US20150192049A1 - Catalytic reactor and vehicle equipped with said catalytic reactor - Google Patents

Catalytic reactor and vehicle equipped with said catalytic reactor Download PDF

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Publication number
US20150192049A1
US20150192049A1 US14/419,265 US201314419265A US2015192049A1 US 20150192049 A1 US20150192049 A1 US 20150192049A1 US 201314419265 A US201314419265 A US 201314419265A US 2015192049 A1 US2015192049 A1 US 2015192049A1
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United States
Prior art keywords
ammonia
heat storage
warming
section
storage material
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US14/419,265
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English (en)
Inventor
Junya Suzuki
Takafumi Yamasaki
Satoshi Hariu
Takafumi Yamauchi
Yasuki Hirota
Takashi Shimazu
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Toyota Industries Corp
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Toyota Industries Corp
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Assigned to KABUSHIKI KAISHA TOYOTA JIDOSHOKKI reassignment KABUSHIKI KAISHA TOYOTA JIDOSHOKKI ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HIROTA, YASUKI, SHIMAZU, TAKASHI, YAMAUCHI, TAKAFUMI, YAMASAKI, Takafumi, HARIU, SATOSHI, SUZUKI, JUNYA
Publication of US20150192049A1 publication Critical patent/US20150192049A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • 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
    • F01N3/2006—Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating
    • 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
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features
    • F01N13/009—Exhaust or silencing apparatus characterised by constructional features having two or more separate purifying devices arranged in series
    • 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
    • F01N3/206—Adding periodically or continuously substances to exhaust gases for promoting purification, e.g. catalytic material in liquid form, NOx reducing agents
    • 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
    • F01N3/206—Adding periodically or continuously substances to exhaust gases for promoting purification, e.g. catalytic material in liquid form, NOx reducing agents
    • F01N3/208—Control of selective catalytic reduction [SCR], e.g. by adjusting the dosing of reducing agent
    • 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
    • F01N5/00—Exhaust or silencing apparatus combined or associated with devices profiting by exhaust energy
    • F01N5/02—Exhaust or silencing apparatus combined or associated with devices profiting by exhaust energy the devices using heat
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B17/00—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type
    • F25B17/08—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type the absorbent or adsorbent being a solid, e.g. salt
    • 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
    • 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
    • B01D53/90—Injecting reactants
    • 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
    • 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
    • F01N2240/02—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 heat exchanger
    • 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
    • F01N2240/12—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 thermal 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
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/063—Surface coverings for exhaust purification, e.g. catalytic reaction zeolites
    • 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
    • F01N2610/10—Adding substances to exhaust gases the substance being heated, e.g. by heating tank or supply line of the added substance
    • F01N2610/102—Adding substances to exhaust gases the substance being heated, e.g. by heating tank or supply line of the added substance after addition to exhaust gases, e.g. by a passively or actively heated surface in the exhaust conduit
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B30/00—Heat pumps
    • F25B30/04—Heat pumps of the sorption type
    • 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
    • Y02A30/00—Adapting or protecting infrastructure or their operation
    • Y02A30/27—Relating to heating, ventilation or air conditioning [HVAC] technologies
    • 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
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
    • 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
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
    • Y02B30/62—Absorption based systems
    • 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
    • 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 present invention relates to a catalytic reactor utilizing a chemical heat storage material and a vehicle equipped with the catalytic reactor.
  • Patent Document 1 states that when a chloride of an alkaline earth metal or a chloride of a transition metal occludes ammonia, heat is generated, and when ammonia is discharged, heat is absorbed.
  • Patent Document 1 states as a specific example thereof a chemical heat storage apparatus equipped with a solid phase reactor and a condenser connected to the solid phase reactor. In the interior of the solid phase reactor, an ammine complex of a metal chloride is charged. Ammonia gas is released from the ammine complex of the metal chloride by supply of a heating source. The solid phase reactor holds the pressure of the ammonia gas. The condenser condenses the ammonia gas by supply of cooling water.
  • Patent Document 2 discloses a catalyst warming-up apparatus for warming-up a purification catalyst of a purification apparatus for exhaust gas by utilizing the following reversible reaction, and carrying out an exothermic reaction by supplying water to calcium oxide under a low-temperature environment.
  • the chemical heat storage apparatus needs to have a mechanism to control the gas/liquid phase change because the chemical heat storage apparatus is equipped with a condenser to condense ammonia gas.
  • the apparatus is therefore likely to become complicated.
  • the catalyst warming-up apparatus since needing water, is difficult to operate below the freezing point. Heat is necessary that equates to a temperature of 400° C. or higher for the regeneration reaction (CaO+H 2 O ⁇ Ca(OH) 2 +Q) of calcium oxide after the warming-up. If the heat is intended to be obtained from exhaust gas from an internal combustion engine (hereinafter, engine), a long time is necessary. The regeneration is not completed depending on the operation state, and the warming-up of the purification catalyst may possibly not be carried out at the succeeding starting time.
  • exhaust gas discharged from their engine usually contains, in addition to nitrogen oxides (NO x ), carbon monoxide (CO), hydrocarbons (HC) and the like, particulate matter (hereinafter, abbreviated to PM in some cases) containing as main components carbonaceous substances including a soluble organic fraction (SOF), which is cinder of soot, fuel and engine oil. Therefore, purification of exhaust gas by a filter (DPF: Diesel particulate filter; hereinafter, DPF) is carried out by equipping the vehicles with the filter to reduce the particulate substances in the exhaust gases.
  • DPF Diesel particulate filter
  • An example of the DPF includes DPF catalysts in which a noble metal is supported on a base material.
  • the present invention has been achieved based on the following findings. That is, if exothermic and endothermic reactions when ammonia is adsorbed to and desorbed from a chemical heat storage material are utilized, the warming-up function can be maintained even under a low-temperature environment.
  • ammonia is exposed to a high temperature, for example, in an exhaust system carrying out a high-temperature treatment in order to remove PM, such as in a diesel engine.
  • the temperature of its exhaust gas reaches 400° C. or higher. In such a temperature range, ammonia is pyrolyzed, and the initial warming-up function cannot continuously be maintained in some cases.
  • the warming-up is usually carried out by heat generation by adsorption of ammonia to a chemical heat storage material. After the warming-up termination, ammonia is recovered for preparation for the succeeding warming-up, and the chemical heat storage material is regenerated to a state of having desorbed ammonia, thereby enabling to carry out repeatedly the warming-up. It is important from the viewpoint of retaining the warming-up function for a long period that ammonia remaining in the system including the piping is previously separated from a high-temperature region, that is, the pressure of ammonia in the system exposed to a high temperature is reduced.
  • ammonia fixation material developing a high ammonia adsorption capacity even at a low temperature and being capable of removing ammonia remaining in the system by adsorption.
  • a catalytic reactor that includes a catalytic reaction section, a warming-up section, an ammonia supply section, and an ammonia depressurization section.
  • the catalytic reaction section has a purification catalyst for purifying gas.
  • the warming-up section is located at a position capable of heat-exchanging with the purification catalyst.
  • the warming-up section has a chemical heat storage material that generates heat when ammonia is fixed and absorbs heat when ammonia is desorbed.
  • the ammonia supply section has an adsorbent capable of adsorbing ammonia.
  • the ammonia supply section transfers ammonia from and to the warming-up section by adsorption and desorption of ammonia.
  • the ammonia depressurization section has an ammonia fixation section for fixing ammonia and reduces an ammonia partial pressure at least in the warming-up section after the desorption of ammonia from the chemical heat storage material.
  • the catalytic reaction section provided with the purification catalyst to purify exhaust gas discharged from an internal combustion engine is equipped with the warming-up section using the chemical heat storage material to absorb and generate heat by adsorption and desorption of ammonia.
  • the purification catalyst is warmed up by the warming-up section to thereby improve the catalytic activity under a low-temperature environment (including below the freezing point).
  • the catalytic reactor is provided further with the ammonia supply section to desorb ammonia when the purification catalyst is warmed up by the warming-up section, and to adsorb ammonia for preparation for the succeeding warming-up after the warming-up, and the ammonia depressurization section to reduce the ammonia pressure by chemically or physically adsorbing ammonia that has not been completely adsorbed and recovered by the ammonia supply section when ammonia was adsorbed for preparation for the warming-up and remains in the warming-up section, the piping and the like.
  • the temperature of a catalyst is normal temperature (25° C.) or lower, the catalytic activity to exhaust gas would be usually insufficient, the warming-up function can thereby be maintained stably.
  • the catalytic reaction section is thereby heated (for example, to about 150° C.) and the catalytic activity is highly maintained and the purification function to the exhaust gas is improved.
  • exhaust gas of a high temperature reaching 400° C. or higher is discharged from an internal combustion engine in some cases. If ammonia is exposed to exhaust gas of such a high temperature, ammonia is pyrolyzed and the initial warming-up function cannot be retained in some cases.
  • ammonia adsorbed to the chemical heat storage material of the warming-up section is gradually desorbed and returns to the ammonia supply section as the chemical heat storage material of the warming-up section is heated by the temperature rise of the exhaust gas after the warming-up, and ammonia remaining in the warming-up section and the piping is further separated by the ammonia depressurization section. Minimization of pyrolysis of ammonia used for warming-up is thereby achieved.
  • the use of ammonia as a medium for heat transport ensures a stable warming-up function under a low-temperature environment (including below the freezing point), and prevents the pyrolysis of ammonia when the catalytic reactor is applied to a gas flow system in which a high-temperature gas to be purified is flowed. Therefore, the use of the catalytic reactor according to the present invention can construct a catalytic purification system capable of stably developing an exhaust gas purification function using a catalyst.
  • the adsorbent of the ammonia supply section is preferably a physical adsorbent capable of physically adsorbing ammonia.
  • the use of the physical adsorbent can make small the heat quantity necessary for fixation and desorption of ammonia, and can make the adsorption and desorption of ammonia to be easily carried out with lower energy.
  • the warming-up section preferably has at least one ammonia supply port and a porous body member arranged between the chemical heat storage material and the ammonia supply port, and the porous body member is preferably arranged such that ammonia supplied to the warming-up section through the at least one ammonia supply port diffuses in the porous body member and contacts the chemical heat storage material.
  • One or more of ammonia supply ports for supplying ammonia are provided, and when ammonia is supplied to the chemical heat storage material located in the warming-up section, the warming-up of a catalyst is started by the exothermic reaction accompanying the chemical adsorption of ammonia to the chemical heat storage material.
  • the porous body member having a large number of gas-diffusible pores is provided between the ammonia supply ports and the chemical heat storage material, ammonia is flowed and diffused through the porous body member and supplied to the chemical heat storage material.
  • the exothermic reaction in the chemical heat storage material can uniformly be caused across the broad range.
  • the ammonia fixation section is preferably formed by using a chemical heat storage material to generate heat when ammonia is fixed and to absorb heat when ammonia is desorbed.
  • the ammonia fixation section of the ammonia depressurization section has, for example, a function of removing ammonia gas remaining in the warming-up section and in the piping between the warming-up section and the ammonia supply section, and reducing the ammonia pressure (partial pressure).
  • the ammonia fixation section is preferably formed by using a chemical heat storage material.
  • the chemical heat storage material preferably has a higher adsorption capacity of ammonia than that of an adsorbent of the ammonia supply section, and easily chemically adsorb ammonia in a lower temperature range than the chemical heat storage material of the warming-up section. Further providing such an ammonia fixation section separately from the ammonia supply section enables to reduce the pressure of ammonia remaining in the warming-up section and the piping after the warming-up.
  • the chemical heat storage material preferably contains at least a metal chloride. More preferably, the metal chloride is selected from the group consisting of alkali metal chlorides, alkaline earth metal chlorides and transition metal chlorides.
  • Metal chlorides are suitable in the point of being capable of providing a high heat storage density (kJ/kg).
  • the use of a metal chloride enhances the warming-up function of the purification catalyst.
  • Alkali metal chlorides, alkaline earth metal chlorides, and transition metal chlorides are useful in the point of more enhancing the warming-up function.
  • the heat storage density indicates a heat quantity (kJ) absorbed per kilogram of a metal chloride by desorption of ammonia.
  • the ammonia supply section can contain a physical adsorbent selected from the group consisting of activated carbon, mesoporous silica, zeolite, silica gel, and clay minerals.
  • the chemical heat storage material preferably contains at least one of MgCl 2 , MnCl 2 , CoCl 2 , NiCl 2 , MgBr 2 and MgI 2 .
  • the ammonia fixation section of the ammonia depressurization section preferably has a chemical heat storage material that generates heat when ammonia is fixed and absorbs heat when ammonia is desorbed.
  • the second chemical heat storage material contains at least one of BaCl 2 , CaCl 2 , and SrCl 2 .
  • MgCl 2 , MnCl 2 , CoCl 2 , NiCl 2 , MgBr 2 or MgI 2 provides a high heat storage density (kJ/kg), and is useful in the point of enhancing the warming-up function, and BaCl 2 , CaCl 2 or SrCl 2 easily desorbs fixed ammonia and can supply ammonia to the warming-up section at a lower temperature.
  • the ammonia depressurization section preferably has a heating section that heats the ammonia fixation section by heat-exchanging with the ammonia fixation section through flow of a heat medium.
  • a vehicle in accordance with another aspect of the present invention, includes an internal combustion engine and a catalytic reactor that is adapted such that exhaust gas discharged from the internal combustion engine flows into the catalytic reactor.
  • the purification function can stably be developed even when the usage environment is a low-temperature range (including below the freezing point). The removal of the exhaust gas discharged from the vehicle is thereby carried out at a high efficiency.
  • the internal combustion engine is a diesel engine
  • the vehicle further includes a carbonaceous substance purification section (for example, DPF) downstream of the catalytic reactor in an exhaust gas flow direction.
  • the carbonaceous substance purification section reduces particular matter (PM) in exhaust gas.
  • FIG. 1 is a schematic diagram showing a part of a thermal system of an automobile mounting a catalytic reactor having a warming-up function according to one embodiment of the present invention
  • FIG. 2 is a schematic diagram showing one example of the catalytic reactor of FIG. 1 ;
  • FIG. 3 is a schematic perspective view specifically showing one example of the gas purifier of FIG. 1 ;
  • FIG. 4 is a graph showing relationships between the heat storage temperature and the heat storage density in each compound
  • FIG. 5 is a schematic diagram showing the catalytic reactor of FIG. 1 carrying out warming-up by introducing ammonia gas at a cold start;
  • FIG. 6 is a schematic diagram showing a flow of ammonia gas after warming-up in the catalytic reactor of FIG. 1 ;
  • FIG. 7 is a schematic diagram showing the catalytic reactor of FIG. 1 from which remaining ammonia is being removed by an NH 3 depressurization heat storage reactor;
  • FIG. 8 is a schematic diagram showing a valve state of the catalytic reactor of FIG. 1 in a DPF regeneration mode
  • FIG. 9 is a schematic diagram showing the catalytic reactor of FIG. 1 in which ammonia desorbed from the NH 3 depressurization heat storage reactor is returned to an NH 3 adsorption-desorption apparatus to thereby complete regeneration; and.
  • FIG. 10 is a flowchart showing a warming-up control routine of the catalytic reactor of FIG. 1 .
  • FIGS. 1 to 10 one embodiment of the catalytic reactor and the vehicle equipped therewith according to the present invention will be described.
  • the present invention is not limited to the embodiment described below.
  • a thermal system of an automobile as a vehicle to which a catalytic reactor 20 having a warming-up function is applied will first be described simply, and then, the catalytic reactor 20 mounted on the automobile will be described in detail.
  • an automobile according to the present embodiment is provided with a diesel engine 10 , which is an example of an internal combustion engine, a catalytic reactor 20 for purifying exhaust gas discharged from the diesel engine 10 , and a PM removal filter (DPF: Diesel particulate filter) 80 , which is a carbonaceous substance removal section for removing carbonaceous particulate substances (PM) contained in the exhaust gas, in order in the exhaust direction of the exhaust gas.
  • the diesel engine 10 , the catalytic reactor 20 and the like are electrically connected to a controller 100 .
  • the automobile according to the present embodiment is equipped with the diesel engine 10 .
  • PM in the exhaust gas from the diesel engine 10 is deposited on the DPF.
  • the catalytic reactor 20 is exposed to a high-temperature environment of 400° C. or higher by the flow of the exhaust gas of a high temperature reaching 400° C. or higher.
  • the catalytic reactor 20 according to the present embodiment is, as described later, equipped with an NH 3 depressurization heat storage reactor. Since in the catalytic reactor 20 , ammonia is therefore not exposed to a high-temperature environment, the catalytic reactor 20 can retain an ammonia partial pressure in the reactor, that is, a warming-up function, over a long period.
  • a base material for DPF or a DPF catalyst composed of a base material for DPF and a catalytic metal supported thereon is usually used.
  • the DPF is a catalyst composed of a porous wall material such as a honeycomb base material composed of cordierite, silicon carbide, a metal or the like, and catalytic particles supported on the interior or the surface of the wall material.
  • the catalytic particle is composed of a noble metal such as platinum (Pt), palladium (Pd) or rhodium (Rh), and a carrier carrying the noble metal.
  • a catalytic reactor 20 is equipped with a gas purifier 30 for purification of exhaust gas having a purification catalyst and a warming-up heat storage reactor, which is a warming-up mechanism, an NH 3 adsorption-desorption apparatus 60 , which is one example of an ammonia supply section capable of adsorbing and desorbing ammonia gas (hereinafter, abbreviated to NH 3 in some cases), and an NH 3 depressurization heat storage reactor 70 , which is an ammonia pressure reduction section for reducing the ammonia pressure in the apparatuses and pipes by removing ammonia gas (remaining ammonia) remaining in the apparatuses and piping by adsorption.
  • a gas purifier 30 for purification of exhaust gas having a purification catalyst and a warming-up heat storage reactor, which is a warming-up mechanism
  • an NH 3 adsorption-desorption apparatus 60 which is one example of an ammonia supply section capable of adsorbing and desorbing ammonia gas (
  • the catalytic activity of a purification catalyst for purifying exhaust gas is usually low.
  • the temperature of the exhaust gas is low, for example, at the time of engine starting and during the engine operation after the engine starting and until the temperature of the exhaust gas rises, a desired purification performance cannot be attained in some cases. This becomes remarkable particularly when the engine is started under a low-temperature environment such as below the freezing point, and in other cases.
  • the catalytic reactor 20 according to the present embodiment is equipped with the warming-up mechanism using ammonia as a warming-up mechanism to previously warm up the purification catalyst. Hence, the catalytic activity is highly maintained even in a low-temperature environment, and the gas purification is promoted.
  • the warming-up heat storage reactor which is a warming-up mechanism, since utilizing an exothermic reaction accompanying adsorption of ammonia as described below instead of an exothermic reaction utilizing water, can utilize the exothermic reaction even in an environment below the freezing point.
  • the catalytic reactor 20 which is equipped with the NH 3 depressurization heat storage reactor 70 , can remove ammonia remaining in the apparatuses such as the warming-up heat storage reactor and the piping from the apparatuses and piping. Even when the warming-up heat storage reactor reaches a high temperature of 400° C. or higher, the pyrolysis of ammonia contributing to warming-up, and a decrease in the warming-up function accompanying the pyrolysis are thereby prevented.
  • the gas purifier 30 is equipped with a catalytic reaction apparatus 40 , which is one example of a catalytic reaction section for purifying the exhaust gas by the built-in purification catalyst, and the warming-up heat storage reactor 50 , which is one example of a warming-up section having a warming-up function of the purification catalyst.
  • a catalytic reaction apparatus 40 which is one example of a catalytic reaction section for purifying the exhaust gas by the built-in purification catalyst
  • the warming-up heat storage reactor 50 which is one example of a warming-up section having a warming-up function of the purification catalyst.
  • the catalytic reaction apparatus 40 is equipped with a honeycomb monolith base material 42 to form a honeycomb structure as a support base material, and a catalyst layer provided on the support base material. In the catalyst layer, catalyst particles are supported on carriers.
  • gas components such as HC and CO in the exhaust gas are decomposed by the purification catalyst, and removed from the exhaust gas.
  • the support base material include SiC honeycomb base materials, cordierite honeycomb base materials, and metal honeycomb base materials.
  • the catalyst particle include particles of noble metals such as platinum (Pt), palladium (Pd), and rhodium (Rh).
  • the carrier carrying the particles includes particles of oxides such as zirconium dioxide (ZrO 2 ), aluminum oxide (Al 2 O 3 ), silica, silica-alumina, ceria (CeO 2 ), and zeolite.
  • a temperature detection sensor 44 for detecting the temperature of the catalyst layer is attached, and the temperature of the catalyst can be detected at the warming-up or the like.
  • the warming-up heat storage reactor 50 is arranged to cover the outer peripheral surface of the catalytic reaction apparatus 40 to be able to heat-exchange with the purification catalyst in the catalytic reaction apparatus 40 .
  • FIG. 3 shows a specific structure of the warming-up heat storage reactor. As shown in FIG. 3 , the warming-up heat storage reactor 50 is provided with a plurality of plat-like heat storage materials 52 arranged along the outer peripheral surface of the honeycomb monolith base material 42 of the catalytic reaction apparatus 40 , and a porous body member 54 covering over the plurality of heat storage materials 52 and spaces between the heat storage materials (that is, the outer peripheral surface of the base material 42 ).
  • An armor material 56 is arranged on the periphery of the porous body member 54 so as to cover the entire surface of the porous body member; and to the armor material 56 , an NH 3 inlet port 58 , which is an ammonia supply port for introducing ammonia gas (NH 3 ), is attached. That is, the porous body member 54 is arranged between the heat storage materials 52 and the NH 3 inlet port 58 . In the porous body member 54 , flow paths are formed through which NH 3 passes through pores of the porous body member 54 and is able to flow.
  • the heat storage material 52 is formed into a plate shape by pressing a powder of magnesium chloride (MgCl 2 ), which is a chemical heat storage material.
  • MgCl 2 magnesium chloride
  • the heat storage material 52 is constituted by arranging plate-like molded bodies of the heat storage material.
  • the heat storage material 52 may be arranged as a single continuous layer on the entire surface along the outer peripheral surface of the honeycomb monolith base material 42 .
  • the warming-up heat storage reactor 50 is provided with MgCl 2 (magnesium chloride) as a chemical heat storage material.
  • MgCl 2 magnesium chloride
  • the reaction between magnesium chloride and ammonia is the following reversible reaction (1), and the warming-up of the purification catalyst can be repeatedly carried out according to the reaction, in accordance with to requirements. That is, when the reaction proceeds in the right direction in the following reversible reaction (1), ammonia is fixed (adsorbed) on the heat storage material, and the heat generation is caused. When the reaction proceeds in the left direction in the following reversible reaction (1), ammonia is desorbed from the heat storage material, and the heat absorption is caused.
  • the chemical heat storage material is not limited to MgCl 2 , and a compound generating an exothermic reaction at the adsorption of ammonia can be applied.
  • the chemical heat storage material is, from the viewpoint of enhancing the heat storage density in the reactor, preferably metal chlorides, metal bromides, and metal iodides.
  • the chemical heat storage material is more preferably, for example, alkali metal chlorides, alkaline earth metal chlorides, transition metal chlorides, alkali metals bromide, alkaline earth metal bromides, transition metal bromides, alkali metal iodides, alkaline earth metal iodides, and transition metal iodides, and is particularly preferably LiCl, MgCl 2 , CaCl 2 , SrCl 2 , BaCl 2 , MnCl 2 , CoCl 2 , NiCl 2 , MgBr 2 , or MgI 2 .
  • the metal chlorides, metal bromides and metal iodides may be used singly or in combinations of two or more.
  • FIG. 4 shows, for each compound of LiCl, MgCl 2 , CaCl 2 , SrCl 2 , BaCl 2 , MnCl 2 , CoCl 2 , NiCl 2 , MgBr 2 , and MgI 2 , a relationship between the heat storage temperature (° C.) and the heat storage density (kJ/kg).
  • the heat storage temperature (° C.) indicates one example of a temperature at which ammonia can be desorbed.
  • the heat storage density (kJ/kg) indicates a heat quantity (kJ) capable of being absorbed by desorption of ammonia per kilogram of the each compound. As shown in FIG.
  • LiCl, MgCl 2 , CaCl 2 , SrCl 2 , BaCl 2 , MnCl 2 , CoCl 2 and NiCl 2 indicate high heat storage densities of about 800 kJ/kg to 1,470 kJ/kg.
  • the heat storage temperature depends on the kind of the compound, and is in the range of about 30° C. to 300° C.
  • the kind of the compound can suitably be selected according to the desired ammonia pressure and temperature. Therefore, the breadths of the ammonia pressure and temperature being able to be selected according to an object of the heat utilization are made large.
  • the adsorption temperature of ammonia is desired to be made low, BaCl 2 , CaCl 2 or SrCl 2 can be selected.
  • MgCl 2 , MnCl 2 , CoCl 2 , NiCl 2 , MgBr 2 , or MgI 2 can be selected.
  • a molding method is not particularly limited.
  • a known molding method such as pressure molding or extrusion is applicable to, for example, a heat storage material (or a slurry containing the heat storage material) containing a chemical heat storage material and, as required, other components such as a binder.
  • the pressure at the molding can be made to be, for example 20 to 100 MPa, and is preferably 20 to 40 MPa.
  • an activated carbon as a physical adsorbent to adsorb ammonia is provided in the interior of the NH 3 adsorption-desorption apparatus 60 .
  • the NH 3 adsorption-desorption apparatus 60 communicates with the warming-up heat storage reactor 50 through an NH 3 flow pipe 62 through which NH 3 is flowed.
  • the NH 3 adsorption-desorption apparatus 60 at the warming-up of the purification catalyst, discharges ammonia gas and supplies the ammonia gas to the warming-up heat storage reactor 50 , and after the warming-up termination, again adsorbs ammonia gas discharged from the warming-up heat storage reactor 50 and recovers the ammonia gas. In such a manner, the NH 3 adsorption-desorption apparatus 60 transfers ammonia to and from the warming-up heat storage reactor 50 .
  • an adsorbent capable of adsorbing ammonia reduces the heat quantity necessary for the fixation and desorption of ammonia, and thus can make ammonia to be easily adsorbed and desorbed in a lower energy.
  • the heat quantity necessary for the fixation and desorption of 1 mole of ammonia is 40 to 60 kJ/mol for a chemical heat storage material (for example, LiCl, MgCl 2 , CaCl 2 , SrCl 2 , BaCl 2 , MnCl 2 , CoCl 2 , NiCl 2 , MgBr 2 or MgI 2 ), that can be suppressed to 20 to 30 kJ/mol for the physical adsorbent.
  • the NH 3 adsorption-desorption apparatus 60 communicates with the warming-up heat storage reactor 50 through the NH 3 flow pipe 62 . If there are differences in ammonia pressure between the NH 3 adsorption-desorption apparatus 60 , and the warming-up heat storage reactor 50 and the NH 3 flow pipe 62 , the pressure differences can flow ammonia gas therebetween. For example, when the purification catalyst is warmed up, the ammonia partial pressure in the NH 3 adsorption-desorption apparatus 60 is higher than the ammonia partial pressure in the warming-up heat storage reactor 50 and the NH 3 flow pipe 62 due to adsorbed ammonia. Therefore, by making valves V 1 and V 2 attached to the NH 3 flow pipe 62 in the opened state, ammonia gas can be supplied to the warming-up heat storage reactor 50 .
  • the temperature of the warming-up heat storage reactor 50 Due to the heat generation by supply of ammonia, the temperature of the warming-up heat storage reactor 50 is raised. Since the heat absorption and generation caused by the desorption and adsorption of ammonia in the adsorbent is based on a fixed reversible reaction, for example, by regulating the NH 3 partial pressure in the warming-up heat storage reactor 50 in a certain range, the temperature of the warming-up heat storage reactor 50 is maintained at a desired temperature (a constant temperature near 150° C.)
  • a porous body member can be used as the adsorbent.
  • the pore diameter of the porous body member is preferably 10 nm or smaller from the viewpoint of more improving the reactivity of the fixation and desorption of ammonia by adsorption (preferably physical adsorption).
  • the lower limit value of the pore diameter is preferably 0.5 nm from the viewpoint of the production suitability and the like.
  • the porous body member is preferably a primary particle aggregate obtained by aggregating primary particles having an average primary particle diameter of 50 ⁇ m or smaller.
  • the lower limit of the average primary particle diameter is preferably 1 ⁇ m from the viewpoint of the production suitability and the like.
  • Examples of the adsorbent include, in addition to the activated carbon used in the present embodiment, mesoporous silica, zeolite, silica gel and clay minerals.
  • the activated carbon has a specific surface area by BET method of preferably 500 m 2 /g or larger and 2,500 m 2 /g or smaller, and more preferably 1,000 m 2 /g or larger and 2,500 m 2 /g or smaller.
  • the clay minerals may be non-bridged clay minerals, or may be bridged clay minerals. Examples of the clay mineral include sepiolite.
  • the kind of the adsorbent (preferably a porous body member) can suitably be selected according to the pressure and temperature of ammonia.
  • the adsorbent preferably contains at least an activated carbon from the viewpoint of more improving the reactivity of the fixation and desorption of ammonia by adsorption.
  • the content ratio of the adsorbent in the heat storage material is, from the viewpoint of more highly maintaining the reactivity of the fixation and desorption of ammonia, preferably 80% by volume or higher, and more preferably 90% by volume or higher.
  • the heat storage material When the heat storage material using the adsorbent is utilized as a molded body, the heat storage material preferably contains, in addition to the adsorbent, a binder.
  • the incorporation of the binder since making the shape of the molded body to be more easily maintained, more improves the reactivity of the fixation and desorption of ammonia by adsorption.
  • the heat storage material may contain, as required, in addition to the adsorbent and the binder, other components. Examples of the other components include heat-conductive inorganic materials such as carbon fibers and metal fibers.
  • the binder is preferably a water-soluble binder.
  • the water-soluble binder include polyvinyl alcohols and trimethyl cellulose.
  • the content ratio of the binder in the heat storage material is, from the viewpoint of more effectively maintaining the shape of the molded body, preferably 5% by volume or higher, and more preferably 10% by volume or higher.
  • a molding method of the molded body is not particularly limited.
  • the method include a method for molding, for example, a heat storage material (or a slurry containing the heat storage material) containing an adsorbent (and as required, a binder and other components) by known molding means such as pressure molding or extrusion.
  • the pressure at the molding can be made to be, for example 20 to 100 MPa, and is preferably 20 to 40 MPa.
  • the NH 3 depressurization heat storage reactor 70 In the interior of the NH 3 depressurization heat storage reactor 70 , a chemical heat storage material as an ammonia fixation section to fix ammonia is provided.
  • the NH 3 depressurization heat storage reactor 70 is a low-temperature operation type heat storage reactor.
  • the NH 3 depressurization heat storage reactor 70 is connected to a midway section of the NH 3 flow pipe 62 through an NH 3 flow pipe 72 .
  • the NH 3 depressurization heat storage reactor 70 communicates with the warming-up heat storage reactor 50 and the NH 3 adsorption-desorption apparatus 60 through the NH 3 flow pipes 62 and 72 .
  • the NH 3 depressurization heat storage reactor 70 after the warming-up termination of the purification catalyst, recovers ammonia gas by adsorbing ammonia gas present in the warming-up heat storage reactor 50 and the NH 3 flow pipe 62 . That is, after the warming-up termination of the purification catalyst, when the warming-up heat storage reactor 50 is further heated along with a temperature rise of the warming-up exhaust gas, NH 3 adsorbed by the warming-up heat storage reactor 50 (heat storage material 52 ) is desorbed from the heat storage reactor 50 , and desorbed NH 3 is returned to the NH 3 adsorption-desorption apparatus 60 through the NH 3 flow pipe 62 and again adsorbed by the NH 3 adsorption-desorption apparatus 60 .
  • the NH 3 depressurization heat storage reactor 70 is a low-temperature operation type heat storage reactor equipped with the heat storage material exhibiting a high NH 3 adsorption power at a lower temperature than the NH 3 adsorption-desorption apparatus 60 . Hence, the remaining NH 3 is removed and the ammonia pressure in the warming-up heat storage reactor 50 and the NH 3 flow pipe 62 can be reduced.
  • the heat storage material provided in the NH 3 depressurization heat storage reactor 70 may be a heat storage material using chemical adsorption or physical adsorption as long as the material is able to reduce the ammonia pressure in the reactor and the piping.
  • the NH 3 depressurization heat storage reactor 70 can be equipped with, but not limited to the chemical heat storage material used in the present embodiment, another chemical heat storage material, or a physical adsorbent to fix NH 3 by physical adsorption.
  • a chemical adsorbent is suitably used from the viewpoint of rapidly reducing the ammonia pressure in the apparatuses and piping.
  • the use of the chemical heat storage material since the chemical heat storage material has a high heat storage density and is excellent in the adsorbability of ammonia gas, can ensure a higher NH 3 adsorbability in the NH 3 depressurization heat storage reactor 70 than in the NH 3 adsorption-desorption apparatus 60 .
  • the chemical heat storage material of the ammonia fixation section is preferably a metal chloride.
  • the chemical heat storage material is more preferably, for example, a chloride of an alkali metal, a chloride of an alkaline earth metal, or a chloride of a transition metal.
  • Examples of the chemical heat storage material include the compounds similar to those for the warming-up heat storage reactor 50 .
  • the chemical heat storage material causes an exothermic reaction at the ammonia adsorption, and causes an endothermic reaction at the ammonia desorption.
  • the NH 3 depressurization heat storage reactor 70 using the chemical heat storage material adsorbs ammonia by being regulated to a temperature easily generating heat, and discharges ammonia by being heated to thereby regenerate the heat storage material.
  • the chemical heat storage material of the NH 3 depressurization heat storage reactor 70 is suitably BaCl 2 , CaCl 2 or SrCl 2 in the point of ensuring a good adsorption effect of ammonia in a low thermal energy.
  • the details of the physical adsorbents have already been described.
  • the chemical heat storage material of the NH 3 depressurization heat storage reactor 70 is molded by press-molding a powder of calcium chloride (CaCl 2 ).
  • CaCl 2 can lead to such an anticipation that the NH 3 depressurization heat storage reactor 70 has a higher NH 3 adsorbability than the warming-up heat storage reactor 50 using MgCl 2 in a low-temperature region.
  • the adsorption-desorption of ammonia is carried out according to the following reversible reaction (2), accompanied by heat generation and absorption.
  • the NH 3 depressurization heat storage reactor 70 is connected to the warming-up heat storage reactor 50 and the NH 3 adsorption-desorption apparatus 60 through the NH 3 flow pipes 62 and 72 .
  • Ammonia desorbed from the warming-up heat storage reactor 50 by a temperature rise after the warming-up termination of the warming-up heat storage reactor 50 is again adsorbed to the NH 3 adsorption-desorption apparatus 60 , and thereafter, by making a valve V 3 attached to the NH 3 flow pipe 72 to be in the opened state, ammonia gas remaining in the warming-up heat storage reactor 50 and the NH 3 flow pipes 62 and 72 can be recovered. It can be thereby avoided that ammonia is decomposed in DPF by being heated to 400° C. or higher by a high-temperature exhaust gas flowed when PM is subjected to a combustion treatment in DPF.
  • the warming-up heat storage reactor 50 which is the warming-up section, contains MgCl 2 , MnCl 2 , CoCl 2 , NiCl 2 , MgBr 2 or MgI 2 as the heat storage material 52
  • the NH 3 depressurization heat storage reactor 70 contains BaCl 2 , CaCl 2 or SrCl 2 as the heat storage material.
  • the temperature range where the catalytic reactor is operated can be made to be in the range of ⁇ 30° C. or higher and 250° C. or lower.
  • the ammonia pressure (operating pressure) in the catalytic reactor can be made to be, for example, in the range of 0.1 atm or higher and 10 atm or lower.
  • the purification catalyst of the catalytic reaction apparatus 40 is in a low temperature.
  • the valves V 1 and V 2 are opened to thereby introduce ammonia gas from the NH 3 adsorption-desorption apparatus 60 to the warming-up heat storage reactor 50 .
  • the NH 3 adsorption-desorption apparatus 60 is in such a state in which ammonia is beforehand adsorbed.
  • ammonia gas is transferred to the warming-up heat storage reactor 50 through the NH 3 flow pipe 62 by the differential pressure by following the opening of the valves.
  • the ammonia gas introduced from the NH 3 inlet port 58 flows in the porous body member 54 and contacts each of the heat storage materials 52 .
  • Each of the heat storage materials reacts with ammonia and generates heat.
  • the purification catalyst is warmed up to a predetermined temperature (for example, 150° C.).
  • a predetermined temperature for example, 150° C.
  • the exhaust gas of, for example, 100° C. discharged from the diesel engine is discharged after being purified with the purification catalyst of, for example, 150° C.
  • the NH 3 adsorption-desorption apparatus 60 does not necessarily need a mechanism of heating the physical adsorbent.
  • a heater which heats the physical adsorbent by heat exchange between the physical adsorbent and a heat medium through flowing the heat medium such as water, alcohol, or mixture thereof, may be arranged as a heat exchanger, from the viewpoint of more effectively carrying out desorption of ammonia in a low-temperature environment such as below the freezing point.
  • the purification catalyst When the purification catalyst is warmed up to a target temperature (for example, 150° C.), the warming-up is terminated. After the termination of the warming-up, the chemical heat storage material of the warming-up heat storage reactor 50 is also heated along with the temperature rise of the purification catalyst due to the temperature rise of the exhaust gas. As shown in FIG. 6 , if the exhaust gas of, for example, 200° C. is delivered to the catalytic reaction apparatus 40 with the valves V 1 and V 2 , which are maintained in the opened state, NH 3 coordinated (adsorbed) to MgCl 2 is desorbed.
  • a target temperature for example, 150° C.
  • the ammonia pressure in the warming-up heat storage reactor 50 thereby becomes higher than the ammonia pressure in the NH 3 adsorption-desorption apparatus 60 and the NH 3 flow pipe 62 .
  • the ammonia gas returns to the NH 3 adsorption-desorption apparatus 60 through the NH 3 flow pipe 62 due to the differential pressure.
  • the ammonia gas adsorbed by the warming-up heat storage reactor 50 (heat storage material 52 ) at the warming-up is desorbed by the temperature rise of the purification catalyst along with the temperature rise of the exhaust gas, and again adsorbed to the NH 3 adsorption-desorption apparatus 60 .
  • the NH 3 adsorption-desorption apparatus 60 is regenerated (heat storage) for preparation for the succeeding warming-up. Since the NH 3 desorption at this time is an endothermic reaction, the temperature of the exhaust gas becomes lower than the temperature of the exhaust gas at the introduction.
  • the valve V 2 is closed. The regeneration completion can be determined from the ammonia pressure in the NH 3 adsorption-desorption apparatus 60 caused by the ammonia adsorbed in the NH 3 adsorption-desorption apparatus 60 .
  • ammonia of a high pressure (for example, 4 atm) still remains in the warming-up heat storage reactor 50 and the NH 3 flow pipe 62 and a part of the NH 3 flow pipe 72 (a part excluding the section between the valve V 3 and the NH 3 depressurization heat storage reactor 70 ).
  • a high pressure for example, 4 atm
  • the differential pressure between the NH 3 adsorption-desorption apparatus 60 and the NH 3 flow pipe 62 is small, all of the ammonia gas in the NH 3 flow pipe 62 and the above-mentioned part of the NH 3 flow pipe 72 does not completely return to the NH 3 adsorption-desorption apparatus 60 .
  • the valve V 3 is opened with the valve V 2 being closed to thereby connect the warming-up heat storage reactor 50 and the NH 3 depressurization heat storage reactor 70 .
  • the valve V 1 remains in the opened state.
  • ammonia gas remaining in the reactors and the pipes is introduced to the NH 3 depressurization heat storage reactor 70 , which is a low-temperature operation type heat storage apparatus capable of coordination-bonding and adsorbing ammonia at a low pressure, and adsorbed to the chemical heat storage material.
  • the NH 3 depressurization heat storage reactor 70 is further equipped with a flow pipe to flow a heat medium, and a heater 74 , which heats the chemical heat storage material by heat exchange between the chemical heat storage material and the heat medium through the flow of the heat medium, is provided as a heat exchanger.
  • the heater 74 is equipped with a circulation system utilizing a flow pipe to circulate the heat medium.
  • the flow pipe is provided with a heater (not shown in Fig.) that heats the heat medium to a desired temperature.
  • the heat medium water, an organic solvent (an alcohol such as ethanol, a glycol such as ethylene glycol, or the like), or a mixture thereof can be used.
  • a treatment to regenerate the DPF is carried out by burning and removing PM deposited on the DPF.
  • the regeneration treatment of the PM removal filter (DPF) 80 is carried out at a high temperature of, for example, 600° C., as shown in FIGS. 1 and 8 , a high-temperature gas of 600° C. is flowed also to the catalytic reaction apparatus 40 arranged upstream of the DPF 80 in the exhaust gas flow direction. Therefore, the warming-up heat storage reactor 50 is exposed to a high-temperature environment of 600° C.
  • the warming-up heat storage reactor 50 and a part of the NH 3 flow pipe 62 connected thereto are in such a state in which remaining ammonia has already been removed, the decrease of the warming-up function by the pyrolysis of the remaining ammonia is prevented.
  • the warming-up function and the purification function of the exhaust gas of the catalyst in the gas purifier 30 are thereby enabled to be stably maintained over a long period.
  • valves V 1 to V 3 are closed as described above, as shown in FIG. 9 , the valves V 2 and V 3 are opened to thereby connect the NH 3 adsorption-desorption apparatus 60 with the NH 3 depressurization heat storage reactor 70 .
  • the valve V 1 remains in the closed state.
  • the chemical heat storage material in the NH 3 depressurization heat storage reactor 70 is heated to about 70° C. by the heater 74 located in the NH 3 depressurization heat storage reactor 70 as described before.
  • the physical adsorbent in the NH 3 adsorption-desorption apparatus 60 since generating heat by adsorption of ammonia, is cooled by being exposed to the outside air.
  • the chemical heat storage material (CaCl 2 ) built in the NH 3 depressurization heat storage reactor 70 is able to desorb NH 3 at a low temperature of about 70° C. (the reversible reaction (2): CaCl 2 .8NH 3 +Q 2 ⁇ CaCl 2 .2NH 3 +6NH 3 ).
  • Ammonia gas is transferred and again adsorbed to the NH 3 adsorption-desorption apparatus 60 by the differential pressure between the ammonia pressure in the NH 3 depressurization heat storage reactor 70 and the ammonia pressure in the NH 3 adsorption-desorption apparatus 60 and the NH 3 flow pipe 72 at this time.
  • the NH 3 adsorption-desorption apparatus 60 is thereby regenerated into the initial state in which ammonia is adsorbed, and the warming-up similar to the above can be carried out repeatedly.
  • the warming-up function by the warming-up heat storage reactor 50 can be stably maintained over a long period, and the catalytic activity of the purification catalyst can be stably maintained irrespective of the usage environment.
  • a control routine by a controller 100 which is a control section for controlling the diesel engine (internal combustion engine) according to the present embodiment, will be described.
  • a warming-up control routine for removing ammonia gas will be mainly described by reference to FIG. 10 , in association with warming-up of the catalytic reaction apparatus 40 in the catalytic reactor 20 and the execution of the DPF regeneration mode for regenerating the DPF by burning and removing PM deposited on the DPF after the warming-up.
  • the system When the ignition switch (IG switch) is turned on to thereby turn on the power source of the controller 100 , the system is started, and the warming-up control routine for controlling the warming-up in the catalytic reactor 20 is executed.
  • the starting of the system may be made automatically or manually.
  • step 100 it is first determined whether the purification function by the purification catalyst of the catalytic reaction apparatus 40 normally works, that is, whether warming-up of the purification catalyst is necessary. That is, in step 100 , the temperature of the catalyst is detected by the temperature detection sensor 44 attached to the purification catalyst, and it is determined whether the detected temperature is lower than a predetermined temperature T (for example, 180° C.) at which the purification of the exhaust gas can be carried out.
  • a predetermined temperature T for example, 180° C.
  • step 100 when it is determined that the detected temperature is lower than the predetermined temperature T, and has not reached a temperature at which the purification of the exhaust gas can be reliably carried out, since the temperature of the catalyst needs to be raised, the process proceeds to step 120 .
  • the present routine process is terminated.
  • step 120 the ammonia pressure of the NH 3 adsorption-desorption apparatus 60 is measured for preparation for warming-up, and it is determined whether the ammonia pressure exceeds a predetermined pressure P, that is, whether ammonia is in such a state in which the ammonia of an amount necessary for warming-up is adsorbed in the NH 3 adsorption-desorption apparatus 60 .
  • a predetermined pressure P that is, whether ammonia is in such a state in which the ammonia of an amount necessary for warming-up is adsorbed in the NH 3 adsorption-desorption apparatus 60 .
  • the valves V 1 and V 2 are opened. At this time, the valve V 3 remains in the closed state.
  • step 140 after the valves V 1 and V 3 are opened to thereby make remaining ammonia to be adsorbed to the NH 3 depressurization heat storage reactor 70 , the valve V 1 is closed and the valves V 2 and V 3 are opened.
  • the heater 74 is turned on to thereby heat the chemical heat storage material of the NH 3 depressurization heat storage reactor 70 by the heater 74 .
  • ammonia adsorbed in the NH 3 depressurization heat storage reactor 70 is desorbed from the NH 3 depressurization heat storage reactor 70 , and the desorbed ammonia is transferred to the NH 3 adsorption-desorption apparatus 60 .
  • step 120 it is determined whether the ammonia pressure exceeds the predetermined pressure P. Until it is determined that the ammonia pressure exceeds the predetermined pressure P, steps 120 , 140 and 160 are similarly repeated. When it is determined that the ammonia pressure exceeds the pressure P, the process proceeds to the following step 180 , and the valves V 1 and V 2 are opened.
  • the temperature of the purification catalyst is self-regulated to a predetermined temperature (for example, 150° C.), which is a target temperature.
  • the temperature of the purification catalyst is raised along with the temperature rise of the exhaust gas, and also the temperature of the chemical heat storage material of the warming-up heat storage reactor 50 is resultantly raised.
  • the valves V 1 and V 2 being maintained in the opened state, when the exhaust gas of, for example, 200° C. is flowed in the catalytic reaction apparatus 40 , NH 3 coordinated (adsorbed) to MgCl 2 (chemical heat storage material) of the warming-up heat storage reactor 50 is desorbed.
  • the ammonia pressure in the warming-up heat storage reactor 50 becomes higher than the ammonia pressure in the NH 3 adsorption-desorption apparatus 60 and the NH 3 flow pipe 62 , and ammonia gas returns to the NH 3 adsorption-desorption apparatus 60 through the NH 3 flow pipe 62 by the differential pressure, and the regeneration is started.
  • step 200 it is determined whether the ammonia pressure in the NH 3 adsorption-desorption apparatus 60 exceeds a predetermined pressure value P 1 (P 1 ⁇ P) indicating that a certain or greater amount of NH 3 has been adsorbed.
  • P 1 a predetermined pressure value
  • step 200 when it is determined that the ammonia pressure in the NH 3 adsorption-desorption apparatus 60 exceeds the pressure value P 1 , since the regeneration of the NH 3 adsorption-desorption apparatus 60 , which automatically proceeds along with the temperature rise of the catalyst is terminated, in step 220 , the valve V 2 is closed, and the valve V 3 is opened. The valve V 1 remains in the opened state.
  • the interior of the warming-up heat storage reactor 50 and the interior of the NH 3 flow pipe 62 are in a state in which high-pressure ammonia remains.
  • the valve V 3 By opening the valve V 3 , the remaining ammonia is adsorbed and rapidly removed by the low-temperature operation type NH 3 depressurization heat storage reactor 70 . In such a manner, the ammonia pressure in the warming-up heat storage reactor 50 and the NH 3 flow pipe 62 is reduced.
  • step 200 when it is determined that the ammonia pressure in the NH 3 adsorption-desorption apparatus 60 is lower than the pressure value P 1 , since the warming-up has not proceeded, or the regeneration of the NH 3 adsorption-desorption apparatus 60 after the warming-up has not proceeded, the process returns to step 180 , and steps 180 and 200 are similarly repeated.
  • step 240 it is determined whether the DPF regeneration mode for burning and removing PM deposited on the DPF needs to be executed.
  • step 240 when it is determined that the DPF regeneration mode needs to be executed, in the following step 260 , the valves V 1 and V 3 are closed in order to avoid pyrolysis of ammonia due to the flow of the exhaust gas of a high temperature at the DPF regeneration.
  • step 240 when it is determined that the DPF regeneration mode does not need to be executed, since there is no fear of the pyrolysis of ammonia, the process proceeds to step 340 , and all the valves (V 1 to V 3 ) are closed and the process of the present routine is terminated.
  • step 280 the NH 3 depressurization heat storage reactor 70 is heated by the heater 74 in order to return the remaining ammonia adsorbed in the NH 3 depressurization heat storage reactor 70 to the NH 3 adsorption-desorption apparatus 60 , irrespective of before or after the execution of the DPF regeneration mode.
  • step 300 the valves V 2 and V 3 are opened to connect the NH 3 adsorption-desorption apparatus 60 with the NH 3 depressurization heat storage reactor to thereby return the remaining ammonia to the NH 3 adsorption-desorption apparatus 60 .
  • step 320 it is determined whether the ammonia pressure in the NH 3 adsorption-desorption apparatus 60 is restored to a predetermined value P 3 or higher, which can be regarded to be substantially the same as the predetermined pressure P before the start of the warming-up.
  • a predetermined value P 3 or higher which can be regarded to be substantially the same as the predetermined pressure P before the start of the warming-up.
  • step 320 when it is determined that the ammonia pressure in the NH 3 adsorption-desorption apparatus 60 is lower than the predetermined value P 3 , it is assumed that ammonia gas still remains in the NH 3 depressurization heat storage reactor 70 and the NH 3 flow pipe 62 . Since the regeneration of the NH 3 adsorption-desorption apparatus 60 is not completed, by repeating step 320 until the ammonia pressure reaches the predetermined value P 3 or higher, the completion of the regeneration is watched and waited.
  • step 340 when it is determined that the ammonia pressure in the NH 3 adsorption-desorption apparatus 60 is the predetermined value P 3 or higher, the process proceeds to step 340 , and all the valves are closed, and the process of the present routine is thereafter terminated.
  • the case where MgCl 2 and CaCl 2 are used as the chemical heat storage materials, and the activated carbon, which is a physical adsorbent, is used as the adsorbent capable of adsorbing ammonia has been mainly described.
  • the chemical heat storage materials and the adsorbent are not limited thereto. If other chemical heat storage materials and adsorbents described above other than MgCl 2 , CaCl 2 and the activated carbon are used, the same advantages as in the above embodiment are attained.
  • the case where the chemical heat storage material is used as the ammonia fixation section of the NH 3 depressurization heat storage reactor 70 has been mainly described, but a physical adsorbent may be used in place of the chemical heat storage material. Also in this case, by making the adsorbability of ammonia of the ammonia fixation section of the NH 3 depressurization heat storage reactor 70 superior to that of the chemical heat storage material of the warming-up heat storage reactor 50 , the same advantages as in the above embodiment using the chemical heat storage material can be attained.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
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  • Organic Chemistry (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
US14/419,265 2012-08-09 2013-08-09 Catalytic reactor and vehicle equipped with said catalytic reactor Abandoned US20150192049A1 (en)

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JP2013165453A JP5860852B2 (ja) 2012-08-09 2013-08-08 触媒反応装置及び車両
JP2013-165453 2013-08-08
PCT/JP2013/071687 WO2014025024A1 (fr) 2012-08-09 2013-08-09 Réacteur catalytique et véhicule équipé dudit réacteur catalytique

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US20170120726A1 (en) * 2014-05-16 2017-05-04 Perkins Engines Company Limited Heating and Cooling System for a Vehicle
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US10180094B2 (en) 2015-08-10 2019-01-15 Toyota Jidosha Kabushiki Kaisha Internal combustion engine
US20170058738A1 (en) * 2015-08-28 2017-03-02 General Electric Company Treatment of emissions in power plants
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JP2017129080A (ja) * 2016-01-21 2017-07-27 株式会社豊田中央研究所 排ガス循環システム
US11686236B1 (en) 2022-02-18 2023-06-27 Saudi Arabian Oil Company Device for the reduction of ammonia and nitrogen oxides emissions
CN116927933A (zh) * 2023-08-26 2023-10-24 福州大学 一种车辆用高氨柴比发动机尾气净化装置及方法

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WO2014025024A1 (fr) 2014-02-13
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