JPH05168861A - Method for purifying combustion exhaust gas and device therefor - Google Patents
Method for purifying combustion exhaust gas and device thereforInfo
- Publication number
- JPH05168861A JPH05168861A JP3353269A JP35326991A JPH05168861A JP H05168861 A JPH05168861 A JP H05168861A JP 3353269 A JP3353269 A JP 3353269A JP 35326991 A JP35326991 A JP 35326991A JP H05168861 A JPH05168861 A JP H05168861A
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- combustion exhaust
- catalyst
- preheater
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 23
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 23
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 4
- 238000000746 purification Methods 0.000 claims description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 7
- 239000004071 soot Substances 0.000 abstract description 6
- 230000001678 irradiating effect Effects 0.000 abstract description 3
- 230000006698 induction Effects 0.000 abstract description 2
- 229910002187 La0.8Sr0.2CoO3 Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910018921 CoO 3 Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GQHZBSPNWMRGMM-UHFFFAOYSA-N [Co].[Sr] Chemical compound [Co].[Sr] GQHZBSPNWMRGMM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910021094 Co(NO3)2-6H2O Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QIMZHEUFJYROIY-UHFFFAOYSA-N [Co].[La] Chemical compound [Co].[La] QIMZHEUFJYROIY-UHFFFAOYSA-N 0.000 description 1
- QBYHSJRFOXINMH-UHFFFAOYSA-N [Co].[Sr].[La] Chemical compound [Co].[Sr].[La] QBYHSJRFOXINMH-UHFFFAOYSA-N 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電磁波を照射すること
により発熱する金属酸化物を用いた燃焼排気ガス、特に
自動車等の内燃機関の燃焼排気ガスを浄化する方法及び
装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for purifying combustion exhaust gas using a metal oxide which generates heat by irradiating electromagnetic waves, particularly combustion exhaust gas of an internal combustion engine such as an automobile.
【０００２】[0002]
【従来の技術】自動車の燃焼排気ガスの浄化は、一般に
燃焼排気ガスを触媒と接触させることにより、ガス中の
ハイドロカーボン、すす、ＮＯx 等を酸化及び還元させ
ることにより行われる。しかし、これらハイドロカーボ
ン等の酸化及び還元には、約４００〜４５０℃の温度が
必要である。触媒の加熱には、燃焼排気ガスの熱を利用
するのが一般的であり、触媒が上記温度域に達するには
５〜１０分程度の時間が必要である。そのため、エンジ
ンのコールドスタート後、触媒の浄化性能発揮温度に達
するまでの間は、触媒の働きが不十分となり、未浄化の
排気ガスがそのまま排出されてしまうというという問題
がある。2. Description of the Related Art Purification of combustion exhaust gas from an automobile is generally carried out by bringing the combustion exhaust gas into contact with a catalyst to oxidize and reduce hydrocarbons, soot, NOx and the like in the gas. However, a temperature of about 400 to 450 ° C. is required for the oxidation and reduction of these hydrocarbons. The heat of the combustion exhaust gas is generally used to heat the catalyst, and it takes about 5 to 10 minutes for the catalyst to reach the above temperature range. Therefore, after the cold start of the engine, the function of the catalyst is insufficient until the temperature reaches the purification performance performance of the catalyst, and unpurified exhaust gas is discharged as it is.
【０００３】[0003]
【発明が解決しようとする課題】そこでエンジンのコー
ルドスタート直後で触媒の温度が上昇しきらない時点で
も、燃焼排気ガスの浄化をすることができる方法の提供
が望まれている。また、米国では、エンジンのコールド
スタート直後の燃焼排気ガスを浄化することを義務付け
ることも検討されている。Therefore, it is desired to provide a method capable of purifying the combustion exhaust gas even when the temperature of the catalyst does not rise completely immediately after the cold start of the engine. In the United States, it is also considered to obligate the purification of combustion exhaust gas immediately after the engine cold start.
【０００４】このような問題の解決策として、電気ヒー
ターにより触媒を加熱する方法（例えば、特開昭４９−
２２３７６号公報、実開昭６１−１３４５１７号公
報）、電気ヒーターにより遠赤外線放出セラミックスを
加熱して遠赤外線により触媒を加熱する方法（実開平２
−９４３１６号公報）が提案されている。As a solution to such a problem, a method of heating a catalyst with an electric heater (see, for example, JP-A-49-
No. 22376, No. 61-134517, and a method of heating far infrared ray emitting ceramics with an electric heater to heat a catalyst with far infrared rays (Actual No. 2).
-94316).
【０００５】しかし、これらの方法では、ヒーター近傍
の触媒とヒーターから離れた位置の触媒との間に、浄化
性能発揮温度到達時間に差が生じ、触媒全体として浄化
性能を発揮するのに数分程度の時間を要する。その結
果、その間は燃焼排気ガスの浄化が不十分となる。ま
た、ヒーターは触媒担体の内部又は外部に分散配置され
るので、構造が複雑になるという難点もある。さらに、
数分間もヒーターに通電するために、電力消費が大きく
なり、バッテリーに負荷が掛かるという問題もある。However, in these methods, there is a difference in the purifying performance exhibiting temperature reaching time between the catalyst near the heater and the catalyst located away from the heater, and it takes several minutes for the purifying performance of the catalyst as a whole to be exhibited. It takes some time. As a result, the combustion exhaust gas is not sufficiently purified during that period. Further, since the heaters are dispersed and arranged inside or outside the catalyst carrier, there is a problem that the structure becomes complicated. further,
Since the heater is energized for several minutes, the power consumption becomes large and the battery is loaded.
【０００６】そこで、本発明の目的は、エンジン等の内
燃機関のコールドスタート直後でも、燃焼排気ガス中の
ハイドロカーボン、すす、ＮＯx 等を酸化及び還元させ
て浄化することができる方法及び装置を提供することで
ある。Therefore, an object of the present invention is to provide a method and an apparatus capable of oxidizing and reducing hydrocarbons, soot, NOx, etc. in combustion exhaust gas even immediately after a cold start of an internal combustion engine such as an engine. It is to be.
【０００７】[0007]
【課題を解決するための手段】本発明は、電磁波を照射
して発熱させた金属酸化物を含むプレヒーターに、燃焼
排気ガスを接触させて、該燃焼排気ガスを加熱し、次い
で加熱された燃焼排気ガスを燃焼排気ガス浄化触媒に接
触させることを特徴とする燃焼排気ガス浄化方法に関す
る。According to the present invention, a combustion exhaust gas is brought into contact with a preheater containing a metal oxide which is irradiated with electromagnetic waves to generate heat, and the combustion exhaust gas is heated, and then heated. The present invention relates to a method for purifying combustion exhaust gas, which comprises bringing combustion exhaust gas into contact with a combustion exhaust gas purification catalyst.
【０００８】さらに本発明は、燃焼排気ガス流入口と排
出口とを有する触媒チャンバー及び該チャンバー中に保
持された燃焼排気ガス浄化触媒成形体を含む装置であっ
て、上記チャンバー中の上記燃焼排気ガス浄化触媒成形
体より上流に、燃焼排気ガス流入口から流入する燃焼排
気ガスと接触するように、金属酸化物を含むプレヒータ
ーを設け、かつ、電磁波が上記プレヒーターに照射され
るように電磁波発生部を設けたことを特徴とする燃焼排
気ガス浄化装置に関する。Further, the present invention is an apparatus including a catalyst chamber having a combustion exhaust gas inlet and an exhaust port and a combustion exhaust gas purifying catalyst molded body held in the chamber, wherein the combustion exhaust gas in the chamber is provided. A preheater containing a metal oxide is provided upstream of the gas purification catalyst molded body so as to come into contact with the combustion exhaust gas flowing from the combustion exhaust gas inlet, and the electromagnetic wave is irradiated so that the preheater is irradiated with the electromagnetic wave. The present invention relates to a combustion exhaust gas purification device characterized in that a generator is provided.
【０００９】以下本発明について説明する。本発明にお
いて、金属酸化物は、ペロブスカイト型複合酸化物、酸
化鉄、酸化マンガン及び酸化コバルトからなる群から選
ばれることが、電磁波を照射して短時間に所定の温度に
まで発熱させることができるという観点から適当であ
る。The present invention will be described below. In the present invention, the metal oxide is selected from the group consisting of perovskite-type composite oxides, iron oxide, manganese oxide and cobalt oxide, and it is possible to radiate electromagnetic waves to generate heat up to a predetermined temperature in a short time. It is suitable from the viewpoint.
【００１０】ペロブスカイト型複合酸化物としては、ラ
ンタン・コバルト系複合酸化物、ストロンチウム・コバ
ルト系複合酸化物及びランタン・ストロンチウム・コバ
ルト系複合酸化物を好ましいものとして例示できる。ラ
ンタン及び／又はストロンチウム・コバルト系複合酸化
物は、一般式La1-x SrX CoO3で表され、式中ｘは、０〜
１の任意の数である。具体的には、LaCoO3、SrCoO3、La
0.6Sr0.4CoO3、La0.8Sr0.2CoO3等を例示できる。Preferred examples of the perovskite type complex oxide include lanthanum-cobalt type complex oxide, strontium-cobalt type complex oxide and lanthanum-strontium-cobalt type complex oxide. The lanthanum and / or strontium-cobalt composite oxide is represented by the general formula La 1-x Sr X CoO 3, where x is 0 to 0.
It is an arbitrary number of 1. Specifically, LaCoO 3 , SrCoO 3 , La
Examples include 0.6 Sr 0.4 CoO 3 and La 0.8 Sr 0.2 CoO 3 .
【００１１】その他のペロブスカイト型複合酸化物とし
ては、一般式La1-x SrX Co1-y M y O3で表される酸化物
を例示できる。式中、ｘは、０〜１の任意の数であり、
ｙは、０〜１の任意の数であり、Ｍは、クロム、マンガ
ン、鉄、ニッケル、銅、バナジウム及びチタンからなる
群から選ばれる少なくとも１種の金属である。さらに、
高温超伝導体YBa2Cu3O7-y 等を例示することもできる。Examples of other perovskite type complex oxides include oxides represented by the general formula La 1-x Sr X Co 1-y M y O 3 . In the formula, x is an arbitrary number from 0 to 1, and
y is an arbitrary number from 0 to 1, and M is at least one metal selected from the group consisting of chromium, manganese, iron, nickel, copper, vanadium and titanium. further,
The high temperature superconductor YBa 2 Cu 3 O 7-y and the like can also be exemplified.
【００１２】ペロブスカイト型複合酸化物は、それ自身
優れた酸化還元触媒であり、燃焼排気ガス中のハイドロ
カーボン、すす、ＮＯx 等を酸化及び還元させて浄化す
る能力があることから特に好ましい。従って、金属酸化
物としてペロブスカイト型複合酸化物を用いる場合に
は、ペロブスカイト型複合酸化物に電磁波を照射するこ
とにより発熱させて、プレヒーターとしてのみならず、
これ自身が燃焼排気ガス浄化用触媒としても作用する。The perovskite type complex oxide is an excellent redox catalyst by itself, and is particularly preferable because it has an ability to oxidize and reduce hydrocarbons, soot, NOx and the like in combustion exhaust gas to purify them. Therefore, when a perovskite-type composite oxide is used as the metal oxide, the perovskite-type composite oxide is irradiated with electromagnetic waves to generate heat, and not only as a preheater,
It also acts as a catalyst for purifying combustion exhaust gas.
【００１３】酸化鉄としては、γ−Fe2O3 、α−Fe2O3
等を例示でき、酸化マンガンとしてはMn3O4 等を例示で
き、酸化コバルトとしてはCo3O4 等を例示できる。Examples of iron oxide include γ-Fe 2 O 3 and α-Fe 2 O 3
And the like, Mn 3 O 4 and the like can be exemplified as manganese oxide, and Co 3 O 4 and the like can be exemplified as cobalt oxide.
【００１４】本発明の排気ガス浄化方法に用いる金属酸
化物を含むプレヒーターは、粉末であっても、成形体で
あっても良い。但し、ガスとの接触の効率の点から、ハ
ニカム構造等の成形体や、顆粒状や適当な大きさの粒子
であることもできる。使用の目的、条件等により適宜選
択することができる。例えば、ハニカム構造等の成形体
は、担体に金属酸化物を担持することにより作成するこ
とができる。担体への金属酸化物の担持は、金属酸化物
またはその原料となる化合物を含む水溶液又はスラリー
に担体を浸漬し、乾燥、焼成等することにより、行うこ
とができる。尚、担体への金属酸化物またはその原料と
なる化合物の付着を容易にするために、ポリエチレング
リコール等の増粘剤を、上記水溶液又はスラリーに添加
することもできる。The preheater containing a metal oxide used in the exhaust gas purification method of the present invention may be a powder or a molded body. However, in terms of the efficiency of contact with gas, a molded body having a honeycomb structure or the like, or a granular shape or particles having an appropriate size can be used. It can be appropriately selected depending on the purpose of use, conditions and the like. For example, a molded body having a honeycomb structure or the like can be prepared by supporting a metal oxide on a carrier. The support of the metal oxide on the carrier can be carried out by immersing the carrier in an aqueous solution or slurry containing the metal oxide or the compound as a raw material thereof, and drying and firing. A thickener such as polyethylene glycol may be added to the aqueous solution or slurry in order to facilitate the attachment of the metal oxide or the compound as the raw material thereof to the carrier.
【００１５】また、燃焼排気ガス浄化用触媒としては、
従来から燃焼排気ガス浄化用に用いられている触媒をそ
のまま用いることができる。例えば、白金・ロジウム・
パラジウム系３元触媒、酸化触媒等の排気ガス浄化触媒
を例示できる。燃焼排気ガス浄化用触媒は、通常、ハニ
カム構造等の成形体であるが、他の形態であってもよ
い。Further, as the combustion exhaust gas purifying catalyst,
The catalyst conventionally used for purification of combustion exhaust gas can be used as it is. For example, platinum, rhodium,
Exhaust gas purification catalysts such as palladium-based three-way catalysts and oxidation catalysts can be exemplified. The combustion exhaust gas purifying catalyst is usually a molded body having a honeycomb structure or the like, but may have another form.
【００１６】本発明の燃焼排気ガス浄化方法及び装置の
浄化対象である燃焼排気ガスは、例えば、エンジン等の
内燃機関から排出される燃焼排気ガスである。The combustion exhaust gas to be purified by the combustion exhaust gas purification method and apparatus of the present invention is, for example, combustion exhaust gas discharged from an internal combustion engine such as an engine.
【００１７】本発明において用いる電磁波としては、マ
イクロ波を例示できる。マイクロ波の周波数には、特に
限定はなく、使用する金属酸化物の種類、所望の発熱温
度及び時間により適宜選択することができる。例えば、
２．４５ＧＨｚのマイクロ波を例示することができる。
また、電磁波のパワー（電力）、照射時間、照射方法等
は、適宜決めることができる。上記金属酸化物を含むプ
レヒーターに、マイクロ波等の電磁波を照射することに
より、極めて短時間、例えば、５〜１０秒以内に約２０
０〜５００℃の温度に、プレヒーターを発熱させること
ができる。Microwaves can be exemplified as the electromagnetic waves used in the present invention. The frequency of the microwave is not particularly limited and can be appropriately selected depending on the type of metal oxide used, the desired exothermic temperature and time. For example,
The microwave of 2.45 GHz can be illustrated.
Moreover, the power of the electromagnetic wave, the irradiation time, the irradiation method, and the like can be appropriately determined. By irradiating the preheater containing the metal oxide with an electromagnetic wave such as a microwave, the preheater can be heated to about 20 in an extremely short time, for example, within 5 to 10 seconds.
The preheater can generate heat at a temperature of 0 to 500 ° C.
【００１８】電磁波を照射して発熱したプレヒーターと
燃焼排気ガスとを接触させることにより、燃焼排気ガス
を加熱し、加熱した燃焼排気ガスと燃焼排気ガス浄化用
触媒とを接触させることにより、ガス中のハイドロカー
ボン、すす、ＮＯx 等が酸化及び還元されて浄化され
る。The combustion exhaust gas is heated by bringing the preheater which has been heated by the irradiation of electromagnetic waves into contact with the combustion exhaust gas, and the heated combustion exhaust gas is brought into contact with the combustion exhaust gas purifying catalyst. Hydrocarbons, soot, NOx, etc. inside are oxidized and reduced to be purified.
【００１９】以下本発明の燃焼排気ガス浄化装置につい
て説明する。図１は本発明の装置の一態様を示す説明図
である。この装置は、燃焼排気ガス流入口１１と排出口
１２とを有する触媒チャンバー１３及び該チャンバー１
３中に保持された燃焼排気ガス浄化触媒成形体１４を含
む。上記チャンバー１３中の上記燃焼排気ガス浄化触媒
成形体１４より上流に、燃焼排気ガス流入口１１から流
入する燃焼排気ガスと接触するように、金属酸化物を含
むプレヒーター１５が設けられている。さらに、電磁波
が上記プレヒーター１５に照射されるように電磁波発生
部１６が設けられている。The combustion exhaust gas purification apparatus of the present invention will be described below. FIG. 1 is an explanatory view showing one embodiment of the apparatus of the present invention. This apparatus comprises a catalyst chamber 13 having a combustion exhaust gas inlet 11 and an outlet 12, and the chamber 1.
3 includes a combustion exhaust gas purifying catalyst molded body 14 held therein. A preheater 15 containing a metal oxide is provided upstream of the combustion exhaust gas purification catalyst molded body 14 in the chamber 13 so as to come into contact with the combustion exhaust gas flowing from the combustion exhaust gas inlet 11. Further, an electromagnetic wave generator 16 is provided so that the preheater 15 is irradiated with electromagnetic waves.
【００２０】これとは別に図２に示すように、触媒チャ
ンバーがプレヒーター１５を収納してあるチャンバー１
７と触媒成形体１４を収納してあるチャンバー１８とに
分かれたものも本発明に包含される。チャンバー１７と
チャンバー１８との間は通路１９で連絡されており、チ
ャンバー１７内で加熱された排気ガスはチャンバー１８
内で触媒成形体１４と接触する。Separately from this, as shown in FIG. 2, the catalyst chamber is a chamber 1 containing a preheater 15.
The present invention also includes a chamber and a chamber 18 in which the catalyst molded body 14 is housed. A communication path 19 is provided between the chamber 17 and the chamber 18 so that the exhaust gas heated in the chamber 17 can be discharged from the chamber 18.
It contacts the catalyst compact 14 inside.
【００２１】電磁波発生部１６は、プレヒーター１５に
電磁波を照射できれば、配置等には特に制限はない。例
えば、図１及び図２に示すように排気ガスの流れとほぼ
平行する方向から照射することができる。図３に示すよ
うにガスの流れと斜めの方向又は図４に示すようにガス
の流れとほぼ垂直の方向からも照射することができる。
また、電磁波発生部１６は、１つ又は２つ以上であって
も良い。The electromagnetic wave generator 16 is not particularly limited in its arrangement and the like as long as it can irradiate the preheater 15 with an electromagnetic wave. For example, irradiation can be performed from a direction substantially parallel to the flow of exhaust gas as shown in FIGS. 1 and 2. Irradiation can be performed from a direction oblique to the gas flow as shown in FIG. 3 or from a direction substantially perpendicular to the gas flow as shown in FIG.
Moreover, the electromagnetic wave generation part 16 may be one or two or more.
【００２２】電磁波発生部１６とチャンバー１３又はチ
ャンバー１７との間は電磁波誘導路２０で連絡して、電
磁波発生部１６内で発生した電磁波を、チャンバー１３
又はチャンバー１７に誘導することができる。電磁波誘
導路２０は、導波管及び同軸ケーブル等を用いることが
できる。又、その形状等は適宜決めることができる。The electromagnetic wave generating section 16 is connected to the chamber 13 or the chamber 17 by an electromagnetic wave guiding path 20 so that the electromagnetic wave generated in the electromagnetic wave generating section 16 is transferred to the chamber 13
Alternatively, it can be guided to the chamber 17. As the electromagnetic wave guide path 20, a waveguide, a coaxial cable, or the like can be used. Further, its shape and the like can be appropriately determined.
【００２３】本発明の装置では、エンジン等の内燃機関
始動の前若しくは後、又は始動と同時に、プレヒーター
１５への電磁波の照射を開始する。電磁波を照射して発
熱したプレヒーター１５に、内燃機関からの燃焼排気ガ
スを接触させて燃焼排気ガスの温度を高める。温度を高
められた燃焼排気ガスは、次いで触媒成形体１４と接触
して、燃焼排気ガス中のハイドロカーボン、すす、ＮＯ
x 等は酸化及び還元され、浄化される。In the device of the present invention, irradiation of the electromagnetic wave to the preheater 15 is started before or after the internal combustion engine such as the engine is started, or at the same time. Combustion exhaust gas from the internal combustion engine is brought into contact with the preheater 15 that has generated heat by being irradiated with electromagnetic waves to raise the temperature of the combustion exhaust gas. The combustion exhaust gas whose temperature has been raised then comes into contact with the catalyst molded body 14 and the hydrocarbons, soot, NO in the combustion exhaust gas.
x and the like are oxidized and reduced and purified.
【００２４】[0024]
【発明の効果】本発明によれば、エンジンのコールドス
タート直後でも、燃焼排気ガスの浄化反応が起こる温度
に触媒を加熱して、燃焼排気ガスの浄化をすることがで
きる。According to the present invention, the combustion exhaust gas can be purified by heating the catalyst to a temperature at which the combustion exhaust gas purification reaction occurs even immediately after the cold start of the engine.
【００２５】[0025]
【実施例】以下、本発明を実施例によりさらに詳細に説
明する。EXAMPLES The present invention will now be described in more detail with reference to examples.
【００２６】参考例 図５に示すマイクロ波発生装置３０を組み込んだ装置を
用いて、表１に示す各金属酸化物の発熱状況を調べた。
各金属酸化物サンプル３１は反応管３２内に入れ、サン
プルの温度は、反射板３３を介してデジタル温度計３４
で、マイクロ波照射開始後１０秒毎に読み取った。結果
を表１及び図６〜８に示す。尚、図７及び図８には、そ
れぞれLa0.8Sr0.2CoO3及びLaCoO3に複数回繰り返しマイ
クロ波を照射したときの経時変化（１回目、２回目、３
回目）を示す。その結果、複数回繰り返しマイクロ波を
照射しても、発熱状況にほとほど変化はなく、繰り返し
使用できることが明らかになった。Reference Example Using a device incorporating the microwave generator 30 shown in FIG. 5, the heat generation state of each metal oxide shown in Table 1 was examined.
Each metal oxide sample 31 is put into a reaction tube 32, and the temperature of the sample is measured by a digital thermometer 34 through a reflector 33.
Then, it was read every 10 seconds after the start of microwave irradiation. The results are shown in Table 1 and FIGS. 7 and 8 show changes over time when microwaves were repeatedly irradiated to La 0.8 Sr 0.2 CoO 3 and LaCoO 3 (first, second, and third, respectively).
Time). As a result, it was clarified that even if the microwave irradiation was repeated several times, the heat generation condition did not change so much and the microwave could be used repeatedly.
【００２７】[0027]
【表１】 [Table 1]
【００２８】実施例 ２２０．５ｇの硝酸ランタンLa(NO3)6H2O 、２６．９５
ｇの硝酸ストロンチウムSr(NO3)2、１８５．５ｇの硝酸
コバルトCo(NO3)26H2O、９２５ｇのクエン酸、９２５ｍ
ｌのエチレングリコールを純水に溶解して全量が１リッ
トルの水飴状の溶液を調製した。この溶液にコージェラ
イト製ハニカム（直径１０ｃｍ、高さ１２ｃｍ）を浸漬
した後室温で乾燥し、次いで８００℃３時間大気中で焼
結した。その結果、La0.8Sr0.2CoO3を４．０重量％担持
したハニカム（プレヒーター）が得られた。Example 22 0.5 g of lanthanum nitrate La (NO 3 ) 6 H 2 O, 26.95
g strontium nitrate Sr (NO 3 ) 2 , 185.5 g cobalt nitrate Co (NO 3 ) 2 6H 2 O, 925 g citric acid, 925 m
1 liter of ethylene glycol was dissolved in pure water to prepare a syrup-like solution having a total amount of 1 liter. A cordierite honeycomb (diameter: 10 cm, height: 12 cm) was immersed in this solution, dried at room temperature, and then sintered in the air at 800 ° C. for 3 hours. As a result, a honeycomb (preheater) supporting 4.0 wt% of La 0.8 Sr 0.2 CoO 3 was obtained.
【００２９】このハニカム（プレヒーター）にマイクロ
波（周波数２．４５ＧＨｚ、入力１００〜１５０Ｗ）を
印加した。その結果、１０秒足らずで４００℃以上に昇
温することが判明した。さらに、４００℃に昇温する時
間を繰り返し測定した。その結果を図９に示す。図９か
ら明らかなように、昇温時間にバラツキもなく、繰り返
し使用に充分耐え得ることが判明した。Microwave (frequency: 2.45 GHz, input: 100 to 150 W) was applied to this honeycomb (preheater). As a result, it was found that the temperature was raised to 400 ° C or higher in less than 10 seconds. Further, the time for raising the temperature to 400 ° C. was repeatedly measured. The result is shown in FIG. As is clear from FIG. 9, it was found that there was no variation in the temperature rising time and that it could withstand repeated use sufficiently.
【図１】本発明の装置の説明図である。FIG. 1 is an explanatory diagram of a device of the present invention.
【図２】本発明の装置の説明図である。FIG. 2 is an explanatory diagram of the device of the present invention.
【図３】本発明の装置のプレヒーター１５を収納するチ
ャンバー１７付近の説明図である。FIG. 3 is an explanatory view of the vicinity of a chamber 17 that houses a preheater 15 of the apparatus of the present invention.
【図４】本発明の装置のプレヒーター１５を収納するチ
ャンバー１７付近の説明図である。FIG. 4 is an explanatory diagram of the vicinity of a chamber 17 that houses a preheater 15 of the device of the present invention.
【図５】マイクロ波発生装置３０を組み込んだ金属酸化
物発熱装置の説明図である。FIG. 5 is an explanatory diagram of a metal oxide heating device incorporating a microwave generator 30.
【図６】マイクロ波を照射したLa1-x SrX CoO3の温度の
経時変化を示す。FIG. 6 shows a time-dependent change in temperature of La 1-x Sr X CoO 3 irradiated with microwaves.
【図７】マイクロ波を照射したLa0.8Sr0.2CoO3の温度の
経時変化（１回目、２回目、３回目）を示す。FIG. 7 shows changes with time of temperature of La 0.8 Sr 0.2 CoO 3 irradiated with microwaves (first time, second time, third time).
【図８】マイクロ波を照射したLaCoO3の温度の経時変化
（１回目、２回目、３回目）を示す。FIG. 8 shows changes with time of temperature of LaCoO 3 irradiated with microwaves (first time, second time, third time).
【図９】実施例のハニカム（プレヒーター）の繰り返し
昇温試験結果を示す。[Fig. 9] Fig. 9 shows the results of repeated temperature rising test of the honeycomb (preheater) of the example.
１１ 燃焼排気ガス流入口 １２ 燃焼排気ガス排出口 １３ 触媒チャンバー １４ 燃焼排気ガス浄化触媒成形体 １５ プレヒーター １６ 電磁波発生部 １７ チャンバー １８ チャンバー １９ 通路 ２０ 電磁波誘導路 ３０ マイクロ波発生装置 ３１ 金属酸化物サンプル ３２ 反応管 ３３ 反射板 ３４ デジタル温度計 11 Combustion Exhaust Gas Inlet 12 Combustion Exhaust Gas Outlet 13 Catalyst Chamber 14 Combustion Exhaust Gas Purification Catalyst Molded Body 15 Preheater 16 Electromagnetic Wave Generation Section 17 Chamber 18 Chamber 19 Passage 20 Electromagnetic Wave Induction Path 30 Microwave Generator 31 Metal Oxide Sample 32 reaction tube 33 reflector 34 digital thermometer
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｆ０１Ｎ 3/10 Ａ 7910−3Ｇ 3/20 Ｋ 9150−3Ｇ (72)発明者 山中 稔 埼玉県東松山市箭弓町３−13−26 株式会 社ゼクセル東松山工場内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location F01N 3/10 A 7910-3G 3/20 K 9150-3G (72) Minor Minoru Yamanaka Higashimatsuyama, Saitama Prefecture 3-13-26, Yasumicho, Ichi XXEL Higashi Matsuyama Factory
Claims (4)
を含むプレヒーターに、燃焼排気ガスを接触させて、該
燃焼排気ガスを加熱し、次いで加熱された燃焼排気ガス
を燃焼排気ガス浄化触媒に接触させることを特徴とする
燃焼排気ガス浄化方法。1. A preheater containing a metal oxide, which is heated by being irradiated with electromagnetic waves, is contacted with combustion exhaust gas to heat the combustion exhaust gas, and then the heated combustion exhaust gas is purified by the combustion exhaust gas. A method for purifying combustion exhaust gas, which comprises contacting with a catalyst.
物、酸化鉄、酸化マンガン及び酸化コバルトから選ばれ
る少なくとも１種の酸化物である請求項１記載の方法。2. The method according to claim 1, wherein the metal oxide is at least one oxide selected from perovskite type complex oxide, iron oxide, manganese oxide and cobalt oxide.
触媒チャンバー及び該チャンバー中に保持された燃焼排
気ガス浄化触媒成形体を含む装置であって、上記チャン
バー中の上記燃焼排気ガス浄化触媒成形体より上流に、
燃焼排気ガス流入口から流入する燃焼排気ガスと接触す
るように、金属酸化物を含むプレヒーターを設け、か
つ、電磁波が上記プレヒーターに照射されるように電磁
波発生部を設けたことを特徴とする燃焼排気ガス浄化装
置。3. An apparatus comprising a catalyst chamber having a combustion exhaust gas inflow port and an exhaust port, and a combustion exhaust gas purification catalyst molded body held in the chamber, wherein the combustion exhaust gas purification catalyst in the chamber. Upstream from the molded body,
A preheater containing a metal oxide is provided so as to come into contact with the combustion exhaust gas flowing in from the combustion exhaust gas inlet, and an electromagnetic wave generation unit is provided so that the preheater is irradiated with electromagnetic waves. Combustion exhaust gas purification device.
物、酸化鉄、酸化マンガン及び酸化コバルトからなる群
から選ばれる少なくとも１種の酸化物である請求項３記
載の燃焼排気ガス浄化装置。4. The combustion exhaust gas purification apparatus according to claim 3, wherein the metal oxide is at least one oxide selected from the group consisting of perovskite type complex oxide, iron oxide, manganese oxide and cobalt oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3353269A JPH05168861A (en) | 1991-12-17 | 1991-12-17 | Method for purifying combustion exhaust gas and device therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3353269A JPH05168861A (en) | 1991-12-17 | 1991-12-17 | Method for purifying combustion exhaust gas and device therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05168861A true JPH05168861A (en) | 1993-07-02 |
Family
ID=18429690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3353269A Pending JPH05168861A (en) | 1991-12-17 | 1991-12-17 | Method for purifying combustion exhaust gas and device therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05168861A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003071298A (en) * | 2001-09-05 | 2003-03-11 | Toyota Central Res & Dev Lab Inc | Composite material and its production method, catalyst and its production method, NOx storage method and NOx storage reduction method |
| US20120207657A1 (en) * | 2011-02-11 | 2012-08-16 | General Electric Company | System and method for controlling emissions in a combustion system |
| CN115779913A (en) * | 2021-09-10 | 2023-03-14 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene glycol from glucose and preparation method and application thereof |
| US11876262B2 (en) | 2021-03-05 | 2024-01-16 | Toyota Motor Engineering & Manufacturing North America, Inc. | Fuel cell power unbalancing to control degradation and improve performance |
-
1991
- 1991-12-17 JP JP3353269A patent/JPH05168861A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003071298A (en) * | 2001-09-05 | 2003-03-11 | Toyota Central Res & Dev Lab Inc | Composite material and its production method, catalyst and its production method, NOx storage method and NOx storage reduction method |
| US20120207657A1 (en) * | 2011-02-11 | 2012-08-16 | General Electric Company | System and method for controlling emissions in a combustion system |
| CN102720574A (en) * | 2011-02-11 | 2012-10-10 | 通用电气公司 | System and method for controlling emissions in a combustion system |
| US8309045B2 (en) * | 2011-02-11 | 2012-11-13 | General Electric Company | System and method for controlling emissions in a combustion system |
| US11876262B2 (en) | 2021-03-05 | 2024-01-16 | Toyota Motor Engineering & Manufacturing North America, Inc. | Fuel cell power unbalancing to control degradation and improve performance |
| CN115779913A (en) * | 2021-09-10 | 2023-03-14 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene glycol from glucose and preparation method and application thereof |
| CN115779913B (en) * | 2021-09-10 | 2024-03-26 | 中国石油化工股份有限公司 | Catalyst for preparing glycol from glucose, and preparation method and application thereof |
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