JP4494068B2 - Catalyst for oxidation removal of methane in exhaust gas and exhaust gas purification method - Google Patents
Catalyst for oxidation removal of methane in exhaust gas and exhaust gas purification method Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 148
- 239000003054 catalyst Substances 0.000 title claims description 108
- 230000003647 oxidation Effects 0.000 title claims description 62
- 238000007254 oxidation reaction Methods 0.000 title claims description 62
- 238000000034 method Methods 0.000 title claims description 32
- 238000000746 purification Methods 0.000 title 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 75
- 239000007789 gas Substances 0.000 claims description 73
- 238000002485 combustion reaction Methods 0.000 claims description 57
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 35
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 35
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 35
- 229910052697 platinum Inorganic materials 0.000 claims description 32
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 26
- 239000008188 pellet Substances 0.000 claims description 25
- 230000001590 oxidative effect Effects 0.000 claims description 18
- 150000003058 platinum compounds Chemical class 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229910052815 sulfur oxide Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000003546 flue gas Substances 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 239000003826 tablet Substances 0.000 claims 2
- 239000002699 waste material Substances 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 31
- 229910052763 palladium Inorganic materials 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000011056 performance test Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- 229910018879 Pt—Pd Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- -1 that is Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 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
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Description
本発明は、硫黄酸化物を含む燃焼排ガス中のメタンを低温域において酸化して除去するための触媒、該低温酸化除去用触媒を用いて硫黄酸化物を含む燃焼排ガス中のメタンを低温域において酸化除去する方法及び該低温酸化除去用触媒の製造方法に関する。 The present invention relates to a catalyst for oxidizing and removing methane in combustion exhaust gas containing sulfur oxide in a low temperature region, and using the low temperature oxidation removal catalyst, methane in combustion exhaust gas containing sulfur oxide in a low temperature region. The present invention relates to a method for oxidation removal and a method for producing the catalyst for low temperature oxidation removal.
ボイラー、加熱炉、あるいはガスエンジンやディーゼルエンジンやガスタービンなどの燃料としては天然ガス、都市ガス、軽油、灯油などの炭化水素系燃料が使用される。それらの燃料を燃焼させた排ガスには窒素酸化物（ＮＯX）、硫黄酸化物（ＳＯX）、一酸化炭素、あるいは臭気物質、ばいじん等のほか、未燃焼の炭化水素が含有されている。これらの成分は環境汚染の原因となるので無害にして排出する必要がある。 Hydrocarbon fuels such as natural gas, city gas, light oil, and kerosene are used as fuel for boilers, furnaces, gas engines, diesel engines, and gas turbines. The exhaust gas from which these fuels are burned contains nitrogen oxides (NO x ), sulfur oxides (SO x ), carbon monoxide, odorous substances, soot and the like, as well as unburned hydrocarbons. These components cause environmental pollution and must be discharged harmlessly.
そして、この点は、コージェネレーションシステムやＧＨＰ（Gas Heat Pump）における希薄燃焼式エンジンからの燃焼排ガスについても同様である。希薄燃焼式エンジンのような希薄燃焼方式の場合には、その排ガス中に少量の炭化水素、特にメタン、窒素酸化物、一酸化炭素等とともに、多量の酸素及び水蒸気が共存することになる。従来、排ガス中の３成分すなわち炭化水素、窒素酸化物、一酸化炭素を同時に浄化する三元触媒による処理法が開発されている。 This also applies to combustion exhaust gas from a lean combustion engine in a cogeneration system or GHP (Gas Heat Pump). In the case of a lean combustion system such as a lean combustion engine, a large amount of oxygen and water vapor coexist in the exhaust gas together with a small amount of hydrocarbons, particularly methane, nitrogen oxide, carbon monoxide and the like. Conventionally, a treatment method using a three-way catalyst that simultaneously purifies three components in exhaust gas, that is, hydrocarbon, nitrogen oxide, and carbon monoxide, has been developed.
ところが、三元触媒による処理法は酸素が殆んど存在しない燃焼排ガスに対してしか有効に適用することはできず、三元触媒は酸素過剰で且つ燃焼排ガス中の炭化水素がとりわけメタンである場合には有効に作用しない。炭化水素の酸化触媒としてはパラジウム、白金、ロジウムなどの貴金属が用いられるが、それら貴金属触媒は担体に担持した形で使用される。その担体としてはアルミナ（Ａｌ2Ｏ3）やジルコニア（ＺｒＯ2）などが知られている。 However, the treatment method using a three-way catalyst can be effectively applied only to combustion exhaust gas in which almost no oxygen is present. The three-way catalyst is oxygen-excess and the hydrocarbon in the combustion exhaust gas is especially methane. In some cases it does not work effectively. Noble metals such as palladium, platinum and rhodium are used as the hydrocarbon oxidation catalyst, and these noble metal catalysts are used in a form supported on a carrier. As the carrier, alumina (Al 2 O 3 ), zirconia (ZrO 2 ) and the like are known.
ところで、炭化水素が特にメタンの場合には、従来、その酸化にはパラジウムが有効とされ、白金についてはそれ単独では有効でなく、補助的に使用されているだけである。例えば特開平１１−３１９５５９号公報には、酸化ジルコニウム担体にパラジウムを担持してなる触媒が硫黄酸化物による触媒活性の阻害に対して高い抵抗性を示すことが示されている。同公報には、酸化スズ担体にパラジウムと白金を担持してなる触媒についても開示されているが、白金はパラジウムと一緒に補助的に使用されるに過ぎない。 By the way, in the case where the hydrocarbon is methane in particular, conventionally, palladium is effective for the oxidation, and platinum is not effective by itself, but only used as an auxiliary. For example, Japanese Patent Application Laid-Open No. 11-319559 shows that a catalyst in which palladium is supported on a zirconium oxide support exhibits high resistance to inhibition of catalytic activity by sulfur oxides. The publication also discloses a catalyst in which palladium and platinum are supported on a tin oxide carrier, but platinum is only used in an auxiliary manner together with palladium.
また、例えば希薄燃焼式エンジンからの燃焼排ガスの温度は５００℃以下、通常５００〜４００℃程度と低いため、酸化触媒によるメタンの酸化は困難である。特に４５０℃以下という低温域においては、酸化触媒は、排ガス中に含まれる微量の硫黄酸化物の蓄積による被毒劣化が著しく、これによりメタンの酸化除去性能は経時的に劣化してしまい、実用に供し得る十分な耐久性能が得られないのが現状である。 Further, for example, the temperature of combustion exhaust gas from a lean combustion engine is as low as 500 ° C. or less, usually about 500 to 400 ° C., so that it is difficult to oxidize methane with an oxidation catalyst. Particularly in the low temperature range of 450 ° C. or less, the oxidation catalyst is significantly deteriorated in poisoning due to accumulation of a small amount of sulfur oxide contained in the exhaust gas. In the present situation, sufficient durability performance that can be used for the above is not obtained.
本発明者らは、白金、ルテニウム、パラジウムなどの貴金属と各種多孔質担体とを組み合せて実験、検討を繰り返して追求したところ、全く偶然にも、従来メタンの酸化活性貴金属と考えられていたパラジウムを一切含まず、また、従来、単独では有効でないと考えられていた白金をそれ単独で、すなわち白金のみを多孔質の酸化スズに担持した触媒が低温域、特に４５０℃以下という低温域におけるメタンの酸化除去用触媒として有効で、高い耐ＳＯX性を有することを見い出し、この知見に基づく酸化触媒を先に開発し、出願している（特願２００３−１４８２７９号）。 The present inventors have repeatedly pursued experiments and examinations by combining noble metals such as platinum, ruthenium and palladium with various porous carriers. In addition, platinum, which has been conventionally considered to be ineffective by itself, is a methane in a low temperature region, particularly a low temperature region of 450 ° C. or less, in which a catalyst in which only platinum is supported on porous tin oxide is used. It has been found that the catalyst is effective as an oxidation removal catalyst and has high SO X resistance, and an oxidation catalyst based on this finding has been developed and applied (Japanese Patent Application No. 2003-148279).
本発明者らは、上記白金、ルテニウム、パラジウムなどの貴金属と各種多孔質担体とを組み合せてさらに実験、検討を繰り返して追求したところ、上記白金と多孔質酸化スズの組み合わせの場合のほか、白金と多孔質の酸化ジルコニウムの組み合わせの場合にも、白金と多孔質酸化スズの組み合わせの場合に準じて、低温域、特に４５０℃以下という低温域におけるメタンの酸化除去用触媒として有効で、良好な耐ＳＯX性を有することを見い出した。 The inventors of the present invention have repeatedly pursued experiments and examinations by combining the above-mentioned noble metals such as platinum, ruthenium and palladium with various porous carriers, and in addition to the combination of the above platinum and porous tin oxide, In the case of a combination of platinum and porous zirconium oxide, it is effective as a catalyst for oxidative removal of methane in a low temperature range, particularly at a low temperature range of 450 ° C. or lower, in accordance with the combination of platinum and porous tin oxide. It was found to have SO X resistance.
すなわち、本発明は、白金をそれ単独で、多孔質の酸化ジルコニウムに担持してなる硫黄酸化物を含む燃焼排ガス中のメタン酸化除去用触媒を提供することを目的とし、また、硫黄酸化物を含む燃焼排ガスを該メタン酸化除去用触媒に５００℃以下の低温域、特に４５０〜３５０℃という低温域で通すことにより燃焼排ガス中のメタンを長期にわたり有効に酸化除去する方法を提供することを目的とし、さらに、メタンの低温酸化酸化除去用触媒の製造方法を提供することを目的とする。 That is, an object of the present invention is to provide a catalyst for removing methane oxidation in combustion exhaust gas containing sulfur oxide formed by supporting platinum alone on porous zirconium oxide. An object of the present invention is to provide a method for effectively oxidizing and removing methane in combustion exhaust gas over a long period of time by passing the combustion exhaust gas containing the exhaust gas through the catalyst for removing methane oxidation in a low temperature range of 500 ° C. or lower, particularly 450 to 350 ° C. Furthermore, it aims at providing the manufacturing method of the catalyst for low temperature oxidation oxidation removal of methane.
本発明は、（１）硫黄酸化物を含む燃焼排ガス中のメタンを低温域において酸化除去するための触媒であって、該酸化除去用触媒が多孔質の酸化ジルコニウムに白金を担持させてなる触媒であることを特徴とする硫黄酸化物を含む燃焼排ガス中のメタンの低温酸化除去用触媒を提供する。 The present invention is (1) a catalyst for oxidizing and removing methane in combustion exhaust gas containing sulfur oxides in a low temperature range, wherein the catalyst for oxidizing and removing platinum is supported on porous zirconium oxide. The present invention provides a catalyst for low-temperature oxidation removal of methane in combustion exhaust gas containing sulfur oxide.
また、本発明は、（２）硫黄酸化物を含む燃焼排ガス中のメタンを低温域で酸化除去する方法であって、該燃焼排ガスを多孔質の酸化ジルコニウムに白金を担持させてなる酸化除去用触媒に低温域で通すことによりメタンを酸化除去することを特徴とする硫黄酸化物を含む燃焼排ガス中のメタンの低温酸化除去方法を提供する。 Further, the present invention is (2) a method for oxidizing and removing methane in combustion exhaust gas containing sulfur oxide at a low temperature range, and for oxidizing and removing the combustion exhaust gas by carrying platinum on porous zirconium oxide. Provided is a low-temperature oxidative removal method for methane in combustion exhaust gas containing sulfur oxide, characterized by oxidizing and removing methane by passing it through a catalyst in a low-temperature region.
さらに、本発明は、（３）多孔質の酸化ジルコニウムに白金を担持してなる硫黄酸化物を含む燃焼排ガス中のメタンの低温酸化除去用触媒の製造方法であって、白金化合物を多孔質の酸化ジルコニウムに対して白金化合物の水溶液による含浸法または平衡吸着法により担持させた後、焼成することを特徴とする硫黄酸化物を含む燃焼排ガス中のメタンの低温酸化除去用触媒の製造方法を提供する。 The present invention further relates to (3) a method for producing a catalyst for low-temperature oxidation removal of methane in combustion exhaust gas containing sulfur oxide in which platinum is supported on porous zirconium oxide, wherein the platinum compound is porous. Provided is a method for producing a catalyst for low-temperature oxidation removal of methane in combustion exhaust gas containing sulfur oxide, characterized in that zirconium oxide is supported by an impregnation method or an equilibrium adsorption method with an aqueous solution of a platinum compound and then calcined. To do.
本発明（１）は、硫黄酸化物を含む燃焼排ガス中のメタンを低温域において酸化除去するための触媒である。そして、該酸化除去用触媒が多孔質の酸化ジルコニウムに白金を担持させてなる触媒であることを特徴とする。また、本発明（２）は、硫黄酸化物を含む燃焼排ガス中のメタンを低温域で酸化除去する方法である。そして、該燃焼排ガスを多孔質の酸化ジルコニウムに白金を担持させてなる酸化除去用触媒に低温域で通すことによりメタンを酸化除去することを特徴とする。 The present invention (1) is a catalyst for oxidizing and removing methane in combustion exhaust gas containing sulfur oxide in a low temperature range. The oxidation removal catalyst is a catalyst in which platinum is supported on porous zirconium oxide. Further, the present invention (2) is a method for oxidizing and removing methane in combustion exhaust gas containing sulfur oxides in a low temperature range. The combustion exhaust gas is passed through an oxidation removal catalyst in which platinum is supported on porous zirconium oxide in a low temperature range to oxidize and remove methane.
本発明（１）〜（２）によれば、従来メタンの酸化活性貴金属と考えられていたパラジウムを一切含まず、また、従来単独では有効でないと考えられていた白金を、それ単独で、多孔質の酸化ジルコニウムに担持することにより、５００℃以下の低温域、特に４５０〜３５０℃という低温域においてメタンを長期にわたり有効に酸化し除去することができる。このため、特に硫黄化合物を付臭剤として含む都市ガスを燃料とする希薄燃焼式エンジンからの燃焼排ガスに対しても有効に適用できる。また、本発明の酸化除去用触媒は、有効な耐久性を有することから、交換頻度を少なくでき、排ガス処理システムの低コスト化を図ることができる。 According to the present invention (1) to (2), any platinum that has not been considered to be effective by itself alone, including no palladium that has been conventionally considered as an oxidation active noble metal of methane, can be made porous by itself. By being supported on high quality zirconium oxide, methane can be effectively oxidized and removed over a long period of time in a low temperature range of 500 ° C. or lower, particularly in a low temperature range of 450 to 350 ° C. Therefore, the present invention can be effectively applied particularly to combustion exhaust gas from a lean combustion engine using city gas containing a sulfur compound as an odorant as fuel. Moreover, since the oxidation removal catalyst of the present invention has effective durability, the replacement frequency can be reduced, and the cost of the exhaust gas treatment system can be reduced.
また、本発明（３）は、多孔質の酸化ジルコニウムに白金を担持してなる硫黄酸化物を含む燃焼排ガス中のメタンの低温酸化除去用触媒の製造方法である。そして、白金化合物を多孔質の酸化ジルコニウムに対して白金化合物の水溶液による含浸法または平衡吸着法により担持させた後、焼成することを特徴とする。 In addition, the present invention (3) is a method for producing a low-temperature oxidation removal catalyst for methane in combustion exhaust gas containing sulfur oxide obtained by supporting platinum on porous zirconium oxide. The platinum compound is supported on porous zirconium oxide by an impregnation method using an aqueous solution of a platinum compound or an equilibrium adsorption method, and then fired.
本メタンの低温酸化除去用触媒の製造法としては、多孔質の酸化ジルコニウムに対して白金を均一に担持させ得る手法であれば特に限定はないが、好ましくは含浸法や平衡吸着法が適用される。担体である酸化ジルコニウム（ＺｒＯ2）は多孔質であればよい。白金の原料としては白金化合物を用いる。その例としては白金の硝酸塩、塩化物、酢酸塩、錯塩（テトラアンミン白金塩、ジニトロジアンミン白金等）などが挙げられる。 There is no particular limitation on the method for producing the low-temperature oxidative removal catalyst for methane as long as it is a method capable of uniformly supporting platinum on porous zirconium oxide, but preferably an impregnation method or an equilibrium adsorption method is applied. The Zirconium oxide (ZrO 2 ) as a support may be porous. A platinum compound is used as a raw material for platinum. Examples thereof include platinum nitrate, chloride, acetate, complex salt (tetraammine platinum salt, dinitrodiammine platinum, etc.), and the like.
一例として含浸法の場合の態様例を述べると、白金化合物を水に溶解して水溶液とし、その水溶液に粉末状等の多孔質の酸化ジルコニウムを投入して撹拌し、該酸化ジルコニウムに白金化合物を含浸させて担持する。ここで、白金化合物水溶液のｐＨは、酸性域からアルカリ性域まで広い範囲で設定できるが、ｐＨ値をより大きくするのが好ましく、これによりメタンの酸化性能を向上させることができる。そのｐＨ値は特に１２以上であるのが好ましい。その後、常法により乾燥し、焼成する。 As an example, an embodiment example in the case of the impregnation method is described. A platinum compound is dissolved in water to form an aqueous solution, and porous zirconium oxide such as powder is added to the aqueous solution and stirred, and the platinum compound is added to the zirconium oxide. Impregnate and carry. Here, the pH of the platinum compound aqueous solution can be set in a wide range from an acidic range to an alkaline range, but it is preferable to increase the pH value, thereby improving the oxidation performance of methane. The pH value is particularly preferably 12 or more. Thereafter, it is dried and fired by a conventional method.
本酸化触媒における酸化ジルコニウム担体に対する白金の担持量は、酸化ジルコニウムに対して０．０２５〜１５．０ｗｔ％の範囲であり、より好ましくは０．８〜９．０ｗｔ％の範囲である。白金の担持量が０．０２５ｗｔ％を下回る場合にもなお有効であるが、その分触媒効果は減少する。その担持量が１５．０ｗｔ％程度を上回る場合にも同様に有効な触媒効果が得られるが、白金を１５ｗｔ％程度まで担持させていれば所期の触媒効果が得られるのでコスト等の面からしても上限１５．０ｗｔ％程度で十分である。もちろん、上記範囲０．０２５〜１５．０ｗｔ％の前後としても差し支えない。本発明の酸化触媒をハニカム状の形態で使用する場合には、これらに準じた量を担持させる。 The amount of platinum supported on the zirconium oxide support in the present oxidation catalyst is in the range of 0.025 to 15.0 wt%, more preferably in the range of 0.8 to 9.0 wt% with respect to zirconium oxide. Although it is still effective when the supported amount of platinum is less than 0.025 wt%, the catalytic effect is reduced accordingly. An effective catalytic effect can be obtained when the loading amount exceeds about 15.0 wt%. However, if platinum is supported up to about 15 wt%, the desired catalytic effect can be obtained, so from the viewpoint of cost and the like. Even so, an upper limit of about 15.0 wt% is sufficient. Of course, the range may be around 0.025 to 15.0 wt%. When the oxidation catalyst of the present invention is used in the form of a honeycomb, an amount according to these is supported.
触媒の形態としては粉末状、粒状、顆粒状（含：球状）、ペレット（円筒型、環状型）状、タブレット（錠剤）状、或いはハニカム（モノリス体）状等適宜の形状として使用することができる。なお、本発明ではこれら形状の触媒に排ガスを通す必要があるため、粉末状の場合には、これを充填した触媒層から逸散しないように所定粒度範囲に整粒するか、または造粒し、あるいは加圧成形や押出し成形して用いるのが望ましい。このうち押出し成形の場合には適宜所定長さに切断してペレット化して使用される。 The catalyst may be used in an appropriate shape such as powder, granule, granule (including sphere), pellet (cylindrical or annular), tablet (tablet), or honeycomb (monolith). it can. In the present invention, since it is necessary to pass exhaust gas through the catalyst of these shapes, in the case of a powder, it is sized within a predetermined particle size range or granulated so as not to escape from the catalyst layer filled with the catalyst. Alternatively, it is desirable to use by pressure molding or extrusion molding. Of these, in the case of extrusion molding, it is cut into a predetermined length and pelletized.
本触媒の形態としてハニカム（モノリス体）状の形態は好ましい形状である。特に希薄燃焼式エンジンからの排ガスを処理する場合には、好ましくはハニカム状として用いられる。ハニカム状触媒の製造態様としては、例えば（１）ハニカム状構造の基材に酸化ジルコニウムをウォッシュコートして担持させた後、該酸化ジルコニウム担持のハニカム基材に白金化合物の水溶液を担持させる、（２）白金化合物の水溶液に酸化ジルコニウムを分散させてスラリーとし、これをハニカム状構造の基材にウォッシュコートして担持させる。次いで、常法により乾燥させ、焼成する。 As a form of the present catalyst, a honeycomb (monolith body) form is a preferred form. In particular, when treating exhaust gas from a lean combustion engine, it is preferably used as a honeycomb. For example, the honeycomb-shaped catalyst may be manufactured by (1) washing and supporting zirconium oxide on a honeycomb-structured base material, and then supporting an aqueous platinum compound solution on the zirconium oxide-supported honeycomb base material. 2) Zirconium oxide is dispersed in an aqueous solution of a platinum compound to form a slurry, which is washed and supported on a substrate having a honeycomb structure. Next, it is dried and fired by a conventional method.
ハニカム状の形態での基材としてはセラミックス製またはメタル製の基材を使用することができる。セラミックスの好ましい例としてはコージェライトが挙げられ、メタルの好ましい例としてはステンレス鋼や鉄ーアルミニウムークロム系合金などが挙げられる。 As the substrate in the honeycomb form, a ceramic or metal substrate can be used. Preferable examples of ceramics include cordierite, and preferable examples of metals include stainless steel and iron-aluminum-chromium alloys.
従来、貴金属触媒は、排ガス中のＳＯ2により被毒し性能劣化を来すことが知られている。これに対して、本発明に係る酸化ジルコニウム（ＺｒＯ2）担体に白金を担持した酸化触媒は、長期間にわたり良好な耐ＳＯX性を有する。 Conventionally, it is known that a noble metal catalyst is poisoned by SO 2 in exhaust gas and deteriorates its performance. In contrast, the oxidation catalyst in which platinum is supported on a zirconium oxide (ZrO 2 ) support according to the present invention has good SO X resistance over a long period of time.
本発明の酸化除去用触媒を使用する装置としては固定床流通型反応装置などを用いることができる。図１は本発明の酸化除去用触媒を使用する装置態様例を示す図である。図１中、Ａは被処理燃焼排ガス導入管、Ｂは酸化除去用触媒層（反応管）、Ｃは処理済み排ガスの導出管であり、矢印（→）は燃焼排ガスの流れ方向を示している。本酸化除去用触媒は、図１のような装置態様とは限らず、燃焼排ガス流に対して配置し得る態様であれば各種装置態様で使用される。ハニカム状の本酸化除去用触媒を図１のような触媒層にセットするには、その断面開口が燃焼排ガスの流れ方向に向くように配置される。 As the apparatus using the oxidation removal catalyst of the present invention, a fixed bed flow type reaction apparatus or the like can be used. FIG. 1 is a view showing an example of an apparatus using the oxidation removal catalyst of the present invention. In FIG. 1, A is a treated exhaust gas introduction pipe, B is a catalyst layer for oxidation removal (reaction pipe), C is a treated exhaust gas outlet pipe, and an arrow (→) indicates the flow direction of the combustion exhaust gas. . The present catalyst for oxidation removal is not limited to the apparatus mode as shown in FIG. 1, and may be used in various apparatus modes as long as it can be arranged with respect to the combustion exhaust gas flow. In order to set the honeycomb-shaped main catalyst for oxidation removal in the catalyst layer as shown in FIG. 1, the cross-sectional opening is arranged to face the flow direction of the combustion exhaust gas.
以下、実施例に基づき本発明をさらに詳しく説明するが、本発明が実施例に限定されないことはもちろんである。 EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, it cannot be overemphasized that this invention is not limited to an Example.
《実施例１》
〈実施例ペレット触媒の調製〉
ペレット触媒を含浸法により調製した。担体粉末は、原料酸化ジルコニウム〔第一希元素化学工業社製、表面積＝４０ｍ2/ｇ〕を昇温速度１℃／ｍｉｎ、６００℃で３時間焼成して得た。該担体粉末とジニトロジアンミン白金〔Ｐｔ（ＮＯ2）2（ＮＨ3）2〕の硝酸酸性水溶液（ｐＨ＝１）の所定量をフラスコに入れ、ロータリーエバポレータにより、５０℃で減圧乾燥させた後、残った粉末を１７５℃で６時間、次いで２７５℃で１２時間乾燥し、その後順次、昇温速度１０℃／ｍｉｎ、２００℃で３時間、昇温速度１℃／ｍｉｎ、２７０℃で６時間、昇温速度１℃／ｍｉｎ、５５０℃で３時間焼成して触媒粉末を得た。得られた触媒粉末を打錠成形器により５００ｋｇ／ｃｍ2で成形した後、３５５〜７１０μｍ（＝３５〜３１メッシュ）に分級した。こうしてペレット触媒を得た。
Example 1
<Preparation of Example Pellet Catalyst>
A pellet catalyst was prepared by an impregnation method. The carrier powder was obtained by calcining raw material zirconium oxide (manufactured by Daiichi Kagaku Kagaku Kogyo Co., Ltd., surface area = 40 m 2 / g) at a heating rate of 1 ° C./min and 600 ° C. for 3 hours. A predetermined amount of nitric acid aqueous solution (pH = 1) of the carrier powder and dinitrodiammine platinum [Pt (NO 2 ) 2 (NH 3 ) 2 ] is placed in a flask and dried under reduced pressure at 50 ° C. by a rotary evaporator. The remaining powder was dried at 175 ° C. for 6 hours, then at 275 ° C. for 12 hours, and then sequentially heated at a rate of 10 ° C./min, 200 ° C. for 3 hours, heated at a rate of 1 ° C./min, 270 ° C. for 6 hours, The catalyst powder was obtained by calcining at a heating rate of 1 ° C./min at 550 ° C. for 3 hours. The obtained catalyst powder was molded at 500 kg / cm 2 by a tableting machine and then classified into 355 to 710 μm (= 35 to 31 mesh). In this way, a pellet catalyst was obtained.
〈比較例ペレット触媒の調製〉
上記と同様にして、酸化ジルコニウム担体にＰｔとＰｄを担持したペレット触媒（Ｐｔ-Ｐｄ/ＺｒＯ2ペレット触媒）、酸化ジルコニウム担体にＰｄを担持したペレット触媒（Ｐｄ/ＺｒＯ2ペレット触媒）を調製した。Ｐｔ源としてジニトロジアンミン白金を用い、Ｐｄ源としては硝酸パラジウム〔Ｐｄ（ＮＯ3）2〕を用い、酸化ジルコニウム担体は、前記と同じ原料酸化ジルコニウムを用いて前記と同じ処理をして得た担体粉末である。
<Preparation of Comparative Example Pellet Catalyst>
In the same manner as above, a pellet catalyst (Pt—Pd / ZrO 2 pellet catalyst) supporting Pt and Pd on a zirconium oxide support and a pellet catalyst (Pd / ZrO 2 pellet catalyst) supporting Pd on a zirconium oxide support were prepared. . Dinitrodiammine platinum was used as the Pt source, palladium nitrate [Pd (NO 3 ) 2 ] was used as the Pd source, and the zirconium oxide support was obtained by the same treatment as described above using the same raw material zirconium oxide. It is a powder.
〈性能試験〉
上記ペレット触媒の調製で得た各ペレット触媒を用いて、図１に示すような通常の固定床流通型反応装置を用いて触媒性能試験及び耐久試験を実施した。使用ペレット触媒は、Ｐｔ/ＺｒＯ2（Ｐｔ＝６ｗｔ％：ＺｒＯ2に対する担持量、以下同じ）、Ｐｔ-Ｐｄ/ＺｒＯ2（Ｐｔ＝３ｗｔ％、Ｐｄ＝３ｗｔ％）、Ｐｄ/ＺｒＯ2（Ｐｄ＝６ｗｔ％）である。
<performance test>
Using each pellet catalyst obtained in the preparation of the pellet catalyst, a catalyst performance test and a durability test were performed using a normal fixed bed flow type reactor as shown in FIG. The pellet catalyst used is Pt / ZrO 2 (Pt = 6 wt%: supported amount for ZrO 2 , the same applies hereinafter), Pt—Pd / ZrO 2 (Pt = 3 wt%, Pd = 3 wt%), Pd / ZrO 2 (Pd = 6 wt%).
試験条件は下記のとおりとした。排ガス温度（＝反応温度）：４００℃、空間速度（ＳＶ）：１６０，０００ｈ-1（全流量３．３５Ｌ/ｍｉｎ、触媒体積：１．２６ｃｍ3）、排ガスすなわち試験ガス：ＣＨ4＝２０００ｐｐｍ（ｖｏｌｐｐｍ、以下同じ）、ＣＯ＝８２０ｐｐｍ、ＮＯ＝８０ｐｐｍ、ＣＯ2＝４．９％（ｖｏｌ％、以下同じ）、Ｏ2＝１０．５％、Ｈ2Ｏ＝１０％、ＳＯ2＝１ｐｐｍ、Ｎ2＝バランス。 The test conditions were as follows. Exhaust gas temperature (= reaction temperature): 400 ° C., space velocity (SV): 160,000 h −1 (total flow rate 3.35 L / min, catalyst volume: 1.26 cm 3 ), exhaust gas, that is, test gas: CH 4 = 2000 ppm ( vol ppm, the same applies hereinafter), CO = 820 ppm, NO = 80 ppm, CO 2 = 4.9% (vol%, the same applies hereinafter), O 2 = 10.5%, H 2 O = 10%, SO 2 = 1 ppm, N 2 = Balance.
試験ガスの分析は、ＦＩＤ式全炭化水素計、赤外線式ＣＯ／ＣＯ2計、化学発光式ＮＯX計及び磁気式酸素計からなる排ガス分析計（堀場製作所社製）を用いて行った。ＣＨ4の酸化除去活性は、反応管前後のＣＨ4の濃度差から評価した。酸化除去活性〔＝メタン除去率（％）〕は以下の式により求めた。これらの点は、実施例２の性能試験についても同じである。図２は本性能試験の結果を示す図である。 The analysis of the test gas was performed using an exhaust gas analyzer (manufactured by Horiba, Ltd.) consisting of a FID-type total hydrocarbon meter, an infrared CO / CO 2 meter, a chemiluminescent NO x meter, and a magnetic oxygen meter. Oxide removal activity of CH 4 was evaluated from the concentration difference of the reaction tube before and after the CH 4. The oxidation removal activity [= methane removal rate (%)] was determined by the following equation. These points are the same for the performance test of Example 2. FIG. 2 shows the results of this performance test.
図２のとおり、まず、比較例であるＰｔ（３ｗｔ％）-Ｐｄ（３ｗｔ％）/ＺｒＯ2触媒の場合、メタン除去率は初期段階で４３％であり、以降徐々に低下し、５０時間経過時で２２％、１００時間経過時で１４％と低下し、１４５時間経過時においては１２％にまで低下している。次に、同じく比較例であるＰｄ（６ｗｔ％）/ＺｒＯ2触媒の場合、メタン除去率は初期段階では７１％と高いが、以降急激に低下し、５０時間経過時で２０％、１４５時間経過時においては９％に低下している。 As shown in FIG. 2, first, in the case of a Pt (3 wt%)-Pd (3 wt%) / ZrO 2 catalyst as a comparative example, the methane removal rate is 43% at the initial stage, and then gradually decreases and 50 hours elapse. 22% at the time, 14% at the time of 100 hours, and 12% at the time of 145 hours. Next, in the case of the Pd (6 wt%) / ZrO 2 catalyst, which is also a comparative example, the methane removal rate is as high as 71% at the initial stage, but then rapidly decreases, and after 20 hours, 20% and 145 hours have elapsed. At times, it has dropped to 9%.
これに対して、実施例であるＰｔ（６ｗｔ％）/ＺｒＯ2触媒の場合、メタン除去率は初期段階で５２％程度であり、２４時間経過時で４０％、以降徐々に低下はするが、２０％以上の除去率を保持し、１４５時間経過時においても２２％のメタン除去率を維持している。このように、３種のメタン酸化触媒のうち、Ｐｔ/ＺｒＯ2触媒だけが、ＳＯ2を１ｐｐｍ含む試験ガスについて長期間にわたり性能劣化が少なく、良好なメタン除去率を維持している。図２は温度４００℃の場合であるが、それより高い反応温度、例えば５００℃の場合や４５０℃の場合のメタン除去率は相対的に高く、またそれより低い反応温度、例えば３７５℃の場合や３５０℃の場合にも、４００℃の場合と同じく良好なメタン除去率、耐久性を示した。 On the other hand, in the case of the Pt (6 wt%) / ZrO 2 catalyst as an example, the methane removal rate is about 52% at the initial stage, 40% after 24 hours, and gradually decreases thereafter. The removal rate of 20% or more is maintained, and the methane removal rate of 22% is maintained even after 145 hours. Thus, among the three kinds of methane oxidation catalysts, only the Pt / ZrO 2 catalyst has little performance deterioration over a long period of time for the test gas containing 1 ppm of SO 2 and maintains a good methane removal rate. FIG. 2 shows the case where the temperature is 400 ° C., but the methane removal rate is relatively high when the reaction temperature is higher, for example, 500 ° C. or 450 ° C., and the reaction temperature is lower than that, for example, 375 ° C. Also at 350 ° C., the same methane removal rate and durability were exhibited as in the case of 400 ° C.
《実施例２》
〈実施例ペレット触媒の調製〉
Ｐｔの担持時におけるＰｔ化合物水溶液について、アンモニア水により、そのｐＨ値を１２に変えた点以外は、実施例１の〈実施例ペレット触媒の調製〉と同様にしてＰｔ/ＺｒＯ2ペレット触媒を調製した。
Example 2
<Preparation of Example Pellet Catalyst>
A Pt / ZrO 2 pellet catalyst was prepared in the same manner as in <Preparation of Example Pellet Catalyst> in Example 1 except that the pH value of the Pt compound aqueous solution when Pt was supported was changed to 12 with ammonia water. did.
〈比較例ペレット触媒の調製〉
また、ＰｔとＰｄの担持時、Ｐｄの担持時における水溶液について、アンモニア水により、そのｐＨ値を１２に変えた点以外は、実施例１の〈比較例ペレット触媒の調製〉と同様にして、酸化ジルコニウム担体にＰｔとＰｄを担持したペレット触媒（Ｐｔ-Ｐｄ/ＺｒＯ2ペレット触媒）、酸化ジルコニウム担体にＰｄを担持したペレット触媒（Ｐｄ/ＺｒＯ2ペレット触媒）を調製した。
<Preparation of Comparative Example Pellet Catalyst>
Moreover, except that the pH value of the aqueous solution at the time of supporting Pt and Pd was changed to 12 with ammonia water, the same as in <Preparation of Comparative Example Pellet Catalyst> in Example 1, A pellet catalyst (Pt—Pd / ZrO 2 pellet catalyst) supporting Pt and Pd on a zirconium oxide support and a pellet catalyst (Pd / ZrO 2 pellet catalyst) supporting Pd on a zirconium oxide support were prepared.
〈性能試験〉
実施例ペレット触媒及び比較例ペレット触媒について性能試験を実施した。試験条件は実施例１の試験条件と同じである。図３は本性能試験の結果である。図３のとおり、メタン除去率は、ｐＨ値を１２に上げることにより向上させ得ることを示してる。
<performance test>
A performance test was conducted on the example pellet catalyst and the comparative example pellet catalyst. The test conditions are the same as the test conditions of Example 1. FIG. 3 shows the results of this performance test. As shown in FIG. 3, it is shown that the methane removal rate can be improved by raising the pH value to 12.
まず、比較例であるＰｔ（３ｗｔ％）-Ｐｄ（３ｗｔ％）/ＺｒＯ2触媒の場合、メタン除去率は初期段階で４９％であり、以降徐々に低下し、５０時間経過時で２５％、１００時間経過時で１７％と低下し、１４５時間経過時においては１６％にまで低下している。次に、同じく比較例であるＰｄ（６ｗｔ％）/ＺｒＯ2触媒の場合、メタン除去率は初期段階では７１％と高いが、以降急激に低下し、５０時間経過時で２０％、１４５時間経過時においては９％に低下している。 First, in the case of the Pt (3 wt%)-Pd (3 wt%) / ZrO 2 catalyst which is a comparative example, the methane removal rate is 49% in the initial stage, and then gradually decreases, and after the lapse of 50 hours, 25%, It decreases to 17% when 100 hours elapse and decreases to 16% when 145 hours elapses. Next, in the case of the Pd (6 wt%) / ZrO 2 catalyst which is also a comparative example, the methane removal rate is as high as 71% in the initial stage, but then rapidly decreases, and after 20 hours, 20% and 145 hours have passed. At times, it has dropped to 9%.
これに対して、実施例であるＰｔ（６ｗｔ％）/ＺｒＯ2触媒の場合、メタン除去率は初期段階で６６％程度であり、２０時間経過時で６０％、以降徐々に低下はするが、５０時間経過時で５０％、１００時間経過時で４０％の除去率保持し、１４５時間経過時においても３７％のメタン除去率を維持している。このように、３種のメタン酸化触媒のうち、Ｐｔ/ＺｒＯ2触媒だけが、ＳＯ2を１ｐｐｍ含む試験ガスについて長期間にわたり性能劣化が少なく、良好なメタン除去率を維持している。図３は温度４００℃の場合であるが、それより高い反応温度、例えば５００℃の場合や４５０℃の場合のメタン除去率は相対的に高く、またそれより低い反応温度、例えば３７５℃の場合や３５０℃の場合にも、４００℃の場合と同じく良好なメタン除去率、耐久性を示した。 In contrast, in the case of the Pt (6 wt%) / ZrO 2 catalyst as an example, the methane removal rate is about 66% at the initial stage, 60% after 20 hours, and gradually decreases thereafter. The removal rate of 50% is maintained after 50 hours and 40% after 100 hours, and the methane removal rate of 37% is maintained even after 145 hours. Thus, among the three kinds of methane oxidation catalysts, only the Pt / ZrO 2 catalyst has little performance deterioration over a long period of time for the test gas containing 1 ppm of SO 2 and maintains a good methane removal rate. FIG. 3 shows the case where the temperature is 400 ° C., but the methane removal rate is relatively high when the reaction temperature is higher, for example, 500 ° C. or 450 ° C., and the reaction temperature is lower than that, for example, 375 ° C. Also at 350 ° C., the same methane removal rate and durability were exhibited as in the case of 400 ° C.
Ａ 被処理燃焼排ガス導入管
Ｂ 酸化除去用触媒層（反応管）
Ｃ 処理済み排ガスの導出管
A Treated flue gas introduction pipe B Oxidation removal catalyst layer (reaction pipe)
C Outlet pipe for treated exhaust gas
Claims (13)
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Citations (7)
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|---|---|---|---|---|
| JPS5941706A (en) * | 1982-08-31 | 1984-03-08 | Nippon Shokubai Kagaku Kogyo Co Ltd | Combustion catalyst system for methane fuel |
| JPS6051543A (en) * | 1983-08-31 | 1985-03-23 | Mitsubishi Heavy Ind Ltd | Oxidizing catalyst |
| JPH05220395A (en) * | 1992-02-14 | 1993-08-31 | Daihatsu Motor Co Ltd | Production of ternary catalyst excellent in low-temperature activity |
| JPH0724260A (en) * | 1993-07-15 | 1995-01-27 | I C T:Kk | Catalyst for purification of exhaust gas from diesel engine |
| JPH11319559A (en) * | 1998-03-09 | 1999-11-24 | Osaka Gas Co Ltd | Catalyst and method for purifying exhaust gas containing methane |
| JP2002331226A (en) * | 2001-05-09 | 2002-11-19 | Toyota Central Res & Dev Lab Inc | Method and apparatus for cleaning exhaust gas |
| JP2003311153A (en) * | 2002-04-19 | 2003-11-05 | Osaka Gas Co Ltd | Catalyst for oxidation of hydrocarbon in exhaust gas and method for oxidizing and removing hydrocarbon in exhaust gas |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5941706A (en) * | 1982-08-31 | 1984-03-08 | Nippon Shokubai Kagaku Kogyo Co Ltd | Combustion catalyst system for methane fuel |
| JPS6051543A (en) * | 1983-08-31 | 1985-03-23 | Mitsubishi Heavy Ind Ltd | Oxidizing catalyst |
| JPH05220395A (en) * | 1992-02-14 | 1993-08-31 | Daihatsu Motor Co Ltd | Production of ternary catalyst excellent in low-temperature activity |
| JPH0724260A (en) * | 1993-07-15 | 1995-01-27 | I C T:Kk | Catalyst for purification of exhaust gas from diesel engine |
| JPH11319559A (en) * | 1998-03-09 | 1999-11-24 | Osaka Gas Co Ltd | Catalyst and method for purifying exhaust gas containing methane |
| JP2002331226A (en) * | 2001-05-09 | 2002-11-19 | Toyota Central Res & Dev Lab Inc | Method and apparatus for cleaning exhaust gas |
| JP2003311153A (en) * | 2002-04-19 | 2003-11-05 | Osaka Gas Co Ltd | Catalyst for oxidation of hydrocarbon in exhaust gas and method for oxidizing and removing hydrocarbon in exhaust gas |
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