US20020162322A1 - Device for introducing an additive into an exhaust gas - Google Patents

Device for introducing an additive into an exhaust gas Download PDF

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Publication number
US20020162322A1
US20020162322A1 US10/054,443 US5444302A US2002162322A1 US 20020162322 A1 US20020162322 A1 US 20020162322A1 US 5444302 A US5444302 A US 5444302A US 2002162322 A1 US2002162322 A1 US 2002162322A1
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US
United States
Prior art keywords
tubular body
lamellae
exhaust gas
mixer
nozzle
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.)
Abandoned
Application number
US10/054,443
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English (en)
Inventor
Ingo Ganzmann
Werner Langer
Hartmut Ritter
Jurgen Zwack
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Individual
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Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of US20020162322A1 publication Critical patent/US20020162322A1/en
Abandoned legal-status Critical Current

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Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust 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
    • F01N3/18Exhaust 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
    • F01N3/20Exhaust 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
    • F01N3/2066Selective catalytic reduction [SCR]
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust 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
    • F01N3/18Exhaust 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
    • F01N3/20Exhaust 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77Liquid phase processes
    • B01D53/79Injecting reactants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/92Chemical or biological purification of waste gases of engine exhaust gases
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/30Injector mixers
    • B01F25/31Injector mixers in conduits or tubes through which the main component flows
    • B01F25/313Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit
    • B01F25/3131Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit with additional mixing means other than injector mixers, e.g. screens, baffles or rotating elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F2025/93Arrangements, nature or configuration of flow guiding elements
    • B01F2025/931Flow guiding elements surrounding feed openings, e.g. jet nozzles
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2240/00Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being
    • F01N2240/20Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being a flow director or deflector
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2470/00Structure or shape of gas passages, pipes or tubes
    • F01N2470/24Concentric tubes or tubes being concentric to housing, e.g. telescopically assembled
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00Adding substances to exhaust gases
    • F01N2610/02Adding substances to exhaust gases the substance being ammonia or urea
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00Adding substances to exhaust gases
    • F01N2610/14Arrangements for the supply of substances, e.g. conduits
    • F01N2610/1453Sprayers or atomisers; Arrangement thereof in the exhaust apparatus
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/10Internal combustion engine [ICE] based vehicles
    • Y02T10/12Improving ICE efficiencies

Definitions

  • the invention relates to a device for introducing an additive into an exhaust gas or gas stream, which can be introduced into a gas duct, in particular into an exhaust gas line from a diesel engine.
  • the device has at least one nozzle and at least one mixer.
  • the additive may be a reducing agent or a compound that releases such an agent.
  • a device of this type is known, for example, from Published, Non-Prosecuted German Patent Application DE 36 42 612 A.
  • the device introduces a reducing agent into a NOx-containing exhaust-gas duct with intensive mixing.
  • the device is intended to achieve a homogeneous mixing of the reducing agent and the exhaust gas over a relatively short section of duct.
  • the nitrogen oxides are usually catalytically reduced.
  • a reducing agent in the exhaust gas from an energy conversion installation, for example, in a diesel engine. It has proven expedient to admix a reducing agent of this type or an additive that releases it as a reducing-agent carrier, in particular ammonia or urea (dissolved in water), to the exhaust gas only after it has emerged from the energy conversion installation.
  • a device for introducing an additive into an exhaust gas The exhaust gas is introduced into an exhaust gas line from a diesel engine and has a flow direction.
  • the device contains at least one nozzle, and at least one mixer for mixing the exhaust gas with the additive.
  • the mixer and the nozzle combined with one another form a structural and functional unit.
  • the mixer has a tubular body disposed approximately parallel in terms of the flow direction of the exhaust gas and houses the nozzle.
  • the tubular body has an upstream end with a first opening formed therein and a downstream end with a second opening formed therein and communicates with the first opening.
  • the mixer has lamellae supported by the tubular body, and the lamellae, with regard to the flow direction of the exhaust gas, face upstream at the upstream end of the tubular body and face downstream at the downstream end of the tubular body.
  • the mixer and the nozzle for atomizing the additive or the reducing agent itself are combined to form a structural and functional unit.
  • the combination can be introduced into the gas duct, i.e. can be fitted into the duct when the structural unit is operating as intended.
  • the mixer has a tubular body which is open at both ends, is parallel in terms of flow, is advantageously, in the installed state, coaxial with respect to the gas duct and at one end bears lamellae which face upstream and at the other end bears lamellae which face downstream.
  • the tubular body, in a gas duct that is circular in cross section is likewise circular in cross section.
  • the diameter of the gas duct into which the structural unit containing the mixer and the nozzle can be fitted should expediently be no less than approximately 200 mm and no greater than approximately 1000 mm.
  • the tubular body has diameter approximately 0.5 to 0.2 times the diameter of the gas duct.
  • the length of the tubular body approximately corresponds to 0.2 to 0.5 times the diameter of the gas duct.
  • the tubular body is expediently supported by a tubular connection piece that projects into the gas duct transversely with respect to the gas stream and through which a tube, which serves as a feed line and as a support for the nozzle or the injection device, extends as far as the center axis of the tubular body.
  • the nozzle is advantageously disposed in the region of the center axis of the tubular body, and therefore, in the installed state, of the center axis which is common to the gas duct and the tubular body.
  • the nozzle or the injection device atomizes the additive, for example ammonia as the reducing agent or urea solution as the additive, in the direction of flow of the gas stream.
  • a spray cone that emerges from the nozzle includes an angle of 20° to 60°, preferably an angle of 30°, at its cone tip.
  • Lamellae that are supported at the ends of the tubular body preferably form an angle of from 30° to 60°, in particular an angle of 45°, with the axis of the tubular body.
  • the lamellae are oriented in such a manner that, in the installed state of the device, they are supported on the inner side of walls of the gas duct by their free ends. In this case, the lamellae are approximately twice as wide at their free ends as at their root ends that are connected to the tubular body. Free spaces between adjacent lamellae are in this case approximately as wide as the lamellae themselves.
  • the lamellae which face upstream are staggered with respect to the lamellae which face downstream, so that every partial stream of the gas stream is made turbulent, in each case an identical number of the lamellae which face downstream and the lamellae which face upstream are provided.
  • the tubular body expediently bears in each case four to eight lamellae at both end sides, the lamellae preferably are formed of planar metal sheets.
  • FIG. 1 is a diagrammatic, partially, longitudinal sectional-view of a flue-gas cleaning device with a combined mixing and injection device according to the invention
  • FIG. 2 is a partially sectional plan view of the cleaning device
  • FIG. 3 is a front-elevational view of the cleaning device
  • FIG. 4 is a sectional view of the cleaning device taken along the line IV-IV shown in FIG. 1;
  • FIG. 5 is a sectional view of the cleaning device taken along the line V-V shown in FIG. 1.
  • FIG. 5 there is shown a gas or exhaust-gas duct 1 with a diameter d 1 of, for example, 200 mm to 1000 mm is connected, by a flange 2 (FIG. 1) to a preferably non-illustrated stationary diesel engine.
  • An exhaust gas A flows through it in the direction indicated by an arrow 3 .
  • a tubular connection piece 4 penetrates through a wall of the exhaust-gas duct 1 and projects into the exhaust-gas duct 1 transversely with respect to the direction of flow 3 of the exhaust-gas A and therefore at right angles to a duct axis 5 . If the duct cross section is circular, as in the exemplary embodiment, therefore, the tubular connection piece 4 runs in a radial direction. Outside the exhaust-gas duct 1 , the tubular connection piece 4 bears a flange 6 at its free end, on which an end plate 7 rests in a sealed manner, thus closing off an interior of the tubular connection piece 4 with respect to the outside.
  • That end of the tubular connection piece 4 which lies in the exhaust-gas duct 1 bears a tubular body 8 which is open at both end sides and is disposed coaxially with respect to the exhaust-gas duct 1 .
  • the duct axis 5 therefore forms the center axis of both the exhaust-gas duct 1 and the tubular body 8 .
  • the tubular body 8 has a diameter d 2 (FIG. 5) that corresponds to 0.2 to 0.5 times the diameter d 1 of the exhaust-gas duct 1 .
  • the tubular body 8 has a length that is approximately equal to 0.2 to 0.5 times the diameter d 1 of the exhaust-gas duct 1 .
  • first lamellae 9 which face upstream with respect to the direction of flow 3 of the exhaust gas A, are secured to an inflow-side end of the tubular body 8 .
  • second lamellae 10 which correspondingly extend downstream, are secured to an outflow-side end of the tubular body 4 .
  • the lamellae 9 and the lamellae 10 are disposed staggered with respect to one another, i.e. each of the lamellae 9 lies between in each case two lamellae 10 , and vice versa, as seen in the direction of the duct axis 5 . This can be seen relatively clearly from FIGS. 3 to 5 .
  • the free ends 9 a, 10 a of the lamellae 9 and 10 are approximately twice as wide as their root ends 9 b and 10 b, respectively, which are secured to the tubular body 8 .
  • four to eight lamellae 9 , 10 are secured to each end of the tubular body 8 , the lamellae 9 , 10 contain planar metal sheets. Consequently, they cause particularly powerful turbulence in the flowing exhaust gas A.
  • the tubular connection piece 4 contains a tube 11 that is supported by the end plate 6 and on which, at a free end side in the tubular body 8 , a nozzle 12 is held.
  • the tube 11 is connected via a line, in a manner which is not illustrated in more detail, to a reservoir for an additive which releases a reducing agent or for a reducing-agent carrier R, for example for an aqueous urea solution, and expediently, in addition, to an air connection for cooling and atomizing the urea solution which is, for example, aqueous.
  • a non-illustrated pump forces the reducing-agent carrier R, e.g. the aqueous urea solution, or a corresponding reducing agent, e.g. ammonia, through the tube 11 and through the nozzle 12 .
  • the nozzle 12 and the tubular body 8 with the lamellae 9 and 10 therefore form a structural and functional unit, the tubular body 8 and the lamellae 9 , 10 attached thereto representing, in functional terms, a static mixer or a mixing stage.
  • the nozzle 12 in this case lies on the common center axis of the exhaust-gas duct 1 and of the mixer 8 , 9 , 10 , which corresponds to the duct axis 5 .
  • the hot exhaust gas A from the diesel engine flows through the exhaust-gas duct 1 in the direction of flow 3 .
  • a small proportion of the exhaust gas A, and therefore at least one exhaust-gas partial stream flows through the tubular body 8 .
  • the reducing-agent carrier R is sprayed or injected through the nozzle 12 into the flowing exhaust gas A.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Toxicology (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Incineration Of Waste (AREA)
  • Treating Waste Gases (AREA)
US10/054,443 1999-07-22 2002-01-22 Device for introducing an additive into an exhaust gas Abandoned US20020162322A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19934413A DE19934413A1 (de) 1999-07-22 1999-07-22 Vorrichtung zum Einbringen eines Zuschlagstoffes in ein Abgas
JP19934413.2 1999-07-22
PCT/DE2000/002402 WO2001007763A1 (de) 1999-07-22 2000-07-21 Vorrichtung zum einbringen eines zuschlagstoffes in ein abgas

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2000/002402 Continuation WO2001007763A1 (de) 1999-07-22 2000-07-21 Vorrichtung zum einbringen eines zuschlagstoffes in ein abgas

Publications (1)

Publication Number Publication Date
US20020162322A1 true US20020162322A1 (en) 2002-11-07

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Family Applications (1)

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US10/054,443 Abandoned US20020162322A1 (en) 1999-07-22 2002-01-22 Device for introducing an additive into an exhaust gas

Country Status (8)

Country Link
US (1) US20020162322A1 (de)
EP (1) EP1206630B1 (de)
JP (1) JP2003505638A (de)
KR (1) KR100713262B1 (de)
AT (1) ATE291155T1 (de)
DE (2) DE19934413A1 (de)
ES (1) ES2235938T3 (de)
WO (1) WO2001007763A1 (de)

Cited By (37)

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US20030110763A1 (en) * 2001-06-01 2003-06-19 Kenneth Pawson Catalytic converter
EP1514591A1 (de) * 2003-09-15 2005-03-16 J. Eberspächer GmbH & Co. KG Heissgas-Strömungskanal, insbesondere innerhalb einer Abgasanlage eines Verbrennungsmotors stromauf eines Katalysators
US20060176764A1 (en) * 2003-07-28 2006-08-10 Framatome Anp Gmbh Mixing system
US20060191254A1 (en) * 2005-02-28 2006-08-31 Caterpillar Inc. Exhaust gas mixing system
US20070035832A1 (en) * 2004-02-02 2007-02-15 Nissan Diesel Motor Co., Ltd. Exhaust emission purifying apparatus for internal combustion engine
US20070036694A1 (en) * 2005-07-28 2007-02-15 Hitachi, Ltd. Exhaust aftertreatment system using urea water
US20070110642A1 (en) * 2004-09-02 2007-05-17 Nissan Diesel Motor Co., Ltd. Exhaust gas purifying apparatus
US20070163241A1 (en) * 2004-01-30 2007-07-19 Ulrich Meingast Method and apparatus for posttreatment of an exhaust gas from an internal combustion engine
US20070169467A1 (en) * 2004-02-02 2007-07-26 Daisuke Shirai Scr muffler
EP1712751A3 (de) * 2005-04-15 2008-02-20 Iveco S.p.A. Statischer mischer
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US20080295497A1 (en) * 2007-05-08 2008-12-04 Friedrich Boysen Gmbh & Co. Kg Device for the distribution of flowable additives in exhaust gas systems
US20090000287A1 (en) * 2007-05-15 2009-01-01 Jared Dean Blaisdell Exhaust Gas Flow Device
US20090266064A1 (en) * 2008-04-25 2009-10-29 Tenneco Automotive Operating Company Inc. Exhaust gas additive/treatment system and mixer for use therein
US20100212301A1 (en) * 2008-12-17 2010-08-26 Korneel De Rudder Flow Device for an Exhaust System
US20110095105A1 (en) * 2007-12-05 2011-04-28 Grundfos Nonox A/S Nozzle arrangement
US20110167810A1 (en) * 2010-01-12 2011-07-14 Lebas Jerome Flow device for exhaust treatment system
WO2012052690A1 (fr) * 2010-10-21 2012-04-26 Mgi Coutier Dispositif d'introduction d'un additif liquide dans une ligne d'échappement de moteur thermique
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DE10239417B4 (de) * 2002-08-28 2009-09-24 J. Eberspächer GmbH & Co. KG Heißgas-Strömungskanal, insbesondere innerhalb einer Abgasanlage eines Verbrennungsmotors stromauf eines Katalysators
JP3883974B2 (ja) * 2003-03-11 2007-02-21 日産ディーゼル工業株式会社 排気浄化装置
DE10324886B4 (de) * 2003-05-30 2008-02-28 Framatome Anp Gmbh Mischelement und statischer Mischer mit einer Anzahl derartiger Mischelemente
DE102004020138B4 (de) * 2004-04-24 2007-02-08 Daimlerchrysler Ag Reduktionsmittelzugabesystem
JP2005344597A (ja) * 2004-06-02 2005-12-15 Hitachi Ltd エンジン用排気ガス処理装置
ITMI20050653A1 (it) 2005-04-15 2006-10-16 Iveco Spa Modulo di miscelazione per un fluido in una corrente di gas
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DE602008002403D1 (de) 2008-02-12 2010-10-14 Magneti Marelli Spa Abgassystem eines Verbrennungsmotors
DE102008017395C5 (de) * 2008-04-05 2018-01-25 Eberspächer Exhaust Technology GmbH & Co. KG Misch- und/oder Verdampfungseinrichtung
MY158670A (en) * 2008-05-27 2016-10-31 Fuel Tech Inc Selective catalytic nox reduction process and apparatus providing improved gasification of urea to form ammonia-containing gas
WO2011020200A1 (en) * 2009-08-18 2011-02-24 Flowtech Industries Ag Static mixer and its use, f. ex. for catalytic denitrification of exhaust gases and the like
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EP1206630B1 (de) 2005-03-16
DE19934413A1 (de) 2001-01-25
JP2003505638A (ja) 2003-02-12
ES2235938T3 (es) 2005-07-16
WO2001007763A1 (de) 2001-02-01
DE50009808D1 (de) 2005-04-21
KR20020015717A (ko) 2002-02-28
EP1206630A1 (de) 2002-05-22
ATE291155T1 (de) 2005-04-15
KR100713262B1 (ko) 2007-05-04

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