JP4429950B2 - Catalyst for removing oxidation of methane from combustion exhaust gas and exhaust gas purification method - Google Patents
Catalyst for removing oxidation of methane from combustion exhaust gas and exhaust gas purification method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims description 139
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 100
- 238000002485 combustion reaction Methods 0.000 title claims description 38
- 238000007254 oxidation reaction Methods 0.000 title claims description 35
- 230000003647 oxidation Effects 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 26
- 238000000746 purification Methods 0.000 title 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 135
- 239000007789 gas Substances 0.000 claims description 65
- 229910052697 platinum Inorganic materials 0.000 claims description 34
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 32
- 229910001887 tin oxide Inorganic materials 0.000 claims description 32
- 229910052741 iridium Inorganic materials 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 20
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 19
- 230000001590 oxidative effect Effects 0.000 claims description 18
- 150000003058 platinum compounds Chemical class 0.000 claims description 16
- 150000002504 iridium compounds Chemical class 0.000 claims description 15
- 239000008188 pellet Substances 0.000 claims description 13
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 13
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000567 combustion gas Substances 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 6
- 239000003426 co-catalyst Substances 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 229910052815 sulfur oxide Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 239000003826 tablet Substances 0.000 claims 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 62
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 15
- 238000011056 performance test Methods 0.000 description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 description 12
- 238000011068 loading method Methods 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 6
- -1 natural gas Chemical class 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-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
- 239000012153 distilled water Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- ZYSSNSIOLIJYRF-UHFFFAOYSA-H Cl[Ir](Cl)(Cl)(Cl)(Cl)Cl Chemical compound Cl[Ir](Cl)(Cl)(Cl)(Cl)Cl ZYSSNSIOLIJYRF-UHFFFAOYSA-H 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 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 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
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- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001133 acceleration Effects 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
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 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
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical group 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
- 239000010970 precious metal Substances 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 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
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry 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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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除去するための触媒、該酸化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酸化除去する方法及び該酸化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, a method for oxidizing and removing methane in combustion exhaust gas containing sulfur oxide using the oxidation catalyst, and the oxidation catalyst. It relates to the manufacturing method.
ボイラー、加熱炉、あるいはガス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が使用される。それら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（ＣＯ）、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まれており、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。この点は、コージェネレーションシステムやＧＨＰ(Gas Heat Pump）における希薄燃焼ガスエンジンからの排ガスについても同様である。 Hydrocarbons such as natural gas, city gas, light oil and kerosene are used as fuel for boilers, heating furnaces, gas engines and gas turbines. The exhaust gas from burning these fuels contains nitrogen oxides (NO x ), sulfur oxides (SO x ), carbon monoxide (CO), odorous substances, soot, and unburned hydrocarbons. It must be discharged harmlessly because it causes environmental pollution. The same applies to exhaust gas from a lean combustion gas engine in a cogeneration system or GHP (Gas Heat Pump).
希薄燃焼ガスエンジンのような希薄燃焼方式の場合には、その燃焼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、燃焼排ガス中の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除去、浄化する三元触媒による処理法が開発されている。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。 In the case of a lean combustion system such as a lean combustion gas engine, a large amount of oxygen and water vapor coexist in the combustion 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 has been developed that simultaneously removes and purifies three components in combustion exhaust gas, that is, hydrocarbon, nitrogen oxide, and carbon monoxide. 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.
従来、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ているが、それら貴金属触媒は担体に担持した形で使用され、その担体としてはアルミナやジルコニアなどが知られている。しかし、炭化水素が特にメタンの場合、その酸化にはパラジウムが有効とされており、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。 Conventionally, noble metals such as palladium, platinum and rhodium have been used as hydrocarbon oxidation catalysts, but these noble metal catalysts are used in a form supported on a carrier, and alumina and zirconia are known as the carrier. . However, when the hydrocarbon is methane in particular, palladium is effective for its oxidation, and platinum is not effective by itself and is only used as an auxiliary.
例えば、特開２０００−３３２６６号公報や特開２０００−２５４５０５号公報には、酸化スズ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。このうち特開２０００−３３２６６号公報には、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足的に使用されるに過ぎない。この点、特開２００１−１９０９３１号公報においても同様である。 For example, in Japanese Unexamined Patent Publication No. 2000-33266 and Japanese Unexamined Patent Publication No. 2000-254505, a catalyst in which palladium is supported on a tin oxide carrier exhibits high resistance to inhibition of catalytic activity by sulfur oxide. It is shown. Of these, JP-A-2000-33266 discloses a catalyst in which palladium and platinum are supported on a tin oxide carrier, but platinum is only used together with palladium. This also applies to JP 2001-190931 A.
また、例えば希薄燃焼ガスエンジンからの排ガスの温度は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が得られないのが現状である。 Further, for example, since the temperature of exhaust gas from a lean combustion gas engine is as low as 500 ° C. or less, usually about 500-400 ° C., 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. However, the present situation is that sufficient durability that can be used for this is not obtained.
本発明者らは、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、単独では有効でないと考えられていた白金を単独で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触媒として有効であり、しかも高い耐ＳＯX性を有することを見い出し、酸化スズに白金を担持させてなるメタン酸化除去用触媒及びこの触媒による燃焼排ガス中のメタンの酸化除去方法を先に出願している（ＷＯ ２００４/１０３５５４ Ａ１）。 The inventors of the present invention include a catalyst that does not contain any palladium that is conventionally considered to be an oxidation-active noble metal for methane, and that is platinum alone supported on tin oxide, which is considered to be ineffective alone. It has been found that it is effective as a catalyst for removing methane oxidation in the low temperature range as described below, and also has high SO X resistance, and a catalyst for removing methane oxidation comprising platinum supported on tin oxide, and methane in combustion exhaust gas by this catalyst. Has already filed an application for the method of removing oxidization (WO 2004/103554 A1).
上記メタンの酸化除去用触媒は燃焼排ガス中のメタンの酸化除去用として非常に有効であるが、引き続き当該触媒の実用化に向けて追求したところ、耐久性の点でさらに改善の余地があることが分かった。すなわち、本発明は、耐久性を改善した白金を酸化スズに担持してなる、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及び当該触媒による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、また、その酸化触媒の製造方法を提供することを目的とする。 The above methane removal catalyst is very effective for removal of methane in combustion exhaust gas. However, when the catalyst is continuously pursued for practical use, there is room for further improvement in terms of durability. I understood. That is, the present invention provides a catalyst for removing oxidation of methane in combustion exhaust gas containing sulfur oxide, which is obtained by supporting platinum with improved durability on tin oxide, and effectively oxidizing methane in the combustion exhaust gas by the catalyst over a long period of time. It aims at providing the method of removing, and also aims at providing the manufacturing method of the oxidation catalyst.
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除去するための触媒である。そして、酸化スズに白金を担持した触媒に対して助触媒としてイリジウムを担持させてなることを特徴とする。 The present invention is a catalyst for oxidizing and removing methane in combustion exhaust gas containing sulfur oxide in a low temperature range. And it is characterized by carrying iridium as a co-catalyst with respect to the catalyst which carried platinum on tin oxide.
また、本発明は、硫黄酸化物を含む燃焼排ガス中のメタンの酸化除去方法である。そして、該燃焼排ガスを酸化スズに白金を担持した触媒に対して助触媒としてイリジウムを担持させてなるメタンの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。 Moreover, this invention is the oxidation removal method of the methane in the combustion exhaust gas containing a sulfur oxide. The combustion exhaust gas is passed through a methane oxidation removal catalyst in which iridium is supported as a co-catalyst with respect to a catalyst in which platinum is supported on tin oxide, so that methane is oxidized and removed.
さらに、本発明は、酸化スズに白金を担持した触媒に対して助触媒としてイリジウムを担持させてなる、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、白金化合物及びイリジウム化合物を酸化スズに対して白金化合物及びイリジウム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。 Furthermore, the present invention is a method for producing a low-temperature oxidative removal catalyst for methane in combustion exhaust gas containing sulfur oxide, wherein iridium is supported as a co-catalyst on a catalyst in which platinum is supported on tin oxide. The platinum compound and the iridium compound are supported on the tin oxide by an impregnation method using an aqueous solution of the platinum compound and the iridium compound or an equilibrium adsorption method, and then fired.
本発明の触媒は、酸化スズ（ＳｎＯ2）に対して白金及びイリジウムを担持してなるメタンの酸化触媒であり、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触媒である。本発明によれば、酸化スズに、触媒成分としての白金と助触媒成分としてイリジウムを担持することにより、５００℃以下、特に４５０−３５０℃という低温域においてメタンを長期にわたり極めて有効に酸化除去することができる。 The catalyst of the present invention is an oxidation catalyst for methane formed by supporting platinum and iridium with respect to tin oxide (SnO 2 ), and is a catalyst for oxidizing and removing methane in combustion exhaust gas containing sulfur oxides in a low temperature range. . According to the present invention, platinum as a catalyst component and iridium as a promoter component are supported on tin oxide to oxidize and remove methane very effectively over a long period of time at a low temperature of 500 ° C. or lower, particularly 450 to 350 ° C. be able to.
その製造法としては、酸化スズに対して白金とイリジウム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。担体である酸化スズは多孔質であればよい。酸化スズは、特に２０〜５０ｎｍの範囲内にピーク細孔径があり、その範囲内に全細孔容積の６０％以上の細孔容積を有するものであるのが好ましい。 The production method is not particularly limited as long as it is a method capable of uniformly supporting platinum and iridium on tin oxide, but an impregnation method or an equilibrium adsorption method is preferably applied. The tin oxide as the carrier may be porous. Tin oxide preferably has a peak pore diameter in the range of 20 to 50 nm, and preferably has a pore volume of 60% or more of the total pore volume in the range.
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）などが挙げられるが、これらに限定さけない。イリジウムの原料としてはイリジウム化合物を用いる。その例としてはハロゲン化イリジウム、ハロゲン化イリジウム酸（ヘキサクロロイリジウム酸等）などが挙げられるが、これらに限定されない。 A platinum compound is used as a raw material for platinum. Examples thereof include, but are not limited to, platinum nitrate, chloride, acetate, complex salts (tetraammine platinum salt, dinitrodiammine platinum, etc.), and the like. As the iridium raw material, an iridium compound is used. Examples thereof include, but are not limited to, iridium halides, iridium halides (such as hexachloroiridium acid), and the like.
一例として含浸法の場合、酸化スズに白金化合物及びイリジウム化合物を含浸させて担持する。その順序としては、（ａ）白金化合物の水溶液に粉末状等の酸化スズを投入、含浸後、乾燥焼成し、これにイリジウム化合物の水溶液を投入、含浸後、乾燥焼成する、（ｂ）イリジウム化合物の水溶液に粉末状等の酸化スズを投入、含浸後、乾燥焼成し、これに白金化合物の水溶液を投入、含浸後、乾燥焼成する、（ｃ）白金化合物及びイリジウム化合物の水溶液、すなわち白金化合物及びイリジウム化合物を含む水溶液に粉末状等の酸化スズを投入、含浸後、乾燥焼成することにより行うことができる。含浸に際しては適宜撹伴する。 As an example, in the impregnation method, tin oxide is impregnated with a platinum compound and an iridium compound and supported. The order is as follows: (a) tin oxide in powder form is put into an aqueous solution of platinum compound, impregnated, and then dried and fired; an aqueous solution of iridium compound is put into this, impregnated, and then dried and fired; (b) iridium compound (C) An aqueous solution of a platinum compound and an iridium compound, that is, an aqueous solution of a platinum compound and an iridium compound, i.e., an aqueous solution of a platinum compound and an iridium compound. It can be carried out by putting tin oxide such as powder in an aqueous solution containing an iridium compound, impregnating it, and then drying and firing. The impregnation is appropriately stirred.
これら（ａ）〜（ｃ）のいずれの順序でも耐久性向上に有効であるが、このうち（ａ）の順序で担持するのが耐久性向上に最も効果的である。ここで、白金化合物水溶液、イリジウム化合物水溶液のｐＨについては、酸性域からアルカリ性域まで広い範囲でよいが、そのｐＨ値をより大きくするのが好ましく、これによってメタンの酸化性能をより向上させることができる。そのｐＨ値は１２以上であるのが特に好ましい。 Any of these orders (a) to (c) is effective in improving the durability, but among these, supporting in the order (a) is most effective in improving the durability. Here, the pH of the platinum compound aqueous solution and the iridium compound aqueous solution may be in a wide range from the acidic range to the alkaline range, but it is preferable to increase the pH value, thereby further improving the oxidation performance of methane. it can. The pH value is particularly preferably 12 or more.
本酸化触媒における酸化スズ担体に対する白金の担持量は、酸化スズに対して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％の前後としても差支えない。 The amount of platinum supported on the tin oxide carrier 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 tin 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%.
酸化スズ担体に対するイリジウムの担持量は、Ｐｔの担持量に対して１０〜５０ｗｔ％であるのが好ましい。酸化スズに対する白金の担持量の好ましい範囲は０．０２５〜１５．０ｗｔ％の範囲であるので、この場合のイリジウムの担持量は０．００２５〜７．５ｗｔ％である。本発明の酸化触媒をハニカム状の形態とする場合には、これらに準じた量の白金及びイリジウムを担持させる。 The amount of iridium supported on the tin oxide support is preferably 10 to 50 wt% with respect to the amount of Pt supported. Since the preferable range of platinum loading with respect to tin oxide is in the range of 0.025 to 15.0 wt%, the iridium loading in this case is 0.0025 to 7.5 wt%. When the oxidation catalyst of the present invention is in the form of honeycomb, platinum and iridium in amounts corresponding to these are supported.
また、白金については、酸化スズに対して分割担持することによりメタンの酸化性能を格段に向上させることができる。白金の分割担持は、酸化スズに対して白金化合物の水溶液を２回以上に繰り返して担持する。例えば１回で白金を２ｗｔ％（白金換算）担持し、この担持を２回、３回というように複数回繰り返して、４ｗｔ％、６ｗｔ％というように担持する。当該Ｐｔの分割担持は２回以上５回以下であるのが好ましい。前述（ｃ）のとおり、白金及びイリジウムを同時に担持する場合には、白金の分割担持に合わせてイリジウムについても分割担持してよい。 Moreover, about platinum, the oxidation performance of methane can be remarkably improved by carrying | supporting separately with respect to a tin oxide. In the divided support of platinum, an aqueous solution of a platinum compound is repeatedly supported on tin oxide two or more times. For example, platinum is supported at 2 wt% (platinum conversion) at a time, and this support is repeated a plurality of times, such as 2 times and 3 times, and is supported at 4 wt% and 6 wt%. It is preferable that the divided loading of Pt is performed 2 times or more and 5 times or less. As described above (c), when platinum and iridium are simultaneously supported, iridium may be separately supported in accordance with the divided support of platinum.
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、あるいはハニカム（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 powder, it is sized or granulated in a predetermined particle size range so as not to dissipate from the catalyst layer filled with this, Alternatively, it is desirable to use after 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。特に希薄燃焼ガス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、ハニカム状の基材に酸化スズをウォッシュコート法で担持した後、前述（ａ）〜（ｃ）のいずれかの順序で、白金及びイリジウムを担持する。これらの担持は、白金の場合もイリジウムの場合も、その化合物の水溶液を酸化スズを担持したハニカム状基材にウォッシュコート法で担持する。白金及びイリジウムを同時に担持する場合には、白金化合物及びイリジウム化合物の水溶液を酸化スズを担持したハニカム状基材にウォッシュコート法で担持する。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 gas engine, it is preferably used in the form of a honeycomb. As a manufacturing mode of the honeycomb-shaped catalyst, for example, tin oxide is supported on a honeycomb-shaped base material by a wash coat method, and then platinum and iridium are supported in any order of the above-described (a) to (c). In the case of platinum or iridium, these supports are supported by a wash coat method on an aqueous solution of the compound on a honeycomb substrate supporting tin oxide. When platinum and iridium are simultaneously supported, an aqueous solution of a platinum compound and an iridium compound is supported on a honeycomb-shaped substrate supporting tin oxide by a wash coat method. Next, it is dried and fired by a conventional method.
ハニカム状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。 A ceramic or metal substrate can be used as the honeycomb substrate. 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により被毒して性能劣化を来すことが知られている。これに対して、本発明に係る酸化スズ担体に白金及びイリジウムを担持した酸化触媒は、高い耐ＳＯX性を有し、従来における認識とは全く逆に、排ガス中のＳＯ2の存在により、反ってメタンの酸化除去活性が向上する。 Conventionally, it is known that a precious metal catalyst is poisoned by SO 2 in exhaust gas and causes performance deterioration. On the other hand, the oxidation catalyst in which platinum and iridium are supported on the tin oxide support according to the present invention has high SO x resistance and, contrary to the conventional recognition, due to the presence of SO 2 in the exhaust gas, On the other hand, the oxidation removal activity of methane is improved.
本発明のメタンの酸化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は酸化触媒層（反応管）、Ｃは処理済み燃焼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 methane oxidation 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 catalyst of the present invention. In FIG. 1, A is a treated exhaust gas introduction pipe, B is an oxidation catalyst layer (reaction pipe), C is a treated exhaust gas outlet pipe, and an arrow (→) indicates the flow direction of the combustion exhaust gas. The present oxidation catalyst 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 oxidation catalyst in the catalyst layer as shown in FIG. 1, the cross-sectional opening is arranged so as 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》
本実施例１は、Ｐｔ/ＳｎＯ2触媒に対して各種金属を添加担持し、耐久性向上の有無を探査するのに行った実験である。
Example 1
Example 1 is an experiment conducted for exploring the presence or absence of durability improvement by adding and supporting various metals on a Pt / SnO 2 catalyst.
〈ペレット触媒の調製〉
Ｐｔ/ＳｎＯ2触媒及びこれに表１に示す各種金属を担持したペレット触媒を含浸法により調製した。調製で用いる触媒担体粉末は、酸化スズ（関東化学社製）を昇温速度１℃/ｍｉｎで６００℃とし、３時間焼成して得た。Ｐｔ担持時のＰｔ水溶液は、所定量のジニトロジアンミン白金〔Ｐｔ（ＮＯ2）2（ＮＨ2）2〕をアンモニア水で溶解した水溶液を用い、これに硝酸水溶液を加えることでｐＨを調製した。各金属については、Ｖはバナジン酸アンモニウム、Ｗはタングステン酸アンモニウム、Ｍｏはモリブデン酸アンモニウム、Ｂはホウ酸（Ｈ3ＢＯ3）を用い、その他の各金属については硝酸塩を用い、それらの所定量をそれぞれ蒸留水に溶解した溶液として用いた。Ｉｒ担持時のＩｒ水溶液は、所定量のヘキサクロロイリジウム酸（Ｈ2ＩｒＣｌ6）を蒸留水に溶解した溶液を用いた。
<Preparation of pellet catalyst>
A Pt / SnO 2 catalyst and a pellet catalyst carrying various metals shown in Table 1 were prepared by an impregnation method. The catalyst carrier powder used in the preparation was obtained by firing tin oxide (manufactured by Kanto Chemical Co., Ltd.) at 600 ° C. at a temperature rising rate of 1 ° C./min for 3 hours. The aqueous Pt solution at the time of carrying Pt was an aqueous solution in which a predetermined amount of dinitrodiammine platinum [Pt (NO 2 ) 2 (NH 2 ) 2 ] was dissolved in aqueous ammonia, and the pH was adjusted by adding an aqueous nitric acid solution thereto. For each metal, V is ammonium vanadate, W is ammonium tungstate, Mo is ammonium molybdate, B is boric acid (H 3 BO 3 ), and nitrates are used for each of the other metals. Were used as solutions dissolved in distilled water. As the Ir aqueous solution at the time of Ir loading, a solution in which a predetermined amount of hexachloroiridium acid (H 2 IrCl 6 ) was dissolved in distilled water was used.
触媒担体粉末とＰｔ水溶液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時間乾燥した。その後、昇温速度１０℃/ｍｉｎで２００℃とし、この温度に３時間保持した後、昇温速度１℃/ｍｉｎで２７０℃とし、この温度に６時間保持し、さらに昇温速度１℃/ｍｉｎで５５０℃とし、この温度に３時間保持して焼成してＰｔ/ＳｎＯ2触媒粉末を得た。この触媒粉末をＰｔ/ＳｎＯ2のペレット触媒及び各金属担持のＰｔ/ＳｎＯ2ペレット触媒の調製に使用した。 Predetermined amounts of catalyst carrier powder and aqueous Pt solution were placed in a flask and dried under reduced pressure at 50 ° C. using a rotary evaporator. The remaining powder was dried at 175 ° C. for 6 hours and then at 275 ° C. for 12 hours. Thereafter, the temperature was raised to 200 ° C. at a rate of temperature increase of 10 ° C./min, held at this temperature for 3 hours, then set to 270 ° C. at a rate of temperature increase of 1 ° C./min, held at this temperature for 6 hours, The Pt / SnO 2 catalyst powder was obtained by firing at a temperature of 550 ° C. for 3 minutes and holding at this temperature for 3 hours. This catalyst powder was used to prepare the Pt / a SnO 2 catalyst pellets and Pt / SnO 2 catalyst pellets of each metal loading.
得られたＰｔ/ＳｎＯ2触媒粉末のうちの１部を採り、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Ｐｔ/ＳｎＯ2のペレット触媒を得た。 One part of the obtained Pt / SnO 2 catalyst powder was taken and molded at 500 kg / cm 2 with a tableting machine, and then classified into 355-710 μm (= 35-31 mesh). A Pt / SnO 2 pellet catalyst was thus obtained.
また、前記各金属の化合物の水溶液のそれぞれに、前記得られたＰｔ/ＳｎＯ2触媒粉末を添加混合し、前記Ｐｔ/ＳｎＯ2触媒粉末の調製と同様にして各金属を担持したＰｔ/ＳｎＯ2触媒粉末を得た。得られた各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。こうして各金属を担持したＰｔ/ＳｎＯ2ペレット触媒を得た。各金属の担持量は表１に示している。 Further, the each of the aqueous solutions of the compounds of each metal, the resulting Pt / SnO 2 catalyst powder was added and mixed, the Pt / SnO 2 catalyst powder Pt / SnO 2 carrying the metal in a manner similar to the preparation of A catalyst powder was obtained. Each of the obtained catalyst powders was molded at 500 kg / cm 2 by a tableting machine and then classified into 355-710 μm (= 35-31 mesh). Thus, a Pt / SnO 2 pellet catalyst carrying each metal was obtained. Table 1 shows the amount of each metal supported.
〈性能試験〉
上記〈ペレット触媒の調製〉で得た各種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耐久試験を実施した。試験条件は下記のとおりである。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。これら試験条件は、特に記載しない限り、以下の実施例についても同じである。
<performance test>
Using the various pellet catalysts obtained in the above <Preparation of pellet catalyst>, a catalyst durability test was carried out using an ordinary fixed bed flow type reactor as shown in FIG. The test conditions are 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) ), 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. These test conditions are the same for the following examples unless otherwise specified.
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（堀場製作所製）を用いて行った。ＣＨ4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（％）〕は下記式により求めた。これらの点は、特に記載しない限り、以下の性能試験についても同じである。表１に本性能試験の結果を示している。 The analysis of the test gas was performed using an exhaust gas analyzer (manufactured by Horiba Seisakusho) consisting of a FID total hydrocarbon meter, an infrared CO / CO 2 meter, a chemiluminescent NO x meter, and a magnetic oxygen meter. The CH 4 oxidation removal activity was evaluated from the difference in CH 4 concentration before and after the reaction tube. The oxidation removal activity [= methane removal rate (%)] was determined by the following formula. These points are the same for the following performance tests unless otherwise specified. Table 1 shows the results of this performance test.
表１のとおり、金属を担持しないＰｔ/ＳｎＯ2触媒ではＣＨ4除去率５６．３％を示している。また、１８種の金属のうち、Ｉｒを担持したＰｔ/ＳｎＯ2触媒を除く、１７種の金属をそれぞれ担持したＰｔ/ＳｎＯ2触媒では、いずれも金属を担持しないＰｔ/ＳｎＯ2触媒のＣＨ4除去率５６．３％を下回り、耐久性向上に何の効果もなく、反って阻害している。これに対して、Ｉｒを担持したＰｔ/ＳｎＯ2触媒では耐久性が向上している。Ｉｒ担持量０．２ｗｔ％でＣＨ4除去率６９．０％、Ｉｒ担持量２ｗｔ％でＣＨ4除去率６３．９％を示している。このように数多くの金属のうち、唯一Ｉｒを担持したＰｔ/ＳｎＯ2触媒だけがＰｔ/ＳｎＯ2触媒の耐久性を改善することができる。 As shown in Table 1, the Pt / SnO 2 catalyst not supporting a metal shows a CH 4 removal rate of 56.3%. Further, among the 18 kinds of metals, except for the Pt / SnO 2 catalyst carrying Ir, except for the Pt / SnO 2 catalyst carrying 17 kinds of metal, CH 4 of the Pt / SnO 2 catalyst which does not carry any metal. The removal rate is less than 56.3%, which has no effect on improving durability and inhibits warping. On the other hand, durability is improved in the Pt / SnO 2 catalyst supporting Ir. The CH 4 removal rate is 69.0% when the Ir loading amount is 0.2 wt%, and the CH 4 removal rate is 63.9% when the Ir loading amount is 2 wt%. As described above, among the many metals, only the Pt / SnO 2 catalyst supporting Ir can improve the durability of the Pt / SnO 2 catalyst.
《実施例２》
本実施例２は、実施例１の結果を踏まえて、Ｉｒ担持量如何によるＰｔ/ＳｎＯ2触媒の性能試験を行った実施例である。Ｐｔ/ＳｎＯ2触媒及びＩｒ担持量を変えたＰｔ/ＳｎＯ2触媒を実施例１の〈ペレット触媒の調製〉と同様にして調製した。比較のため、同様にして、ＳｎＯ2にＩｒのみを担持したものも調製した。こうして得られた各触媒について実施例１の〈性能試験〉と同様にして性能試験を行った。表２に本性能試験の結果を示している。
Example 2
The present Example 2 is an example in which the performance test of the Pt / SnO 2 catalyst according to the Ir loading amount was performed based on the result of the Example 1. A Pt / SnO 2 catalyst and a Pt / SnO 2 catalyst with different Ir loading were prepared in the same manner as in <Preparation of pellet catalyst> in Example 1. For comparison, in the same manner it was also prepared that carries Ir only SnO 2. Each catalyst thus obtained was subjected to a performance test in the same manner as in <Performance Test> in Example 1. Table 2 shows the results of this performance test.
表２のとおり、Ｉｒを担持しないＰｔ/ＳｎＯ2触媒ではＣＨ4除去率５６．３％である。これに対して、Ｉｒを０．１ｗｔ％担持したＰｔ/ＳｎＯ2触媒ではＣＨ4除去率５８．５％となり、Ｉｒを０．２ｗｔ％担持したＰｔ/ＳｎＯ2触媒では６９．０％、Ｉｒを０．５ｗｔ％担持したＰｔ/ＳｎＯ2触媒では６７．９％、Ｉｒを１．０ｗｔ％担持したＰｔ/ＳｎＯ2触媒では６９．１％のＣＨ4除去率を示し、Ｐｔ/ＳｎＯ2触媒にＩｒを担持することにより、いずれも耐久性が向上している。また、ＳｎＯ2にＩｒのみを担持したものでのＣＨ4除去率は５．９％であり、ＣＨ4除去能は殆ど認められない。このことは、Ｉｒは、それ自体ではＣＨ4除去触媒能を持たず、助触媒として耐久性に寄与することを示している。 As shown in Table 2, the Pt / SnO 2 catalyst not supporting Ir has a CH 4 removal rate of 56.3%. In contrast, the Pt / SnO 2 catalyst supporting 0.1 wt% of Ir has a CH 4 removal rate of 58.5%, the Pt / SnO 2 catalyst supporting 0.2 wt% of Ir is 69.0%, and Ir 67.9% at 0.5 wt% loaded with Pt / SnO 2 catalyst, the Pt / SnO 2 catalyst 1.0 wt% carrying Ir indicates CH 4 removal rate of 69.1%, Ir in Pt / SnO 2 catalyst In any case, the durability is improved. Further, in the case where only Ir is supported on SnO 2 , the CH 4 removal rate is 5.9%, and the CH 4 removal ability is hardly recognized. This indicates that Ir itself does not have a CH 4 removal catalytic ability and contributes to durability as a promoter.
《実施例３》
本実施例３は、ＳｎＯ2に対するＰｔ、Ｉｒの担持順序如何によるＰｔ/ＳｎＯ2触媒の性能試験を行った実施例である。実施例１の〈ペレット触媒の調製〉と同様にして、（ａ）ＳｎＯ2に対してＰｔを担持し、次いでＩｒを担持する、（ｂ）ＳｎＯ2に対してＩｒを担持し、次いでＰｔを担持する、（ｃ）ＳｎＯ2に対してＰｔとＩｒを同時に担持する、の各順序で調製した。またこれらはｐＨを変えて調製した。Ｐｔの担持量は２．０ｗｔ％、Ｉｒの担持量は０．２ｗｔ％とした。こうして得られた各触媒について実施例１の〈性能試験〉と同様にして性能試験を行った。
Example 3
Embodiment 3 is an embodiment of performing Pt, performance tests of Pt / SnO 2 catalyst by carrying the order whether the Ir against SnO 2. In the same manner as in <Preparation of pellet catalyst> in Example 1, (a) Pt is supported on SnO 2 and then Ir is supported. (B) Ir is supported on SnO 2 and then Pt is supported. It was prepared in the following order: (c) Simultaneously supporting Pt and Ir on SnO 2 . These were prepared by changing the pH. The supported amount of Pt was 2.0 wt%, and the supported amount of Ir was 0.2 wt%. Each catalyst thus obtained was subjected to a performance test in the same manner as in <Performance Test> in Example 1.
表３に本性能試験の結果を示している。表３には、比較のため、ＳｎＯ2にＰｔのみを担持したＰｔ/ＳｎＯ2触媒のデータを併記している。表３のとおり、Ｉｒをいずれの順序で担持した場合にも、Ｉｒを担持しないＰｔ/ＳｎＯ2触媒に対して耐久性が改善されている。そのうちでも、Ｐｔを担持し、次いでＩｒを担持した場合が耐久性が最も改善されている。 Table 3 shows the results of this performance test. Table 3, for comparison, are also shown the data of Pt / SnO 2 catalyst carrying Pt only SnO 2. As shown in Table 3, when Ir is supported in any order, durability is improved with respect to the Pt / SnO 2 catalyst not supporting Ir. Among them, the durability is most improved when Pt is supported and then Ir is supported.
《実施例４》
本実施例４は、ハニカム基材を用い、ＳｎＯ2にＰｔのみを担持したＰｔ/ＳｎＯ2触媒とＳｎＯ2にＰｔとＩｒを担持したＩｒ−Ｐｔ/ＳｎＯ2触媒による性能試験を行った実施例である。
Example 4
The fourth embodiment, using a honeycomb substrate, performed were performance tested by Ir-Pt / SnO 2 catalyst only carrying loaded with Pt / SnO 2 catalyst and the SnO 2 Pt and Ir Pt on SnO 2 Example It is.
〈ハニカム触媒の調製〉
コージェライト製ハニカムに対して、ＳｎＯ2粉末の水性スラリーを用いたウォッシュコート法によりＳｎＯ2をコートした。その後、ジニトロジアンミン白金〔Ｐｔ（ＮＯ2）2（ＮＨ2）2〕をアンモニア水に溶解し、アンモニア水、硝酸水溶液を用いてｐＨ＝１２に調製した水溶液中に上記ＳｎＯ2担持のハニカムを室温で３時間浸漬した後、引き上げて、１７５℃で６時間、次いで２７５℃で１２時間乾燥した。この工程を数回繰り返した後、昇温速度１０℃/ｍｉｎで２００℃とし、この温度に３時間保持した後、昇温速度１℃/ｍｉｎで２７０℃とし、この温度に６時間保持し、さらに昇温速度１℃/ｍｉｎで５５０℃とし、この温度に３時間保持して焼成してＰｔ/ＳｎＯ2ハニカム触媒を得た。こうして同じ条件でＰｔ/ＳｎＯ2ハニカム触媒を複数個作製した。
<Preparation of honeycomb catalyst>
A cordierite honeycomb was coated with SnO 2 by a wash coating method using an aqueous slurry of SnO 2 powder. Thereafter, dinitrodiammine platinum [Pt (NO 2 ) 2 (NH 2 ) 2 ] is dissolved in aqueous ammonia, and the above-mentioned SnO 2 -supported honeycomb is placed in an aqueous solution prepared at pH = 12 using aqueous ammonia and nitric acid. After being immersed for 3 hours, it was pulled up and dried at 175 ° C. for 6 hours and then at 275 ° C. for 12 hours. After repeating this process several times, the temperature was increased to 200 ° C. at a temperature increase rate of 10 ° C./min, held at this temperature for 3 hours, then increased to 270 ° C. at a temperature increase rate of 1 ° C./min, held at this temperature for 6 hours, Further, the temperature was increased to 550 ° C. at a rate of temperature increase of 1 ° C./min, and this temperature was maintained for 3 hours and fired to obtain a Pt / SnO 2 honeycomb catalyst. Thus, a plurality of Pt / SnO 2 honeycomb catalysts were produced under the same conditions.
また、塩化イリジウム酸（Ｈ2ＩｒＣｌ6）を蒸留水に溶解した水溶液中に、上記で得られたＰｔ/ＳｎＯ2ハニカム触媒を室温で３時間浸漬した後、引き上げて、１７５℃で６時間、次いで２７５℃で１２時間乾燥した。この工程を数回繰り返した後、昇温速度１０℃/ｍｉｎで２００℃とし、この温度に３時間保持した後、昇温速度１℃/ｍｉｎで２７０℃とし、この温度に６時間保持し、さらに昇温速度１℃/ｍｉｎで５５０℃とし、この温度に３時間保持して焼成してＩｒ−Ｐｔ/ＳｎＯ2ハニカム触媒を得た。 Further, the Pt / SnO 2 honeycomb catalyst obtained above was immersed in an aqueous solution in which chloroiridic acid (H 2 IrCl 6 ) was dissolved in distilled water for 3 hours at room temperature, then pulled up, and heated at 175 ° C. for 6 hours. Subsequently, it dried at 275 degreeC for 12 hours. After repeating this process several times, the temperature was increased to 200 ° C. at a temperature increase rate of 10 ° C./min, held at this temperature for 3 hours, then increased to 270 ° C. at a temperature increase rate of 1 ° C./min, held at this temperature for 6 hours, Further, the temperature was raised to 550 ° C. at a temperature rising rate of 1 ° C./min, and this temperature was maintained for 3 hours, followed by firing to obtain an Ir—Pt / SnO 2 honeycomb catalyst.
〈性能試験〉
上記〈ハニカム触媒の調製〉で得たＰｔ/ＳｎＯ2ハニカム触媒及びＩｒ−Ｐｔ/ＳｎＯ2ハニカム触媒を用いて、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耐久試験を実施した。試験条件は下記のとおりである。排ガス温度（＝反応温度）：４００℃、空間速度（ＳＶ）：４０，０００ｈ-1（全流量３．３５Ｌ/ｍｉｎ、触媒形状２０ｍｍ（直径）×８ｍｍ（長さ）（触媒体積２．５１ｃｍ3）、排ガス＝希薄燃焼ガスエンジンの実機排ガス、実機排ガス組成：ＣＨ4＝１８００〜２０００ｐｐｍ、ＴＨＣ（ＣＨ4を含む全炭化水素濃度）＝２７００〜３２００ｐｐｍ、ＣＯ＝２００〜４００ｐｐｍ、ＮＯX＝２００〜４００ｐｐｍ、ＳＯ2＝０．１〜０．５ｐｐｍ、ＣＯ2＝７〜８％、Ｏ2＝５〜６％（ドライガス組成）。なお、各成分の濃度に幅があるのはその範囲内で変動したことを示している。
<performance test>
Using the Pt / SnO 2 honeycomb catalyst and the Ir-Pt / SnO 2 honeycomb catalyst obtained in the above <Preparation of honeycomb catalyst>, a catalyst endurance test was conducted using a normal fixed bed flow type reactor as shown in FIG. Carried out. The test conditions are as follows. Exhaust gas temperature (= reaction temperature): 400 ° C., space velocity (SV): 40,000 h −1 (total flow rate 3.35 L / min, catalyst shape 20 mm (diameter) × 8 mm (length) (catalyst volume 2.51 cm 3 ), Exhaust gas = actual exhaust gas of lean combustion gas engine, actual exhaust gas composition: CH 4 = 1800 to 2000 ppm, THC (total hydrocarbon concentration including CH 4 ) = 2700 to 3200 ppm, CO = 200 to 400 ppm, NO X = 200 to 400 ppm, SO 2 = 0.1 to 0.5 ppm, CO 2 = 7 to 8%, O 2 = 5 to 6% (dry gas composition) Note that there is a range in the concentration of each component within that range. It shows that it fluctuated.
試験ガスの分析は、赤外線式メタン分析計（島津製作所製）、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（堀場製作所製）を用いて行った。図２に本性能試験の結果を示している。図２のとおり、Ｉｒを担持しないＰｔ/ＳｎＯ2触媒の場合、メタン除去率は初期段階で８９％であり、以降徐々に低下し、１０００時間経過時で８０％、２０００時間経過時で６３％、３０００時間経過時で５４％と低下し、４０００時間経過時においては４５％にまで低下している。 The test gas was analyzed by an exhaust gas analyzer (Horiba) consisting of an infrared methane analyzer (manufactured by Shimadzu Corporation), an FID total hydrocarbon meter, an infrared CO / CO 2 meter, a chemiluminescent NO x meter, and a magnetic oxygen meter. (Manufactured by Seisakusho). FIG. 2 shows the results of this performance test. As shown in FIG. 2, in the case of a Pt / SnO 2 catalyst not supporting Ir, the methane removal rate is 89% at the initial stage, and then gradually decreases, 80% after 1000 hours, and 63% after 2000 hours. It decreases to 54% at the lapse of 3000 hours and decreases to 45% at the lapse of 4000 hours.
これに対して、Ｉｒを担持したＩｒ−Ｐｔ/ＳｎＯ2触媒の場合、メタン除去率は初期段階で９１％であり、以降徐々に低下はするが、Ｉｒを担持しないＰｔ/ＳｎＯ2触媒に比べてその程度は小さく、１０００時間経過時で８３％、２０００時間経過時で７８％、３０００時間経過時で６９％を維持し、４０００時間経過時においても６４％のメタン除去率を示している。このように、Ｐｔ/ＳｎＯ2触媒にＩｒを担持することにより、耐久性が改善され、長期間にわたり高いメタン除去率を維持している。 On the other hand, in the case of an Ir—Pt / SnO 2 catalyst supporting Ir, the methane removal rate is 91% at the initial stage and gradually decreases thereafter, but compared with a Pt / SnO 2 catalyst not supporting Ir. The degree is small, 83% after 1000 hours, 78% after 2000 hours, 69% after 3000 hours, and 64% methane removal rate after 4000 hours. Thus, by supporting Ir on the Pt / SnO 2 catalyst, durability is improved and a high methane removal rate is maintained over a long period of time.
《実施例５》
本実施例５は、Ｐｔ/ＳｎＯ2触媒に対するＩｒ担持による耐久性改善効果の要因解明の一環として試みた実験である。実施例１の〈ペレット触媒の調製〉と同様にして製造した、Ｉｒを担持しないＰｔ/ＳｎＯ2触媒（Ｐｔ＝２ｗｔ％）及びＩｒを担持したＩｒ−Ｐｔ/ＳｎＯ2触媒（Ｐｔ＝２ｗｔ％、Ｉｒ＝０．２ｗｔ％）を、熱劣化加速試験として、１０００℃の空気雰囲気中に１０時間保持した。そして自然冷却後、Ｘ線回折法により分析した。表４にその結果を示している。表４中、結晶子径Ｄ（ｎｍ）は、Scherrerの式：Ｄ＝Ｋ・λ/（β・cosθ）により算出した。ここで、ＫはScherrer定数、λは使用Ｘ線管球の波長、βは半値幅、θは回折角を示す。
Example 5
Example 5 is an experiment which was attempted as part of the elucidation of the cause of the durability improvement effect by Ir loading on the Pt / SnO 2 catalyst. Ir-supported Pt / SnO 2 catalyst (Pt = 2 wt%) and Ir-supported Ir-Pt / SnO 2 catalyst (Pt = 2 wt%) produced in the same manner as in <Preparation of pellet catalyst> in Example 1 Ir = 0.2 wt%) was held in an air atmosphere at 1000 ° C. for 10 hours as a thermal deterioration acceleration test. And after natural cooling, it analyzed by the X ray diffraction method. Table 4 shows the results. In Table 4, the crystallite diameter D (nm) was calculated by Scherrer's formula: D = K · λ / (β · cos θ). Here, K is a Scherrer constant, λ is the wavelength of the X-ray tube used, β is a half width, and θ is a diffraction angle.
表４のとおり、Ｐｔ/ＳｎＯ2触媒でのＰｔの平均結晶子径（＝平均粒子径）は５２ｎｍであった。これに対して、Ｐｔ/ＳｎＯ2触媒にＩｒを担持したＩｒ−Ｐｔ/ＳｎＯ2触媒でのＰｔの平均結晶子径は４１ｎｍであり、ＩｒによるＰｔの粗大化が抑制されている。このことから、Ｐｔ/ＳｎＯ2触媒に対してＩｒを担持することによりＰｔの粗大化（シンタリング）が抑制され、その結果耐熱性が向上し、触媒としての耐久性が向上するものと推認される。 As shown in Table 4, the average crystallite diameter (= average particle diameter) of Pt in the Pt / SnO 2 catalyst was 52 nm. In contrast, the average crystallite size of Pt in Ir-Pt / SnO 2 catalyst supporting Ir on Pt / SnO 2 catalyst was 41 nm, coarsening of Pt by Ir is suppressed. From this, it is presumed that by supporting Ir on the Pt / SnO 2 catalyst, coarsening (sintering) of Pt is suppressed, and as a result, heat resistance is improved and durability as a catalyst is improved. The
Ａ 被処理排ガス導入管
Ｂ 酸化触媒層（反応管）
Ｃ 処理済み排ガスの導出管
A treated exhaust gas introduction pipe B oxidation catalyst layer (reaction pipe)
C Outlet pipe for treated exhaust gas
Claims (11)
11. The method for producing a catalyst for oxidizing and removing methane in combustion exhaust gas according to claim 9 or 10, wherein an aqueous solution of a platinum compound having a pH = 12 or more is used as the platinum compound aqueous solution. For producing a catalyst for use.
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| WO2021230119A1 (en) | 2020-05-15 | 2021-11-18 | 田中貴金属工業株式会社 | Methane combustion catalyst and method for manufacturing same, and method for purifying combustion exhaust gas |
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| JP5030818B2 (en) * | 2007-03-08 | 2012-09-19 | 大阪瓦斯株式会社 | Exhaust gas purification catalyst and exhaust gas purification method |
| JP5030880B2 (en) * | 2007-08-08 | 2012-09-19 | 大阪瓦斯株式会社 | Catalyst for oxidation removal of methane in exhaust gas and method for oxidation removal of methane in exhaust gas |
| JP5541873B2 (en) * | 2008-03-27 | 2014-07-09 | 大阪瓦斯株式会社 | Exhaust gas purification catalyst and exhaust gas purification method |
| JP5541874B2 (en) * | 2008-03-27 | 2014-07-09 | 大阪瓦斯株式会社 | Exhaust gas purification catalyst and exhaust gas purification method |
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| EP4151310A4 (en) * | 2020-05-15 | 2023-10-25 | Tanaka Kikinzoku Kogyo K.K. | Methane combustion catalyst and method for manufacturing same, and method for purifying combustion exhaust gas |
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| JP2006272079A (en) | 2006-10-12 |
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