JP2005118775A - 触媒担持材料、それから製造された触媒及び煙道ガスの処理方法 - Google Patents
触媒担持材料、それから製造された触媒及び煙道ガスの処理方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 239000000463 material Substances 0.000 title claims abstract description 51
- 239000003546 flue gas Substances 0.000 title claims abstract description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000005909 Kieselgur Substances 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000010953 base metal Substances 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 claims 1
- 230000003628 erosive effect Effects 0.000 abstract description 20
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 5
- 238000005299 abrasion Methods 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 10
- 239000010881 fly ash Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004185 countercurrent chromatography Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/58—Fabrics or filaments
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2255/102—Platinum group metals
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- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2255/20723—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2257/402—Dinitrogen oxide
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- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
【解決手段】 本発明は、浸食に対した向上された耐性を持つ、触媒担持材料及びそれから製造される触媒に関する。この触媒担持材料は、主にアナターゼの形で存在するTiO2 を少なくとも20重量%の割合で含む。更に、この触媒担持材料は、それの少なくとも2重量%でかつ80重量%未満の量でケイ藻土を含む。一つの態様では、上記触媒担持材料から製造される触媒は、V、W、Mn、Nb、Mo、Ni、FeもしくはCuの群から選択される卑金属の酸化物もしくは硫酸塩を含む。更に別の可能な態様では、上記触媒担持材料から製造される触媒は、PtもしくはPdを含む。上記触媒は、煙道ガスの処理に使用される。より具体的には、本発明に従い製造される、向上された耐浸食性を有する触媒担持材料は、多量の粒状物を含む煙道ガスに、及び含窒素酸化物の選択的触媒還元法に使用される。
【選択図】 なし
Description
NO+NO2 +2NH3 → 2N2 +3H2 O
石炭燃焼電力プラントでは、典型的には、SCR触媒は、エコノマイザー区域の下流で、かつ空気予熱器及びダストフィルター、例えば静電集塵器の上流に設置される。他の用途での設置法は、その最適な操業温度及び特定のプロセスレイアウトに依存する。SCR触媒の操業温度は、通常は、200℃〜500℃の範囲である。
アナターゼTiO2 粉末900gを、Tiを4重量%及び水を4重量%含むブタノール中のテトライソプロピルチタネートの溶液1100g中に懸濁させた。このスラリーを、実験室用ディスソルバー中で激しく混合して、各成分の緊密な混合及び400メッシュ未満の大きさまでの凝集物破壊を確実にした。これの管理にはエリクセン製グラインドメーターを使用した。約1mmの厚さのガラス繊維マットを、約18×5cmの寸法に切断した。これらのマットを、上記のスラリー中に浸漬して、完全湿潤した繊維マットを得た。乾燥後、この材料を600℃で2時間か焼した。
例2
触媒担持材料の耐摩耗強さの向上のために幾つかの成分を試験した。試験した構造促進材は、以下の成分を含む:
− ルチルTiO2 :200メッシュ(M.O.Knudsen’s Eftf.、デンマーク)
− 石英SiO2 :タイプG140メッシュ(M.O.Knudsen’s Eftf.、デンマーク)
− ガラス繊維タイプ1:ミルドFG400/030(Schwartzwalder Textile Werke、ドイツ)
− ガラス繊維タイプ2:ミルドマイクロガラス3082(Fibertech、米国)
− カオリナイト: スプリーム(ECCインターナショナル、英国)
− ケイ藻土: セライト221M(セライトコーポレーション、米国)
製造手順は例1に記載の通りであるが、アナターゼTiO2 粉末の一部を、上記の様々な添加剤に置き換えた。アナターゼTiO2 の構造促進材による置き換え量を表1に示す。
例3−浸食試験
サンプルという用語は、例1及び2に従い製造した、含浸処理及びか焼後の触媒プレートのことを指す。先ず、試験サンプルを、炉中150℃で30分間、重量が一定するまで乾燥し、次いで気密容器中で冷却した。冷却後、サンプル及びサンプルホルダーを、少なくとも1mgの精度で秤量した。
例1及び2に記載のように作製したサンプルから小さな試験片を切り出した。これらの試験片のうちの4つを、触媒作用試験のために管状反応器に入れた。全暴露面積試験(total exposed area test)は、各々の試験につき約30cm2 であった。触媒作用試験は、反応器入口で表3に記載の組成を有するガスを用いて350℃で行った。面積規準化空間速度(area normalized space velocity; NHAV)は、全ての場合において約70Nm3 /m2 /hrであった。
なお、XNOは、反応器中でのNO転化率である。
Claims (8)
- − 少なくとも20重量%の量の、主にアナターゼの形のTiO2 、
− 少なくとも2重量%でかつ80重量%未満の量のケイ藻土、
からなる触媒担持材料。 - 直線状の流路を複数有するモノリス型構造物に成形されていることを特徴とする、請求項1の触媒担持材料。
- PtもしくはPdを含むか、またはV、W、Mn、Nb、Mo、Ni、Fe及びCuの群から選択される卑金属の少なくとも一種の酸化物もしくは硫酸塩を含むことを特徴とする、請求項1または2の触媒担持材料から製造される触媒。
- 触媒作用反応器中で転化条件下において、煙道ガスを請求項3の触媒と接触させることを特徴とする、煙道ガスの処理方法。
- 固形粒子を含む煙道ガスを触媒と接触させることを特徴とする、請求項4の方法。
- 固形粒子含有率が煙道ガスNm3 当たり2gより多い煙道ガスと触媒を接触させることを特徴とする、請求項5の方法。
- 200℃〜500℃の範囲の温度及び0.5〜5Nm/sの範囲の触媒作用反応器中へのガス空塔速度(Superficial gas velocity)の転化条件下に、煙道ガスを接触させることを特徴とする、請求項6の方法。
- 含窒素酸化物及び/またはジオキシンの触媒選択還元法であることを特徴とする、請求項4〜7のいずれか一つの方法。
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DE602004025657D1 (de) | 2010-04-08 |
EP1524024A1 (en) | 2005-04-20 |
CN1628906A (zh) | 2005-06-22 |
US20050085383A1 (en) | 2005-04-21 |
ES2340678T3 (es) | 2010-06-08 |
ATE458543T1 (de) | 2010-03-15 |
US7431904B2 (en) | 2008-10-07 |
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