US20010053342A1 - Method and device for selective catalytic nox reduction - Google Patents

Method and device for selective catalytic nox reduction Download PDF

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US20010053342A1
US20010053342A1 US09/254,291 US25429199A US2001053342A1 US 20010053342 A1 US20010053342 A1 US 20010053342A1 US 25429199 A US25429199 A US 25429199A US 2001053342 A1 US2001053342 A1 US 2001053342A1
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ammonia
storage medium
container
exhaust gas
heated
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US6387336B2 (en
Inventor
Armin Marko
Thomas Wahl
Ulrich Alkemade
Frank Brenner
Marc Bareis
Horst Harndorf
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Robert Bosch GmbH
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/003—Storage or handling of ammonia
    • C01C1/006—Storage or handling of ammonia making use of solid ammonia storage materials, e.g. complex ammine salts
    • 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
    • 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
    • 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
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • 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
    • 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
    • F01N2610/06—Adding substances to exhaust gases the substance being in the gaseous form
    • 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
    • F01N2610/10—Adding substances to exhaust gases the substance being heated, e.g. by heating tank or supply line of the added substance
    • 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
    • F01N2610/14—Arrangements for the supply of substances, e.g. conduits
    • F01N2610/1406—Storage means for substances, e.g. tanks or reservoirs
    • 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
    • F01N2610/14—Arrangements for the supply of substances, e.g. conduits
    • F01N2610/1446—Means for damping of pressure fluctuations in the delivery system, e.g. by puffer volumes or throttling
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • 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 and a device for selective catalytic reduction of NOx levels in oxygen-containing exhaust gases using ammonia and a reduction catalyst.
  • Ammonia is known as a selective and effective reduction agent for the catalytic reduction (SCR) of nitrogen oxides in oxygen-containing exhaust gases of internal combustion engines, for example.
  • European Patent B1 0 487 886 describes a method of quantitative hydrolysis of urea wherein an aqueous urea solution is sprayed onto an evaporator and forwarded via a hydrolysis catalyst with the surfaces of the evaporator and hydrolysis catalyst being coated with active components that catalyze the quantitative hydrolysis of urea into ammonia and CO 2 and inhibit the formation of solid urea reaction products.
  • the above-mentioned method has the disadvantage that a liquid must be added for preparing the reaction medium, and this liquid cannot be metered as accurately as a gaseous medium. Therefore, the gas stream that leaves the reduction catalyst usually still contains unreacted ammonia, which cannot be simply released into the atmosphere, but must be decomposed into non-toxic components using an oxidation catalyst.
  • the hydrolysis catalyst has the additional disadvantage that it absorbs ammonia at low temperatures. If the temperature rises quickly, most of the absorbed ammonia is released and can no longer be used as a reduction agent for selective catalytic reduction.
  • the use of an aqueous urea solution causes other problems—in winter operation of motor vehicles and due to the drop in exhaust gas temperature because of water evaporating in the exhaust gas: the 30%- 35% aqueous urea solution used in the related art has a freezing point of about ⁇ 11° C. At lower temperatures, particularly at the freezing point of diesel fuel, the operation of the motor vehicle is no longer ensured. While the freezing point can be lowered using additives, additives such as ammonium formiate, for example, are usually particularly corrosive, so that their use poses new problems.
  • the exhaust gas is cooled by about 20 K due to the need of evaporating the water it contains.
  • the unsatisfactory low-temperature performance of SCR catalysts is particularly strongly manifested in this case.
  • the method according to the present invention with the features of the main claim has the advantage over the related art that a gaseous reduction agent is provided, which can be accurately metered, causes no problems in winter operation and thus requires no additional antifreeze measures; the problem of poor low-temperature performance of SCR catalysts is thus somewhat alleviated with its use.
  • the device for carrying out the method according to the present invention is simple, since no urea hydrolysis catalyst is used, in addition to being compact due to the fact that ammonia in the solid storage medium according to the present invention takes up 3 times less space than the aqueous urea solution. The space thus freed up can possibly be used for an additional SCR unit.
  • the solid storage media used according to the present invention are regeneratable, i.e., the emptied container can be refilled with ammonia.
  • the number of regeneration cycles may be as high as 1000.
  • Strontium chloride SrCl2 which has a high storage density for ammonia, comparable to the storage density of solid urea, can be advantageously used as the solid storage medium.
  • Strontium chloride can be replaced totally or in part by calcium chloride, which offers comparable advantages.
  • the device according to the present invention can be advantageously equipped with a buffer container for gaseous ammonia in order to have gaseous ammonia available even in intermittent engine operation and/or in start phases, regardless of the heating phase of container 1 , when there is insufficient energy for heating the ammonia storage medium.
  • FIG. 1 schematically shows a device according to the present invention
  • FIG. 2 shows a specifically adapted embodiment
  • FIG. 3 shows an additional specifically adapted embodiment of a device according to the present invention.
  • the device of FIG. 1 has a container 1 , which can be heated using a heating device 3 and contains ammonia-storing substance 2 .
  • the volume of container 1 is designed so that there is sufficient ammonia available to remove NOx from the exhaust gas of an internal combustion engine with the help of the catalyst system within an interval between servicings of the vehicle. It has been shown that a volume of approximately 10 liters is particularly suitable.
  • Substances that store ammonia at ambient conditions (approx. 20° C.) so that the ammonia vapor pressure over the storage medium is low in a closed system ( ⁇ 0.5 bar) can be used as solid storage media.
  • the solid storage media according to the present invention may contain substances that bind ammonia by physical and/or chemical absorption, such as active carbon, zeolites, etc., for example.
  • Substances that bind ammonia in the form of a chemical complex can also be used as solid storage media. These include, for example, salts, in particular chlorides and/or sulfates of one or more alkaline earth metals and/or of one or more 3d subgroup elements, preferably manganese, iron, cobalt, nickel, copper and/or zinc, can be considered.
  • a solid storage medium containing strontium chloride SrCl2 is advantageously used.
  • Strontium chloride stores up to eight ammonia molecules per strontium ion, forming [(Sr(NH3)8]Cl2. With an approximate density of 1.5 g/cm 3 , a stored amount of 48 moles NH 3 results per liter of storage medium. In comparison, urea, with a density of 1.32 g/cm 3 , provides storage of 44 moles of ammonia per liter of solid urea.
  • Strontium chloride can be replaced totally or in part with calcium chloride.
  • An electric heating system and/or a heating device that uses the waste heat of the engine coolant and/or the exhaust gas can be used as heating device 3 .
  • the gaseous ammonia formed when the solid storage medium is heated is metered via an electrically or pneumatically actuated valve 4 , controlled by a controller 5 , via ammonia supply line 6 , into the exhaust gas line 8 between engine 7 and catalyst 9 .
  • a buffer container 10 is connected between valve 4 and exhaust gas line 8 .
  • Buffer container 10 is connected to exhaust gas line 8 via a valve 4 b controlled by controller 5 .
  • valves 4 and 4 b are closed, so that buffer container 10 is filled with gaseous ammonia under pressure.
  • stored gaseous ammonia can be available even immediately after starting the engine, regardless of the heating phase of container 1 .
  • FIG. 3 One system having additional advantageous devices is illustrated in FIG. 3.
  • a filling nozzle with integrated check valve 16 which prevents ammonia being supplied from escaping through the filling opening, is provided for filling container 1 .
  • a finely porous, sieve-like construction 11 prevents the granulated storage substance 2 in container 1 from being entrained to the outside.
  • a pressure sensor 12 is mounted on container 1 for control and safety; it interrupts the supply of heat when a predefined maximum pressure level is attained. Furthermore, a safety valve 13 (opening pressure approx. 10 to 15 bar) is provided, which responds to an excessively steep increase in the storage container pressure and conducts the released ammonia into the exhaust line, for example.
  • a pressure limiter 14 which ensures the required ammonia pressure of 2 to 3 bar, is provided downstream from buffer container 10 .
  • an ammonia metering station 15 for example, a metering tube with a screen, is provided to guarantee proper mixing of ammonia with the exhaust gas stream.
  • An electronic controller in which additional functions adjusting the amount of ammonia to the actual operating state of the engine are implemented, monitors and controls the procedures.

Abstract

A method and a device for selective catalytic NOx reduction in oxygen-containing exhaust gases using ammonia and a reduction catalyst (9) are described, according to which gaseous ammonia is made available by heating a solid storage medium (2) in a container (1). The method and the device are suitable for use in motor vehicles in particular.

Description

    BACKGROUND INFORMATION
  • The invention relates to a method and a device for selective catalytic reduction of NOx levels in oxygen-containing exhaust gases using ammonia and a reduction catalyst. [0001]
  • Ammonia is known as a selective and effective reduction agent for the catalytic reduction (SCR) of nitrogen oxides in oxygen-containing exhaust gases of internal combustion engines, for example. [0002]
  • For reasons of toxicity and safety problems arising from storing gaseous ammonia, in particular, procedures whereby ammonia is generated at the site of its use as a reduction agent by hydrolysis of urea have been developed. [0003]
  • European Patent B1 0 487 886 describes a method of quantitative hydrolysis of urea wherein an aqueous urea solution is sprayed onto an evaporator and forwarded via a hydrolysis catalyst with the surfaces of the evaporator and hydrolysis catalyst being coated with active components that catalyze the quantitative hydrolysis of urea into ammonia and CO[0004] 2 and inhibit the formation of solid urea reaction products.
  • The above-mentioned method has the disadvantage that a liquid must be added for preparing the reaction medium, and this liquid cannot be metered as accurately as a gaseous medium. Therefore, the gas stream that leaves the reduction catalyst usually still contains unreacted ammonia, which cannot be simply released into the atmosphere, but must be decomposed into non-toxic components using an oxidation catalyst. [0005]
  • The procedure is associated with high equipment costs due to the hydrolysis catalyst, as well as the transport of urea and its introduction, which must be uniform over the cross section of the flow. [0006]
  • The hydrolysis catalyst has the additional disadvantage that it absorbs ammonia at low temperatures. If the temperature rises quickly, most of the absorbed ammonia is released and can no longer be used as a reduction agent for selective catalytic reduction. [0007]
  • The use of an aqueous urea solution causes other problems—in winter operation of motor vehicles and due to the drop in exhaust gas temperature because of water evaporating in the exhaust gas: the 30%- 35% aqueous urea solution used in the related art has a freezing point of about −11° C. At lower temperatures, particularly at the freezing point of diesel fuel, the operation of the motor vehicle is no longer ensured. While the freezing point can be lowered using additives, additives such as ammonium formiate, for example, are usually particularly corrosive, so that their use poses new problems. [0008]
  • The exhaust gas is cooled by about 20 K due to the need of evaporating the water it contains. The unsatisfactory low-temperature performance of SCR catalysts is particularly strongly manifested in this case. [0009]
    • SUMMARY OF THE INVENTION
  • The method according to the present invention with the features of the main claim has the advantage over the related art that a gaseous reduction agent is provided, which can be accurately metered, causes no problems in winter operation and thus requires no additional antifreeze measures; the problem of poor low-temperature performance of SCR catalysts is thus somewhat alleviated with its use. [0010]
  • In addition, the device for carrying out the method according to the present invention is simple, since no urea hydrolysis catalyst is used, in addition to being compact due to the fact that ammonia in the solid storage medium according to the present invention takes up 3 times less space than the aqueous urea solution. The space thus freed up can possibly be used for an additional SCR unit. [0011]
  • The requirements for the metering system are less stringent, since, in contrast with a urea-water solution, clogging problems in the metering components cannot occur. [0012]
  • There is no more need for compressed air support for introducing the reduction agent, since a sufficient pressure gradient with respect to the exhaust system is always created when ammonia is released. The system is therefore equally well suited for use in passenger cars and utility vehicles. [0013]
  • In contrast with methods using gaseous ammonia, safety problems are alleviated, since the ammonia carried in the vehicle is mostly bound to the storage substance, i.e., it is not freely available. [0014]
  • Furthermore, it is particularly advantageous that the solid storage media used according to the present invention are regeneratable, i.e., the emptied container can be refilled with ammonia. The number of regeneration cycles may be as high as 1000. [0015]
  • Advantageous refinements of and improvements on the method described in the main claim are made possible by the measures described in the subclaims. [0016]
  • Strontium chloride SrCl2, which has a high storage density for ammonia, comparable to the storage density of solid urea, can be advantageously used as the solid storage medium. Strontium chloride can be replaced totally or in part by calcium chloride, which offers comparable advantages. [0017]
  • It is particularly advantageous to use the waste heat of the engine coolant and/or the exhaust gas to heat the solid storage medium. [0018]
  • The device according to the present invention can be advantageously equipped with a buffer container for gaseous ammonia in order to have gaseous ammonia available even in intermittent engine operation and/or in start phases, regardless of the heating phase of [0019] container 1, when there is insufficient energy for heating the ammonia storage medium.
    •  BRIEF DESCRIPTION OF THE DRAWINGS
  • The invention is elucidated in the following with reference to the drawings, which illustrate three embodiments of devices intended to carry out the method according to the present invention in a motor vehicle. [0020]
  • In particular, [0021]
  • FIG. 1 schematically shows a device according to the present invention; [0022]
  • FIG. 2 shows a specifically adapted embodiment; and [0023]
  • FIG. 3 shows an additional specifically adapted embodiment of a device according to the present invention.[0024]
    • DETAILED DESCRIPTION
  • The device of FIG. 1 has a [0025] container 1, which can be heated using a heating device 3 and contains ammonia-storing substance 2.
  • The volume of [0026] container 1 is designed so that there is sufficient ammonia available to remove NOx from the exhaust gas of an internal combustion engine with the help of the catalyst system within an interval between servicings of the vehicle. It has been shown that a volume of approximately 10 liters is particularly suitable.
  • Substances that store ammonia at ambient conditions (approx. 20° C.) so that the ammonia vapor pressure over the storage medium is low in a closed system (<0.5 bar) can be used as solid storage media. [0027]
  • The solid storage media according to the present invention may contain substances that bind ammonia by physical and/or chemical absorption, such as active carbon, zeolites, etc., for example. [0028]
  • Substances that bind ammonia in the form of a chemical complex can also be used as solid storage media. These include, for example, salts, in particular chlorides and/or sulfates of one or more alkaline earth metals and/or of one or more 3d subgroup elements, preferably manganese, iron, cobalt, nickel, copper and/or zinc, can be considered. [0029]
  • A solid storage medium containing strontium chloride SrCl2 is advantageously used. Strontium chloride stores up to eight ammonia molecules per strontium ion, forming [(Sr(NH3)8]Cl2. With an approximate density of 1.5 g/cm[0030] 3, a stored amount of 48 moles NH3 results per liter of storage medium. In comparison, urea, with a density of 1.32 g/cm3, provides storage of 44 moles of ammonia per liter of solid urea. Strontium chloride can be replaced totally or in part with calcium chloride.
  • In the case of [(Sr(NH3)8]Cl2, perceptible release of ammonia begins at approximately 30° C., resulting in an ammonia vapor pressure of approximately 0.8 bar. At 80° C., the ammonia vapor pressure is about 8 bar. The device should be operated so that the pressure in [0031] container 1 is preferably between 2 and 10 bar.
  • An electric heating system and/or a heating device that uses the waste heat of the engine coolant and/or the exhaust gas can be used as [0032] heating device 3.
  • The gaseous ammonia formed when the solid storage medium is heated is metered via an electrically or pneumatically actuated [0033] valve 4, controlled by a controller 5, via ammonia supply line 6, into the exhaust gas line 8 between engine 7 and catalyst 9.
  • According to a preferred embodiment (FIG. 2), a [0034] buffer container 10 is connected between valve 4 and exhaust gas line 8. Buffer container 10 is connected to exhaust gas line 8 via a valve 4 b controlled by controller 5. When the vehicle is turned off, valves 4 and 4 b are closed, so that buffer container 10 is filled with gaseous ammonia under pressure. Thus, with the device according to FIG. 2, stored gaseous ammonia can be available even immediately after starting the engine, regardless of the heating phase of container 1.
  • One system having additional advantageous devices is illustrated in FIG. 3. [0035]
  • A filling nozzle with integrated [0036] check valve 16, which prevents ammonia being supplied from escaping through the filling opening, is provided for filling container 1.
  • A finely porous, sieve-like construction [0037] 11 prevents the granulated storage substance 2 in container 1 from being entrained to the outside.
  • A [0038] pressure sensor 12 is mounted on container 1 for control and safety; it interrupts the supply of heat when a predefined maximum pressure level is attained. Furthermore, a safety valve 13 (opening pressure approx. 10 to 15 bar) is provided, which responds to an excessively steep increase in the storage container pressure and conducts the released ammonia into the exhaust line, for example.
  • A [0039] pressure limiter 14, which ensures the required ammonia pressure of 2 to 3 bar, is provided downstream from buffer container 10.
  • At a suitable point upstream from catalyst [0040] 9, an ammonia metering station 15, for example, a metering tube with a screen, is provided to guarantee proper mixing of ammonia with the exhaust gas stream.
  • An electronic controller (Diesel EDC), in which additional functions adjusting the amount of ammonia to the actual operating state of the engine are implemented, monitors and controls the procedures. [0041]

Claims (10)

1. Method of selective catalytic NOx reduction in oxygen-containing exhaust gases using ammonia and a reduction catalyst (9), characterized in that the gaseous ammonia is made available by heating a solid storage medium (2) introduced into a container (1).
2. Method according to
claim 1
, characterized in that the storage medium (2) binds ammonia by absorption.
3. Method according to
claim 1
, characterized in that the storage medium (2) binds ammonia in the form of a chemical complex.
4. Method according to
claim 3
, characterized in that the storage medium (2) contains one or more salts, in particular chlorides and/or sulfates of one or more alkaline earth metals and/or of one or more 3d subgroup elements, preferably manganese, iron, cobalt, nickel, copper and/or zinc.
5. Method according to
claim 4
, characterized in that the storage medium contains strontium chloride and/or calcium chloride.
6. Method according to one of the foregoing claims, characterized in that the storage medium (2) is heated by an electric heating system and/or the waste heat of the engine coolant and/or of the exhaust gas.
7. Method according to
claim 6
, characterized in that the storage medium (2) is heated to 50 to 200° C., preferably to 80 to 150° C.
8. Method according to
claim 6
, characterized in that the storage medium (2) is heated to an ammonia vapor pressure of 0.1 to 30 bar, preferably 2 to 10 bar.
9. Device for carrying out the method according to one of the foregoing claims having a reduction catalyst (9) and a supply line for ammonia (6) in the exhaust gas line (8) between the engine (7) and the reduction catalyst (9), characterized in that the supply line (6) is connected, via a valve (4), to a container (1) that is filled with a solid storage medium (2) and is heatable using a heating device (3).
10. Device according to
claim 9
, characterized in that a buffer container for the gaseous ammonia (10) and a valve (4 b) for metering ammonia from the container (10) into the exhaust gas line (8) is provided in the supply line (6).
US09/254,291 1997-07-03 1998-06-25 Method and device for selective catalytic NOx reduction Expired - Fee Related US6387336B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19728343.8 1997-07-03
DE19728343 1997-07-03
DE19728343A DE19728343C5 (en) 1997-07-03 1997-07-03 Process and apparatus for selective catalytic NOx reduction
PCT/DE1998/001731 WO1999001205A1 (en) 1997-07-03 1998-06-25 METHOD AND DEVICE FOR SELECTIVE CATALYTIC NOx REDUCTION

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US6387336B2 US6387336B2 (en) 2002-05-14

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US (1) US6387336B2 (en)
EP (1) EP0932440B1 (en)
JP (2) JP4873580B2 (en)
DE (2) DE19728343C5 (en)
WO (1) WO1999001205A1 (en)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005091418A2 (en) * 2004-03-23 2005-09-29 Amminex A/S Use of an ammonia storage device in production of energy
US20050247050A1 (en) * 2004-05-05 2005-11-10 Eaton Corporation Adsorption based ammonia storage and regeneration system
US20060051276A1 (en) * 2002-11-06 2006-03-09 Johannes Schaller Device for treatment of exhaust of an internal combustion engine
WO2008043937A2 (en) * 2006-10-13 2008-04-17 Peugeot Citroën Automobiles SA System for treating nitrogen oxides while limiting ammonia emissions
FR2910531A3 (en) * 2006-12-20 2008-06-27 Renault Sas Car engine with post-treatment system for exhaust gas,has a heated ammonia generator containing a metal ammine complex salt which decomposes to ammonia and then to hydrogen and nitrogen
US20090123361A1 (en) * 2005-02-03 2009-05-14 Amminex A/S High Density Storage of Ammonia
EP1911508A3 (en) * 2006-10-13 2010-10-13 Peugeot Citroën Automobiles SA System for treating nitrogen oxides with ammonia trapping system
US20100293927A1 (en) * 2005-06-29 2010-11-25 Tue Johannessen Method and device for safe and controlled delivery of ammonia from a solid ammonia storage medium
FR2950651A1 (en) * 2009-09-29 2011-04-01 Peugeot Citroen Automobiles Sa DEVICE FOR INJECTING AN EXHAUST LINE OF A GASEOUS REDUCING AGENT
WO2011110765A1 (en) * 2010-03-12 2011-09-15 Peugeot Citroën Automobiles SA Cartridge for storing a gas reducing agent for the selective catalytic reduction of nitrogen oxides
WO2012172202A1 (en) 2011-04-20 2012-12-20 Peugeot Citroen Automobiles Sa Method for detecting a change of reducing agent canister in an scr system, exhaust line and vehicle
US20130209316A1 (en) * 2010-02-25 2013-08-15 Amminex A/S Method for determining the degree of saturation of solid ammonia storage materials in containers
US20130216459A1 (en) * 2010-11-01 2013-08-22 Brad J. Adelman Lower temperature mixing zone for nh3
CN103437866A (en) * 2013-07-25 2013-12-11 吉林大学 Method and device for providing reducing agent for full operating condition of automotive selective catalytic reduction system
EP2695858A1 (en) 2012-08-09 2014-02-12 Aaqius & Aaqius S.A. System for storing and delivering gaseous ammonia
US20140224453A1 (en) * 2011-09-26 2014-08-14 Kabushiki Kaisha Toyota Chuo Kenkyusho Heat recovery-type heating device
EP3330222A1 (en) * 2016-12-01 2018-06-06 Loughborough University Process for reducing nitrogen oxides
US11319851B2 (en) 2013-12-19 2022-05-03 Volvo Truck Corporation Exhaust gas treatment system to be fitted on a chassis of an automotive vehicle

Families Citing this family (135)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9927563D0 (en) 1999-11-23 2000-01-19 Williamson Ian A process and method for blending a fuel containing a high molecular weight compound
US6725651B2 (en) * 2000-11-16 2004-04-27 Toyota Jidosha Kabushiki Kaisha Reducing agent for emission control system, reducing-agent supply device, and emission control system using the reducing agent
DE10101364A1 (en) * 2001-01-13 2002-07-18 Fev Motorentech Gmbh Process for converting a solid nitrogenous reducing agent into a gas phase for the reduction of nitrogen oxides in oxygen-containing exhaust gases according to the principle of selective catalytic reduction
DE10155675A1 (en) * 2001-08-18 2003-05-28 Bosch Gmbh Robert Method and device for storing and dosing a reducing agent
DE50211977D1 (en) * 2001-08-18 2008-05-08 Bosch Gmbh Robert METHOD AND DEVICE FOR STORING AND DOSING A REDUCING AGENT
US6601385B2 (en) * 2001-10-17 2003-08-05 Fleetguard, Inc. Impactor for selective catalytic reduction system
DE10206028A1 (en) * 2002-02-14 2003-08-28 Man Nutzfahrzeuge Ag Process and apparatus for producing ammonia
DE10207984A1 (en) * 2002-02-25 2003-10-23 Daimler Chrysler Ag A catalytic reduction system for purification of exhaust gases containing nitrogen oxides, from a vehicle internal combustion engine, is dosed with ammonia gas from a pressure vessel located in a pressure-monitored, gas-tight compartment
US6810661B2 (en) * 2002-08-09 2004-11-02 Ford Global Technologies, Llc Method and system for freeze protecting liquid NOx reductants for vehicle application
DE10237165B4 (en) * 2002-08-14 2015-05-13 Robert Bosch Gmbh Apparatus and method for exhaust treatment of a combustion device and their use
US6834498B2 (en) * 2002-11-21 2004-12-28 Ford Global Technologies, Llc Diesel aftertreatment systems
US6895747B2 (en) * 2002-11-21 2005-05-24 Ford Global Technologies, Llc Diesel aftertreatment systems
US6862879B2 (en) 2002-11-21 2005-03-08 Ford Global Technologies, Llc Diesel aftertreatment system
FI116897B (en) * 2003-02-04 2006-03-31 Kemira Oyj Use of ammonium formate in the reduction process
DE20308348U1 (en) * 2003-02-18 2004-07-01 Hjs Fahrzeugtechnik Gmbh & Co. Assembly to break down ammonium carbonate to ammonium and surrender to an automotive diesel exhaust catalytic converter
US6901748B2 (en) * 2003-05-14 2005-06-07 Detroit Diesel Corporation Heater system for diesel engines having a selective catalytic reduction system
JP3751962B2 (en) * 2003-09-05 2006-03-08 日産ディーゼル工業株式会社 Engine exhaust purification system
EP2426329B1 (en) * 2003-09-19 2013-05-01 Nissan Diesel Motor Co., Ltd. Exhaust gas purification device of engine
AU2004289539C1 (en) 2003-11-14 2012-06-07 Lorus Therapeutics Inc. Aryl imidazoles and their use as anti-cancer agents
US7010909B2 (en) * 2003-12-03 2006-03-14 Zeuna-Starker Gmbh & Co. Kg Motor vehicle equipped with a diesel propulison engine
WO2005073527A1 (en) * 2004-02-02 2005-08-11 Nissan Diesel Motor Co., Ltd. Device for purifying exhaust gas of internal combustion engine
JP2007529678A (en) * 2004-03-16 2007-10-25 パイロバン リミテッド Exhaust filter regeneration process, method and apparatus
FR2867808B1 (en) * 2004-03-17 2006-04-28 Peugeot Citroen Automobiles Sa AMMONIA GENERATION DEVICE AND VEHICLE COMPRISING SUCH A DEVICE
CN101076495B (en) * 2004-08-03 2010-06-16 氨合物公司 A solid ammonia storage and delivery material
KR20070057143A (en) * 2004-08-03 2007-06-04 아미넥스 에이/에스 A solid ammonia storage and delivery material
FI117891B (en) * 2004-08-04 2007-04-13 Kemira Oyj Reducing Agent Composition
JP3686670B1 (en) * 2004-10-29 2005-08-24 日産ディーゼル工業株式会社 Exhaust purification device
CN101128394B (en) * 2005-02-03 2012-07-18 氨合物公司 High density storage of ammonia
US8148392B2 (en) 2005-05-25 2012-04-03 Lorus Therapeutics Inc. 2-indolyl imidazo [4,5-d] phenanthroline derivatives and their use in the treatment of cancer
WO2007095955A1 (en) * 2006-02-27 2007-08-30 Amminex A/S A method of storing and delivering ammonia and the use of electromagnetic radiation for desorption of ammonia from a chemical complex
DE102006032454A1 (en) * 2006-07-13 2008-01-17 Arvinmeritor Emissions Technologies Gmbh Exhaust system for an internal combustion engine
EP2051798B1 (en) * 2006-07-20 2012-01-11 Amminex A/S Method and device for storing and delivering ammonia from a solid ammonia storage medium
DE102006043954A1 (en) * 2006-09-14 2008-03-27 Volkswagen Ag Method of operating an SCR catalyst and SCR catalyst system
US8015801B2 (en) * 2006-09-18 2011-09-13 Ford Global Technologies, Llc Management of a plurality of reductants for selective catalytic reduction
US7726118B2 (en) * 2006-09-18 2010-06-01 Ford Global Technologies, Llc Engine-off ammonia vapor management system and method
US7770384B2 (en) * 2006-09-18 2010-08-10 Ford Global Technologies, Llc Ammonia vapor storage and purge system and method
FR2907026B1 (en) * 2006-10-13 2009-05-15 Peugeot Citroen Automobiles Sa SYSTEM FOR TREATING NITROGEN OXIDES WITH AN AMMONIA TRAPPING SYSTEM
JP2010513004A (en) * 2006-12-22 2010-04-30 アムミネクス・アー／エス Method and device for storage and supply of ammonia utilizing in-situ re-saturation of the supply unit
DE102006061370A1 (en) * 2006-12-22 2008-06-26 Amminex A/S Storing and supplying ammonia comprises using two storage materials, where one has a higher vapor pressure than the other and serves as an ammonia source for the other when it becomes depleted
WO2008078059A1 (en) * 2006-12-22 2008-07-03 Perkins Engines Company Ltd Method and apparatus for selective catalytic nox reduction
DE102007048337A1 (en) 2007-06-27 2009-01-02 Amminex A/S Safe use of materials generating ammonia irreversibly involves bringing ammonia generating material and/or its decomposition product and ammonia storage material and/or its decomposition product into fluid communication with each other
WO2008077626A2 (en) * 2006-12-22 2008-07-03 Amminex A/S Method and device for sage storage and delivery of ammonia and use of ammonia storage materials
DE102007004602B4 (en) * 2007-01-30 2009-05-28 Continental Automotive Gmbh A heating device for heating a complex salt storage
FI120966B (en) * 2007-02-15 2010-05-31 Kemira Oyj Process for preparing a reducing agent composition
US7930878B2 (en) * 2007-02-27 2011-04-26 Ford Global Technologies, Llc Method and apparatus for rapidly thawing frozen NOx reductant
US7954311B2 (en) * 2007-03-15 2011-06-07 Ford Global Technologies, Llc Ammonia vapor management system and method
ATE489158T1 (en) 2007-03-30 2010-12-15 Amminex As SYSTEM FOR STORING AMMONIA IN AND FOR DISCHARGING IT FROM A STORAGE MATERIAL AND METHOD FOR STORING AND DISCHARGING AMMONIA
JP4407717B2 (en) * 2007-04-23 2010-02-03 株式会社デンソー Reducing gas generator, and solid reducing agent SCR system using the same.
DE102007022858A1 (en) 2007-05-15 2008-11-20 Robert Bosch Gmbh Catalytic nitrogen oxide-reduction selecting device for use in internal combustion engine, has larger ammonia storage medium connected with smaller ammonia storage medium by reloading valve
US9400064B2 (en) 2007-05-23 2016-07-26 Amminex A/S Method and device for ammonia storage and delivery using in-situ re-saturation of a delivery unit
DE102007024782B4 (en) * 2007-05-26 2011-08-25 Eichenauer Heizelemente GmbH & Co. KG, 76870 Heating insert and its use in a urea supply system
DE102007042409A1 (en) 2007-09-06 2009-03-12 Robert Bosch Gmbh Exhaust after-treatment arrangement with reducing agent storage and method for aftertreatment of exhaust gases
DE102007058768A1 (en) 2007-12-06 2009-06-10 Robert Bosch Gmbh Exhaust gas post-treatment arrangement for selective catalytic reduction of pollutant i.e. nitrogen oxide, has accumulator indirectly making heat conducting contact with gas pipe via heat transfer medium circulating in circulation circuits
DE102007059850A1 (en) 2007-12-12 2009-06-25 Robert Bosch Gmbh Exhaust gas aftertreatment arrangement for reducing pollutants in exhaust gas has storage container for storing substance which is spatially separated from heating chamber for producing reducing medium from substance
DE102007060221B4 (en) 2007-12-14 2021-12-30 Robert Bosch Gmbh Process for the provision of reducing agents in an exhaust gas aftertreatment system
DE102009005790B4 (en) * 2009-01-22 2023-05-17 Albonair Gmbh dosing system
DE102008012543A1 (en) 2008-03-04 2009-09-10 Robert Bosch Gmbh Storage element manufacturing method for internal combustion engine of motor vehicle, involves inserting metallic structure in storage medium that is pushed to cylindrical and/or hollow cylindrical storage body
DE102008000694A1 (en) 2008-03-17 2009-09-24 Robert Bosch Gmbh Apparatus and method for the thermodynamic and pressure-increasing release of ammonia
DE102008001004A1 (en) 2008-04-04 2009-10-08 Robert Bosch Gmbh Determining ammonia amount in ammonia delivery device of system for selective catalytic reduction of nitrogen oxides in motor vehicles like automobiles, diesel vehicles or combustion plants, involves measuring temperature of storage medium
DE102008022515A1 (en) * 2008-05-07 2009-11-12 Emitec Gesellschaft Für Emissionstechnologie Mbh Tank for a reducing agent, motor vehicle with a tank for a reducing agent and a method for operating an SCR system of a motor vehicle
DE102008001709A1 (en) * 2008-05-13 2009-11-19 Robert Bosch Gmbh Apparatus, system and method for providing a reductant for a selective catalytic reduction system of nitrogen oxides
DE102008002281A1 (en) 2008-06-06 2009-12-10 Robert Bosch Gmbh Method for loading a gas storage
DE102008002335A1 (en) 2008-06-10 2009-12-17 Robert Bosch Gmbh Ammonia storage unit for automotive exhaust system incorporates an embedded powder additive
DE102008002612A1 (en) * 2008-06-24 2009-12-31 Robert Bosch Gmbh Exhaust after-treatment device for an internal combustion engine
DE102008040428A1 (en) 2008-07-14 2010-01-21 Robert Bosch Gmbh Exhaust gas post-treatment installation for diesel engine of vehicle, has tube equipped with selective catalytic reduction catalyst, and pressure limiting valves including respective inlets for receiving pressure reigning in container
DE102008041734A1 (en) 2008-09-01 2010-03-04 Robert Bosch Gmbh Exhaust gas after-treatment device for diesel engine of motor vehicle, has dosing valve discharging active agent for exhaust gas after-treatment, and ammonia producing unit connected with safety absorber for active agent
WO2010025948A1 (en) 2008-09-08 2010-03-11 Amminex A/S Additives for highly compacted ammonia storage materials
EP2342001A1 (en) 2008-09-08 2011-07-13 Amminex A/S Saturation of ammonia storage materials in containers
DE102008041903A1 (en) 2008-09-09 2010-03-11 Robert Bosch Gmbh Exhaust gas post-treatment method for diesel engine of motor vehicle, involves providing auxiliary fluid in auxiliary agent, and supplying fuel to internal-combustion engine from fuel tank that is exclusively refueled with fuel
EP2181963B1 (en) 2008-10-06 2018-12-12 Amminex Emissions Technology A/S Release of stored ammonia at start-up
DE102008042735A1 (en) 2008-10-10 2010-04-15 Robert Bosch Gmbh Ammonia storage and delivery system useful in internal combustion engine of motor vehicle by introducing ammonia into vehicle exhaust gas tract for selective catalytic reaction of exhaust gas, comprises container, and water reception units
EP2204555B1 (en) * 2009-01-02 2011-08-03 Sensirion AG Ammonia storage system
DE102009000280A1 (en) 2009-01-19 2010-07-22 Robert Bosch Gmbh Heating an ammonia storing material of an ammonia reservoir, useful for storing ammonia in the ammonia storing material, where the heat resulting from an adsorption process is used for the heating process
US9272244B2 (en) 2009-01-22 2016-03-01 Albonair Gmbh Metering system
DE102009000411B4 (en) 2009-01-26 2017-06-08 Robert Bosch Gmbh Device for storing and dispensing ammonia and drive device with such a device
DE102009008743B4 (en) 2009-02-12 2023-06-07 Bayerische Motoren Werke Aktiengesellschaft Heating circuit for heating an ammonia storage device when the internal combustion engine is at a standstill
DE102009008744B4 (en) 2009-02-12 2023-05-11 Bayerische Motoren Werke Aktiengesellschaft Heating circuit for heating an ammonia storage device
US8291926B2 (en) * 2009-02-20 2012-10-23 Caterpillar Inc. Reductant dosing system having anti-aeration device
DE102009013260A1 (en) 2009-03-14 2010-09-16 Bayerische Motoren Werke Aktiengesellschaft Device for selective catalytic nitrogen oxide reduction in waste gases containing oxygen, of internal combustion engine of motor vehicle, has heater heating fluid line upstream to injection position up to sediments decomposition temperature
EP2236784B1 (en) 2009-03-18 2012-06-06 Amminex A/S Improved method for storing and delivering ammonia from solid storage materials using a vacuum pump
JP5287404B2 (en) * 2009-03-19 2013-09-11 株式会社豊田中央研究所 Reducing gas generator and catalyst reduction system
CN102395531A (en) 2009-04-15 2012-03-28 氨合物公司 Production of saturated ammonia storage materials
EP2241535B1 (en) 2009-04-15 2013-07-10 Amminex Emissions Technology A/S Production of saturated ammonia storage materials
US8084008B2 (en) 2009-04-16 2011-12-27 Amminex A/S Production of saturated ammonia storage materials
DE102009022884A1 (en) 2009-05-27 2010-12-02 Bayerische Motoren Werke Aktiengesellschaft Method and storage tank for determining the stored amount of ammonia for the catalytic emission control
DE102009030405A1 (en) * 2009-06-25 2010-12-30 Bayerische Motoren Werke Aktiengesellschaft Ammonia storing device for use in selective catalytic reduction process for reducing nitrogen oxides in exhaust gas of e.g. diesel internal-combustion engine, of motor vehicle, has cooling device attached to storage substrate
US20110005213A1 (en) * 2009-07-09 2011-01-13 Li Bob X Apparatus for Maintaining a Urea Solution in a Liquid State for Treatment of Diesel Exhaust
EP2273082A1 (en) 2009-07-09 2011-01-12 Delphi Technologies, Inc. Apparatus for maintening a urea solution in a liquid state for treatment of diesel exhaust
US20110005206A1 (en) * 2009-07-09 2011-01-13 Li Bob X Apparatus for Maintaining a Urea Solution in a Liquid State for Treatment of Diesel Exhaust
DE102009046960A1 (en) 2009-11-23 2011-05-26 Robert Bosch Gmbh Method for loading storage tank in exhaust gas after-treatment device of selective catalytic reduction catalyzer for treating nitrogen oxide in motor vehicle, involves providing storage substance with reducing agent in closed container
DE102009047103A1 (en) 2009-11-25 2011-05-26 Robert Bosch Gmbh Storage tank for use as high temperature pressure tank for reduction medium in device for exhaust gas treatment of internal combustion engine, comprises selective catalytic reduction catalytic converter for storage of reduction medium
DE102009047159A1 (en) 2009-11-26 2011-06-01 Robert Bosch Gmbh Method for determining actual loading condition of ammonia storage container in internal combustion engine in motor vehicle for e.g. reducing of nitrogen oxide, involves calculating heat conductivity value as value that represents condition
DE102009047338A1 (en) 2009-12-01 2011-06-09 Robert Bosch Gmbh Exhaust gas treatment device for internal combustion engine, has exhaust gas pipe, silicon-controlled rectifier catalyst and dosing valve in supply line for inlet of gaseous reduction medium in exhaust gas pipe
DE102009047433A1 (en) 2009-12-03 2011-06-09 Robert Bosch Gmbh Method for filling storage container with reducing agent, particularly ammonia, involves storing reducing agent into storage substance for supply meeting demand in exhaust gas after treatment system for reducing nitrogen oxides
DE102009047475A1 (en) 2009-12-04 2011-06-09 Robert Bosch Gmbh Storage container for storing e.g. ammonia, utilized for reducing nitrogen oxide in exhaust strand in internal combustion engine of motor vehicle, has heating units heating storage area by electricity
DE102009047663A1 (en) 2009-12-08 2011-06-09 Robert Bosch Gmbh Method and apparatus for recharging NOx reducing agent storage tanks
DE102009060288A1 (en) * 2009-12-23 2011-06-30 Volkswagen AG, 38440 Operating ammonia storage system for catalyst system operating based on principle of selective catalytic reduction comprises a main memory that is equipped with heating device and contains ammonia-storing material
FR2956156B1 (en) 2010-02-09 2016-02-12 Peugeot Citroen Automobiles Sa INJECTION DEVICE IN AN EXHAUST LINE OF A GAS REDUCER AGENT
WO2011107279A1 (en) 2010-03-02 2011-09-09 Amminex A/S Apparatus for generating hydrogen from ammonia stored in solid materials and integration thereof into low temperature fuel cells
EP2366448B1 (en) 2010-03-16 2016-07-27 Amminex Emissions Technology A/S Method and device for controlled dosing of a gas with fluctuating supply pressure
FR2957630A1 (en) * 2010-03-19 2011-09-23 Peugeot Citroen Automobiles Sa Device for injecting gas in exhaust line for selective reduction of nitrogen oxides produced by internal combustion engine i.e. diesel engine, of vehicle, has tanks mounted on inlet pipe in serial manner
FR2957970B1 (en) 2010-03-29 2013-01-11 Peugeot Citroen Automobiles Sa DEVICE FOR INJECTING AN EXHAUST LINE OF A GASEOUS REDUCING AGENT
EP2388058A1 (en) * 2010-05-19 2011-11-23 Amminex A/S Method and device for re-saturation of ammonia storage material in containers
US20120011830A1 (en) * 2010-07-14 2012-01-19 International Engine Intellectual Property Company, Llc Method for heating solid ammonia to release gaseous ammonia in exhaust aftertreatment system
EP2412946B1 (en) * 2010-07-28 2015-08-19 Aaqius & Aaqius S.A. Method intended for reducing the amount of NOx in the exhaust fumes of a motor vehicle
FR2966817B1 (en) 2010-10-28 2013-04-12 Peugeot Citroen Automobiles Sa PROCESS FOR THE AMMONIA REFILL OF A CARTRIDGE COMPRISING A SALT CAPABLE OF ABSORBING AMMONIA GAS
US8495869B2 (en) 2010-11-02 2013-07-30 Girtz Industries Inc. Power systems with internally integrated aftertreatment and modular features
EP2705230A1 (en) 2011-05-02 2014-03-12 Peugeot Citroën Automobiles SA Exhaust line and vehicle fitted with this line
FR2974847A1 (en) * 2011-05-02 2012-11-09 Peugeot Citroen Automobiles Sa Exhaust line for diesel engine of thermal vehicle, has tube supporting snap-on element, and non-return valve for preventing increase of particles toward reservoir, and heat resistor placed around valve for heating valve
FR2974850B1 (en) * 2011-05-02 2015-11-20 Peugeot Citroen Automobiles Sa AN EXHAUST LINE AND VEHICLE PROVIDED WITH THIS LINE
FR2974848A1 (en) * 2011-05-02 2012-11-09 Peugeot Citroen Automobiles Sa Exhaust line for use with nitrogen oxide selective catalytic reduction system in diesel engine of thermal vehicle, has non-return valve preventing increase of particles toward reservoir, and heat exchanger placed around valve to heat valve
FR2974849B1 (en) * 2011-05-02 2013-05-10 Peugeot Citroen Automobiles Sa AN EXHAUST LINE AND VEHICLE PROVIDED WITH THIS LINE
JP5609766B2 (en) * 2011-05-13 2014-10-22 株式会社デンソー Fuel supply system
KR20130024079A (en) * 2011-08-30 2013-03-08 현대자동차주식회사 Solid scr system and heating method of solid reductant using the same
DE102011119242B4 (en) 2011-11-22 2014-04-24 Daimler Ag An exhaust gas purification device comprising a heating system for a reducing agent storage device
WO2013082078A1 (en) 2011-12-02 2013-06-06 Cummins Inc. Solid storage media charging with ammonia for use in selective catalytic reduction
JP5846487B2 (en) * 2011-12-13 2016-01-20 三菱自動車工業株式会社 Exhaust gas purification device
JP5979469B2 (en) * 2011-12-20 2016-08-24 三菱自動車工業株式会社 Exhaust gas purification device and purification method for internal combustion engine
JP2013185511A (en) * 2012-03-08 2013-09-19 Mitsubishi Motors Corp Exhaust emission control device of internal combustion engine
US9381466B2 (en) 2012-04-03 2016-07-05 Korea Institute Of Machinery & Materials Exhaust gas purification system
FR2989419B1 (en) * 2012-04-11 2014-05-16 Peugeot Citroen Automobiles Sa INJECTION SYSTEM IN AN EXHAUST LINE OF A GASEOUS REAGENT
WO2013162526A1 (en) * 2012-04-24 2013-10-31 International Engine Intellectual Property Company, Llc Biasing of ammonia lines to facilitate canister removal and insertion
WO2013160712A1 (en) 2012-04-26 2013-10-31 Renault Trucks System and method for treating nitrogen oxides contained in exhaust gases
FR2991712B1 (en) * 2012-06-06 2014-07-04 Faurecia Sys Echappement AMMONIA GENERATION DEVICE
US10067045B2 (en) 2012-11-02 2018-09-04 International Engine Intellectual Property Company, Llc. Ammonia estimation method
JP2016516082A (en) 2013-03-20 2016-06-02 アプトース バイオサイエンシーズ， インコーポレイテッド 2-Substituted imidazo [4,5-D] phenanthroline derivatives and their use in the treatment of cancer
FR3004435B1 (en) * 2013-04-12 2016-10-21 Aaqius & Aaqius Sa AMMONIA STORAGE STRUCTURE AND ASSOCIATED SYSTEMS
EP2986828A1 (en) 2013-04-17 2016-02-24 Volvo Truck Corporation System for injecting reactants in an exhaust line
DK3052102T3 (en) 2013-10-04 2020-03-09 Aptose Biosciences Inc CANCER TREATMENT COMPOSITIONS
RU2683086C2 (en) * 2014-03-10 2019-03-26 САИПЕМ С.п.А. Recovery system and method for processing a gas stream from a urea plant solidification unit
EP3217133A1 (en) * 2014-11-07 2017-09-13 Kabushiki Kaisha Toyota Jidoshokki Chemical heat storage apparatus
US11585253B2 (en) 2015-08-07 2023-02-21 Cummins Emission Solutions Inc. Converging liquid reductant injector nozzle in selective catalytic reduction systems
DE102016224135A1 (en) 2016-12-05 2018-06-07 Robert Bosch Gmbh Method for reducing nitrogen oxide emissions of a diesel vehicle
KR20200096914A (en) 2017-10-30 2020-08-14 압토스 바이오사이언시스 인코포레이티드 Aryl imidazole for cancer treatment
FR3087835B1 (en) * 2018-10-26 2021-03-05 Faurecia Systemes Dechappement INJECTOR FOR INJECTING A GAS REDUCING AGENT INTO THE EXHAUST GAS FLOW OF AN INTERNAL COMBUSTION ENGINE

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3531246A (en) * 1964-04-08 1970-09-29 Exxon Research Engineering Co Molecular sieve sorbent and process for the manufacture of ammonia
JPS5637037A (en) * 1979-09-03 1981-04-10 Kawasaki Heavy Ind Ltd Removing method of ammonium compound from coal ash
US4365475A (en) * 1980-08-29 1982-12-28 The United States Of America As Represented By The Secretary Of The Navy Thermochemical energy storage and mechanical energy converter system
JPS645633U (en) * 1987-06-26 1989-01-12
DE3830045C2 (en) * 1988-09-03 1993-09-30 Bayer Ag Process for the reduction of nitrogen oxides contained in exhaust gases by means of a zeolite-containing catalyst
US5441716A (en) * 1989-03-08 1995-08-15 Rocky Research Method and apparatus for achieving high reaction rates
JPH02258017A (en) * 1989-03-31 1990-10-18 Babcock Hitachi Kk Denitrifying apparatus for waste gas using solid reducing agent
US5342599A (en) * 1990-09-14 1994-08-30 Cummins Power Generation, Inc. Surface stabilized sources of isocyanic acid
DE4038054A1 (en) 1990-11-29 1992-06-04 Man Technologie Gmbh METHOD AND DEVICE FOR SELECTIVE CATALYTIC NO (DOWN ARROW) X (DOWN ARROW) REDUCTION IN OXYGEN-BASED EXHAUST GASES
US5165247A (en) * 1991-02-11 1992-11-24 Rocky Research Refrigerant recycling system
DE4200514A1 (en) * 1992-01-11 1993-07-15 Asea Brown Boveri Removal of nitrogen@ from turbine exhaust gases - by injection of reduction agent broken into transitional substances by exhaust heat energy before injection to catalytic converter
JPH05272331A (en) * 1992-03-25 1993-10-19 Hino Motors Ltd Exhaust emission control device and reducing agent supply method and device used therein
JPH067639A (en) * 1992-04-28 1994-01-18 Mitsubishi Heavy Ind Ltd Method for denitrifying waste combustion gas
DE4221451C2 (en) * 1992-06-30 1996-02-29 Werner Prof Dr Weisweiler Process and device for catalyzed denitrification of the exhaust gases from diesel engines and lean gasoline engines
JPH06341781A (en) * 1993-05-31 1994-12-13 Nok Corp Heat accumulator
EP0638350A3 (en) * 1993-08-09 1995-03-22 Solvay Deutschland GmbH Sorption of NH3 with doped oxidic sorbents followed by the catalytic oxidation of the desorbed product
DE69524838T2 (en) * 1994-10-20 2002-06-20 Mitsubishi Heavy Ind Ltd Process for the adsorption of ammonia
JPH09150037A (en) * 1995-12-01 1997-06-10 Niigata Eng Co Ltd Reducing agent spraying device for exhaust gas denitrification facility
DE19651212C3 (en) 1996-12-10 2003-10-30 Bosch Gmbh Robert Method and device for reducing nitrogen oxides in gas mixtures
US5809775A (en) * 1997-04-02 1998-09-22 Clean Diesel Technologies, Inc. Reducing NOx emissions from an engine by selective catalytic reduction utilizing solid reagents
DE29708491U1 (en) 1997-05-13 1997-07-10 Hergeth Willibald Flooring for sports fields
DE29708591U1 (en) * 1997-05-14 1997-07-17 Hjs Fahrzeugtechnik Gmbh & Co Device for feeding ammonia into the exhaust gas stream of an internal combustion engine

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060051276A1 (en) * 2002-11-06 2006-03-09 Johannes Schaller Device for treatment of exhaust of an internal combustion engine
US7449162B2 (en) * 2002-11-06 2008-11-11 Robert Bosch Gmbh Device for treatment of exhaust of an internal combustion engine
WO2005091418A3 (en) * 2004-03-23 2006-06-01 Amminex As Use of an ammonia storage device in production of energy
US20070207351A1 (en) * 2004-03-23 2007-09-06 Amminex A/S Use Of An Ammonia Storage Device In Production Of Energy
WO2005091418A2 (en) * 2004-03-23 2005-09-29 Amminex A/S Use of an ammonia storage device in production of energy
US20050247050A1 (en) * 2004-05-05 2005-11-10 Eaton Corporation Adsorption based ammonia storage and regeneration system
US20100024403A1 (en) * 2005-02-03 2010-02-04 Amminex A/S High Density Storage of Ammonia
US7964163B2 (en) * 2005-02-03 2011-06-21 Amminex A/S High density storage of ammonia
EP2263975A2 (en) 2005-02-03 2010-12-22 Amminex A/S High density storage of ammonia
US20090123361A1 (en) * 2005-02-03 2009-05-14 Amminex A/S High Density Storage of Ammonia
US20100293927A1 (en) * 2005-06-29 2010-11-25 Tue Johannessen Method and device for safe and controlled delivery of ammonia from a solid ammonia storage medium
WO2008043937A3 (en) * 2006-10-13 2008-07-17 Peugeot Citroen Automobiles Sa System for treating nitrogen oxides while limiting ammonia emissions
EP1911508A3 (en) * 2006-10-13 2010-10-13 Peugeot Citroën Automobiles SA System for treating nitrogen oxides with ammonia trapping system
FR2907027A1 (en) * 2006-10-13 2008-04-18 Peugeot Citroen Automobiles Sa SYSTEM FOR TREATING NITROGEN OXIDES WITH LIMITATION OF AMMONIA RELEASES
WO2008043937A2 (en) * 2006-10-13 2008-04-17 Peugeot Citroën Automobiles SA System for treating nitrogen oxides while limiting ammonia emissions
FR2910531A3 (en) * 2006-12-20 2008-06-27 Renault Sas Car engine with post-treatment system for exhaust gas,has a heated ammonia generator containing a metal ammine complex salt which decomposes to ammonia and then to hydrogen and nitrogen
WO2011039438A1 (en) * 2009-09-29 2011-04-07 Peugeot Citroën Automobiles SA Device for injecting a gaseous reducing agent into an exhaust line
FR2950651A1 (en) * 2009-09-29 2011-04-01 Peugeot Citroen Automobiles Sa DEVICE FOR INJECTING AN EXHAUST LINE OF A GASEOUS REDUCING AGENT
US20130209316A1 (en) * 2010-02-25 2013-08-15 Amminex A/S Method for determining the degree of saturation of solid ammonia storage materials in containers
US8834603B2 (en) * 2010-02-25 2014-09-16 Amminex Emissions Technology A/S Method for determining the degree of saturation of solid ammonia storage materials in containers
WO2011110765A1 (en) * 2010-03-12 2011-09-15 Peugeot Citroën Automobiles SA Cartridge for storing a gas reducing agent for the selective catalytic reduction of nitrogen oxides
FR2957271A1 (en) * 2010-03-12 2011-09-16 Peugeot Citroen Automobiles Sa GAS REDUCER STORAGE CARTRIDGE FOR SELECTIVE CATALYTIC REDUCTION OF NITROGEN OXIDES
US20130216459A1 (en) * 2010-11-01 2013-08-22 Brad J. Adelman Lower temperature mixing zone for nh3
WO2012172202A1 (en) 2011-04-20 2012-12-20 Peugeot Citroen Automobiles Sa Method for detecting a change of reducing agent canister in an scr system, exhaust line and vehicle
US20140224453A1 (en) * 2011-09-26 2014-08-14 Kabushiki Kaisha Toyota Chuo Kenkyusho Heat recovery-type heating device
US9791216B2 (en) * 2011-09-26 2017-10-17 Kabushiki Kaisha Toyota Chuo Kenkyusho Heat recovery-type heating device
WO2014023839A1 (en) 2012-08-09 2014-02-13 Aaqius & Aaqius Sa System for storing and delivering gaseous ammonia
EP2695858A1 (en) 2012-08-09 2014-02-12 Aaqius & Aaqius S.A. System for storing and delivering gaseous ammonia
CN103437866A (en) * 2013-07-25 2013-12-11 吉林大学 Method and device for providing reducing agent for full operating condition of automotive selective catalytic reduction system
US11319851B2 (en) 2013-12-19 2022-05-03 Volvo Truck Corporation Exhaust gas treatment system to be fitted on a chassis of an automotive vehicle
EP3330222A1 (en) * 2016-12-01 2018-06-06 Loughborough University Process for reducing nitrogen oxides
WO2018100187A1 (en) * 2016-12-01 2018-06-07 Loughborough University Producing ammonium carbamate and reducing nitrogen oxides
CN110099866A (en) * 2016-12-01 2019-08-06 拉夫堡大学 Generate aminoquinoxaline and nitrogen oxides reduction
US10695719B2 (en) 2016-12-01 2020-06-30 Loughborough University Producing ammonium carbamate and reducing nitrogen oxides

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EP0932440A1 (en) 1999-08-04
US6387336B2 (en) 2002-05-14

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