JP2007292010A - Purification of exhaust gas exhausted from internal combustion engine and including nitrogen oxides - Google Patents

Purification of exhaust gas exhausted from internal combustion engine and including nitrogen oxides Download PDF

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JP2007292010A
JP2007292010A JP2006123070A JP2006123070A JP2007292010A JP 2007292010 A JP2007292010 A JP 2007292010A JP 2006123070 A JP2006123070 A JP 2006123070A JP 2006123070 A JP2006123070 A JP 2006123070A JP 2007292010 A JP2007292010 A JP 2007292010A
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exhaust gas
fuel cell
hydrogen
purification system
nitrogen oxides
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Hiroyuki Kawai
博之 川合
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Toyota Motor Corp
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Priority to PCT/IB2007/001009 priority patent/WO2007125394A1/en
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Priority to CNA200780008024XA priority patent/CN101394914A/en
Priority to US12/297,353 priority patent/US20090084085A1/en
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    • 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
    • B01D53/32—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 by electrical effects other than those provided for in group B01D61/00
    • B01D53/326—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 by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Multi-step processes
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/0892—Electric or magnetic treatment, e.g. dissociation of noxious components
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0681—Reactant purification by the use of electrochemical cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

<P>PROBLEM TO BE SOLVED: To purify exhaust gas exhausted from an internal combustion engine and including nitrogen oxides without bringing reduction of energy efficiency and enlargement of a system in a system equipped with the internal combustion engine as a power source. <P>SOLUTION: The exhaust gas exhausted from the engine 10 and including the nitrogen oxides is supplied to a cathode of a fuel cell 20, hydrogen-rich gas generated by a hydrogen gas generating device 30 is supplied to an anode of the fuel cell 20, and electric power is generated by electrochemical reaction of hydrogen with the nitride oxides, and the nitride oxides are decomposed. A hydrogen separation type fuel cell operated at a temperature almost equivalent to a temperature of the exhaust gas exhausted from the engine 10 is applied to the fuel cell 20. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、内燃機関から排気される窒素酸化物を含む排気ガスを浄化する技術に関するものである。   The present invention relates to a technology for purifying exhaust gas containing nitrogen oxides exhausted from an internal combustion engine.

従来、車両等の移動体の動力源として、内燃機関が用いられている。この内燃機関では、燃料が燃焼され、排気ガスが排気される。そして、この排気ガスには、窒素酸化物（ＮＯｘ）が含まれる。この窒素酸化物は、大気汚染物質であるため、通常、吸着剤によって吸着除去されたり、ＮＯｘ吸蔵還元触媒等の触媒や、プラズマ照射によって分解されたりする。   Conventionally, an internal combustion engine has been used as a power source for a moving body such as a vehicle. In this internal combustion engine, fuel is burned and exhaust gas is exhausted. The exhaust gas contains nitrogen oxides (NOx). Since this nitrogen oxide is an air pollutant, it is usually adsorbed and removed by an adsorbent, or decomposed by a catalyst such as a NOx storage reduction catalyst or plasma irradiation.

近年では、窒素酸化物を電気化学的に分解する技術も提案されている。例えば、下記特許文献１には、溶融炭酸塩型燃料電池を用いて、燃焼プラントから排出される排出ガスに含まれる窒素酸化物を電気化学的に分解する技術が記載されている。   In recent years, techniques for electrochemically decomposing nitrogen oxides have also been proposed. For example, Patent Document 1 listed below describes a technique for electrochemically decomposing nitrogen oxides contained in exhaust gas discharged from a combustion plant using a molten carbonate fuel cell.

特開２００１−７０７４８号公報JP 2001-70748 A

上記特許文献１に記載された技術を、内燃機関を動力源として用いる車両等の移動体に適用することも可能ではある。しかし、溶融炭酸塩型燃料電池の運転温度は、６００〜７００（℃）と非常に高温であるため、上記特許文献１に記載された技術を、内燃機関を動力源として用いる車両等の移動体に適用する場合、内燃機関の排気ガスを溶融炭酸塩型燃料電池の運転温度付近まで予熱する必要があり、内燃機関の排気ガスを予熱するための予熱装置を併せて搭載する必要があった。これは、内燃機関を備えるシステムのエネルギ効率の低下や、システムの大型化を招く。   It is also possible to apply the technique described in Patent Document 1 to a moving body such as a vehicle using an internal combustion engine as a power source. However, since the operating temperature of the molten carbonate fuel cell is as high as 600 to 700 (° C.), the technique described in Patent Document 1 described above is used as a moving body such as a vehicle using an internal combustion engine as a power source. When it is applied to the above, it is necessary to preheat the exhaust gas of the internal combustion engine to near the operating temperature of the molten carbonate fuel cell, and it is necessary to mount a preheating device for preheating the exhaust gas of the internal combustion engine. This leads to a decrease in energy efficiency of the system including the internal combustion engine and an increase in the size of the system.

本発明は、上述の課題を解決するためになされたものであり、内燃機関を動力源として備えるシステムにおいて、エネルギ効率の低下や、システムの大型化を招くことなく、内燃機関から排気される窒素酸化物を含む排気ガスを浄化する技術を提供することを目的とする。   The present invention has been made to solve the above-described problems, and in a system including an internal combustion engine as a power source, nitrogen exhausted from the internal combustion engine without causing a reduction in energy efficiency or an increase in the size of the system. An object of the present invention is to provide a technique for purifying exhaust gas containing oxides.

上述の課題の少なくとも一部を解決するため、本発明では、以下の構成を採用した。
本発明の排気ガス浄化システムは、
内燃機関から排気される窒素酸化物を含む排気ガスを浄化する排気ガス浄化システムであって、
前記排気ガスの温度を含む所定の温度範囲内で運転される燃料電池であって、所定の燃料ガスと、前記排気ガスに含まれる窒素酸化物との電気化学反応によって、前記窒素酸化物を分解するとともに、発電する燃料電池を備えることを要旨とする。 In order to solve at least a part of the above-described problems, the present invention employs the following configuration.
The exhaust gas purification system of the present invention comprises:
An exhaust gas purification system for purifying exhaust gas containing nitrogen oxides exhausted from an internal combustion engine,
The fuel cell is operated within a predetermined temperature range including the temperature of the exhaust gas, and the nitrogen oxide is decomposed by an electrochemical reaction between the predetermined fuel gas and the nitrogen oxide contained in the exhaust gas. In addition, the gist is to provide a fuel cell for generating electricity.

本発明では、燃料電池が、酸化剤ガスとして内燃機関から排気される排気ガスに含まれる窒素酸化物を利用し、燃料ガスとして水素を利用して、水素と窒素酸化物との電気化学反応によって発電する。この際、燃料電池のアノードでの反応は、Ｈ2→２Ｈ+＋２ｅ-で表され、カソードでの反応は、（２／Ｘ）ＮＯX＋２Ｈ+＋２ｅ-→（１／Ｘ）Ｎ2＋Ｈ2Ｏで表される。そして、窒素酸化物は、２ＮＯX＋ＸＨ2→Ｎ2＋ＸＨ2Ｏで表される反応によって分解される。また、本発明では、燃料電池は、内燃機関から排気される排気ガスの温度を含む所定の温度範囲内で運転される燃料電池であるので、内燃機関の排気ガスを予熱することなく、燃料電池のカソードに供給することができる。したがって、排気ガス浄化システムに、内燃機関の排気ガスを予熱するための予熱装置を設ける必要がなく、システムのエネルギ効率の向上、および、システムの小型化を図ることができる。つまり、本発明によって、エネルギ効率の低下や、システムの大型化を招くことなく、内燃機関から排気される窒素酸化物を含む排気ガスを浄化することができる。 In the present invention, the fuel cell uses nitrogen oxides contained in the exhaust gas exhausted from the internal combustion engine as the oxidant gas, uses hydrogen as the fuel gas, and performs an electrochemical reaction between hydrogen and nitrogen oxides. Generate electricity. At this time, the reaction at the anode of the fuel cell is represented by H 2 → 2H + + 2e − , and the reaction at the cathode is (2 / X) NO x + 2H + + 2e − → (1 / X) N 2 + H 2. Represented by O. Then, nitrogen oxide is decomposed by the reaction represented by 2NO X + XH 2 → N 2 + XH 2 O. In the present invention, since the fuel cell is a fuel cell operated within a predetermined temperature range including the temperature of the exhaust gas exhausted from the internal combustion engine, the fuel cell does not preheat the exhaust gas of the internal combustion engine. Can be supplied to the cathode. Therefore, it is not necessary to provide a preheating device for preheating the exhaust gas of the internal combustion engine in the exhaust gas purification system, so that the energy efficiency of the system can be improved and the system can be downsized. That is, according to the present invention, exhaust gas containing nitrogen oxides exhausted from an internal combustion engine can be purified without causing a decrease in energy efficiency and an increase in the size of the system.

上記排気ガス浄化システムにおいて、
前記燃料電池は、前記燃料ガスとしての水素を選択的に透過させる水素透過性金属層と、プロトン伝導性を有する電解質層とを積層させた電解質膜を備えるものとしてもよい。 In the exhaust gas purification system,
The fuel cell may include an electrolyte membrane in which a hydrogen-permeable metal layer that selectively transmits hydrogen as the fuel gas and an electrolyte layer having proton conductivity are stacked.

本発明では、燃料電池として、水素を選択的に透過させる水素透過性金属層と、プロトン伝導性を有する電解質層とを積層させた電解質膜を備える燃料電池、すなわち、いわゆる水素分離膜型燃料電池を用いる。この水素分離膜型燃料電池の運転温度は、４００（℃）程度であり、一般的な内燃機関の排気ガスの温度と同程度であるので、本発明に適用するのに好適である。また、水素分離膜型燃料電池は、電解質膜が、比較的強度が高い水素透過性金属層を備えるため、電解質膜の強度を維持しつつ、プロトンが伝導する電解質層の厚さを比較的薄くすることができる。したがって、電解質層の膜抵抗を比較的低くすることができる。したがって、本発明に水素分離膜型燃料電池を適用することによって、効率よく窒素酸化物を分解しつつ、発電することができる。   In the present invention, as a fuel cell, a fuel cell including an electrolyte membrane in which a hydrogen-permeable metal layer that selectively permeates hydrogen and an electrolyte layer having proton conductivity is laminated, that is, a so-called hydrogen separation membrane fuel cell. Is used. The operating temperature of this hydrogen separation membrane fuel cell is about 400 (° C.), which is about the same as the temperature of exhaust gas of a general internal combustion engine, and is suitable for application to the present invention. In the hydrogen separation membrane fuel cell, since the electrolyte membrane includes a hydrogen-permeable metal layer having a relatively high strength, the thickness of the electrolyte layer through which protons are conducted is relatively thin while maintaining the strength of the electrolyte membrane. can do. Therefore, the membrane resistance of the electrolyte layer can be made relatively low. Therefore, by applying the hydrogen separation membrane fuel cell to the present invention, it is possible to generate power while efficiently decomposing nitrogen oxides.

なお、水素透過性金属層としては、パラジウム（Ｐｄ）、パラジウム合金などの貴金属や、ＶＡ族元素、例えば、バナジウム（Ｖ）、ニオブ（Ｎｂ）、タンタル（Ｔａ）などを用いることができる。電解質層としては、固体酸化物、例えば、ＢａＣｅＯ3、ＳｒＣｅＯ3系のセラミックスなど、種々の電解質を用いることができる。 As the hydrogen permeable metal layer, a noble metal such as palladium (Pd) or a palladium alloy, or a VA group element such as vanadium (V), niobium (Nb), or tantalum (Ta) can be used. As the electrolyte layer, various electrolytes such as solid oxides such as BaCeO 3 and SrCeO 3 ceramics can be used.

上記いずれかの排気ガス浄化システムにおいて、
前記燃料電池のカソードは、前記電気化学反応を促進するための白金系の触媒を備えるようにすることが好ましい。 In any of the above exhaust gas purification systems,
It is preferable that the cathode of the fuel cell includes a platinum-based catalyst for promoting the electrochemical reaction.

ここで、「白金系の触媒」としては、例えば、白金や、白金・ルテニウム合金等が挙げられる。   Here, examples of the “platinum-based catalyst” include platinum and platinum / ruthenium alloys.

燃料電池のカソードに白金系の触媒を用いることによって、他の触媒を用いるよりも効率よく窒素酸化物を分解することができる。   By using a platinum-based catalyst for the cathode of the fuel cell, nitrogen oxides can be decomposed more efficiently than using other catalysts.

上記いずれかの排気ガス浄化システムにおいて、
さらに、前記燃料電池によって発電された電力を蓄電する二次電池を備えるようにしてもよい。 In any of the above exhaust gas purification systems,
Furthermore, a secondary battery that stores electric power generated by the fuel cell may be provided.

こうすることによって、燃料電池によって発電された電力を、一時的に、二次電池に蓄電しておき、必要に応じて利用することができる。   In this way, the electric power generated by the fuel cell can be temporarily stored in the secondary battery and used as necessary.

本発明は、上述の排気ガス浄化システムとしての構成の他、排気ガスの浄化方法の発明として構成することもできる。また、本発明は、上述の排気ガス浄化システムを搭載した移動体の発明として構成することもできる。なお、それぞれの態様において、先に示した種々の付加的要素を適用することが可能である。   The present invention can be configured as an invention of an exhaust gas purification method in addition to the above-described configuration as an exhaust gas purification system. In addition, the present invention can also be configured as an invention of a moving body equipped with the exhaust gas purification system described above. In addition, in each aspect, it is possible to apply the various additional elements shown above.

以下、本発明の実施の形態について、実施例に基づき以下の順序で説明する。
Ａ．排気ガス浄化システムの構成：
Ｂ．燃料電池の構成：
Ｃ．変形例： Hereinafter, embodiments of the present invention will be described in the following order based on examples.
A. Configuration of exhaust gas purification system:
B. Fuel cell configuration:
C. Variation:

Ａ．排気ガス浄化システムの構成：
図１は、本発明の一実施例としての排気ガス浄化システム１００の概略構成を示す説明図である。本実施例の排気ガス浄化システム１００は、内燃機関を動力源とする車両等の移動体に搭載される。 A. Configuration of exhaust gas purification system:
FIG. 1 is an explanatory diagram showing a schematic configuration of an exhaust gas purification system 100 as an embodiment of the present invention. The exhaust gas purification system 100 of this embodiment is mounted on a moving body such as a vehicle that uses an internal combustion engine as a power source.

図示するように、排気ガス浄化システム１００は、エンジン１０と、燃料電池２０と、水素ガス生成装置３０と、バッテリ４０とを備えている。   As shown in the figure, the exhaust gas purification system 100 includes an engine 10, a fuel cell 20, a hydrogen gas generation device 30, and a battery 40.

エンジン１０は、図示しないガソリンタンクから供給されたガソリンを燃焼し、排気ガスを排気する。なお、この排気ガスの温度は、約４００（℃）である。また、排気ガスには、窒素酸化物（ＮＯｘ）が含まれる。この窒素酸化物は、後述するように、燃料電池２０によって電気化学的に分解される。   The engine 10 burns gasoline supplied from a gasoline tank (not shown) and exhausts exhaust gas. The temperature of the exhaust gas is about 400 (° C.). Further, the exhaust gas contains nitrogen oxide (NOx). The nitrogen oxide is electrochemically decomposed by the fuel cell 20 as will be described later.

水素ガス生成装置３０は、ガソリンと、水と、空気（酸素）を利用して、改質反応や、シフト反応等を行い、水素を主成分とする水素リッチガスを生成する。炭化水素の混合物であるガソリンの改質反応は、次式（１），（２）で表される。この改質反応では、ガソリンと水蒸気との反応によって、さらに、ガソリンと酸素との反応によって、水素と一酸化炭素とが生成される。また、シフト反応は、改質反応で生成された一酸化炭素を、水蒸気を利用して酸化させ、水素を生成する反応であり、次式（３）で表される。このシフト反応では、水素と、二酸化炭素とが生成される。なお、水素ガス生成装置３０によって生成される水素リッチガスの温度は、約４００（℃）である。   The hydrogen gas generation device 30 performs a reforming reaction, a shift reaction, or the like using gasoline, water, and air (oxygen) to generate a hydrogen rich gas mainly containing hydrogen. The reforming reaction of gasoline, which is a mixture of hydrocarbons, is expressed by the following formulas (1) and (2). In this reforming reaction, hydrogen and carbon monoxide are generated by the reaction between gasoline and steam, and further by the reaction between gasoline and oxygen. The shift reaction is a reaction in which carbon monoxide generated in the reforming reaction is oxidized using steam to generate hydrogen, and is represented by the following formula (3). In this shift reaction, hydrogen and carbon dioxide are generated. In addition, the temperature of the hydrogen rich gas produced | generated by the hydrogen gas production | generation apparatus 30 is about 400 (degreeC).

ＣnＨm＋ｎＨ2Ｏ →ｎＣＯ＋（ｎ＋ｍ／２）Ｈ2 …（１）；
ＣnＨm＋ｎ／２Ｏ2 →ｎＣＯ＋ｍ／２Ｈ2 …（２）；
ＣＯ＋Ｈ2Ｏ→Ｈ2＋ＣＯ2 …（３）； C n H m + nH 2 O → nCO + (n + m / 2) H 2 (1);
C n H m + n / 2O 2 → nCO + m / 2H 2 (2);
CO + H 2 O → H 2 + CO 2 (3);

本実施例における燃料電池２０は、後述するように、水素を選択的に透過させる水素透過性金属層と、プロトン伝導性を有する電解質層とを積層させた電解質膜を備える、いわゆる水素分離膜型燃料電池であり、アノードに供給された燃料ガスと、カソードに供給された酸化剤ガスとの電気化学反応によって発電する。なお、この水素分離膜型燃料電池の運転温度は、約４００（℃）である。燃料電池２０の構成については、後から詳述する。   As will be described later, the fuel cell 20 in the present embodiment includes a so-called hydrogen separation membrane type that includes an electrolyte membrane in which a hydrogen-permeable metal layer that selectively transmits hydrogen and an electrolyte layer having proton conductivity are stacked. A fuel cell, which generates electric power by an electrochemical reaction between a fuel gas supplied to an anode and an oxidant gas supplied to a cathode. The operating temperature of this hydrogen separation membrane fuel cell is about 400 (° C.). The configuration of the fuel cell 20 will be described in detail later.

燃料電池２０のカソードには、エンジン１０から排気された窒素酸化物を含む排気ガスが、配管５２を介して供給され、排気ガスに含まれる窒素酸化物が、酸化剤ガスとして利用される。燃料電池２０のカソードから排出されるカソードオフガスは、配管５４を介して外部に排気される。   Exhaust gas containing nitrogen oxides exhausted from the engine 10 is supplied to the cathode of the fuel cell 20 via the pipe 52, and nitrogen oxides contained in the exhaust gas are used as oxidant gas. Cathode off-gas discharged from the cathode of the fuel cell 20 is exhausted to the outside through the pipe 54.

燃料電池２０のアノードには、水素ガス生成装置３０によって生成された水素リッチガスが、配管５６を介して供給され、水素リッチガスに含まれる水素が、燃料ガスとして利用される。燃料電池２０のアノードから排出されるアノードオフガスは、配管５８を介して外部に排気される。アノードオフガスに含まれる発電で未消費の水素を配管５６に再循環させるようにしてもよい。   A hydrogen rich gas generated by the hydrogen gas generator 30 is supplied to the anode of the fuel cell 20 via a pipe 56, and hydrogen contained in the hydrogen rich gas is used as a fuel gas. The anode off gas discharged from the anode of the fuel cell 20 is exhausted to the outside through the pipe 58. Hydrogen that is not consumed by power generation contained in the anode off-gas may be recycled to the pipe 56.

なお、燃料電池２０では、アノード、および、カソードにおいて、次式（４）、（５）で表される反応によって、発電が行われる。そして、この発電時には、次式（６）で表される反応によって、窒素酸化物（ＮＯｘ）が電気化学的に窒素と水に分解される。こうすることによって、エンジン１０から排気される窒素酸化物を含む排気ガスを、燃料電池２０によって浄化するとともに、発電することができる。   In the fuel cell 20, power generation is performed by the reactions represented by the following formulas (4) and (5) at the anode and the cathode. During power generation, nitrogen oxide (NOx) is electrochemically decomposed into nitrogen and water by the reaction represented by the following formula (6). By doing so, the exhaust gas containing nitrogen oxides exhausted from the engine 10 can be purified by the fuel cell 20 and can be generated.

アノード：Ｈ2→２Ｈ+＋２ｅ- …（４）；
カソード：（２／Ｘ）ＮＯX＋２Ｈ+＋２ｅ-→（１／Ｘ）Ｎ2＋Ｈ2Ｏ …（５）；
２ＮＯX＋ＸＨ2→Ｎ2＋ＸＨ2Ｏ …（６）； Anode: H 2 → 2H + + 2e − (4);
Cathode: (2 / X) NO x + 2H + + 2e − → (1 / X) N 2 + H 2 O (5);
2NO x + XH 2 → N 2 + XH 2 O (6);

バッテリ４０は、燃料電池２０によって発電された電力を、一時的に蓄電する。こうすることによって、バッテリ４０に蓄電した電力を必要に応じて利用することができる。   The battery 40 temporarily stores the power generated by the fuel cell 20. By doing so, the electric power stored in the battery 40 can be used as needed.

Ｂ．燃料電池の構成：
図２は、燃料電池２０の概略構成を示す説明図である。ここでは、燃料電池２０を構成する単セル２００の断面構造を模式的に示した。この単セル２００は、膜電極接合体２１０の両面を、セパレータ２２０で挟持することによって構成されている。 B. Fuel cell configuration:
FIG. 2 is an explanatory diagram showing a schematic configuration of the fuel cell 20. Here, the cross-sectional structure of the unit cell 200 constituting the fuel cell 20 is schematically shown. The single cell 200 is configured by sandwiching both surfaces of a membrane electrode assembly 210 with a separator 220.

セパレータ２２０は、図示するように、凹凸形状を有しており、膜電極接合体２１０のアノード側、および、カソード側に、それぞれ燃料ガスとしての水素、および、酸化ガスとしてのエンジン１０の排気ガスを流すための流路を形成する。セパレータ２２０の材料としては、カーボンや、金属など、導電性を有する種々の材料を適用可能である。   As shown in the figure, the separator 220 has a concavo-convex shape, and hydrogen as a fuel gas and exhaust gas of the engine 10 as an oxidant gas on the anode side and the cathode side of the membrane electrode assembly 210, respectively. A flow path for flowing the water is formed. As a material of the separator 220, various conductive materials such as carbon and metal can be used.

膜電極接合体２１０は、水素を選択的に透過する水素透過性金属層２１２と、プロトン伝導性を有する電解質層２１４と、カソード２１６とを、この順序で積層することによって構成されている。水素透過性金属層２１２は、アノードとしての機能も有している。これらの各層は、物理蒸着等、種々の手法によって、形成することができる。   The membrane electrode assembly 210 is configured by laminating a hydrogen permeable metal layer 212 that selectively permeates hydrogen, an electrolyte layer 214 having proton conductivity, and a cathode 216 in this order. The hydrogen permeable metal layer 212 also has a function as an anode. Each of these layers can be formed by various methods such as physical vapor deposition.

本実施例では、水素透過性金属層２１２として、パラジウム膜を用いるものとした。また、電解質層２１４として、ペロブスカイト型の固体電解質を用いるものとした。また、カソード２１６として、電気化学反応を促進する触媒能を有する白金を用いるものとした。これらの材質および膜厚は、任意に選択、設定可能である。   In this embodiment, a palladium film is used as the hydrogen permeable metal layer 212. In addition, as the electrolyte layer 214, a perovskite solid electrolyte is used. As the cathode 216, platinum having a catalytic ability to promote an electrochemical reaction is used. These materials and film thicknesses can be arbitrarily selected and set.

なお、本実施例における燃料電池２０は、上述したように、いわゆる水素分離膜型燃料電池である。この水素分離膜型燃料電池は、膜電極接合体２１０が、比較的強度が高い水素透過性金属層２１２を備えるため、膜電極接合体２１０の強度を維持しつつ、プロトン伝導性を有する電解質層２１４の厚さを比較的薄くすることができる。したがって、電解質層２１４の膜抵抗を比較的低くすることができる。したがって、燃料電池２０として水素分離膜型燃料電池を用いることによって、効率よく窒素酸化物を分解しつつ、発電することができる。   The fuel cell 20 in this embodiment is a so-called hydrogen separation membrane fuel cell as described above. In this hydrogen separation membrane fuel cell, since the membrane electrode assembly 210 includes the hydrogen permeable metal layer 212 having a relatively high strength, the electrolyte layer has proton conductivity while maintaining the strength of the membrane electrode assembly 210. The thickness of 214 can be made relatively thin. Therefore, the membrane resistance of the electrolyte layer 214 can be made relatively low. Therefore, by using a hydrogen separation membrane fuel cell as the fuel cell 20, it is possible to generate power while efficiently decomposing nitrogen oxides.

以上説明した排気ガス浄化システム１００によれば、燃料電池２０が、酸化剤ガスとしてエンジン１０から排気される排気ガスに含まれる窒素酸化物を利用し、燃料ガスとして水素を利用して、水素と窒素酸化物との電気化学反応によって発電する。このとき、窒素酸化物は、先に示した式（６）で表される反応によって分解される。また、燃料電池２０は、エンジン１０から排気される排気ガスの温度とほぼ等しい温度で運転される水素分離型燃料電池であるので、エンジン１０の排気ガスを予熱することなく、燃料電池２０のカソードに供給することができる。したがって、排気ガス浄化システム１００に、エンジン１０の排気ガスを予熱するための予熱装置を設ける必要がなく、システムのエネルギ効率の向上、および、システムの小型化を図ることができる。つまり、本実施例の排気ガス浄化システム１００によって、エネルギ効率の低下や、システムの大型化を招くことなく、エンジン１０から排気される窒素酸化物を含む排気ガスを浄化することができる。   According to the exhaust gas purification system 100 described above, the fuel cell 20 uses nitrogen oxides contained in the exhaust gas exhausted from the engine 10 as the oxidant gas, uses hydrogen as the fuel gas, Power is generated by an electrochemical reaction with nitrogen oxides. At this time, the nitrogen oxide is decomposed by the reaction represented by the above-described formula (6). Further, since the fuel cell 20 is a hydrogen separation type fuel cell that is operated at a temperature substantially equal to the temperature of the exhaust gas exhausted from the engine 10, the cathode of the fuel cell 20 is not heated without preheating the exhaust gas of the engine 10. Can be supplied to. Therefore, it is not necessary to provide the exhaust gas purification system 100 with a preheating device for preheating the exhaust gas of the engine 10, and the energy efficiency of the system can be improved and the system can be downsized. That is, the exhaust gas purification system 100 of the present embodiment can purify exhaust gas containing nitrogen oxides exhausted from the engine 10 without reducing energy efficiency and increasing the size of the system.

Ｃ．変形例：
以上、本発明の実施の形態について説明したが、本発明はこのような実施の形態になんら限定されるものではなく、その要旨を逸脱しない範囲内において種々なる態様での実施が可能である。例えば、以下のような変形が可能である。 C. Variation:
Although the embodiments of the present invention have been described above, the present invention is not limited to such embodiments, and can be implemented in various modes without departing from the scope of the present invention. For example, the following modifications are possible.

Ｃ１．変形例１：
上記実施例では、燃料電池２０のアノードに水素ガス生成装置３０によって生成された水素リッチガスを供給するものとしたが、これに限られない。例えば、水素ガス生成装置３０の代わりに水素タンクを備えるようにし、この水素タンクから水素を供給するようにしてもよい。 C1. Modification 1:
In the above embodiment, the hydrogen-rich gas generated by the hydrogen gas generator 30 is supplied to the anode of the fuel cell 20, but the present invention is not limited to this. For example, a hydrogen tank may be provided instead of the hydrogen gas generation device 30, and hydrogen may be supplied from this hydrogen tank.

Ｃ２．変形例２：
上記実施例では、排気ガス浄化システム１００は、バッテリ４０を備えるものとしたが、バッテリ４０を備えないようにしてもよい。この場合、燃料電池２０によって発電された電力を順次利用するようにすればよい。 C2. Modification 2:
In the above embodiment, the exhaust gas purification system 100 includes the battery 40. However, the exhaust gas purification system 100 may not include the battery 40. In this case, the power generated by the fuel cell 20 may be used sequentially.

Ｃ３．変形例３：
上記実施例では、カソード２１６として、白金を用いるものとしたが、これに限られない。ただし、カソード２１６として白金系の触媒を用いることによって、他の触媒を用いるよりも効率よく窒素酸化物を分解するとともに、発電することができる。 C3. Modification 3:
In the above embodiment, platinum is used as the cathode 216, but the present invention is not limited to this. However, by using a platinum-based catalyst as the cathode 216, nitrogen oxides can be decomposed more efficiently and power can be generated than when other catalysts are used.

Ｃ４．変形例４：
上記実施例では、エンジン１０の排気ガスの温度が約４００（℃）であるから、燃料電池２０として、約４００（℃）で運転する、いわゆる水素分離膜型燃料電池を用いるものとしたが、これに限られない。一般に、内燃機関から排気される排気ガスの温度を含む所定の温度範囲内で運転される燃料電池を用いるようにすればよい。 C4. Modification 4:
In the above embodiment, since the exhaust gas temperature of the engine 10 is about 400 (° C.), a so-called hydrogen separation membrane fuel cell that operates at about 400 (° C.) is used as the fuel cell 20. It is not limited to this. In general, a fuel cell operated within a predetermined temperature range including the temperature of exhaust gas exhausted from the internal combustion engine may be used.

本発明の一実施例としての排気ガス浄化システム１００の概略構成を示す説明図である。It is explanatory drawing which shows schematic structure of the exhaust-gas purification system 100 as one Example of this invention. 燃料電池２０の概略構成を示す説明図である。2 is an explanatory diagram showing a schematic configuration of a fuel cell 20. FIG.

符号の説明Explanation of symbols

１００…排気ガス浄化システム
１０…エンジン
２０…燃料電池
２００…単セル
２１０…膜電極接合体
２１２…水素透過性金属層
２１４…電解質層
２１６…カソード
２２０…セパレータ
３０…水素ガス生成装置
４０…バッテリ
５２，５４，５６，５８…配管 DESCRIPTION OF SYMBOLS 100 ... Exhaust gas purification system 10 ... Engine 20 ... Fuel cell 200 ... Single cell 210 ... Membrane electrode assembly 212 ... Hydrogen permeable metal layer 214 ... Electrolyte layer 216 ... Cathode 220 ... Separator 30 ... Hydrogen gas generation device 40 ... Battery 52 , 54, 56, 58 ... piping

Claims (5)

内燃機関から排気される窒素酸化物を含む排気ガスを浄化する排気ガス浄化システムであって、
前記排気ガスの温度を含む所定の温度範囲内で運転される燃料電池であって、所定の燃料ガスと、前記排気ガスに含まれる窒素酸化物との電気化学反応によって、前記窒素酸化物を分解するとともに、発電する燃料電池を備える排気ガス浄化システム。 An exhaust gas purification system for purifying exhaust gas containing nitrogen oxides exhausted from an internal combustion engine,
The fuel cell is operated within a predetermined temperature range including the temperature of the exhaust gas, and the nitrogen oxide is decomposed by an electrochemical reaction between the predetermined fuel gas and the nitrogen oxide contained in the exhaust gas. And an exhaust gas purification system comprising a fuel cell for generating electricity. 請求項１に記載の排気ガス浄化システムであって、
前記燃料電池は、前記燃料ガスとしての水素を選択的に透過させる水素透過性金属層と、プロトン伝導性を有する電解質層とを積層させた電解質膜を備える、
排気ガス浄化システム。 The exhaust gas purification system according to claim 1,
The fuel cell includes an electrolyte membrane in which a hydrogen permeable metal layer that selectively permeates hydrogen as the fuel gas and an electrolyte layer having proton conductivity are stacked.
Exhaust gas purification system. 請求項１または２記載の排気ガス浄化システムであって、
前記燃料電池のカソードは、前記電気化学反応を促進するための白金系の触媒を備える、
排気ガス浄化システム。 The exhaust gas purification system according to claim 1 or 2,
The cathode of the fuel cell includes a platinum-based catalyst for promoting the electrochemical reaction.
Exhaust gas purification system. 請求項１ないし３のいずれかに記載の排気ガス浄化システムであって、
さらに、前記燃料電池によって発電された電力を蓄電する二次電池を備える、
排気ガス浄化システム。 An exhaust gas purification system according to any one of claims 1 to 3,
Furthermore, a secondary battery that stores electric power generated by the fuel cell is provided.
Exhaust gas purification system. 内燃機関から排気される窒素酸化物を含む排気ガスの浄化方法であって、
前記排気ガスの温度を含む所定の温度範囲内で運転される燃料電池であって、所定の燃料ガスと、前記排気ガスに含まれる窒素酸化物との電気化学反応によって発電する燃料電池を用意する工程と、
前記燃料ガスを前記燃料電池のアノードに供給するとともに、前記排気ガスを前記燃料電池のカソードに供給し、前記電気化学反応によって、前記窒素酸化物を分解するとともに、発電する工程と、
を備える浄化方法。 A method for purifying exhaust gas containing nitrogen oxides exhausted from an internal combustion engine,
A fuel cell that is operated within a predetermined temperature range including the temperature of the exhaust gas, and that generates power by an electrochemical reaction between the predetermined fuel gas and nitrogen oxides contained in the exhaust gas is prepared. Process,
Supplying the fuel gas to the anode of the fuel cell, supplying the exhaust gas to the cathode of the fuel cell, decomposing the nitrogen oxides by the electrochemical reaction, and generating power;
A purification method comprising:
JP2006123070A 2006-04-27 2006-04-27 Purification of exhaust gas exhausted from internal combustion engine and including nitrogen oxides Pending JP2007292010A (en)

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DE112007000948T DE112007000948T5 (en) 2006-04-27 2007-04-19 Exhaust gas purification system and method for purifying exhaust gases
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