synthetischem Zeolith sind bekannt. In der DE-PS 3 912 596 wird ein Verfahren zur Herstellung eines Katalysators für die Abgasreinigung mit einem Kupfer enthaltenden synthetischen Zeolith beschrieben. Die Herstellung erfolgt dabei durch einen Ionenaustausch, in dem ein mit dem Zeolith beschichteter feuerfester Träger zum Ionenaustausch in eine gemischte Lösung von einem Kupfercarboxylat und Ammoniak eingetaucht wird. Ein auf diese Weise hergestellter Katalysator ist für die Verwendung von Autoabgasen vorgesehen. Nachteilig sind jedoch die hohen Kosten der synthetischen Zeolithe. Der Einsatz in den großtechnischen Verbrennungseinrichtungen ist unwirtschaf lich.Processes for producing fine-grain catalysts from synthetic zeolite are known. DE-PS 3 912 596 describes a process for producing a catalyst for exhaust gas purification with a copper-containing synthetic zeolite. The production takes place by an ion exchange in which a refractory support coated with the zeolite is immersed for the ion exchange in a mixed solution of a copper carboxylate and ammonia. On Catalyst produced in this way is intended for the use of automobile exhaust gases. However, the high costs of synthetic zeolites are disadvantageous. Use in large-scale combustion facilities is inefficient.
Aus der DE-OS 44 43 401 ist ein Verfahren zur Herstellung eines Katalysators für die Reinigung von Gasen und Abgasen von NOx mit Ammoniak und/oder Harnstoff als Reduktionsmittel unter Verwendung von kupferhaltigem synthetischem Zeolith bekannt. Der hydrophobe dealuminierte Zeolith des Y-Typs wird mit einer wäßrigen Lösung einer Kupferverbindung, insbesondere Kupferchlorid, behandelt und der feuchte Zeolith bei Temperaturen von 110 bis 200 °C getrocknet. Der Kupfergehalt beträgt bis zu 20 %. Der Nachteil eines auf diese Weise hergestellten Katalysators besteht darin, daß das auf der Oberfläche des Zeoliths befindliche Kupfersalz abgerieben und aus dem Reaktionsraum ausgetragen wird.From DE-OS 44 43 401 a method for producing a catalyst for the purification of gases and exhaust gases of NO x with ammonia and / or urea as a reducing agent is known using copper-containing synthetic zeolite. The hydrophobic dealuminated Y-type zeolite is treated with an aqueous solution of a copper compound, in particular copper chloride, and the moist zeolite is dried at from 110 to 200 ° C. The copper content is up to 20%. The disadvantage of a catalyst produced in this way is that the copper salt on the surface of the zeolite is rubbed off and discharged from the reaction space.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung von feinkörnigen Katalysatoren aus natürlich vorkommendem Zeolith zu schaffen, mit dem eine hohe Entstickungsleistung erzielbar ist, bei dem die katalytische Substanz fest mit dem Zeolith verbunden bleibt und somit eine Konstanz der Entstickungsleistung gewährleistet ist.The invention has for its object to provide a process for the production of fine-grained catalysts from naturally occurring zeolite, with which a high denitrification performance can be achieved, in which the catalytic substance remains firmly connected to the zeolite and thus a constant denitrification performance is ensured.
Die der Erfindung zugrunde liegende Aufgabe wird dadurch gelöst, daß die bei natürlich vorkommendem Zeolith im Gitter als Kompensationsionen vorhandenen Wasserstoffionen und/oder Alkali- und/oder Erdalkali-Metallionen teilweise oder vollständig durch Kationenaustausch in einer wäßrigen Suspension durch Ionen von Fe und/oder Cu und/oder Mn und/oder V und/oder Cr und/oder Ni und/oder Co und/oder Zn und/oder Mo und/oder Nb und/oder W ersetzt werden. Bei dem Kationenaustausch erfolgt der Einbau der Metallionen in das Gitter des Zeoliths. Es hat sich überraschenderweise gezeigt, daß der Einbau dieser Metallionen durch Kationenaustausch in natürlichen Zeolith in vorteilhaf er Weise möglich ist, so daß die Katalysatoren eine hohe Entstickungsleistung besonders in einem Suspensionsreaktor besitzen.The object on which the invention is based is achieved in that the hydrogen ions and / or alkali metal and / or alkaline earth metal ions present as compensation ions in naturally occurring zeolite in the lattice partially or completely by cation exchange in an aqueous suspension by ions of Fe and / or Cu and / or Mn and / or V and / or Cr and / or Ni and / or Co and / or Zn and / or Mo and / or Nb and / or W can be replaced. During the cation exchange, the metal ions are incorporated into the lattice of the zeolite. It has surprisingly been found that the incorporation of these metal ions by cation exchange in natural zeolite is possible in an advantageous manner, so that the catalysts have a high denitrification performance, particularly in a suspension reactor.
Das Verfahren ist einfach und aufgrund der preiswerten, natürlich vorkommenden Zeolithe wirtschaftlich kostengünstig durchführbar .The process is simple and, because of the inexpensive, naturally occurring zeolites, can be carried out economically and economically.
Eine bevorzugte Ausgestaltung der Erfindung besteht darin, daß als natürlich vorkommender Zeolith Mordenit eingesetzt wird. Der Einsatz von Mordenit ermöglicht einen einfachen und schnellen Kationenaustausch der im Gitter vorhandenen Verunreinigungen durch Metallionen. Der Kationenaustausch kann relativ schnell und vollständig realisiert werden.A preferred embodiment of the invention is that mordenite is used as the naturally occurring zeolite. The use of mordenite enables simple and quick cation exchange of the contaminants present in the lattice due to metal ions. The cation exchange can be realized relatively quickly and completely.
Gemäß einer weiteren bevorzugten Ausgestaltung der Erfindung liegt das Molverhältnis von Si02 zu A1203 des Mordenits im Bereich von 2 bis 10. Diese Maßnahme wirkt sich vorteilhaft auf die Entstickungsleistung des Katalysators aus.According to a further preferred embodiment of the invention, the molar ratio of Si0 2 to A1 2 0 3 of the mordenite is in the range from 2 to 10. This measure has an advantageous effect on the denitrification performance of the catalyst.
Nach einer weiteren bevorzugten Ausgestaltung der Erfindung besteht der natürlich vorkommende Zeolith aus 10 bis 20 Gew.-% Mordenit, 60 bis 70 Gew.-% Clinoptilolit, 0 bis 5 Gew.-% Montmorillonit , Rest Si02 und Eisen. Zeolith mit diesen Komponenten läßt sich in besonders vorteilhafter Weise als Entstickungskatalysator einsetzen . Eine weitere bevorzugte Ausgestaltung der Erfindung besteht darin, daß die Suspension vor dem Kationenaustausch mit flüssigen oder gasförmigen Ammoniakverbindungen und/oder Ammoniak behandelt wird. Als Ammoniakverbindungen werden beispielsweise Ammoniumchlorid oder Ammoniumsulfat eingesetzt. Die Vorbehandlung mit Ammoniak und/oder Ammoniakverbindungen erleichtert den Einbau der Metallionen in das Zeolithgitter beim Kationenaustausch. Der Kationenaustausch kann dabei in vorteilhafter Weise in kurzer Zeit erfolgen.According to a further preferred embodiment of the invention, the naturally occurring zeolite consists of 10 to 20% by weight mordenite, 60 to 70% by weight clinoptilolite, 0 to 5% by weight montmorillonite, the rest Si0 2 and iron. Zeolite with these components can be used in a particularly advantageous manner as a denitrification catalyst. Another preferred embodiment of the invention is that the suspension is treated with liquid or gaseous ammonia compounds and / or ammonia before the cation exchange. For example, ammonium chloride or ammonium sulfate are used as ammonia compounds. The pretreatment with ammonia and / or ammonia compounds facilitates the incorporation of the metal ions into the zeolite lattice during the cation exchange. The cation exchange can advantageously take place in a short time.
Weiterhin hat es sich als vorteilhaft erwiesen, daß die natürlichen Zeolithe vor dem Ionenaustausch mit verdünnter Säure behandelt werden. Dies erleichtert den Metallionenaustausch.Furthermore, it has proven advantageous that the natural zeolites are treated with dilute acid before the ion exchange. This facilitates the metal ion exchange.
Gemäß einer weiteren bevorzugten Ausgestaltung der Erfindung wird der Kationenaustausch bei einer Temperatur der wäßrigen Suspension von 10 bis 50°C durchgeführt, wodurch ein relativ einfacher Einbau der Metallionen in das Zeolithgitter in relativ kurzer Zeit möglich ist.According to a further preferred embodiment of the invention, the cation exchange is carried out at a temperature of the aqueous suspension of 10 to 50 ° C., which enables a relatively simple incorporation of the metal ions into the zeolite lattice in a relatively short time.
Nach einer weiteren bevorzugten Ausgestaltung der Erfindung wird der Kationenaustausch durch 2- bis 24-stündiges Rühren in der wäßrigen Suspension durchgeführt, wobei die Metallionen von Fe und/oder Cu und/oder Mn und/oder V und/oder Cr und/oder Ni und/oder Co und/oder Zn und/oder Mo und/oder Nb und/oder W sowie die Ionen der Ammoniakverbindungen in Form ihrer Chloride, Sulfate, Nitrate oder anderer löslicher Salze eingesetzt werden. Die nach diesem Verfahren hergestellten Katalysatoren aus natürlich vorkommendem Zeolith weisen eine relativ hohe Entstickungsleistung auf. Nach einer weiteren bevorzugten Ausgestaltung der Erfindung wird in der Suspension ein Molverhältnis von Alkali-Ionen zu eingebrachten Metallionen von 0,1 bis 10 eingestellt. Durch die Einstellung dieses Molverhältnisses kann der Verbrauch der für den Kationenaustausch notwendigen Chemikalien reduziert werden.According to a further preferred embodiment of the invention, the cation exchange is carried out by stirring in the aqueous suspension for 2 to 24 hours, the metal ions of Fe and / or Cu and / or Mn and / or V and / or Cr and / or Ni and / or Co and / or Zn and / or Mo and / or Nb and / or W and the ions of the ammonia compounds in the form of their chlorides, sulfates, nitrates or other soluble salts. The naturally occurring zeolite catalysts produced by this process have a relatively high denitrification performance. According to a further preferred embodiment of the invention, a molar ratio of alkali ions to introduced metal ions of 0.1 to 10 is set in the suspension. By setting this molar ratio, the consumption of the chemicals necessary for the cation exchange can be reduced.
Gemäß einer weiteren bevorzugten Ausgestaltung der Erfindung wird in der wäßrigen Suspension ein Molverhältnis von Natrium- und/oder Kalium- Ionen zu eingebrachten Metallionen von 1 bis 5 eingestellt. Auch diese Maßnahme wirkt sich in vorteilhafter Weise auf den Verbrauch von Chemikalien beim Kationenaustausch aus .According to a further preferred embodiment of the invention, a molar ratio of sodium and / or potassium ions to introduced metal ions of 1 to 5 is set in the aqueous suspension. This measure also has an advantageous effect on the consumption of chemicals during cation exchange.
Als vorteilhaft für die Entstickungsleistung hat sich für den Katalysator eine mittlere Teilchengröße dso von < 0,2 mm, vorzugsweise 5 bis 50 μm, erwiesen.As advantageous for the denitration an average particle size for the catalyst has become so d <0.2 mm, preferably from 5 microns to 50 proved.
Von besonders vorteilhafter Verwendung ist der Einsatz des erfindungsgemäß hergestellten Katalysators in den von stickoxidhaltigen Abgasen durchströmten Reaktionsräumen von Suspensionsreaktoren, wie Wirbelschichtanlagen, Flugstomreaktoren usw. mit oder ohne Staubrückführung.Of particular advantage is the use of the catalyst produced according to the invention in the reaction spaces of suspension reactors through which nitrogen oxide-containing exhaust gases flow, such as fluidized bed systems, flight flow reactors, etc., with or without dust recirculation.
Beispiel :For example:
1500 kg natürlicher Zeolith, der zu 50 % besteht aus Na3Al8Si4o096 • 24 H20 werden dreimal mit jeweils 3 m3 FeCl3-Lösung versetzt und bei 25°C 48 Stunden gerührt, um die Na+- Ionen durch Fe3+-Ionen im natürlichen Zeolith auszutauschen. Die Zugabe an Fe3*-Ionen zu den Na*-Ionen im natürlichen Zeolith erfolgt dabei jeweils stöchiometrisch, zweifach stöchiometrisch und dreifach stöchiometrisch. Anschließend wird der jeweils so erhaltene Zeolith-Katalysator dreimal mit Wasser gewaschen, wobei Salze entfernt werden. Danach wird der jeweilige Zeolith-Katalysator bei 200°C getrocknet. Die Analyse des Zeolith-Katalysators bei der stöchiometrischen Zugabe der Fe3*-Ionen ergab einen Anteil von 0,79 Gew.-% Fe3* . Bei der zweifach stöchiometrischen Zugabe lag dieser Anteil bei 1,4 Gew.-% und bei der dreifach stöchiometrischen Zugabe bei 1,8 Gew.-%. Jeweils 1 kg der so erhaltenen Zeolith-Katalysatoren wurden in einer zirkulierenden Wirbelschicht mit einem Rohgas in Kontakt gebracht, das 1140 mg NOx/m3 enthält. Der Sauerstoffgehalt des Rohgases lag bei 6 Gew.-%. Ferner enthielt das Rohgas NH3, wobei das stöchiometrische Verhältnis NH3 zu NO 0,9 betrug. Das Rohgas wurde einmal bei 200°C und einmal bei 300°C durch die jeweiligen Katalysatoren geleitet. Den gemessenen NOx-Abbau, bezogen auf die jeweilige Stöchiometrie und die Temperatur, zeigt die nachstehende Tabelle:1500 kg of natural zeolite, which consists of 50% Na 3 Al 8 Si 4o 0 96 • 24 H 2 0, are mixed three times with 3 m 3 FeCl 3 solution each time and stirred at 25 ° C. for 48 hours to remove the Na + - Exchanging ions with Fe 3+ ions in natural zeolite. Fe 3 * ions are added to the Na * ions in natural zeolite in each case stoichiometrically, twice stoichiometrically and tri-stoichiometrically. Then the one obtained in each case Zeolite catalyst washed three times with water, removing salts. The respective zeolite catalyst is then dried at 200 ° C. Analysis of the zeolite catalyst with the stoichiometric addition of the Fe 3 * ions showed a proportion of 0.79% by weight of Fe 3 * . With the double stoichiometric addition this proportion was 1.4% by weight and with the triple stoichiometric addition it was 1.8% by weight. In each case 1 kg of the zeolite catalysts obtained in this way were brought into contact with a raw gas which contains 1140 mg NO x / m 3 in a circulating fluidized bed. The oxygen content of the raw gas was 6% by weight. The crude gas also contained NH 3 , the stoichiometric ratio of NH 3 to NO being 0.9. The raw gas was passed once at 200 ° C and once at 300 ° C through the respective catalysts. The table below shows the measured NO x breakdown, based on the respective stoichiometry and the temperature:
Tabelle:Table:
Figure imgf000008_0001
Figure imgf000008_0001
Bei allen Versuchen ist kein NH3-Schlupf im Reingas gemessen worden . No NH 3 slip in the clean gas was measured in all experiments.

Claims

Patentansprüche claims
1. ■ Verfahren zur Herstellung feinkörniger Katalysatoren aus natürlich vorkommendem Zeolith zur katalytischen Reduktion von in sauerstoffhaltigen Abgasen von1. ■ Process for the production of fine-grained catalysts from naturally occurring zeolite for the catalytic reduction of in oxygen-containing exhaust gases from
Verbrennungseinrichtungen enthaltenden Stickoxiden, bei dem die in dem Gitter von natürlich vorkommenden Zeolithen vorhandenen Wasserstoffionen und/oder Alkali- und/oder Erdalkali-Metallionen teilweise oder vollständig durch Kationenaustausch in wäßriger Suspension durch Ionen von Fe und/oder Cu und/oder Mn und/oder V und/oder Cr und/oder Ni und/oder Co und/oder Zn und/oder Mo und/oder Nb und/oder W ersetzt werden.Combustion devices containing nitrogen oxides, in which the hydrogen ions and / or alkali and / or alkaline earth metal ions present in the lattice of naturally occurring zeolites are partially or completely by cation exchange in aqueous suspension by ions of Fe and / or Cu and / or Mn and / or V and / or Cr and / or Ni and / or Co and / or Zn and / or Mo and / or Nb and / or W can be replaced.
2. Verfahren nach Anspruch 1, bei dem als natürlich vorkommender Zeolith Mordenit eingesetzt wird.2. The method according to claim 1, in which mordenite is used as the naturally occurring zeolite.
3. Verfahren nach Anspruch 2, bei dem das Molverhältnis von Si02 zu A1203 des Mordenits im Bereich von 2 bis 10 liegt.3. The method according to claim 2, wherein the molar ratio of Si0 2 to A1 2 0 3 of the mordenite is in the range of 2 to 10.
4. Verfahren nach einem der Ansprüche 1 bis 3, bei dem eine natürlich vorkommende Zeolithmischung aus 10 bis 20 Gew.-% Mordenit, 60 bis 70 Gew.-% Clinoptilolit, 0 bis 5 Gew.-% Montmorillonit, Rest Si02 und Eisen, besteht.4. The method according to any one of claims 1 to 3, in which a naturally occurring zeolite mixture of 10 to 20 wt .-% mordenite, 60 to 70 wt .-% clinoptilolite, 0 to 5 wt .-% montmorillonite, balance Si0 2 and iron , consists.
5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem die wäßrige Suspension vor dem Kationenaustausch mit flüssigen oder gasförmigen Ammoniakverbindungen und/oder Ammoniak behandelt wird.5. The method according to any one of claims 1 to 4, in which the aqueous suspension is treated with liquid or gaseous ammonia compounds and / or ammonia before the cation exchange.
6. Verfahren nach einem der Ansprüche 1 bis 5, bei dem vor dem Kationenaustausch die Zeolithe mit verdünnter Säure behandelt werden. 6. The method according to any one of claims 1 to 5, in which the zeolites are treated with dilute acid before the cation exchange.
7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem der Kationenaustausch in der wäßrigen Suspension bei einer Temperatur von 5 bis 40°C durchgeführt wird.7. The method according to any one of claims 1 to 6, in which the cation exchange in the aqueous suspension is carried out at a temperature of 5 to 40 ° C.
8. Verfahren nach einem der Ansprüche 1 bis 7, bei dem der Kationenaustausch durch 4- bis 24-stündiges Rühren der wäßrigen Suspension durchgeführt wird, wobei die Ionen von Fe und/oder Cu und/oder Mn und/oder V und/oder Cr und/oder Ni und/oder Co und/oder Zn und/oder Mo und/oder Nb und/oder W sowie die Ionen der Ammoniakverbindungen in Form ihrer Chloride, Sulfate, Nitrate oder anderer löslicher Salze eingesetzt werden.8. The method according to any one of claims 1 to 7, in which the cation exchange is carried out by stirring the aqueous suspension for 4 to 24 hours, the ions of Fe and / or Cu and / or Mn and / or V and / or Cr and / or Ni and / or Co and / or Zn and / or Mo and / or Nb and / or W and the ions of the ammonia compounds in the form of their chlorides, sulfates, nitrates or other soluble salts.
9. Verfahren nach einem der Ansprüche 1 bis 8, bei dem in der wäßrigen Suspension ein Molverhältnis von Alkali-Ionen zu eingebrachten Metall-Ionen von 0,1 bis 10 eingestellt wird.9. The method according to any one of claims 1 to 8, in which a molar ratio of alkali ions to introduced metal ions of 0.1 to 10 is set in the aqueous suspension.
10. Verfahren nach einem der Ansprüche 1 bis 9, bei dem in der wäßrigen Suspension ein Molverhältnis von Natrium- und/oder Kalium-Ionen zu eingebrachten Metallionen von 0,1 bis 5 eingestellt wird.10. The method according to any one of claims 1 to 9, in which a molar ratio of sodium and / or potassium ions to introduced metal ions of 0.1 to 5 is set in the aqueous suspension.
11. Verfahren nach einem der Ansprüche 1 bis 10, bei dem die mittlere Teilchengröße des Katalysators d50 < 0,2 mm, vorzugsweise 5 bis 50 μm, beträgt.11. The method according to any one of claims 1 to 10, wherein the average particle size of the catalyst d 50 <0.2 mm, preferably 5 to 50 microns.
12. Verwendung des nach dem Verfahren gemäß einem der Ansprüche 1 bis 11 hergestellten Katalysators in von Abgasen durchströmten Reaktionsräumen von Suspensionsreaktoren, wie Wirbelschichtanlagen, Flugstromreaktoren usw. mit oder ohne Staubrückführung. 12. Use of the catalyst produced by the process according to one of claims 1 to 11 in reaction chambers of suspension reactors through which exhaust gases flow, such as fluidized bed plants, entrained flow reactors, etc., with or without dust recirculation.
PCT/EP1998/004119 1997-07-04 1998-07-03 Method for producing fine-grained catalysts from natural zeolite WO1999001203A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6835687B2 (en) 2000-04-20 2004-12-28 Bayer Aktiengesellschaft Method for producing double metal cyanide (DMC) catalysts
CN114072222A (en) * 2018-08-31 2022-02-18 庄信万丰股份有限公司 Bimetallic Cu/Mn catalyst for selective catalytic reduction

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113368865B (en) * 2021-06-08 2022-12-02 中国科学院山西煤炭化学研究所 Denitration catalyst, preparation method thereof and waste gas denitration method

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2411853A1 (en) * 1973-03-13 1974-09-19 Us Atomic Energy Commission Wa METHOD FOR CATALYTIC REDUCTION OF NITROGEN OXYDES
US4046888A (en) * 1975-06-12 1977-09-06 Toa Nenryo Kogyo Kabushiki Kaisha Methods for catalytic reduction of nitrogen oxides
US4571329A (en) * 1984-08-13 1986-02-18 Babcock-Hitachi Kabushiki Kaisha Ammonia reduction-denitration process and apparatus therefor
US4735927A (en) * 1985-10-22 1988-04-05 Norton Company Catalyst for the reduction of oxides of nitrogen
US5270024A (en) * 1989-08-31 1993-12-14 Tosoh Corporation Process for reducing nitrogen oxides from exhaust gas
US5433933A (en) * 1989-12-21 1995-07-18 Toyota Jidosha Kabushiki Kaisha Method of purifying oxygen-excess exhaust gas
US5543125A (en) * 1994-02-15 1996-08-06 Tokyo Gas Co., Ltd. Method of purifying non-containing exhaust gases using iron containing mordenite

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3379640A (en) * 1966-01-24 1968-04-23 Mobil Oil Corp Selective catalytic conversion with a crystalline aluminosilicate
DE3841990A1 (en) * 1988-12-14 1990-06-21 Degussa PROCESS FOR REDUCING STICK OXIDES FROM EXHAUST GASES

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2411853A1 (en) * 1973-03-13 1974-09-19 Us Atomic Energy Commission Wa METHOD FOR CATALYTIC REDUCTION OF NITROGEN OXYDES
US4046888A (en) * 1975-06-12 1977-09-06 Toa Nenryo Kogyo Kabushiki Kaisha Methods for catalytic reduction of nitrogen oxides
US4571329A (en) * 1984-08-13 1986-02-18 Babcock-Hitachi Kabushiki Kaisha Ammonia reduction-denitration process and apparatus therefor
US4735927A (en) * 1985-10-22 1988-04-05 Norton Company Catalyst for the reduction of oxides of nitrogen
US5270024A (en) * 1989-08-31 1993-12-14 Tosoh Corporation Process for reducing nitrogen oxides from exhaust gas
US5433933A (en) * 1989-12-21 1995-07-18 Toyota Jidosha Kabushiki Kaisha Method of purifying oxygen-excess exhaust gas
US5543125A (en) * 1994-02-15 1996-08-06 Tokyo Gas Co., Ltd. Method of purifying non-containing exhaust gases using iron containing mordenite

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6835687B2 (en) 2000-04-20 2004-12-28 Bayer Aktiengesellschaft Method for producing double metal cyanide (DMC) catalysts
CN114072222A (en) * 2018-08-31 2022-02-18 庄信万丰股份有限公司 Bimetallic Cu/Mn catalyst for selective catalytic reduction

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