EP1280594A1 - Verfahren und vorrichtung zur abgasreinigung - Google Patents

Verfahren und vorrichtung zur abgasreinigung

Info

Publication number
EP1280594A1
EP1280594A1 EP01943014A EP01943014A EP1280594A1 EP 1280594 A1 EP1280594 A1 EP 1280594A1 EP 01943014 A EP01943014 A EP 01943014A EP 01943014 A EP01943014 A EP 01943014A EP 1280594 A1 EP1280594 A1 EP 1280594A1
Authority
EP
European Patent Office
Prior art keywords
exhaust gas
scr
reducing agent
exhaust gases
exhaust
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Withdrawn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
EP01943014A
Other languages
German (de)
English (en)
French (fr)
Inventor
Thomas Hammer
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.)
Siemens AG
Original Assignee
Siemens AG
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 Siemens AG filed Critical Siemens AG
Publication of EP1280594A1 publication Critical patent/EP1280594A1/de
Withdrawn legal-status Critical Current

Links

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
    • F01N3/18—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]
    • 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
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9431—Processes characterised by a specific device
    • 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
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9495—Controlling the catalytic process
    • 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
    • F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
    • 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
    • F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
    • F01N3/0814—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents combined with catalytic converters, e.g. NOx absorption/storage reduction catalysts
    • 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
    • F01N3/0892—Electric or magnetic treatment, e.g. dissociation of noxious components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/818—Employing electrical discharges or the generation of a plasma
    • 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
    • F01N2240/00—Combination 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
    • F01N2240/28—Combination 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 plasma reactor
    • 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
    • F01N2250/00—Combinations of different methods of purification
    • F01N2250/12—Combinations of different methods of purification absorption or adsorption, and catalytic conversion
    • 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
    • F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/12—Hydrocarbons
    • 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
    • F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/14—Nitrogen oxides
    • 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
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/02—Adding substances to exhaust gases the substance being ammonia or urea
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the invention relates to a method for cleaning exhaust gases, in particular for cleaning exhaust gases from diesel engines and / or lean-burn engines, using an SCR catalytic converter for the selective catalytic reduction of nitrogen oxides and with activation of the exhaust gases by non-thermal gas discharge plasmas.
  • the invention also relates to the associated device with means for performing the specified method.
  • the selective catalytic reduction (SCR) of nitrogen oxides in diesel and lean engine exhaust gas with monolithic V 2 0 5 -W ⁇ 3 / Ti0 2 catalysts and with ammonia-based reducing agents, such as urea, is an effective process for exhaust gas purification at catalyst temperatures above 200 ° C Motor vehicles (Kfz), in particular trucks see. This process not only reduces nitrogen oxide emissions, but also hydrocarbon emissions if the catalyst composition is properly matched.
  • Heating catalysts could reduce nitrogen oxide emissions in city traffic by quickly reaching the working temperature for selective catalytic reduction.
  • this presupposes the use of catalysts with metallic supports, which have serious disadvantages for the urea SCR process, such as low ammonia storage capacity, and have high costs in comparison with monolithic catalysts.
  • the object of the invention is to provide a method and an associated device with which both the nitrogen oxide emissions are reduced and the emission of hydrocarbons in high concentrations is prevented regardless of the hydrocarbon content of the exhaust gas at low catalyst temperatures.
  • the hydrocarbons contained in the exhaust gas are adsorbed in the first step.
  • the exhaust gas which now has a low hydrocarbon content, is exposed to a non-thermal gas discharge plasma in order to oxidize part of the NO to NO 2 .
  • an ammonia-based reducing agent is added to the exhaust gas.
  • the exhaust gas is fed to the SCR catalytic converter to reduce nitrogen oxides.
  • the associated device has a first close to the engine in the Exhaust system accommodated hydrocarbon adsorbers, a reactor for generating non-thermal gas discharge plasmas, a metering unit for a reducing agent and an SCR catalyst.
  • the hydrocarbon adsorber can advantageously be designed such that the hydrocarbons are desorbed at temperatures at which the SCR catalyst oxidizes hydrocarbons.
  • the hydrocarbon adsorber is selected such that, at higher exhaust gas temperatures, the hydrocarbons are catalytically oxidized to form carbon dioxide and water in addition to the adsorption.
  • the course of the process is then preferably the oxidation of the hydrocarbons, plasma-induced oxidation of the NO to NO 2 , addition of the reducing agent and selective catalytic reduction of the NO x .
  • a further advantageous development of the method can consist in that the hydrocarbon adsorber used oxidizes hydrocarbons to carbon dioxide and water and at the same time a part of the NO to NO 2 at higher exhaust gas temperatures.
  • the course of the process then includes the catalytic oxidation of the hydrocarbons and part of the NO, the addition of the reducing agent and the selective catalytic reduction of the NO x .
  • SCR Selective Catalytic Reduction
  • the adsorbed hydrocarbons reduce the N0 2 generated from NO in the non-thermal gas discharge plasma back to NO.
  • FIG. 1 shows a device for realizing the method in a motor vehicle that is not shown in detail.
  • An internal combustion engine 1 with an exhaust line 2 has a first hydrocarbon adsorber 3, which is accommodated close to the engine in the exhaust line 2, a reactor 4 for generating non-thermal gas discharge plasmas, an electrical supply unit 5 being assigned to the reactor 4, and a metering unit 6 for a reducing agent RM, which is in a storage tank 7 is stored, and an SCR catalytic converter 8.
  • sensors 9 to 12 for registering operating states of the engine 1, for registering exhaust gas properties such as temperature and / or exhaust gas composition and for registering catalyst properties, all in one unit be evaluated.
  • a hydrocarbon adsorber 3 is advantageously a material with a large pore volume and a large pore diameter that has catalytic properties: Zeolites such as NH 4 ZSM5 or NaZSM5 are suitable for this purpose, the properties of which can be adapted to the respective application by metallic doping. Due to the low response temperatures for the catalytic oxidation of the hydrocarbons, platinum-doped Pt-NHZSM5 and copper-doped Cu-NaZSM5 are particularly suitable. Furthermore, ⁇ -aluminum oxide can be used, which can also be doped with Pt. These materials can be applied to Al 2 0 3 ceramic or to cordierite as the carrier material.
  • the material of the SCR catalytic converter 8 itself - that is, typically a V 2 ⁇ 5-W0 3 / Ti ⁇ 2 catalytic converter - can also be used for the hydrocarbon adsorber 3 , the material here also being able to be applied to a support.
  • the full extrudate which can be prepared with the addition of fiber materials and a binder, is preferred. This is described in detail in “Hydrocarbon Sorption and Oxidation Catalyst for Heavy Duty Engines *, SAE Technical Paper Series, Paper No. 1999-01-3560 (1999).
  • a noble metal such as Pt or Pd
  • the hydrocarbon concentration in the exhaust gas can be drastically reduced over the temperature range from 50 ° C to 500 ° C.
  • the hydrocarbons are adsorbed on the adsorber 3 to such an extent that they at low exhaust gas temperature do not affect the absorption capacity of the SCR catalyst 8 for the reducing agent RM.
  • the exhaust gas pretreated in this way is exposed to the non-thermal gas discharge plasma in the reactor 4 in order to oxidize part of the NO present in the nitrogen oxides to NO 2 .
  • An ammonia-based reducing agent RM is then added to this pretreated exhaust gas via the metering unit 6.
  • the exhaust gas including reducing agent RM is then fed to the SCR catalytic converter 8 for reduction.
  • the hydrocarbons can be catalytically oxidized to carbon dioxide and water at a sufficient temperature.
  • part of the NO contained in the nitrogen oxides is catalytically oxidized to N0 2 .
EP01943014A 2000-05-04 2001-05-03 Verfahren und vorrichtung zur abgasreinigung Withdrawn EP1280594A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10021693 2000-05-04
DE10021693A DE10021693C2 (de) 2000-05-04 2000-05-04 Verfahren und Vorrichtung zur Abgasreinigung
PCT/DE2001/001686 WO2001083087A1 (de) 2000-05-04 2001-05-03 Verfahren und vorrichtung zur abgasreinigung

Publications (1)

Publication Number Publication Date
EP1280594A1 true EP1280594A1 (de) 2003-02-05

Family

ID=7640747

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01943014A Withdrawn EP1280594A1 (de) 2000-05-04 2001-05-03 Verfahren und vorrichtung zur abgasreinigung

Country Status (5)

Country Link
US (1) US20030077212A1 (ja)
EP (1) EP1280594A1 (ja)
JP (1) JP2003531721A (ja)
DE (1) DE10021693C2 (ja)
WO (1) WO2001083087A1 (ja)

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DE10159849A1 (de) * 2001-12-06 2003-06-26 Bosch Gmbh Robert Verfahren zur Nachbehandlung von Abgasen von Brennkraftmaschinen und Einrichtung hierfür
US7575931B2 (en) * 2002-06-19 2009-08-18 E.I. Du Pont De Nemours And Company Method and apparatus for reducing a nitrogen oxide, and control thereof
JP2004346772A (ja) * 2003-05-20 2004-12-09 Toyota Motor Corp 排気浄化装置及び方法
US7090811B2 (en) * 2003-12-11 2006-08-15 General Motors Corporation Method of reducing NOx in diesel engine exhaust
US7776265B2 (en) * 2004-03-18 2010-08-17 Cummins Filtration Ip, Inc. System for diagnosing reagent solution quality
WO2006022213A1 (ja) * 2004-08-23 2006-03-02 Hino Motors, Ltd. 排気浄化装置
FR2883199B1 (fr) * 2005-03-18 2007-06-22 Peugeot Citroen Automobiles Sa Filtre a particules pour vehicule automobile et systeme et ligne d'echappement comprenant un tel filtre a particules
US20070012032A1 (en) * 2005-07-12 2007-01-18 Eaton Corporation Hybrid system comprising HC-SCR, NOx-trapping, and NH3-SCR for exhaust emission reduction
JP4595926B2 (ja) * 2006-11-13 2010-12-08 トヨタ自動車株式会社 内燃機関の排気浄化装置
JP2009150279A (ja) * 2007-12-19 2009-07-09 Hino Motors Ltd 排気処理装置
CN101680331B (zh) 2008-03-04 2012-06-27 丰田自动车株式会社 内燃机的排气净化装置
US8161731B2 (en) * 2008-05-12 2012-04-24 Caterpillar Inc. Selective catalytic reduction using controlled catalytic deactivation
EP2301650B1 (en) * 2009-09-24 2016-11-02 Haldor Topsøe A/S Process and catalyst system for scr of nox
US8444941B2 (en) 2010-05-25 2013-05-21 Intercat Equipment, Inc. Cracking catalysts, additives, methods of making them and using them
FR2963444B1 (fr) * 2010-07-30 2013-05-17 Faurecia Sys Echappement Systeme de dosage de gaz et procede associe.
FR2981862A3 (fr) * 2011-10-27 2013-05-03 Renault Sa Controle du ratio no2/nox pour la scr par procede plasma
PL2841183T3 (pl) 2012-03-26 2019-05-31 Fluor Tech Corp Redukcja emisji dla wychwytu CO<sub>2</sub>
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CN104524932A (zh) * 2014-11-28 2015-04-22 上海译琅环保科技有限公司 一种采用低温等离子技术净化工业废气的方法及设备
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Also Published As

Publication number Publication date
US20030077212A1 (en) 2003-04-24
DE10021693A1 (de) 2001-11-15
DE10021693C2 (de) 2003-08-07
JP2003531721A (ja) 2003-10-28
WO2001083087A1 (de) 2001-11-08

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