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DE19927562A1 - Catalyst made entirely from metal and used for oxidation of gaseous reductant pollutants, is made by hot oxidation and reduction treatment of alloy, with structure designed to limit turbulent regions and avoid hot spots - Google Patents

Catalyst made entirely from metal and used for oxidation of gaseous reductant pollutants, is made by hot oxidation and reduction treatment of alloy, with structure designed to limit turbulent regions and avoid hot spots

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Publication number
DE19927562A1
DE19927562A1 DE1999127562 DE19927562A DE19927562A1 DE 19927562 A1 DE19927562 A1 DE 19927562A1 DE 1999127562 DE1999127562 DE 1999127562 DE 19927562 A DE19927562 A DE 19927562A DE 19927562 A1 DE19927562 A1 DE 19927562A1
Authority
DE
Germany
Prior art keywords
partitions
metal catalyst
oxidation
catalyst
full metal
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.)
Withdrawn
Application number
DE1999127562
Other languages
German (de)
Inventor
Juergen Koppe
Hartmut Lausch
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.)
Krupp VDM GmbH
Original Assignee
Krupp VDM GmbH
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 Krupp VDM GmbH filed Critical Krupp VDM GmbH
Priority to DE1999127562 priority Critical patent/DE19927562A1/en
Publication of DE19927562A1 publication Critical patent/DE19927562A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • B01J23/76—Catalysts 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
    • B01J23/84—Catalysts 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
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • 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
    • B01J23/76—Catalysts 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
    • B01J23/84—Catalysts 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
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/12—Oxidising
    • B01J37/14—Oxidising with gases containing free oxygen
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

The pollutants, CO, HC, and/or soot are oxidized by a catalyst. This is a hot-oxidized, solid metal alloy. The catalyst is treated in an oxygen-containing atmosphere at 250 deg C - 1250 deg C, for 0.05-5 hours. Treatment with an organic reductant follows. A structure of continuous separation walls or partitions is provided to limit turbulent flow regions. The cross sectional area is 0.01-1000,000 m<2>, with spacing measured transversely with respect to the flow, of 0.1-100 mm. Preferred features: The partitions are thin sheet and/or band- and/or tube materials, formed from activated material. The exclusively metal catalyst is composed entirely of partitions. In addition to the partitions, the catalyst also includes wire and/or swarf-like materials, which are activated.

Description

Die Erfindung betrifft einen Vollmetallkatalysator für die Oxidation kohlenmonoxid- und/oder kohlenwasserstoff- und/oder rußhaltiger Gemische in der Gasphase.The invention relates to a full metal catalyst for the oxidation mixtures containing carbon monoxide and / or hydrocarbon and / or carbon black in the gas phase.

Der DE-C 196 30 250 ist ein vollmetallischer Oxidationskatalysator zu entnehmen, der für die Oxidation kohlenmonoxid- und/oder kohlenwasserstoff- und/oder rußhaltiger Gemische in der Gasphase einsetzbar ist.DE-C 196 30 250 is a fully metallic oxidation catalyst refer to the carbon monoxide and / or hydrocarbon and / or mixtures containing soot can be used in the gas phase.

Der Katalysator ist erhältlich durch oxidierende thermische Behandlung einer gegebenenfalls Mangan, Nickel, Kupfer, Chrom und Eisen enthaltenden Legierung in sauerstoffhaltiger Atmosphäre bei einer Temperatur von 250 bis 1250°C für 0,05 bis 5 Std. und anschließender Behandlung mit einer oxidierbaren organischen Substanz. Hierbei wird eine, mindestens drei der Elemente Mangan, Nickel, Kupfer, Kobalt, Chrom, Molybdän, Wolfram, Titan, Zirkonium, Vanadium, Niob, Aluminium und Eisen enthaltende Legierung, bei der der Gesamtgehalt dieser Elemente mindestens 95 Masse-% beträgt, und die bis zu insgesamt 5 Masse-% Phosphor, Stickstoff, Silicium und Schwefel sowie weitere übliche Verunreinigungen enthält, der oxidierenden thermischen Behandlung unterworfen, wobei die Legierung nach dem Abkühlen mit einer, eine oxidierbare organische Substanz enthaltenden wäßrigen Lösung oder Emulsion behandelt wird. Die Oberfläche und/oder die oberflächennahen Bereiche der Legierung werden mit einem der Elemente Bor, Aluminium, Indium, Germanium, Zinn, Blei, Scandium, Yttrium, Lanthan, Titan, Zirkonium, Vanadium, Niob, Chrom, Molybdän, Wolfram, Mangan, Technetium, Rhenium, Eisen, Kobalt, Nickel, Kupfer, Cer, Praseodym oder Neodym dotiert, wobei die Legierung danach einer zweiten thermischen Behandlung in sauerstoffhaltiger Atmosphäre über einen Zeitraum von 5 min. bis 3 Std. bei einer Temperatur von 250 bis 1250°C unterworfen wird. The catalyst is obtainable by an oxidizing thermal treatment of a optionally containing manganese, nickel, copper, chromium and iron Alloy in an oxygen-containing atmosphere at a temperature of 250 to 1250 ° C for 0.05 to 5 hours and subsequent treatment with a oxidizable organic substance. Here, one, at least three of the Elements manganese, nickel, copper, cobalt, chrome, molybdenum, tungsten, titanium, Alloy containing zirconium, vanadium, niobium, aluminum and iron the total content of these elements is at least 95% by mass, and which up to a total of 5% by mass of phosphorus, nitrogen, silicon and sulfur as well as other common impurities, the oxidizing thermal Subjected to treatment, the alloy after cooling with a an aqueous solution containing an oxidizable organic substance or Emulsion is treated. The surface and / or near the surface Areas of the alloy are coated with one of the elements boron, aluminum, Indium, germanium, tin, lead, scandium, yttrium, lanthanum, titanium, zirconium, Vanadium, niobium, chromium, molybdenum, tungsten, manganese, technetium, rhenium, Iron, cobalt, nickel, copper, cerium, praseodymium or neodymium doped, the Alloy after a second thermal treatment in oxygen-containing Atmosphere over a period of 5 min. up to 3 hours at one temperature from 250 to 1250 ° C is subjected.  

Die Anordnung eines Vollmetallkatalysators in Draht- oder Spanform bewirkt eine starke turbulente Strömung der Reaktionsgase im Katalysatorkörper. Dieser über den gesamten Strömungsquerschnitt reichende turbulente Strömung bewirkt einen starken Wärmetransport zur Reaktorwand. Dadurch bedingt können sehr starke Überhitzungen im Katalysatorbett auftreten, die unter Umständen ein Schmelzen des Vollmetallkatalysators bewirken.The arrangement of a full metal catalyst in wire or chip form a strong turbulent flow of the reaction gases in the catalyst body. This turbulent flow across the entire flow cross-section Flow causes a strong heat transfer to the reactor wall. Thereby due to very strong overheating in the catalyst bed can occur possibly cause the full metal catalyst to melt.

Ziel des Erfindungsgegenstandes ist es, eine einfache leistungsfähige und betriebssichere Vollmetallkatalysatoranordnung zu konzipieren, bei welcher Überhitzungen im Katalysatorbett, die unter Umständen ein Schmelzen des Katalysators bewirken können, sicher vermieden wird.The object of the invention is to provide a simple powerful and to design reliable all-metal catalyst arrangement, in which Overheating in the catalyst bed, which may cause melting of the Can cause catalyst is safely avoided.

Dieses Ziel wird erreicht durch einen Vollmetallkatalysator für die Oxidation kohlenmonoxid- und/oder kohlenwasserstoff- und/oder rußhaltiger Gemische in der Gasphase, erhältlich durch oxidierende thermische Behandlung einer gegebenenfalls Mangan, Nickel, Kupfer, Chrom, Eisen, Kobalt, Molybdän, Wolfram, Titan, Zirkonium, Vanadium, Niob, Aluminium und Silicium enthaltenden Legierung in sauerstoffhaltiger Atmosphäre bei einer Temperatur von 250 bis 1250°C für 0,05 bis 5 Stunden und anschließender Behandlung mit einer oxidierbaren organischen Substanz, der zur Begrenzung der turbulenten Strömungsbereiche auf eine Querschnittsfläche von jeweils 0,01 bis 100.000 mm2 und einem Abstand quer zur Strömungsrichtung des Gases von 0,1 bis 100 mm mit insbesondere durchgehenden Trennwänden versehen ist.This goal is achieved by a full metal catalyst for the oxidation of carbon monoxide and / or hydrocarbon and / or soot-containing mixtures in the gas phase, obtainable by oxidizing thermal treatment of an optionally manganese, nickel, copper, chromium, iron, cobalt, molybdenum, tungsten, titanium Alloy containing zirconium, vanadium, niobium, aluminum and silicon in an oxygen-containing atmosphere at a temperature of 250 to 1250 ° C. for 0.05 to 5 hours and subsequent treatment with an oxidizable organic substance which is used to limit the turbulent flow areas to a cross-sectional area of 0.01 to 100,000 mm 2 and a distance transversely to the flow direction of the gas of 0.1 to 100 mm is provided in particular with continuous partitions.

Vorteilhafte Weiterbildungen des Erfindungsgegenstandes sind den Unteransprüchen zu entnehmen.Advantageous developments of the subject matter of the invention See subclaims.

Der Erfindungsgegenstand stellt durch seinen optimierten konstruktiven Aufbau nun sicher, daß derartige Betriebszustände (Schmelzen des Katalysators) nicht mehr auftreten können, da die Strömungsquerschnitte durch Erzeugung von Trennwänden, ggf. unter Einbeziehung von draht- und/oder spanartig ausgebildeten Materialien, optimiert werden.The object of the invention is due to its optimized construction now sure that such operating conditions (melting of the catalyst) are not more can occur because the flow cross sections by generating  Partitions, possibly including wire and / or chip-like trained materials.

Der erfindungsgemäße Vollmetallkatalysator bewirkt somit eine deutliche Erhöhung der katalytischen Aktivität, eine hohe Betriebssicherheit und einen geringen Druckabfall.The full metal catalyst according to the invention thus brings about a clear one Increase in catalytic activity, a high level of operational safety and one low pressure drop.

Die Trennwände und/oder die draht- bzw. spanartig ausgebildeten Materialien sind analog zur DE-C 196 30 250 aktiviert.The partitions and / or the wire or chip-like materials are activated analogously to DE-C 196 30 250.

Claims (6)

1. Vollmetallkatalysator für die Oxidation kohlenmonoxid- und/oder kohlenwasserstoff- und/oder rußhaltiger Gemische in der Gasphase, erhältlich durch oxidierende thermische Behandlung einer gegebenenfalls Mangan, Nickel, Kupfer, Chrom, Eisen, Molybdän, Wolfram, Titan, Zirkonium, Vanadium, Niob, Aluminium und Silicium enthaltenden Legierung in sauerstoffhaltiger Atmosphäre bei einer Temperatur von 250 bis 1250°C für 0,05 bis 5 Stunden und anschließender Behandlung mit einer oxidierbaren organischen Substanz, der zur Begrenzung der turbulenten Strömungsbereiche auf eine Querschnittsfläche von jeweils 0,01 bis 100.000 mm2 und einem Abstand quer zur Strömungsrichtung des Gases von 0,1 bis 100 mm mit insbesondere durchgehenden Trennwänden versehen ist.1. Full metal catalyst for the oxidation of carbon monoxide and / or hydrocarbon and / or soot-containing mixtures in the gas phase, obtainable by oxidizing thermal treatment of an optionally manganese, nickel, copper, chromium, iron, molybdenum, tungsten, titanium, zirconium, vanadium, niobium , Aluminum and silicon containing alloy in an oxygen-containing atmosphere at a temperature of 250 to 1250 ° C for 0.05 to 5 hours and subsequent treatment with an oxidizable organic substance, which is used to limit the turbulent flow areas to a cross-sectional area of 0.01 to 100,000 each mm 2 and a distance transversely to the flow direction of the gas of 0.1 to 100 mm is provided with continuous dividing walls in particular. 2. Vollmetallkatalysator nach Anspruch 1, dadurch gekennzeichnet, daß die Trennwände aus dünnen Blech- und/oder Band- und/oder Rohrmaterialien gebildet sind.2. Full metal catalyst according to claim 1, characterized in that the Partitions made of thin sheet metal and / or strip and / or pipe materials are formed. 3. Vollmetallkatalysator nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Trennwände aus aktiviertem Material gebildet sind.3. full metal catalyst according to claim 1 or 2, characterized in that the partitions are made of activated material. 4. Vollmetallkatalysator nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der Vollmetallkatalysator ausschließlich aus Trennwänden zusammengesetzt ist.4. Full metal catalyst according to one of claims 1 to 3, characterized characterized in that the full metal catalyst exclusively Partitions is composed. 5. Vollmetallkatalysator nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Katalysator neben den Trennwänden auch draht- und/oder spanartig ausgebildete Materialien beinhaltet. 5. All-metal catalyst according to one of claims 1 to 4, characterized characterized in that the catalyst in addition to the partitions includes wire and / or chip-like materials.   6. Vollmetallkatalysator nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das draht- und/oder spanartig ausgebildete Material aktiviert ist.6. Full metal catalyst according to one of claims 1 to 5, characterized characterized in that the wire and / or chip-like material is activated.
DE1999127562 1999-06-17 1999-06-17 Catalyst made entirely from metal and used for oxidation of gaseous reductant pollutants, is made by hot oxidation and reduction treatment of alloy, with structure designed to limit turbulent regions and avoid hot spots Withdrawn DE19927562A1 (en)

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DE1999127562 DE19927562A1 (en) 1999-06-17 1999-06-17 Catalyst made entirely from metal and used for oxidation of gaseous reductant pollutants, is made by hot oxidation and reduction treatment of alloy, with structure designed to limit turbulent regions and avoid hot spots

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DE1999127562 DE19927562A1 (en) 1999-06-17 1999-06-17 Catalyst made entirely from metal and used for oxidation of gaseous reductant pollutants, is made by hot oxidation and reduction treatment of alloy, with structure designed to limit turbulent regions and avoid hot spots

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DE1999127562 Withdrawn DE19927562A1 (en) 1999-06-17 1999-06-17 Catalyst made entirely from metal and used for oxidation of gaseous reductant pollutants, is made by hot oxidation and reduction treatment of alloy, with structure designed to limit turbulent regions and avoid hot spots

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111186918A (en) * 2020-02-17 2020-05-22 罗光政 Adjustable turbulence scale inhibitor and scale inhibition method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4116884A (en) * 1976-08-06 1978-09-26 Honda Giken Kogyo Kabushiki Kaisha Oxidizing catalyzer
DE4416469C1 (en) * 1994-05-10 1995-09-07 Juergen Dr Koppe Easily mfd. and regenerated fully metallic oxidn. catalyst
DE19630250C1 (en) * 1996-07-26 1997-08-28 Krupp Vdm Gmbh Metal alloy catalyst for the total oxidation carbon mon:oxide, soot and/or hydrocarbon

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4116884A (en) * 1976-08-06 1978-09-26 Honda Giken Kogyo Kabushiki Kaisha Oxidizing catalyzer
DE4416469C1 (en) * 1994-05-10 1995-09-07 Juergen Dr Koppe Easily mfd. and regenerated fully metallic oxidn. catalyst
DE19630250C1 (en) * 1996-07-26 1997-08-28 Krupp Vdm Gmbh Metal alloy catalyst for the total oxidation carbon mon:oxide, soot and/or hydrocarbon

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111186918A (en) * 2020-02-17 2020-05-22 罗光政 Adjustable turbulence scale inhibitor and scale inhibition method
CN111186918B (en) * 2020-02-17 2024-02-20 罗光政 Adjustable turbulence scale inhibitor and scale inhibition method

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