JPH07136463A - Method for treating exhaust gas - Google Patents
Method for treating exhaust gasInfo
- Publication number
- JPH07136463A JPH07136463A JP5287986A JP28798693A JPH07136463A JP H07136463 A JPH07136463 A JP H07136463A JP 5287986 A JP5287986 A JP 5287986A JP 28798693 A JP28798693 A JP 28798693A JP H07136463 A JPH07136463 A JP H07136463A
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- catalyst
- exhaust
- zro
- tio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 93
- 239000007789 gas Substances 0.000 claims abstract description 63
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 19
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 14
- 239000010457 zeolite Substances 0.000 claims abstract description 14
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 12
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 21
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 15
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 15
- 229910052741 iridium Inorganic materials 0.000 claims description 14
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 14
- 239000010948 rhodium Substances 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 238000002441 X-ray diffraction Methods 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052680 mordenite Inorganic materials 0.000 claims description 4
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- -1 silicalite Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910021472 group 8 element Inorganic materials 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052961 molybdenite Inorganic materials 0.000 abstract 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 1
- 239000004215 Carbon black (E152) Substances 0.000 description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000004760 silicates Chemical class 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052878 cordierite Inorganic materials 0.000 description 4
- 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 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 3
- 239000001639 calcium acetate Substances 0.000 description 3
- 229960005147 calcium acetate Drugs 0.000 description 3
- 235000011092 calcium acetate Nutrition 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 101100476210 Caenorhabditis elegans rnt-1 gene Proteins 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052649 zeolite group Inorganic materials 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B1/00—Engines characterised by fuel-air mixture compression
- F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
- F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は窒素酸化物（以下、ＮＯ
ｘと略す）、一酸化炭素（ＣＯ）、炭化水素（以下、Ｈ
Ｃと略す）を含有する排気ガスを処理する方法に関す
る。The present invention relates to nitrogen oxides (hereinafter referred to as NO
abbreviated as x), carbon monoxide (CO), hydrocarbon (hereinafter, H)
A method for treating an exhaust gas containing C).
【０００２】[0002]
【従来の技術】自動車等の排ガス処理においては、排ガ
ス中のＣＯ、ＨＣを利用して、理論空燃比付近の極めて
狭い範囲でＮＯｘを浄化しているのが一般的である。近
年、地球環境問題の高まりの中で自動車の低燃費化の要
求は強く理論空燃比以上で燃焼させるリーンバーンエン
ジンがキーテクノロジーとして注目されている。ただ
し、自動車の走行性、加速性を考慮に入れるとリーン領
域のみのエンジンは不具合点が多く、実際は理論空燃比
（ストイキオ）付近、リーン領域の双方で燃焼を行わせ
る必要がある。最近、リーン領域のＮＯｘの浄化に関し
ては、コバルト又は銅を含有した結晶性シリケート触媒
が高性能を有する触媒として脚光をあびている。2. Description of the Related Art In the treatment of exhaust gas from automobiles and the like, it is common to use CO and HC in the exhaust gas to purify NOx in an extremely narrow range near the stoichiometric air-fuel ratio. In recent years, the demand for low fuel consumption of automobiles has been strongly demanded due to the increase of global environmental problems, and a lean burn engine that burns at a ratio higher than the theoretical air-fuel ratio has been attracting attention as a key technology. However, considering the driving and acceleration characteristics of the automobile, there are many problems with the engine only in the lean region, and it is necessary to actually perform combustion both in the vicinity of the stoichiometric air-fuel ratio (Stoichio) and in the lean region. Recently, regarding purification of NOx in the lean region, a crystalline silicate catalyst containing cobalt or copper has been highlighted as a catalyst having high performance.
【０００３】しかし、これらの触媒を用いて加速する場
合、ガス温度が瞬時に高温になり、かつ、この時のガス
組成は水素等の還元剤が過剰に存在するリッチ雰囲気に
なる。この条件においては、上記コバルト又は銅を含有
した結晶性シリケートを適用しても触媒の劣化を防ぐこ
とができないため、高温リッチ雰囲気の触媒の耐久性向
上がこれらの触媒の実用化上の大きな課題となってい
る。However, when accelerating using these catalysts, the gas temperature instantly rises to a high temperature, and the gas composition at this time becomes a rich atmosphere in which a reducing agent such as hydrogen is excessively present. Under this condition, even if the crystalline silicate containing cobalt or copper is applied, deterioration of the catalyst cannot be prevented, and therefore improvement of durability of the catalyst in a high temperature rich atmosphere is a major problem in practical application of these catalysts. Has become.
【０００４】[0004]
【発明が解決しようとする課題】上記不具合点を克服す
るため、本発明者らは鋭意検討を行ったところイリジウ
ムを担持した触媒が耐久性を有する触媒であることを見
い出している（特願平５−２６３６９など参照）。さら
に、本発明者らはＰｔ，Ｒｈ等の酸化触媒がＣＯ，ＨＣ
の燃焼に加えて２００〜３５０℃の低温域で脱硝作用を
有することを見い出している（特願平４−２３０７０
０，特願平５−１３５７５，特願平５−１３５７６参
照）。In order to overcome the above-mentioned problems, the present inventors have conducted diligent studies and found that the catalyst carrying iridium is a durable catalyst (Japanese Patent Application No. Hei 10-135242). 5-26369 etc.). Furthermore, the present inventors have found that the oxidation catalysts such as Pt and Rh are CO and HC.
It has been found that, in addition to the combustion of NOx, it has a denitration action in a low temperature range of 200 to 350 ° C (Japanese Patent Application No. 4-23070).
0, Japanese Patent Application No. 5-13575, Japanese Patent Application No. 5-13576).
【０００５】リーンバーンエンジン、ディーゼルエンジ
ンの排ガス条件（ガス組成、ガス量、温度等）はボイラ
排ガスに比べ幅広く、特に温度が２００〜６００℃の広
範囲にて随時存在するため、高活性、長寿命な触媒を組
み合わせて適用する方法が望まれている。本発明はこの
要望に応じうるＮＯｘ，ＣＯ及びＣＨを含有する排気ガ
スを浄化する方法を提供しようとするものである。Exhaust gas conditions (gas composition, gas amount, temperature, etc.) of lean burn engines and diesel engines are wider than those of boiler exhaust gas, and particularly, they exist in a wide temperature range of 200 to 600 ° C. at any time, so they have high activity and long life. A method of applying various catalysts in combination is desired. The present invention seeks to provide a method of purifying exhaust gas containing NOx, CO and CH which can meet this demand.
【０００６】[0006]
【課題を解決するための手段】上記状況を鑑み筆者らは
鋭意好ましい排ガス処理方法を検討したところ、排気流
入側にイリジウムを含有した触媒を排気流出側に酸化触
媒を配置させることにより上記目的に適した方法である
ことを見い出し、本発明を完成するに至った。In view of the above situation, the inventors of the present invention have studied earnestly the exhaust gas treatment method, and as a result, by arranging an oxidation catalyst on the exhaust gas outflow side with a catalyst containing iridium on the exhaust gas inflow side, The inventors have found that it is a suitable method and completed the present invention.
【０００７】すなわち、本発明は （１）窒素酸化物を含有する排気ガスを炭化水素の存在
下で処理する方法において、排気流入側にイリジウムを
含有した触媒を排気流出側に酸化触媒を配置することを
特徴とする排気ガス処理方法。 （２）排気流入側に配置するイリジウムを含有した触媒
の担体が （１±0.8 ）Ｒ2 Ｏ・〔ａＭ2 Ｏ3 ・ｂＭ′Ｏ・ｃＡｌ
2 Ｏ3 〕・ｙＳｉＯ2 （但し、上記式中、Ｒはアルカリ金属イオン及び／又は
水素イオン、ＭはVIII族元素、希土類元素、チタン、バ
ナジウム、クロム、ニオブ、アンチモン及びガリウムか
らなる群より選ばれた少なくとも１種以上の元素イオ
ン、Ｍ′はマグネシウム、カルシウム、ストロンチウ
ム、バリウムのアルカリ土類金属イオン、ａ≧０、２０
＞ｂ≧０、ａ＋ｃ＝１、３０００＞ｙ＞１１）なる化学
式を有し、本文で詳記する表Ａに示すＸ線回折パターン
を有する結晶性シリケートであることを特徴とする上記
（１）記載の排気ガス処理方法。 （３）排気流入側に配置するイリジウムを含有した触媒
の担体が組成式でγ−Ａｌ2 Ｏ3 、Ａｌ2 Ｏ3 ・ＺｒＯ
2 、ＴｉＯ2 、ＺｒＯ2 、ＳｉＯ2 ・Ａｌ2 Ｏ3、Ａｌ
2 Ｏ3 ・ＴｉＯ2 、ＴｉＯ2 ・ＺｒＯ2 、ＳＯ4 ／Ｚｒ
Ｏ2 、ＳＯ4 ／ＺｒＯ2 ・Ａｌ2 Ｏ3 、ＳＯ4 ／ＺｒＯ
2 ・ＴｉＯ2 、６Ａｌ2 Ｏ3 ・ＢａＯ、１１Ａｌ2 Ｏ3
・Ｌａ2 Ｏ3 、Ｙ型ゼオライト、Ａ型ゼオライト、シリ
カライト、モルデナイト、Ｘ型ゼオライトからなる群か
ら選ばれた１種以上の多孔質物質であることを特徴とす
る上記（１）記載の排気ガス処理方法。 （４）排気流出側に配置する酸化触媒の元素が白金、パ
ラジウム、ロジウム及びルテニウムよりなる群から選ば
れた１種以上の活性金属を含有するものであることを特
徴とする上記（１）〜（３）いずれかに記載の排気ガス
処理方法。 （５）排気流出側に配置する酸化触媒において、排気の
上流側にロジウムを含有する触媒を排気の下流側に白金
を含有する触媒を直列に組み合わせて設置することを特
徴とする上記（４）記載の排気ガス処理方法。である。That is, the present invention is: (1) In a method of treating exhaust gas containing nitrogen oxides in the presence of hydrocarbons, a catalyst containing iridium is arranged on the exhaust inflow side and an oxidation catalyst is arranged on the exhaust outflow side. An exhaust gas treatment method characterized by the above. (2) The carrier of the catalyst containing iridium placed on the exhaust inflow side is (1 ± 0.8) R 2 O. [aM 2 O 3 .bM'O.cAl
2 O 3 ] .ySiO 2 (wherein R is an alkali metal ion and / or hydrogen ion, M is a group VIII element, a rare earth element, titanium, vanadium, chromium, niobium, antimony and gallium. At least one elemental ion, M ′ is an alkaline earth metal ion of magnesium, calcium, strontium or barium, a ≧ 0, 20
> B ≧ 0, a + c = 1, 3000>y> 11), and the crystalline silicate having the X-ray diffraction pattern shown in Table A described in detail in the present text. Exhaust gas treatment method described. (3) The catalyst carrier containing iridium disposed on the exhaust inflow side has a composition formula of γ-Al 2 O 3 , Al 2 O 3 .ZrO.
2 , TiO 2 , ZrO 2 , SiO 2 · Al 2 O 3 , Al
2 O 3 · TiO 2 , TiO 2 · ZrO 2 , SO 4 / Zr
O 2 , SO 4 / ZrO 2 · Al 2 O 3 , SO 4 / ZrO
2・ TiO 2 , 6Al 2 O 3・ BaO, 11Al 2 O 3
The exhaust gas according to (1) above, which is one or more kinds of porous substances selected from the group consisting of La 2 O 3 , Y-type zeolite, A-type zeolite, silicalite, mordenite, and X-type zeolite. Gas treatment method. (4) The above (1) to (1), wherein the element of the oxidation catalyst arranged on the exhaust gas outflow side contains at least one active metal selected from the group consisting of platinum, palladium, rhodium and ruthenium. (3) The exhaust gas treatment method according to any one of the above. (5) In the oxidation catalyst arranged on the exhaust gas outflow side, the catalyst containing rhodium is installed upstream of the exhaust gas in combination with the catalyst containing platinum on the downstream side of the exhaust gas in series, and the above-mentioned (4) Exhaust gas treatment method described. Is.
【０００８】本発明の排気流入側に配置する触媒におい
て、担体として使用する結晶性シリケートは下記表Ａに
示すＸ線回折パターンを有する。In the catalyst disposed on the exhaust gas inflow side of the present invention, the crystalline silicate used as the carrier has the X-ray diffraction pattern shown in Table A below.
【０００９】[0009]
【表１】 ＶＳ：非常に強い Ｓ：強い Ｍ：中級 Ｗ：弱い Ｘ線源：Ｃｕ Ｋα[Table 1] VS: Very strong S: Strong M: Intermediate W: Weak X-ray source: Cu Kα
【００１０】該結晶性シリケートにイリジウムを担持す
る方法としては、結晶性シリケートをイリジウム塩溶液
に浸漬し、イオン交換法又は含浸法によって担持するこ
とができる。担持するイリジウムは０．００２ｗｔ％以
上で十分に活性が発現し、好ましくは０．０２ｗｔ％以
上で高い活性を有する。As a method for supporting iridium on the crystalline silicate, the crystalline silicate can be supported by immersing the crystalline silicate in an iridium salt solution and then carrying out an ion exchange method or an impregnation method. The supported iridium has a sufficient activity at 0.002 wt% or more, and preferably has a high activity at 0.02 wt% or more.
【００１１】前記結晶性シリケート以外の担体としては
単独酸化物であるγ−Ａｌ2 Ｏ3 、ＴｉＯ2 、Ｚｒ
Ｏ2 、複合酸化物であるＡｌ2 Ｏ3 ・ＺｒＯ2 、ＳｉＯ
2 ・Ａｌ 2 Ｏ3 、Ａｌ2 Ｏ3 ・ＴｉＯ2 、ＴｉＯ2 ・Ｚ
ｒＯ2 、６Ａｌ2 Ｏ3 ・ＢａＯ、１１Ａｌ2 Ｏ3 ・Ｌａ
2 Ｏ3 、固体超強酸であるＳＯ4 ／ＺｒＯ2 、ＳＯ4 ／
ＺｒＯ2 ・Ａｌ2 Ｏ3 、ＳＯ4 ／ＺｒＯ2 ・ＴｉＯ
2 （これらの固体強酸は各元素の水酸化物、複合水酸化
物を１ＮのＨ2 ＳＯ4 に約１時間室温で浸漬し、ろ過、
乾燥、焼成することによって得られる）及びゼオライト
群であるＹ型ゼオライト、Ａ型ゼオライト、シリカライ
ト（ペンタシル型構造を有したゼオライトの１種で、Ｓ
ｉとＯのみで構成されているもの）、モルデナイト、Ｘ
型ゼオライトが用いられる。この群の担体を使用する場
合のイリジウムの担持方法及び担持量は前記結晶性シリ
ケートを担体として用いた場合と同様である。As a carrier other than the crystalline silicate,
Γ-Al which is a single oxide2O3, TiO2, Zr
O2, Al that is a complex oxide2O3・ ZrO2, SiO
2・ Al 2O3, Al2O3・ TiO2, TiO2・ Z
rO2, 6Al2O3・ BaO, 11Al2O3・ La
2O3, Solid super acid SOFour/ ZrO2, SOFour/
ZrO2・ Al2O3, SOFour/ ZrO2・ TiO
2(These solid strong acids are hydroxides and complex hydroxides of each element.
1N H2SOFourSoak for about 1 hour at room temperature, filter,
Obtained by drying and calcining) and zeolite
Group Y-type zeolite, A-type zeolite, silicalite
To (a type of zeolite with a pentasil-type structure, S
i consisting of only i and O), mordenite, X
Type zeolite is used. When using this group of carriers
The loading method and loading amount of iridium in the
This is the same as when cate is used as a carrier.
【００１２】本発明の排気流出側に配置する白金、パラ
ジウム、ロジウム及びルテニウムよりなる群から選ばれ
た１種以上の活性金属を含有する酸化触媒の担体として
は、一般的にＡｌ2 Ｏ3 、ＺｒＯ2 、ＳｉＯ2 、ＴｉＯ
2 などの高比表面積の材料が使用される。ディーゼル排
気ガスを処理するに際してはＳＯｘ耐久性を考慮に入れ
るとＴｉＯ2 を担体として使用することが好ましい。な
お、酸化触媒の担持する活性金属の量は上記触媒と同じ
範囲で十分である。The carrier of the oxidation catalyst containing at least one active metal selected from the group consisting of platinum, palladium, rhodium and ruthenium arranged on the exhaust gas outlet side of the present invention is generally Al 2 O 3 , ZrO 2 , SiO 2 , TiO
High specific surface area materials such as 2 are used. In treating diesel exhaust gas, it is preferable to use TiO 2 as a carrier in consideration of SOx durability. The amount of active metal supported by the oxidation catalyst is sufficient in the same range as the above catalyst.
【００１３】なお、本発明の排気流出側に配置する酸化
触媒としては、ガソリンエンジン排気ガス浄化用として
用いられている３元触媒（理論空燃比付近でＮＯｘ，Ｃ
Ｏ，ＨＣを同時に除去することができる触媒）を使用す
ることもできる。As the oxidation catalyst arranged on the exhaust gas outflow side of the present invention, a three-way catalyst (NOx, C near the theoretical air-fuel ratio) used for purifying exhaust gas of a gasoline engine is used.
It is also possible to use a catalyst capable of simultaneously removing O and HC.
【００１４】また、排気流出側に配置する酸化触媒とし
て、排気の上流側にロジウムを含有する触媒を排気の下
流側に白金を含有する触媒を分割して直列に組み合わせ
て配置することによって、より広範囲の温度域で脱硝を
行うようにすることもできる。ロジウムを含有する触媒
と白金を含有する触媒とを組み合せる理由は、通常のリ
ーンバーンエンジン、ディーゼルエンジン排気ガスでは
約２００℃付近で白金を含有する触媒が高い脱硝活性を
有し、一方約３００℃付近でロジウムを含有する触媒が
高い脱硝活性を有するため、これらを組み合わせること
により２００〜３００℃の低温領域で幅広い脱硝活性を
保つことができるからである。Further, as the oxidation catalyst to be arranged on the exhaust gas outflow side, a catalyst containing rhodium on the upstream side of the exhaust gas and a catalyst containing platinum on the downstream side of the exhaust gas are divided and arranged in series, whereby It is also possible to perform denitration in a wide temperature range. The reason why the catalyst containing rhodium and the catalyst containing platinum are combined is that the catalyst containing platinum has a high denitration activity at about 200 ° C. in the exhaust gas of a normal lean burn engine or diesel engine, while the catalyst has about 300 This is because the catalyst containing rhodium has a high denitrification activity at around 0 ° C, and by combining these, a wide range of denitrification activity can be maintained in the low temperature range of 200 to 300 ° C.
【００１５】なお、本発明の排気流出側に配置される酸
化触媒は低温領域での脱硝を促進させるだけではなく、
当然のごとくＣＯ，ＨＣの可燃性ガスの低温燃焼も可能
にするものである。It should be noted that the oxidation catalyst arranged on the exhaust gas outflow side of the present invention not only promotes denitration in the low temperature region, but also
As a matter of course, it also enables low temperature combustion of combustible gases such as CO and HC.
【００１６】[0016]
【作用】通常、イリジウムを担持した触媒及び白金、パ
ラジウム、ロジウム、ルテニウムを担持した酸化触媒に
より、ＮＯｘ、ＣＯ、ＨＣを含有する排気ガスを浄化す
る浄化反応式は下記のとおりである。The purifying reaction formula for purifying exhaust gas containing NOx, CO, and HC by a catalyst carrying iridium and an oxidation catalyst carrying platinum, palladium, rhodium, and ruthenium is as follows.
【００１７】[0017]
【化１】 ＊１）炭化水素（ＨＣ）の例としてＣ3 Ｈ6 を代表とし
て示した。 ＊２）含酸素炭化水素の例としてＣＨ2 Ｏを代表として
示した。 上記反応式において、（１）はＨＣの活性化、（２）は
ＨＣの燃焼、（３）は脱硝反応、（４）はＣＯの燃焼を
意味している。[Chemical 1] * 1) As an example of hydrocarbon (HC), C 3 H 6 is shown as a representative. * 2) CH 2 O is shown as an example of the oxygen-containing hydrocarbon. In the above reaction formula, (1) means activation of HC, (2) means combustion of HC, (3) means denitration reaction, and (4) means combustion of CO.
【００１８】本発明で排気流入側に配置するイリジウム
を有した触媒の好ましい脱硝温度は３００〜５００℃、
一方排気流出側に配置する酸化触媒はいずれも３００℃
以下が好ましい脱硝温度である。脱硝反応は上式で示す
ように、ＨＣ，ＣＯの燃焼反応と併発して生じているた
め、排気流入側のイリジウムを担持した触媒で未燃とし
て残るＨＣが排気流出側の酸化触媒の脱硝反応への有効
な還元剤として作用する。In the present invention, the catalyst having iridium disposed on the exhaust gas inflow side has a preferable denitration temperature of 300 to 500 ° C.
On the other hand, all the oxidation catalysts placed on the exhaust gas outflow side are
The following are preferable denitration temperatures. As shown in the above equation, the denitration reaction occurs in parallel with the combustion reaction of HC and CO. Therefore, the HC remaining unburned in the catalyst carrying iridium on the exhaust inflow side is the denitrification reaction of the oxidation catalyst on the exhaust outflow side. Acts as an effective reducing agent to
【００１９】本発明において用いる触媒は、貴金属触媒
のため７００℃以上の高温リーン又はリッチ雰囲気に長
時間さらされても上記ｋ1 ，ｋ2 ，ｋ3 及びｋ4 の反応
速度定数はほとんど変化せず、耐久性を有する触媒であ
ることを見い出している。Since the catalyst used in the present invention is a precious metal catalyst, the reaction rate constants of k 1 , k 2 , k 3 and k 4 hardly change even when exposed to a high temperature lean or rich atmosphere of 700 ° C. or higher for a long time. However, it has been found to be a durable catalyst.
【００２０】[0020]
【実施例】 〇触媒１の調製 水ガラス１号（ＳｉＯ2 ：３０％）：５６１６ｇを水：
５４２９ｇに溶解し、この溶液を溶液Ａとする。一方、
水：４１７５ｇに硫酸アルミニウム：７１８．９ｇ、塩
化第二鉄：１１０ｇ、酢酸カルシウム：４７．２ｇ、塩
化ナトリウム：２６２ｇ、濃塩酸：２０２０ｇを溶解
し、この溶液を溶液Ｂとする。溶液Ａと溶液Ｂを一定割
合で供給し、沈殿を生成させ、十分攪拌してｐＨ＝８．
０のスラリを得る。このスラリを２０リットルのオート
クレーブに仕込み、さらにテトラプロピルアンモニウム
ブロマイドを５００ｇ添加し、１６０℃にて７２時間水
熱合成を行い、合成後水洗して乾燥させ、さらに５００
℃、３時間焼成させ結晶性シリケート１を得る。この結
晶性シリケート１は酸化物のモル比で（結晶水を省く）
下記の組成式で表され、結晶構造はＸ線回折で前記表Ａ
にて表示されるものである。 ０．５ＮａＯ2 ・０．５Ｈ2 Ｏ・〔０．８Ａｌ2 Ｏ3 ・
０．２Ｆｅ2 Ｏ3 ・０．２５ＣａＯ〕・２５ＳｉＯ2 上記結晶性シリケート１を４ＮのＮＨ4 Ｃｌ水溶液４０
℃に３時間攪拌してＮＨ4 イオン交換を実施した。イオ
ン交換後洗浄して１００℃、２４時間乾燥させた後、４
００℃、３時間焼成してＨ型の結晶性シリケート１を得
た。Example Preparation of Catalyst 1 Water glass No. 1 (SiO 2 : 30%): 5616 g of water:
It is dissolved in 5429 g, and this solution is referred to as solution A. on the other hand,
Aluminum sulfate: 718.9 g, ferric chloride: 110 g, calcium acetate: 47.2 g, sodium chloride: 262 g, concentrated hydrochloric acid: 2020 g are dissolved in water: 4175 g, and this solution is referred to as solution B. Solution A and solution B were supplied at a constant ratio to form a precipitate, which was sufficiently stirred to pH = 8.
Get a zero slurry. This slurry was charged into a 20 liter autoclave, 500 g of tetrapropylammonium bromide was further added, and hydrothermal synthesis was carried out at 160 ° C. for 72 hours. After the synthesis, washing with water and drying were carried out, and further 500
The crystalline silicate 1 is obtained by baking at 3 ° C. for 3 hours. This crystalline silicate 1 has a molar ratio of oxides (the water of crystallization is omitted).
It is represented by the following composition formula and its crystal structure is determined by X-ray diffraction as shown in Table A above.
Is displayed in. 0.5NaO 2 · 0.5H 2 O · [0.8Al 2 O 3 ·
0.2Fe 2 O 3 · 0.25CaO] · 25SiO 2 The above crystalline silicate 1 was added with 4N NH 4 Cl aqueous solution 40
NH 4 ion exchange was carried out by stirring at ℃ for 3 hours. After washing after ion exchange and drying at 100 ° C for 24 hours, 4
H-type crystalline silicate 1 was obtained by baking at 00 ° C. for 3 hours.
【００２１】次に、上記１００部のＨ型の結晶性シリケ
ート１に対して、バインダとしてアルミナゾル：３部、
シリカゾル：５５部（ＳｉＯ2 ：２０％）及び水：２０
０部加え、充分攪拌を行いウォッシュコート用スラリと
した。次にコージェライト用モノリス基材（４００セル
の格子目）を上記スラリに浸漬し、取り出した後余分な
スラリを吹きはらい２００℃で乾燥させた。コート量は
基材１リットルあたり２００ｇ担持し、このコート物を
ハニカムコート物１とする。次に、塩化イリジウム（Ｉ
ｒＣｌ4 ・Ｈ2 Ｏ：２．８８ｇ／Ｈ2 Ｏ：２００ｃｃ）
に上記ハニカムコート物１を浸漬し１時間含浸した後、
基材の壁の付着した液をふきとり２００℃で乾燥させ
た。次で５００℃で窒素雰囲気で１２時間パージ処理を
行い、ハニカム触媒１を得た。Next, with respect to 100 parts of the above H-type crystalline silicate 1, alumina sol as a binder: 3 parts,
Silica sol: 55 parts (SiO 2 : 20%) and water: 20
0 part was added and sufficiently stirred to obtain a wash coat slurry. Next, the monolith substrate for cordierite (lattice of 400 cells) was immersed in the slurry, taken out, and then excess slurry was blown off and dried at 200 ° C. The coated amount is 200 g per liter of the substrate, and this coated product is referred to as honeycomb coated product 1. Next, iridium chloride (I
rCl 4 · H 2 O: 2.88 g / H 2 O: 200 cc)
After immersing the honeycomb coated article 1 in the above and impregnating it for 1 hour,
The liquid adhering to the wall of the substrate was wiped off and dried at 200 ° C. Next, a purging process was performed at 500 ° C. in a nitrogen atmosphere for 12 hours to obtain a honeycomb catalyst 1.
【００２２】〇触媒２〜１６の調製 触媒１の結晶性シリケート１の合成法において、塩化第
二鉄の代わりに塩化コバルト、塩化ルテニウム、塩化ロ
ジウム、塩化ランタン、塩化セリウム、塩化チタン、塩
化バナジウム、塩化クロム、塩化アンチモン、塩化ガリ
ウム及び塩化ニオブを各々酸化物換算でＦｅ2 Ｏ3 と同
じモル数だけ添加した以外は結晶性シリケート１と同様
の操作を繰り返して結晶性シリケート２〜１２を調製し
た。これらの結晶性シリケートの結晶構造はＸ線回折で
前記表Ａに表示されるものであり、その組成は酸化物の
モル比（脱水された形態）で表わして０．５ＮａＯ2 ・
０．５Ｈ2 Ｏ・（０．２Ｍ2 Ｏ3 ・０．８Ａｌ2 Ｏ3 ・
０．２５ＣａＯ）・２５ＳｉＯ2 である。ここでＭはＣ
ｏ，Ｒｕ，Ｒｈ，Ｌａ，Ｃｅ，Ｔｉ，Ｖ，Ｃｒ，Ｓｂ，
Ｇａ，Ｎｂである。また、塩化第二鉄及び酢酸カルシウ
ムの代わりに何も添加せず結晶性シリケート１と同様の
方法において、結晶性シリケート１３を得た。Preparation of Catalysts 2 to 16 In the method for synthesizing the crystalline silicate 1 of catalyst 1, cobalt chloride, ruthenium chloride, rhodium chloride, lanthanum chloride, cerium chloride, titanium chloride, vanadium chloride, in place of ferric chloride, Crystalline silicates 2 to 12 were prepared by repeating the same operation as in crystalline silicate 1 except that chromium chloride, antimony chloride, gallium chloride and niobium chloride were added in the same mole number as Fe 2 O 3 in terms of oxide. . The crystal structure of these crystalline silicates is shown in Table A above by X-ray diffraction, and its composition is expressed by the molar ratio of oxides (dehydrated form) of 0.5 NaO 2 ·.
0.5H 2 O ・ (0.2M 2 O 3・ 0.8Al 2 O 3・
0.25CaO) · 25SiO 2 . Where M is C
o, Ru, Rh, La, Ce, Ti, V, Cr, Sb,
Ga and Nb. Also, crystalline silicate 13 was obtained in the same manner as crystalline silicate 1 without adding anything in place of ferric chloride and calcium acetate.
【００２３】さらに、触媒１の結晶性シリケート１の合
成法において、酢酸カルシウムの代わりに酢酸マグネシ
ウム、酢酸ストロンチウム、酢酸バリウムを各々酸化物
換算でＣａＯと同じモル数だけ添加した以外は結晶性シ
リケート１と同様の操作を繰り返して結晶性シリケート
１４〜１６を調製した。これらの結晶性シリケートの結
晶構造はＸ線回折で前記表Ａに表示されるものであり、
その組成は酸化物のモル比（脱水された形態）で表わし
て０．５Ｎａ2 Ｏ・０．５Ｈ2 Ｏ・（０．２Ｆｅ2 Ｏ3
・０．８Ａｌ2 Ｏ3 ・０．２５ＭｅＯ）・２５ＳｉＯ2
である。ここでＭｅはＭｇ，Ｓｒ，Ｂａである。上記結
晶性シリケート２〜１６を用いて実施例１と同様の方法
でＨ型の結晶性シリケート２〜１６を得、このシリケー
トをさらに実施例１の触媒の調製と同様の工程にてコー
ジェライトモノリス基材にコートしてハニカムコート物
２〜１６を得た。次に塩化イリジウム水溶液に浸漬し触
媒１と同様の処理にてハニカム触媒２〜１６を得た。Further, in the method for synthesizing crystalline silicate 1 of catalyst 1, crystalline silicate 1 is used except that magnesium acetate, strontium acetate, and barium acetate are added in the same molar number as CaO in terms of oxide instead of calcium acetate. The same operation as above was repeated to prepare crystalline silicates 14 to 16. The crystal structures of these crystalline silicates are those shown in Table A above by X-ray diffraction,
The composition is expressed by the molar ratio of oxides (dehydrated form) of 0.5Na 2 O.0.5H 2 O. (0.2Fe 2 O 3
・ 0.8Al 2 O 3・ 0.25MeO) ・ 25SiO 2
Is. Here, Me is Mg, Sr, or Ba. Using the above crystalline silicates 2 to 16, H type crystalline silicates 2 to 16 were obtained in the same manner as in Example 1, and the silicates were further subjected to the same steps as in the preparation of the catalyst of Example 1 to form cordierite monolith. The substrate was coated to obtain honeycomb coated products 2 to 16. Next, the honeycomb catalysts 2 to 16 were obtained by immersing in an iridium chloride aqueous solution and performing the same treatment as that of the catalyst 1.
【００２４】〇触媒１７〜３３の調製 さらに、組成式で、γ−Ａｌ2 Ｏ3 、Ａｌ2 Ｏ3 ・Ｚｒ
Ｏ2 、ＴｉＯ2 、ＺｒＯ2 、ＳｉＯ2 ・Ａｌ2 Ｏ3 、Ａ
ｌ2 Ｏ3 ・ＴｉＯ2 、ＴｉＯ2 ・ＺｒＯ2 、ＳＯ4 ／Ｚ
ｒＯ2 、ＳＯ4 ／ＺｒＯ2 ・Ａｌ2 Ｏ3 、ＳＯ4 ／Ｚｒ
Ｏ2 ・ＴｉＯ2、６Ａｌ2 Ｏ3 ・ＢａＯ、１１Ａｌ2 Ｏ
3 ・Ｌａ2 Ｏ3 、Ｙ型ゼオライト、Ａ型ゼオライト、シ
リカライト、モルデナイト及びＸ型ゼオライトを担体に
用いて実施例１と同様の工程にてコージェライトモノリ
ス基材にコートしてハニカムコート物１７〜３３を得
た。次に塩化イリジウム水溶液に浸漬し触媒１と同様の
処理にてハニカム触媒１７〜３３を得た。Preparation of Catalysts 17 to 33 Furthermore, in the composition formula, γ-Al 2 O 3 , Al 2 O 3 .Zr
O 2 , TiO 2 , ZrO 2 , SiO 2 · Al 2 O 3 , A
l 2 O 3 · TiO 2 , TiO 2 · ZrO 2 , SO 4 / Z
rO 2 , SO 4 / ZrO 2 · Al 2 O 3 , SO 4 / Zr
O 2 · TiO 2 , 6Al 2 O 3 · BaO, 11Al 2 O
A honeycomb-coated article 17 was prepared by coating a cordierite monolith substrate with 3 · La 2 O 3 , Y-type zeolite, A-type zeolite, silicalite, mordenite and X-type zeolite as a carrier in the same process as in Example 1. ~ 33 were obtained. Next, the honeycomb catalysts 17 to 33 were obtained by immersing in an aqueous solution of iridium chloride and performing the same treatment as that of the catalyst 1.
【００２５】〇触媒３４〜３７の調製 ハニカム触媒１９と同様の方法でＴｉＯ2 （アナターゼ
型）をコージェライトモノリス基材にコートしたハニカ
ムコート物１９に、塩化白金酸（Ｈ2 ＰｔＣｌ 6 ・６Ｈ
2 Ｏ：４．２ｇ／Ｈ2 Ｏ：２００ｃｃ）、硝酸パラジウ
ム（Ｐｄ（ＮＯ 3 ）3 ：１．９ｇ／Ｈ2 Ｏ：２００ｃ
ｃ）、塩化ロジウム（ＲｈＣｌ3 ：１．７ｇ／Ｈ2 Ｏ：
２００ｃｃ）、塩化ルテニウム（ＲｕＣｌ3 ・５Ｈ
2 Ｏ：２．７ｇ／Ｈ2 Ｏ：２００ｃｃ）の各水溶液に各
々浸漬し触媒１と同様の方法でハニカム触媒３４〜３７
を得た。以上の触媒１〜３７の触媒の性状を表Ｂにまと
めて示す。Preparation of Catalysts 34 to 37 TiO 2 was prepared in the same manner as the honeycomb catalyst 19.2(Anatase
Type) coated on a cordierite monolith substrate
Chloroplatinic acid (H2PtCl 6・ 6H
2O: 4.2 g / H2O: 200 cc), paradiu nitrate
Mu (Pd (NO 3)3: 1.9 g / H2O: 200c
c), rhodium chloride (RhCl3: 1.7 g / H2O:
200 cc), ruthenium chloride (RuCl3・ 5H
2O: 2.7 g / H2O: 200 cc) for each aqueous solution
Each of the honeycomb catalysts 34 to 37 in the same manner as the catalyst 1
Got The properties of the above catalysts 1 to 37 are summarized in Table B.
I will show you.
【００２６】[0026]
【表２】 [Table 2]
【００２７】[0027]
【表３】 [Table 3]
【００２８】[0028]
【表４】 [Table 4]
【００２９】（実験例１）実施例にて調製したハニカム
触媒１〜３３を排気流入側に、白金を担持したハニカム
触媒３４を排気流出側に設置し、活性評価試験Ｒｕｎ１
〜Ｒｕｎ３３を実施した。活性評価条件は下記のとお
り。(Experimental Example 1) The honeycomb catalysts 1 to 33 prepared in the examples are installed on the exhaust gas inflow side, and the honeycomb catalyst 34 carrying platinum is installed on the exhaust gas outflow side, and the activity evaluation test Run1 is performed.
~ Run 33 was performed. The activity evaluation conditions are as follows.
【００３０】〇（ガス組成） ＮＯ：５００ｐｐｍ、ＣＯ：１０００ｐｐｍ、Ｃ
2 Ｈ4 ：１５００ｐｐｍ、Ｏ 2 ：８％、ＣＯ2 ：１０
％、Ｈ2 Ｏ：１０％、残：Ｎ2 〇ガス量：４０５Ｎｌ／ｍｉｎ、ＧＨＳＶ １５，００
０ｈ-1 〇触媒形状：１５ｍｍ×１５ｍｍ×６０ｍｍ（１４４セ
ル数）１３５ｃｃを２個直列に配置（計２７ｃｃ） 〇反応温度：２５０，３５０，４５０℃ 初期状態の触媒の脱硝率を後記表Ｃに示す。O (gas composition) NO: 500 ppm, CO: 1000 ppm, C
2HFour: 1500ppm, O 2: 8%, CO2: 10
%, H2O: 10%, balance: N2 O Gas amount: 405 Nl / min, GHSV 15,000
0h-1 〇Catalyst shape: 15mm × 15mm × 60mm (144s
No.) 135cc two in series (27cc in total) Reaction temperature: 250, 350, 450 ° C The denitration rate of the catalyst in the initial state is shown in Table C below.
【００３１】また、排気流入側にハニカム触媒１を排気
流出側にハニカム触媒３５〜３７を設置し活性評価試験
Ｒｕｎ３４〜Ｒｕｎ３６を実施した。さらに、排気流出
側の触媒を２分割して、前段と後段に分け前段の排気上
流側にハニカム触媒３６を後段の排気下流側にハニカム
触媒３４を設置し、活性評価試験Ｒｕｎ３７を実施し
た。Further, the honeycomb catalyst 1 was installed on the exhaust inflow side and the honeycomb catalysts 35 to 37 were installed on the exhaust outflow side, and activity evaluation tests Run34 to Run36 were carried out. Further, the catalyst on the exhaust outflow side was divided into two, and was divided into a front stage and a rear stage, the honeycomb catalyst 36 was installed on the exhaust upstream side of the front stage, and the honeycomb catalyst 34 was installed on the exhaust downstream side of the rear stage, and the activity evaluation test Run 37 was performed.
【００３２】（実験例２）Ｒｕｎ Ｎｏ．１〜３７で配
置した触媒をリッチ雰囲気（還元雰囲気）で強制劣化試
験を実施した。強制劣化試験は下記の通り。 〇（ガス条件） Ｈ2 ：５％、Ｈ2 Ｏ：１０％、残：Ｎ2 ＧＨＳＶ：５０００ｈ-1、温度：７５０℃、ガス供給時
間：６時間 触媒形状：１５ｍｍ×１５ｍｍ×６０ｍｍ（１４４セ
ル）(Experimental Example 2) Run No. The catalysts arranged in 1 to 37 were subjected to a forced deterioration test in a rich atmosphere (reducing atmosphere). The forced deterioration test is as follows. 〇 (Gas condition) H 2 : 5%, H 2 O: 10%, balance: N 2 GHSV: 5000 h −1 , temperature: 750 ° C., gas supply time: 6 hours Catalyst shape: 15 mm × 15 mm × 60 mm (144 cells )
【００３３】上記強制劣化条件にて処理したＲｕｎ Ｎ
ｏ．１〜３７の組み合わせ触媒を実験例１の活性評価条
件において活性評価試験を実施した。反応温度２５０
℃、３５０、４５０℃における強制劣化試験後の触媒の
脱硝率を表Ｃに併せて示す。表Ｃに示すように本組み合
わせ触媒であるＲｕｎ Ｎｏ．１〜３７は高温還元雰囲
気においても触媒の活性を高く維持することを確認し
た。なお、ＣＯ及びＨＣの除去率は本反応温度では全て
１００％であることを確認している。Run N processed under the above-mentioned forced deterioration condition
o. An activity evaluation test was carried out on the combination catalysts 1 to 37 under the activity evaluation conditions of Experimental Example 1. Reaction temperature 250
Table C also shows the denitration rate of the catalyst after the forced deterioration test at 350 ° C, 350 ° C, and 450 ° C. As shown in Table C, this combination catalyst Run No. It was confirmed that 1 to 37 maintain high catalyst activity even in a high temperature reducing atmosphere. It has been confirmed that the removal rates of CO and HC are all 100% at this reaction temperature.
【００３４】[0034]
【表５】 [Table 5]
【００３５】[0035]
【表６】 [Table 6]
【００３６】[0036]
【表７】 [Table 7]
【００３７】[0037]
【発明の効果】以上、説明したように、本発明による排
気ガス浄化に際して使用する触媒は耐久性に富む安定な
触媒であり、本発明はガソリン車のリーンバーンエンジ
ン排ガス用やディーゼルエンジン排ガス浄化に極めて有
利に利用し得る。As described above, the catalyst used for purifying the exhaust gas according to the present invention is a stable and durable catalyst, and the present invention is applicable to lean burn engine exhaust gas of gasoline vehicles and diesel engine exhaust gas purification. It can be used very advantageously.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 29/22 ＺＡＢ Ａ 9343−4Ｇ 29/74 ＺＡＢ Ａ 9343−4Ｇ 35/02 ＺＡＢ Ｐ 8017−4Ｇ 35/04 ＺＡＢ 8017−4Ｇ ３０１ Ｌ 8017−4Ｇ Ｆ０１Ｎ 3/28 ３０１ Ｄ Ｂ０１Ｄ 53/36 １０２ Ｈ (72)発明者 芹沢 暁 長崎県長崎市飽の浦町１番１号 三菱重工 業株式会社長崎造船所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location B01J 29/22 ZAB A 9343-4G 29/74 ZAB A 9343-4G 35/02 ZAB P 8017-4G 35/04 ZAB 8017-4G 301 L 8017-4G F01N 3/28 301 D B01D 53/36 102 H (72) Inventor Akira Serizawa 1-1, Atsunoura Town, Nagasaki City, Nagasaki Prefecture Mitsubishi Heavy Industries Nagasaki Shipbuilding Co., Ltd.
Claims (5)
素の存在下で処理する方法において、排気流入側にイリ
ジウムを含有した触媒を排気流出側に酸化触媒を配置す
ることを特徴とする排気ガス処理方法。1. A method for treating an exhaust gas containing nitrogen oxides in the presence of hydrocarbons, wherein an iridium-containing catalyst is disposed on the exhaust inflow side and an oxidation catalyst is disposed on the exhaust outflow side. Gas treatment method.
した触媒の担体が （１±0.8 ）Ｒ2 Ｏ・〔ａＭ2 Ｏ3 ・ｂＭ′Ｏ・ｃＡｌ
2 Ｏ3 〕・ｙＳｉＯ2 （但し、上記式中、Ｒはアルカリ金属イオン及び／又は
水素イオン、ＭはVIII族元素、希土類元素、チタン、バ
ナジウム、クロム、ニオブ、アンチモン及びガリウムか
らなる群より選ばれた少なくとも１種以上の元素イオ
ン、Ｍ′はマグネシウム、カルシウム、ストロンチウ
ム、バリウムのアルカリ土類金属イオン、ａ≧０、２０
＞ｂ≧０、ａ＋ｃ＝１、３０００＞ｙ＞１１）なる化学
式を有し、本文で詳記する表Ａに示すＸ線回折パターン
を有する結晶性シリケートであることを特徴とする請求
項１記載の排気ガス処理方法。2. The catalyst carrier containing iridium disposed on the exhaust gas inflow side is (1 ± 0.8) R 2 O. [aM 2 O 3 .bM'O.cAl
2 O 3 ] .ySiO 2 (wherein R is an alkali metal ion and / or hydrogen ion, M is a group VIII element, a rare earth element, titanium, vanadium, chromium, niobium, antimony and gallium. At least one elemental ion, M ′ is an alkaline earth metal ion of magnesium, calcium, strontium or barium, a ≧ 0, 20
> B ≧ 0, a + c = 1, 3000>y> 11), and a crystalline silicate having an X-ray diffraction pattern shown in Table A described in detail herein. Exhaust gas treatment method.
した触媒の担体が組成式でγ−Ａｌ2 Ｏ3 、Ａｌ2 Ｏ3
・ＺｒＯ2 、ＴｉＯ2 、ＺｒＯ2 、ＳｉＯ2・Ａｌ2 Ｏ
3 、Ａｌ2 Ｏ3 ・ＴｉＯ2 、ＴｉＯ2 ・ＺｒＯ2 、ＳＯ
4 ／ＺｒＯ2、ＳＯ4 ／ＺｒＯ2 ・Ａｌ2 Ｏ3 、ＳＯ4
／ＺｒＯ2 ・ＴｉＯ2 、６Ａｌ2 Ｏ3・ＢａＯ、１１Ａ
ｌ2 Ｏ3 ・Ｌａ2 Ｏ3 、Ｙ型ゼオライト、Ａ型ゼオライ
ト、シリカライト、モルデナイト、Ｘ型ゼオライトから
なる群から選ばれた１種以上の多孔質物質であることを
特徴とする請求項１記載の排気ガス処理方法。3. A catalyst carrier containing iridium arranged on the exhaust gas inflow side has a composition formula of γ-Al 2 O 3 , Al 2 O 3
・ ZrO 2 , TiO 2 , ZrO 2 , SiO 2 .Al 2 O
3 , Al 2 O 3 · TiO 2 , TiO 2 · ZrO 2 , SO
4 / ZrO 2 , SO 4 / ZrO 2 · Al 2 O 3 , SO 4
/ ZrO 2 · TiO 2 , 6Al 2 O 3 · BaO, 11A
2. One or more kinds of porous substances selected from the group consisting of l 2 O 3 .La 2 O 3 , Y-type zeolite, A-type zeolite, silicalite, mordenite, and X-type zeolite. Exhaust gas treatment method described.
白金、パラジウム、ロジウム及びルテニウムよりなる群
から選ばれた１種以上の活性金属を含有するものである
ことを特徴とする請求項１〜３いずれかに記載の排気ガ
ス処理方法。4. The element of the oxidation catalyst disposed on the exhaust gas outflow side contains at least one active metal selected from the group consisting of platinum, palladium, rhodium and ruthenium. 4. The exhaust gas treatment method according to any one of 3 to 3.
て、排気の上流側にロジウムを含有する触媒を排気の下
流側に白金を含有する触媒を直列に組み合わせて設置す
ることを特徴とする請求項４記載の排気ガス処理方法。5. The oxidation catalyst disposed on the exhaust gas outflow side is characterized in that a catalyst containing rhodium is installed upstream of the exhaust gas and a catalyst containing platinum is installed in series on the downstream side of the exhaust gas. 4. The exhaust gas treatment method according to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28798693A JP3212429B2 (en) | 1993-11-17 | 1993-11-17 | Exhaust gas treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28798693A JP3212429B2 (en) | 1993-11-17 | 1993-11-17 | Exhaust gas treatment method |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000235302A Division JP3576471B2 (en) | 2000-08-03 | 2000-08-03 | Exhaust gas treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07136463A true JPH07136463A (en) | 1995-05-30 |
| JP3212429B2 JP3212429B2 (en) | 2001-09-25 |
Family
ID=17724321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28798693A Expired - Lifetime JP3212429B2 (en) | 1993-11-17 | 1993-11-17 | Exhaust gas treatment method |
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| Country | Link |
|---|---|
| JP (1) | JP3212429B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0696470A1 (en) | 1994-08-12 | 1996-02-14 | Mitsubishi Jukogyo Kabushiki Kaisha | Catalysts for cleaning exhaust gases |
| WO1997037761A1 (en) * | 1996-04-11 | 1997-10-16 | Ict Co., Ltd. | Exhaust gas purifying catalyst and exhaust gas purifying method |
| JPH10156184A (en) * | 1996-11-29 | 1998-06-16 | Ict:Kk | Catalyst for removing nitrogen oxide |
| KR19980085499A (en) * | 1997-05-29 | 1998-12-05 | 김영귀 | How to improve heat resistance of ZSM-5 automotive catalyst for lean burn zeolite system |
| WO2007049778A1 (en) * | 2005-10-24 | 2007-05-03 | Toyota Jidosha Kabushiki Kaisha | Catalyst support and catalyst for exhaust-gas purification |
-
1993
- 1993-11-17 JP JP28798693A patent/JP3212429B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0696470A1 (en) | 1994-08-12 | 1996-02-14 | Mitsubishi Jukogyo Kabushiki Kaisha | Catalysts for cleaning exhaust gases |
| US5710084A (en) * | 1994-08-12 | 1998-01-20 | Mitsubishi Jukogyo Kabushiki Kaisha | Catalysts for cleaning exhaust gases |
| WO1997037761A1 (en) * | 1996-04-11 | 1997-10-16 | Ict Co., Ltd. | Exhaust gas purifying catalyst and exhaust gas purifying method |
| US6214307B1 (en) | 1996-04-11 | 2001-04-10 | Ict Co., Ltd. | Exhaust gas purifying catalyst and exhaust gas purifying method |
| KR100300825B1 (en) * | 1996-04-11 | 2002-02-28 | 준쵸 셈바 | Catalyst for exhaust gas purification and exhaust gas purification method |
| JPH10156184A (en) * | 1996-11-29 | 1998-06-16 | Ict:Kk | Catalyst for removing nitrogen oxide |
| KR19980085499A (en) * | 1997-05-29 | 1998-12-05 | 김영귀 | How to improve heat resistance of ZSM-5 automotive catalyst for lean burn zeolite system |
| WO2007049778A1 (en) * | 2005-10-24 | 2007-05-03 | Toyota Jidosha Kabushiki Kaisha | Catalyst support and catalyst for exhaust-gas purification |
| US7776783B2 (en) | 2005-10-24 | 2010-08-17 | Toyota Jidosha Kabushiki Kaisha | Catalyst carrier and exhaust gas purification catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3212429B2 (en) | 2001-09-25 |
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