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DE102007048521A1 - Method for preventing or reducing corrosion in inner casings of selective catalytic reduction catalyst, involves applying layer on inner surface of case, where applied layer is hardened by heating - Google Patents

Method for preventing or reducing corrosion in inner casings of selective catalytic reduction catalyst, involves applying layer on inner surface of case, where applied layer is hardened by heating Download PDF

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Publication number
DE102007048521A1
DE102007048521A1 DE102007048521A DE102007048521A DE102007048521A1 DE 102007048521 A1 DE102007048521 A1 DE 102007048521A1 DE 102007048521 A DE102007048521 A DE 102007048521A DE 102007048521 A DE102007048521 A DE 102007048521A DE 102007048521 A1 DE102007048521 A1 DE 102007048521A1
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Germany
Prior art keywords
layer
hardened
heating
case
preventing
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DE102007048521A
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German (de)
Inventor
Jürgen Rickertsen
Georg Reuther
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Tenneco GmbH
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Heinrich Gillet GmbH
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Priority to DE102007048521A priority Critical patent/DE102007048521A1/en
Publication of DE102007048521A1 publication Critical patent/DE102007048521A1/en
Withdrawn legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/08—Surface coverings for corrosion prevention
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2066—Selective catalytic reduction [SCR]

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Exhaust Gas After Treatment (AREA)

Abstract

Corrosion prevention involves applying a layer on inner surface of case. The applied layer is hardened by heating. Another layer contains methyltriethoxysilane or tetraethoxysilane. The latter layer is dried at 80[deg] C and then hardened at 350-500[deg] C in air atmosphere. Corrosion prevention is carried out by applying a layer on inner surface of case, where the applied layer is hardened by heating, which has one or multiple silanes of general formula (I) or a compound from oxide or hydroxide of alkali and alkaline earth metals in presence of nanoscale silicon dioxide particles. R n-Si-X 4 - n(I) X : same or different hydroxyl group or hydrolytic leaving group; R : same or different hydrolytic non leaving group; and n : 0-2 or 2. .

Description

Die Erfindung betrifft Verfahren zum Verhindern bzw. Reduzieren der Innenkorrosion in Gehäusen von SCR-Katalysatoren gemäß dem Oberbegriff des Anspruchs 1.The The invention relates to methods for preventing or reducing the Internal corrosion in housings of SCR catalysts according to the preamble of Claim 1.

Abgasanlagen für Kraftfahrzeuge mit Verbrennungsmotor umfassen mehrere Komponenten, nämlich einen oder mehrere Krümmer, Verbindungsrohre und Gehäuse für Katalysatoren, Rußfilter und Schalldämpfer sowie Endrohre. Diese Komponenten werden von den beim Verbrennen von Benzin oder Diesel entstehenden Abgasen durchströmt. Die Abgase enthalten unter anderem Kohlenmonoxid, Kohlendioxid, Stickoxide, Schwefeloxide, Ammoniumverbindungen und Wasserdampf. Wird der Taupunkt der Abgase unterschritten, insbesondere im Start- und Teillastbereich, so bildet sich im Inneren der Abgasanlage ein flüssiges Kondensat, dessen pH-Wert sich im Bereich zwischen 6,5 und 2,5 bewegt. Dieses Kondensat führt zu einer Korrosion des Stahlmaterials, aus dem die Abgasanlage hergestellt ist.exhaust systems for motor vehicles with internal combustion engine include several components, namely one or multiple manifolds, Connecting pipes and housing for catalysts, soot filter and silencers as well as tailpipes. These components are burned off when burning flowed through by gasoline or diesel exhaust gases. The Exhaust gases contain, inter alia, carbon monoxide, carbon dioxide, nitrogen oxides, Sulfur oxides, ammonium compounds and water vapor. Becomes the dew point the exhaust gases have fallen below, especially in the start and part load range, so forms inside the exhaust system, a liquid condensate whose pH ranges from 6.5 to 2.5. This condensate leads to a Corrosion of the steel material from which the exhaust system is made is.

Die Automobilhersteller fordern von Jahr zu Jahr eine höhere Lebensdauer der Abgasanlage. Angestrebt wird die lebenslange Brauchbarkeit. Die Hersteller von Abgasanlagen sind daher gezwungen, anstelle von oberflächlich passivierten Stählen, beispielsweise aluminiertem Stahl, zu Edelstählen überzugehen. Allerdings unterliegen auch Edelstähle einer Korrosion durch die kombinierte Einwirkung von Säure und Hitze. Aus diesem Grund muss das Blechmaterial, aus dem die Rohre und Gehäuse hergestellt werden, eine erhebliche Dicke haben. Das erschwert die Bearbeitung und erhöht sowohl das Gewicht als auch die Kosten.The Automobile manufacturers demand a longer service life from year to year the exhaust system. The aim is the lifelong usability. The manufacturers of exhaust systems are therefore forced, instead of superficial passivated steels, For example, aluminized steel to convert to stainless steels. However, subject also stainless steels corrosion by the combined action of acid and Heat. For this reason, the sheet metal material from which the pipes must and housing produced to have a considerable thickness. That makes it difficult Editing and increased both the weight and the cost.

Ein besonderer Problemfall sind in diesem Zusammenhang die SCR-Katalysatoren, in denen mit Hilfe von Harnstoff bzw. Ammoniak eine selektive Reduktion der Stickoxide zu Stickstoff und Wasser bewirkt wird. Leider entstehen dabei jedoch weitere Reaktionsprodukte, die äußerst aggressiv sind und auch bei bisher bewährten Edelstählen extreme Korrosionsschäden verursachen. Das ist unbefriedigend.One particular problem in this context are the SCR catalysts, in which with the help of urea or ammonia, a selective reduction the nitrogen oxides to nitrogen and water is effected. Unfortunately arise However, there are other reaction products that are extremely aggressive and also in previously proven stainless steels extreme corrosion damage cause. That is unsatisfactory.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Verfahren anzugeben, mit dessen Hilfe die Innenkorrosion der SCR-Katalysatorgehäuse reduziert bzw. beseitigt werden kann.Of the The present invention is based on the object, a method which helps to reduce the internal corrosion of the SCR catalytic converter housings or can be eliminated.

Diese Aufgabe wird gelöst durch ein Verfahren mit den Merkmalen des Anspruchs 1.These Task is solved by a method having the features of claim 1.

Wesentlicher Vorteil dieser Beschichtung ist ihr hervorragender Schutz gegen die Oxidation von Metallteilen, ihre ausgezeichnete Haftung an den Metallteilen, ihre Dauerhaftigkeit und ihre Langlebigkeit. Es hat sich überraschenderweise herausgestellt, dass die üblichen Abgasbestandteile wie Ruß und Kondensat wenig anhaften. Außerdem ist die so hergestellte Korrosionsschutzschicht ausreichend beständig gegen die in SCR-Katalysatoren auftretenden Temperaturen.essential The advantage of this coating is its excellent protection against the oxidation of metal parts, their excellent adhesion to the metal parts, their durability and longevity. It has surprisingly turned out that the usual Exhaust gas components such as soot and Condensate little stick. Furthermore the corrosion protection layer produced in this way is sufficiently resistant to those in SCR catalysts occurring temperatures.

Als optimale Silane haben sich insbesondere Methyltriethyloxysilan und/oder Tetraethyloxysilan herausgestellt.When optimal silanes have in particular methyltriethyloxysilane and / or Tetraethyloxysilane exposed.

Ein weiterer Vorteil ist, dass gemäß einer Weiterbildung der Erfindung die Schicht bei nur ca. 80°C getrocknet werden kann.One Another advantage is that according to a further development the invention, the layer can be dried at only about 80 ° C.

Die Härtung erfolgt vorteilhafterweise bei nur 350°C bis 500°C in beliebiger Atmosphäre, der Einfachheit halber in Luftatmosphäre. Die gehärtete Schicht selbst ist dann bis ca. 800°C wirksam.The hardening takes place advantageously at only 350 ° C to 500 ° C in any atmosphere, the For simplicity in air atmosphere. The hardened layer itself is then up to approx. 800 ° C effective.

Vorteilhafterweise ist die gehärtete Schicht transparent, maximal 3 μm dick und farb- und geruchslos.advantageously, is the hardened Layer transparent, maximum 3 μm thick and colorless and odorless.

Um die gewünschte Dauerhaftigkeit der Abgasanlagenkomponenten zu gewährleisten, können alle Gehäuse und/oder Rohre der Abgasanlage ganz oder wenigstens bereichsweise innen und gegebenenfalls auch außen beschichtet werden.Around the desired To ensure durability of the exhaust system components, can all casing and / or pipes of the exhaust system wholly or at least partially inside and possibly also outside coated.

Es hat sich herausgestellt, dass Ruß und Schmutz an der erfindungsgemäßen Schicht wenig anhaften. Werden die Abgasanlagenkomponenten mit dieser Schicht auch auf der Außenseite beschichtet, so lassen sie sich sehr einfach sauberhalten.It it has been found that soot and dirt on the layer according to the invention to adhere little. Be the exhaust system components with this layer also on the outside Coated, they are very easy to keep clean.

Claims (7)

Verfahren zum Verhindern bzw. Reduzieren der Innenkorrosion in Gehäusen von SCR-Katalysatoren, dadurch gekennzeichnet, dass auf die Innenfläche des Gehäuses wenigstens bereichsweise eine Schicht aufgetragen und anschließend thermisch gehärtet wird, die folgende Eigenschaft aufweist: – ein oder mehrere Silane der allgemeinen Formel Rn-Si-X4-n – worin die Reste X gleich oder verschieden sind und Hydroxylgruppen oder hydrolytisch abspaltbare Gruppen darstellen, – worin die Reste R gleich oder verschieden sind und hydrolytisch nicht abspaltbare Gruppen darstellen, – und worin n den Wert, 0, 1, 2 oder 2 hat, wobei bei mindestens 50 Stoffmengen-% der Silane n ≥ 1 ist, – in Anwesenheit nanoskaliger SiO2-Teilchen und mindestens einer Verbindung aus der Gruppe der Oxide und Hydroxide der Alkali- und Erdalkalimetalle.A method for preventing or reducing the internal corrosion in housings of SCR catalysts, characterized in that applied to the inner surface of the housing at least partially a layer and then thermally cured, having the following property: - one or more silanes of the general formula R n -Si-X 4-n - wherein the radicals X are the same or different and represent hydroxyl groups or hydrolytically cleavable groups, - wherein the radicals R are the same or different and represent hydrolytically non-cleavable groups, - and wherein n is the value, 0, 1 , 2 or 2, wherein at least 50 mole% of the silanes n ≥ 1, - in the presence of nanoscale SiO 2 particles and at least one compound from the group of oxides and hydroxides of the alkali and alkaline earth metals. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die zweite Schicht Methyltriethyloxysilan enthält.Method according to claim 1, characterized in that that the second layer contains methyltriethyloxysilane. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die zweite Schicht Tetraethyloxysilan enthält.Method according to claim 1 or 2, characterized that the second layer contains tetraethyloxysilane. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, dass die zweite Schicht bei ca. 80°C getrocknet und dann gehärtet wird.Method according to claim 1, 2 or 3, characterized that the second layer is dried at about 80 ° C and then cured. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die zweite Schicht bei ca. 350°C bis 500°C mit oder ohne Luftatmosphäre gehärtet wird.Method according to one of claims 1 to 4, characterized that the second layer is cured at about 350 ° C to 500 ° C with or without air atmosphere. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die gehärtete Schicht transparent, farb- und geruchslos und maximal 3 μm dick aufgetragen wird.Method according to one of claims 1 to 5, characterized that the hardened Layer transparent, colorless and odorless and applied a maximum of 3 μm thick becomes. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass alle Gehäuse und/oder Rohre der Abgasanlage wenigstens bereichsweise innen und gegebenenfalls außen beschichtet werden.Method according to one of claims 1 to 6, characterized that all housing and / or Pipes of the exhaust system at least partially inside and possibly Outside be coated.
DE102007048521A 2007-10-10 2007-10-10 Method for preventing or reducing corrosion in inner casings of selective catalytic reduction catalyst, involves applying layer on inner surface of case, where applied layer is hardened by heating Withdrawn DE102007048521A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104368331A (en) * 2014-09-19 2015-02-25 李灏呈 Honeycomb type SCR denitrification catalyst end portion hardening liquid and hardening treatment method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19714949A1 (en) * 1997-04-10 1998-10-15 Inst Neue Mat Gemein Gmbh Process for providing a metallic surface with a glass-like layer
DE10059487A1 (en) * 2000-11-30 2002-06-06 Inst Neue Mat Gemein Gmbh Use of coating compositions for protective vitreous coatings on metal involves using compositions obtained by hydrolysis and polycondensation of organosilane in presence of nano-scale silica particles and alkali hydroxide
DE102006014745A1 (en) * 2006-03-30 2007-10-04 Heinrich Gillet Gmbh Preserving the optical characteristics of component surface of exhaust gas system for motor vehicles comprises applying silane compound containing layer in the presence of e.g. silicon dioxide-particle and thermal hardening

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19714949A1 (en) * 1997-04-10 1998-10-15 Inst Neue Mat Gemein Gmbh Process for providing a metallic surface with a glass-like layer
DE10059487A1 (en) * 2000-11-30 2002-06-06 Inst Neue Mat Gemein Gmbh Use of coating compositions for protective vitreous coatings on metal involves using compositions obtained by hydrolysis and polycondensation of organosilane in presence of nano-scale silica particles and alkali hydroxide
DE102006014745A1 (en) * 2006-03-30 2007-10-04 Heinrich Gillet Gmbh Preserving the optical characteristics of component surface of exhaust gas system for motor vehicles comprises applying silane compound containing layer in the presence of e.g. silicon dioxide-particle and thermal hardening

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104368331A (en) * 2014-09-19 2015-02-25 李灏呈 Honeycomb type SCR denitrification catalyst end portion hardening liquid and hardening treatment method

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