WO2003068363A1 - Multi-stage exhaust gas purifier - Google Patents
Multi-stage exhaust gas purifier Download PDFInfo
- Publication number
- WO2003068363A1 WO2003068363A1 PCT/US2003/003796 US0303796W WO03068363A1 WO 2003068363 A1 WO2003068363 A1 WO 2003068363A1 US 0303796 W US0303796 W US 0303796W WO 03068363 A1 WO03068363 A1 WO 03068363A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- platinum
- iron
- cerium
- employed
- process according
- Prior art date
Links
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 98
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910052742 iron Inorganic materials 0.000 claims abstract description 42
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 40
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 239000000446 fuel Substances 0.000 claims abstract description 34
- 238000002485 combustion reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 11
- -1 platinum group metal compound Chemical class 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- 239000000344 soap Substances 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- 125000005474 octanoate group Chemical group 0.000 claims description 6
- FXNONNRUNQPNLF-UHFFFAOYSA-N cerium;2-ethylhexanoic acid Chemical compound [Ce].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O FXNONNRUNQPNLF-UHFFFAOYSA-N 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 4
- YPIFGDQKSSMYHQ-UHFFFAOYSA-M 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC([O-])=O YPIFGDQKSSMYHQ-UHFFFAOYSA-M 0.000 claims description 3
- 229910017147 Fe(CO)5 Inorganic materials 0.000 claims description 3
- HZMBANJECWHRGE-GNOQXXQHSA-K cerium(3+);(z)-octadec-9-enoate Chemical compound [Ce+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O HZMBANJECWHRGE-GNOQXXQHSA-K 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 239000000567 combustion gas Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims 1
- 239000013618 particulate matter Substances 0.000 description 15
- 239000004071 soot Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000010948 rhodium Substances 0.000 description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 239000005749 Copper compound Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001785 cerium compounds Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000010763 heavy fuel oil Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229940049964 oleate Drugs 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 150000003682 vanadium compounds Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910002262 LaCrO3 Inorganic materials 0.000 description 1
- 229910002328 LaMnO3 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004165 Methyl ester of fatty acids Substances 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000000828 canola oil Substances 0.000 description 1
- 235000019519 canola oil Nutrition 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- HOIQWTMREPWSJY-GNOQXXQHSA-K iron(3+);(z)-octadec-9-enoate Chemical compound [Fe+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O HOIQWTMREPWSJY-GNOQXXQHSA-K 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- RAVDHKVWJUPFPT-UHFFFAOYSA-N silver;oxido(dioxo)vanadium Chemical compound [Ag+].[O-][V](=O)=O RAVDHKVWJUPFPT-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2896—Liquid catalyst carrier
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9431—Processes characterised by a specific device
-
- B01J35/56—
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
- F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
- F01N13/0097—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series the purifying devices are arranged in a single housing
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
- F01N3/0222—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
- F01N3/0226—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being fibrous
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/023—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
- F01N3/0231—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles using special exhaust apparatus upstream of the filter for producing nitrogen dioxide, e.g. for continuous filter regeneration systems [CRT]
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
- F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1021—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/915—Catalyst supported on particulate filters
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/06—Ceramic, e.g. monoliths
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/10—Fibrous material, e.g. mineral or metallic wool
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/12—Metallic wire mesh fabric or knitting
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/14—Sintered material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
- F01N2570/14—Nitrogen oxides
Definitions
- the invention concerns a new device and process for improving purifying internal combustion engine exhaust gas by effectively removing particulate matter (PM) at low cost.
- the invention provides an economical and effective answer to the problems associated with controlling particulates and permits using effective measures for reducing NO ⁇ without suffering major penalties in fuel consumption, particularly for mobile diesel and other lean-burn engines.
- Diesel and lean-burn gasoline engines provide advantages in fuel economy and are favored for this reason.
- they when operated for fuel economy and low PM emissions, they produce large quantities of NO x during normal operation, and there is no known technology that is available to take advantage of their economy without suffering the penalty of NO x emissions.
- primary measures actions that affect the combustion process itself
- fuel economy is also usually reduced and PM emissions are increased. This has led to the development of a variety of means to handle PM formed as combustion is conducted under conditions lowering the production of NO x .
- particulate filters which encompass a wide variety of forms. They may be particulate or reticulated ceramic foam. They may encompass honeycomb-like structures, often with blocked passageways and small openings between adjacent passageways. Metal mesh filters, pelletized refractory materials such as alumina, and ceramic fibrous mats are all used as diesel particulate filters. Most current diesel particulate filters (DPF) are single stage devices. There are two primary types: extruded monolith filters and candle filters made from woven or wound fiber. Filters are usually designed for 85% reduction of PM by mass in one stage. Both types have been prone to failure; the failures are caused by excessive buildup of heat and/or pressure resulting in a localized fracture or hole in the filter. The result can be a massive loss in efficiency and effective failure.
- DPF diesel particulate filters
- Catalysts can enhance oxidation. There are several oxidation mechanisms available for use in PM filters. The soot primarily contains carbon and absorbed hydrocarbons. While the hydrocarbons can be quite easily oxidized by oxygen in the presence of catalysts, the elemental carbon is not easily oxidized at the temperatures prevailing in typical diesel engine exhausts.
- Carbon can be catalytically oxidized in at least two ways in a typical exhaust gas mixture containing NO x , excess oxygen and particulates, usually at temperatures over 400°C. In some systems, heat must be added to the exhaust to obtain the necessary temperature to initiate combustion of the soot.
- carbon-NO reaction carbon is selective in reducing NO to N 2 at temperatures of 600°C and above by surface chemistry. It has been shown in engine tests that when platinum and cerium are used as a fuel borne catalyst (FBC), there is substantial reduction of NO x to N 2 simultaneous with the oxidation of carbon; it has been postulated that the combination of platinum and cerium is catalyzing the selective reduction of NO by carbon. Some of the NO x reduction is measured “engine out” but more reduction is measured when a particulate filter is used - consistent with the fact that more residence time is provided in the filter.
- FBC fuel borne catalyst
- the carbon-NO 2 reaction is the reaction in the presence of NO .
- NO in exhaust is oxidized over a catalyst, typically of platinum, to NO 2 .
- the resulting NO 2 reacts with carbon to form CO or C0 2 and NO (again).
- a catalyst typically of platinum
- U.S. Patent No. 5,203,166, to Miller describes a diesel engine emissions control system including a particulate filter system and a pair of heaters on catalyzed particulate filters. The heaters operate to regenerate one of the filters while the other is being used.
- European Patent Application No. 743 429 describes a diesel exhaust particulate filter that includes an oxidation catalyst. Diesel fuel is introduced upstream of the oxidation catalyst to raise the temperature of the exhaust gas to heat the catalyst to burn away the PM.
- European Patent Application No. 764 455 describes a sintered fiber web as the device for removing PM from the exhaust gas.
- the web may be treated to form an alumina film on the surface of the fibers and optionally a catalyst may be placed on those alumina-coated fibers.
- U.S. Patent No. 4,510,265 Hartwig, describes a diesel engine exhaust gas catalyzed filter which is said to be self-cleaning and employs an oxidation catalyst of a combination of platinum and silver vanadate material.
- the example shows removal of accumulated carbon by placement of the filter in a furnace variously at temperatures of just greater than 475° C for 20% burn off to just over 600° C for 80% burn off.
- U.S. Patent No. 4,711,870 to Yamada, et al, also shows a porous ceramic body used to oxidize diesel soot.
- the active catalyst is said to be one comprising: (a) copper or a copper compound; (b) vanadium or a vanadium compound; (c) zirconium, aluminum, nickel, iron, manganese, lanthanum, chromium, zinc, lead or cerium, or a compound thereof; and optionally, (d) platinum, rhodium, or palladium, or a compound thereof.
- These catalysts are also said to allow the particulate burning temperature to be lowered below that required prior to the date of the Yamada, et al., patent.
- Example 12 The temperature for removing 90% of the soot found in a control sample of the catalyzed porous body is shown in Example 12 to be in the neighborhood of 460° to 470° C.
- U.S. Patent No. 4,759,918, to Homeier, et al. shows a Platinum Group metal (platinum, palladium, or rhodium) as a catalytic soot removal device.
- Example 6 of the patent shows a diesel soot combustion efficiency of 95% at 400° C by use of a platinum catalyst on a titania support.
- U.S. Patent No. 5,000,929 shows a similar catalyst for diesel soot removal made up of a support, typically of an inorganic refractory oxide, and having palladium and the oxide of at least one of praseodymium, neodymium, and samarium as components.
- U.S. Patent No. 5,213,781 to Abe et al, and its division, U.S. Pat. No. 5,340,548, describe a porous diesel engine exliaust filter also catalyzed, e.g., using an alkali metal, a copper metal, a vanadium element, and at least one rare earth element.
- the PM is said to be oxidized at 400° C.
- U.S. Patent No. 5,330,945 to Beckmeyer, et al., shows a diesel fuel exhaust filter containing a zeolite-based wash coat material.
- the preferred Y-type zeolite is exchanged with a precious metal to form the active material.
- European Patent Application No. 714 652 shows a catalyst for treatment of diesel engine exhaust gas comprising a three-dimensional support structure coated with a platinum and/or a palladium carrying refractory inorganic oxide powder further containing a metal selected from the group consisting of tungsten, antimony, molybdenum, nickel, vanadium, manganese, iron, bismuth, cobalt, zinc, and the alkaline earth metals.
- European Patent Application No. 508 513 shows use of a Y-type zeolite supported on a ceramic or a metal monolith.
- the monolith is used in treating diesel fueled engine exhaust.
- European Patent Application No. 160 482 shows a self-cleaning diesel exhaust particulate filter having as its oxidic catalyst mixture, a platinum group metal and an alkaline earth metal. Oxidation temperatures in the neighborhood of 350°C appear to have been achieved using such technology.
- European Patent Application No. 600 442 to Nippon Shokuvai Company, utilizes iron as the active catalytic component in a diesel engine exhaust gas purification catalyst.
- European Patent Application No. 658 369 utilizes a diesel exhaust trap utilizing an oxidizing catalyst made up of platinum, rhodium, copper or vanadium oxide, composite oxides such as perovskites such as LaMnO 3 and LaCrO 3 , a part of which may be replaced with alkali metals or alkaline earth metals such as strontium, potassium, or lithium.
- the examples showed initial oxidation temperatures (for carbon particulates) to be from about 280° to 427° C.
- European Patent Application No. 092 023 shows a diesel exhaust trap having an oxidation catalyst of metallic copper or copper compound, metallic molybdenum, metallic vanadium, a molybdenum or vanadium compound, and an alkali metal compound.
- the catalytic material is preferably placed on a carrier of titania, ⁇ -alumina, or silica-alumina. It is preferably used with a metallic platinum, palladium, or rhodium component for enhanced catalytic activity.
- the invention provides a new device and a new process addressing the above needs.
- a multi-stage filter is made in which each stage is designed for partial reduction of particulate matter (PM) - in some cases only 20 to 50% as opposed to 85% in current single stage filters.
- PM particulate matter
- a multi-stage filter filtering at 50% efficiency requires four stages to achieve an equivalent overall filtration rate, and a filter with a filtration efficiency of 20% per stage requires nine stages.
- a multi-stage filter can be made using segments of monolith "flow through" section alternatively with filtration segments.
- the monolith can be cordierite, silicon carbide or other material and may be catalyzed during the manufacture as is done for diesel oxidizers or catalyzed by deposit over time of a fuel borne catalyst (FBC).
- FBC fuel borne catalyst
- the filter segments can be of ceramic foam, sintered metal or compressed wire or fiber. Essentially, these filter sections are more open in pore size that single filters and will often be of a deep bed form, not a membrane.
- the filter is an assembly of stages with a monolith followed by a filter segment followed by a monolith and so on (as illustrated in the accompanying drawings).
- the overall efficiency will depend upon the volume available for the components, the number of stages for a particular designed efficiency and the back pressure limit of the system.
- Monolith sections can be directly abutted to the filter section, but it may be advantageous t provide a gap between sections to allow mixing.
- the invention provides a method comprising passing combustion gases through a multi-stage treatment zone containing at least one monolith section and one filter screen section within a treatment chamber.
- a fuel borne catalyst e.g., containing platinum or other platinum group metal (PGM), including palladium, rhodium, ruthenium, osmium, and iridium, and/or other metal such as cerium or iron.
- PGM platinum or other platinum group metal
- the invention provides a device comprising a multi-stage treatment zone containing at least one monolith section and one filter screen section within a treatment chamber.
- Figure 1 is a schematic view of an embodiment of the invention wherein a portion of the exhaust gas, produced by the combustion of diesel fuel is passed through an exhaust purification device in accord with the invention;
- FIG 2 is a schematic view of an embodiment of the invention, showing the exhaust purification device in accord with the invention in greater detail than in Figure 1.
- the invention relates to a new device and a new process addressing the above needs and is intended for use with combustors such as turbines, boilers, furnaces, process heaters, heat recovery units, diesel engines, spark ignition engines and the like, utilizing carbonaceous, e.g., fossil or bio-derived, fuels such as distillates, residual and gaseous fuels and various fatty acid esters and like fuels.
- combustors such as turbines, boilers, furnaces, process heaters, heat recovery units, diesel engines, spark ignition engines and the like
- carbonaceous e.g., fossil or bio-derived, fuels such as distillates, residual and gaseous fuels and various fatty acid esters and like fuels.
- oxidation can be by oxygen at temperatures over 400° C. Catalysts are required to promote oxidation. For oxidization below 400° C, the oxidation reaction mechanism is at least partially the carbon-NO 2 reaction, and the reaction proceeds much more slowly than oxidation at higher temperatures. At the lower temperatures, longer residence time of the soot particle (i.e., carbon, PM) on the catalytic surface is required. Catalytic activity results fro the catalyst on the surface upon which the particle resides and upon catalyst "tightly bound" in the soot particle.
- soot particle i.e., carbon, PM
- each stage includes a catalyzed monolith section (catalyzed by FBC or precatalyzed) to increase NO 2 concentration before each filter section.
- the reacted NO 2 is reduced back to NO after the reaction with carbon, but can be reoxidized to NO 2 at the next stage - thus, using the NO more than once and maximizing the effect of the carbon-NO 2 reaction.
- each stage provides residence time for the soot particles as they progress through the device; and the particles will tend to impinge on the surfaces where they can react with NO or NO 2 and agglomeration is promoted. Larger agglomerations become easier to filter in subsequent stages.
- FBC fuel borne catalyst
- increased residence time while promoting reaction under the carbon-NO reaction, e.g., catalyzed by a fuel borne catalyst (FBC) comprising platinum and cerium, also results in enhanced NO x reduction.
- FBC fuel borne catalyst
- the soot particle is effectively reacting under this carbon-NO reaction whenever and wherever it touches a surface in the monolith or filter segments.
- filter segments may be varied in porosity through the assembly. For optimum efficiency it may be desirable to have the first stages more open in pore size than the latter stages.
- Figure 1 is a schematic view of an embodiment of the invention wherein a portion of the exhaust gas, produced by the combustion of diesel fuel is passed through an exhaust purification device 10 in accord with the invention.
- Figure 1 shows a passage 12 for receiving exhaust from the engine. The exhaust is passed through an opening section 14 in the device 10 to direct flow into a treatment zone containing at least one monolith section 16 and one screen filter section 18. Both sections are shown repeated as 16', etc., and 18', etc., respectively, downstream of opening section 14 of treatment chamber enclosed by wall structure 15. Following treatment, the exhaust gas is passed from the last of the treatment sections to exit 20.
- Figure 2 is a schematic view of an embodiment of the invention, showing the exhaust purification device in accord with the invention in greater detail than in Figure 1.
- section 16 comprises a monolith of the type typically employed for pass through oxidation catalysts. It will preferably be of a suitable ceramic or other core material in a simple honeycomb or other configuration with passages substantially continuously extending through the horizontal extent of the device. If desired, undulations or other discontinuities can be formed into the individual channels extending through the section 16.
- the materials used in the monolith stages 16, 16', etc. can be the same from stage to stage (for multi-stage devices) or could vary between stages, using one or more of extruded sections and metal assemblies or very open foam or sintered materials.
- the monolith is easily made and readily available.
- the monolith sections 16, 16', etc., and the filter or screen filter members 18, 18', etc. may be of similar or the same construction with one another in devices having more than one stage of each, and that more or less screen members may be used.
- the monolith sections and screen sections can be employed as pairs in any number of stages, e.g., from 2 to 10, say 3 to 6, or can be in unequal number together with other functional components where desired.
- Materials of construction for the screen sections may be porous ceramics, porous carbon, porous metal, ceramic foam, carbon foam, and metal foam, sintered metal, ceramic and high temperature fibers, may be used to form screen filter structure 18, either used alone, or in combination with one or more screen members 18', 18", etc.
- fine mesh screens may be formed from expanded metal or of a woven mesh material, such as compressed wire, compressed wire mesh, felted wire or the like.
- screen structure 18 is formed from a corrosion-resistant material that will not impair the operation of the purification module 18 and devices with which the membrane module is used.
- suitable materials for metallic screen members include stainless steels, titanium and alloys thereof, zirconium and alloys thereof, corrosion- resistant alloys, including Inconel® alloys, such as 800H®, and Hastelloy® alloys, and alloys of nickel, such as Monel® metal.
- An example of an expanded metal screen member is shown in Figure 2 and generally indicated at 118. Expanded metal sheets include a latticework of metal that defines a plurality of apertures through which exhaust gas may flow. Although other processes may be used, expanded metal sheets may be formed from scoring a sheet of metal and then stretching the metal to provide apertures, such as apertures at the scores.
- the expanded metal screen member has been schematically illustrated in Figure 2, and that the actual shape of the apertures may vary and will often have shapes that generally appear as geometric or regular shapes.
- the sheet may also include a solid perimeter region, which may extend all the way around the screen member.
- a fuel can be one or a blend of fuels selected from the group consisting of distillate fuels, including diesel fuel, e.g., No. 2 Diesel fuel, gasoline, jet fuel, e.g., Jet A, or the like, and biologically-derived fuels, such as those comprising a "mono-alkyl ester-based oxygenated fuel", i.e., fatty acid esters, preferably methyl esters of fatty acids derived from triglycerides, e.g., soybean oil, Canola oil and/or tallow.
- Other hydrocarbons, including liquids and gases, e.g., natural gas, or fuels derived from gas and/or emulsion components can be employed.
- Cerium and/or iron catalyst levels can be at levels as low as 0.05 ppm and platinum levels can be as low as 0.0005 ppm.
- a regimen of treatment will utilize effective levels within effective ranges for a time and under conditions, which will achieve one or more of the noted improvements.
- the process of the invention can employ as an FBC for catalyzing one or more stages, a fuel-soluble, multi-metal catalyst, preferably comprising fuel-soluble platinum (or other PGM) and either cerium or iron.
- a fuel-soluble, multi-metal catalyst preferably comprising fuel-soluble platinum (or other PGM) and either cerium or iron.
- the cerium and/or iron are typically employed at concentrations of from 0.5 to 20 ppm and the platinum from 0.0005 to 2 ppm, with preferred levels of cerium or iron being from 5 to 10 ppm, e.g., 7.5 ppm, and the PGM being employed at a level of from 0.05 to 0.5ppm, e.g., 0.15 ppm.
- a preferred ratio of cerium and/or iron to PGM is from 75: 1 to 10:1.
- One narrower range is from 60:1 to 15:1.
- the fuel can contain detergent (e.g., 50-300 ppm), lubricity additive (e.g., 25 to about 500 ppm), other additives, and suitable fuel-soluble catalyst metal compositions, e.g., 0.1 - 2 ppm fuel soluble platinum group metal composition, e.g., platinum COD or platinum acetylacetoneate and/or 2-20 ppm fuel soluble cerium or iron composition, e.g., cerium, cerium octoate, ferrocene, iron oleate, iron octoate and the like.
- the fuel as defined, is combusted without the specific need for other treatment devices although they can be used especially for higher levels of control on diesels.
- a combination of PGM with either iron and/or cerium at low concentrations in fuels is as effective as much higher concentrations of cerium, iron or other metals without platinum in reducing carbon or soot deposits or emissions. Concentrations of a few ppm metals in combination are as effective as 30-100 ppm of iron and/or cerium used alone. These traditional levels of cerium and/or iron are high enough to be factors in causing fouling of heat transfer surfaces due to the high ash burden associated with high metal concentrations in the fuel.
- bimetallic and trimetallic platinum combinations are compatible with standard additive components for distillate and residual fuels such as pour point reducers, antioxidant, corrosion inhibitors and the like.
- the catalyst component will preferably comprise a multi-metal fuel soluble catalyst comprised of fuel-soluble platinum (or other PGM) and/or cerium and/or iron.
- the cerium and/or iron are typically employed at concentrations of from 0.5 to 25 ppm and the platinum from 0.0005 to 2 ppm, with preferred levels of cerium or iron being from 5 to 10 ppm, e.g., 7.5 ppm, and the platinum being employed at a level of from 0.05 to 0.5ppm, e.g., 0.15 ppm.
- a preferred ratio of cerium and/or iron to PGM is from 75:1 to 10:1.
- cerium III acetylacetonate cerium III napthenate
- cerium octoate cerium oleate and other soaps such as stearate, neodecanoate, and octoate (2-ethylhexoate).
- cerium compounds are trivalent compounds meeting the formula: Ce (OOCR) 3 wherein RHhydrocarbon, preferably C 2 to C 22 , and including aliphatic, alicyclic, aryl and alkylaryl.
- the cerium is preferred at concentrations of 1 to 15 ppm cerium w/v of fuel.
- the cerium is supplied as cerium hydroxy oleate propionate complex (40% cerium by weight). Preferred levels are toward the lower end of this range.
- iron compounds include ferrocene, ferric and ferrous acetylacetonates, iron soaps like octoate and stearate (commercially available as Fe(UI) compounds, usually), iron pentacarbonyl Fe(CO) 5 , iron napthenate, and iron tallate.
- platinum group metal compositions e.g., 1,5-cyclooctadiene platinum diphenyl (platinum COD), described in U.S. Pat. No. 4,891,050 to Bowers, et al., U.S. Pat. No. 5,034,020 to Epperly, et al., and U.S. Pat. No. 5,266,093 to Peter-Hoblyn, et al, can be employed as the platinum source.
- platinum COD 1,5-cyclooctadiene platinum diphenyl
- platinum group metal catalyst compositions include commercially-available or easily-synthesized platinum group metal acetylacetonates, platinum group metal dibenzylidene acetonates, and fatty acid soaps of tetramine platinum metal complexes, e.g., tetramine platinum oleate.
- the platinum is preferred at concentrations of 0.05 - 2.0 ppm platinum w/v (mg per liter) of fuel, e.g., up to about 1.0 ppm. Preferred levels are toward the lower end of this range, e.g., 0.15 -0.5 ppm.
- Platinum COD is the preferred form of platinum for addition to the fuel.
- the cerium or iron are typically employed at concentrations to provide from 0.5 to 25 ppm of the metal and the platinum from 0.0005 to 2 ppm, with preferred levels of cerium or iron being from 5 to 10 ppm, e.g., 7.5 ppm, and the platinum being employed at a level of from 0.1 to 0.5ppm, e.g., 0.15 ppm.
- a preferred ratio of cerium and/or iron to platinum is
- the combustion according to the invention can be of an emulsion with water, wherein an oil phase is emulsified with water, the water comprising from 1 to 30% water based on the weight of the distillate fuel, residual fuel, aviation kerosene or the like.
- the emulsion will be predominantly of the water-in-oil type and will preferably contain surfactants, lubricity additives and/or corrosion inhibitors in addition to the other components mentioned above.
- surfactants lubricity additives and/or corrosion inhibitors in addition to the other components mentioned above.
- lubricity additives and/or corrosion inhibitors in addition to the other components mentioned above.
- corrosion inhibitors can improve combustion efficiency and reduce particulates without the use of oxidation catalysts or particulate filters for enhanced emissions control on diesel engines. Also, better carbon burn out in open flame combustion sources will lead to lower carbon deposits on heat transfer surfaces and lower soot oxidation temperatures on downstream heat recovery devices.
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AU2003216202A AU2003216202A1 (en) | 2002-02-12 | 2003-02-07 | Multi-stage exhaust gas purifier |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US35636702P | 2002-02-12 | 2002-02-12 | |
US60/356,367 | 2002-02-12 |
Publications (1)
Publication Number | Publication Date |
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WO2003068363A1 true WO2003068363A1 (en) | 2003-08-21 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US2003/003796 WO2003068363A1 (en) | 2002-02-12 | 2003-02-07 | Multi-stage exhaust gas purifier |
Country Status (2)
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AU (1) | AU2003216202A1 (en) |
WO (1) | WO2003068363A1 (en) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1520614A1 (en) * | 2003-06-10 | 2005-04-06 | Ibiden Co., Ltd. | Honeycomb structure body |
WO2007031074A1 (en) * | 2005-09-16 | 2007-03-22 | Lothar Wenzel | Device for eliminating harmful constituents from exhaust gases of internal combustion engines |
EP1544426B1 (en) * | 2003-12-18 | 2008-01-09 | Clean Diesel Technologies Inc. | Apparatus for filtering and burning particulate matter |
US7455709B2 (en) | 2003-07-15 | 2008-11-25 | Ibiden Co., Ltd. | Honeycomb structural body |
EP2640941A1 (en) * | 2010-11-16 | 2013-09-25 | Scania CV AB | Particle filter for an exhaust system of a combustion engine |
US9475005B2 (en) | 2014-06-06 | 2016-10-25 | Clean Diesel Technologies, Inc. | Three-way catalyst systems including Fe-activated Rh and Ba-Pd material compositions |
US9511350B2 (en) | 2013-05-10 | 2016-12-06 | Clean Diesel Technologies, Inc. (Cdti) | ZPGM Diesel Oxidation Catalysts and methods of making and using same |
US9511353B2 (en) | 2013-03-15 | 2016-12-06 | Clean Diesel Technologies, Inc. (Cdti) | Firing (calcination) process and method related to metallic substrates coated with ZPGM catalyst |
US9511358B2 (en) | 2013-11-26 | 2016-12-06 | Clean Diesel Technologies, Inc. | Spinel compositions and applications thereof |
US9545626B2 (en) | 2013-07-12 | 2017-01-17 | Clean Diesel Technologies, Inc. | Optimization of Zero-PGM washcoat and overcoat loadings on metallic substrate |
US9555400B2 (en) | 2013-11-26 | 2017-01-31 | Clean Diesel Technologies, Inc. | Synergized PGM catalyst systems including platinum for TWC application |
US9700841B2 (en) | 2015-03-13 | 2017-07-11 | Byd Company Limited | Synergized PGM close-coupled catalysts for TWC applications |
US9731279B2 (en) | 2014-10-30 | 2017-08-15 | Clean Diesel Technologies, Inc. | Thermal stability of copper-manganese spinel as Zero PGM catalyst for TWC application |
US9771534B2 (en) | 2013-06-06 | 2017-09-26 | Clean Diesel Technologies, Inc. (Cdti) | Diesel exhaust treatment systems and methods |
US9861964B1 (en) | 2016-12-13 | 2018-01-09 | Clean Diesel Technologies, Inc. | Enhanced catalytic activity at the stoichiometric condition of zero-PGM catalysts for TWC applications |
US9951706B2 (en) | 2015-04-21 | 2018-04-24 | Clean Diesel Technologies, Inc. | Calibration strategies to improve spinel mixed metal oxides catalytic converters |
US10265684B2 (en) | 2017-05-04 | 2019-04-23 | Cdti Advanced Materials, Inc. | Highly active and thermally stable coated gasoline particulate filters |
US10533472B2 (en) | 2016-05-12 | 2020-01-14 | Cdti Advanced Materials, Inc. | Application of synergized-PGM with ultra-low PGM loadings as close-coupled three-way catalysts for internal combustion engines |
CN112156749A (en) * | 2020-08-17 | 2021-01-01 | 周悦先 | Preparation method of composite adsorption material of waste gas filtering device |
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- 2003-02-07 WO PCT/US2003/003796 patent/WO2003068363A1/en not_active Application Discontinuation
- 2003-02-07 AU AU2003216202A patent/AU2003216202A1/en not_active Abandoned
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US4072471A (en) * | 1974-05-28 | 1978-02-07 | Mobil Oil Corporation | Catalytic converter for removing noxious components from a gaseous stream |
US4416674A (en) * | 1980-10-27 | 1983-11-22 | Texaco Inc. | Filter for treating a particle-carrying gaseous stream |
US4902487A (en) * | 1988-05-13 | 1990-02-20 | Johnson Matthey, Inc. | Treatment of diesel exhaust gases |
US5318755A (en) * | 1992-11-30 | 1994-06-07 | A. Ahlstrom Corporation | Method and apparatus for cleaning flue gases |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1520614A1 (en) * | 2003-06-10 | 2005-04-06 | Ibiden Co., Ltd. | Honeycomb structure body |
EP1520614A4 (en) * | 2003-06-10 | 2005-06-22 | Ibiden Co Ltd | Honeycomb structure body |
EP1736225A2 (en) * | 2003-06-10 | 2006-12-27 | Ibiden Co., Ltd. | Honeycomb structural body |
EP1736225A3 (en) * | 2003-06-10 | 2007-01-17 | Ibiden Co., Ltd. | Honeycomb structural body |
US7521025B2 (en) | 2003-06-10 | 2009-04-21 | Ibiden Co., Ltd. | Honeycomb structural body |
US7455709B2 (en) | 2003-07-15 | 2008-11-25 | Ibiden Co., Ltd. | Honeycomb structural body |
EP1544426B1 (en) * | 2003-12-18 | 2008-01-09 | Clean Diesel Technologies Inc. | Apparatus for filtering and burning particulate matter |
WO2007031074A1 (en) * | 2005-09-16 | 2007-03-22 | Lothar Wenzel | Device for eliminating harmful constituents from exhaust gases of internal combustion engines |
EP2640941A1 (en) * | 2010-11-16 | 2013-09-25 | Scania CV AB | Particle filter for an exhaust system of a combustion engine |
EP2640941A4 (en) * | 2010-11-16 | 2015-01-28 | Scania Cv Ab | Particle filter for an exhaust system of a combustion engine |
US9511353B2 (en) | 2013-03-15 | 2016-12-06 | Clean Diesel Technologies, Inc. (Cdti) | Firing (calcination) process and method related to metallic substrates coated with ZPGM catalyst |
US9511350B2 (en) | 2013-05-10 | 2016-12-06 | Clean Diesel Technologies, Inc. (Cdti) | ZPGM Diesel Oxidation Catalysts and methods of making and using same |
US9771534B2 (en) | 2013-06-06 | 2017-09-26 | Clean Diesel Technologies, Inc. (Cdti) | Diesel exhaust treatment systems and methods |
US9545626B2 (en) | 2013-07-12 | 2017-01-17 | Clean Diesel Technologies, Inc. | Optimization of Zero-PGM washcoat and overcoat loadings on metallic substrate |
US9511358B2 (en) | 2013-11-26 | 2016-12-06 | Clean Diesel Technologies, Inc. | Spinel compositions and applications thereof |
US9555400B2 (en) | 2013-11-26 | 2017-01-31 | Clean Diesel Technologies, Inc. | Synergized PGM catalyst systems including platinum for TWC application |
US9475005B2 (en) | 2014-06-06 | 2016-10-25 | Clean Diesel Technologies, Inc. | Three-way catalyst systems including Fe-activated Rh and Ba-Pd material compositions |
US9579604B2 (en) | 2014-06-06 | 2017-02-28 | Clean Diesel Technologies, Inc. | Base metal activated rhodium coatings for catalysts in three-way catalyst (TWC) applications |
US9475004B2 (en) | 2014-06-06 | 2016-10-25 | Clean Diesel Technologies, Inc. | Rhodium-iron catalysts |
US9731279B2 (en) | 2014-10-30 | 2017-08-15 | Clean Diesel Technologies, Inc. | Thermal stability of copper-manganese spinel as Zero PGM catalyst for TWC application |
US9700841B2 (en) | 2015-03-13 | 2017-07-11 | Byd Company Limited | Synergized PGM close-coupled catalysts for TWC applications |
US9951706B2 (en) | 2015-04-21 | 2018-04-24 | Clean Diesel Technologies, Inc. | Calibration strategies to improve spinel mixed metal oxides catalytic converters |
US10533472B2 (en) | 2016-05-12 | 2020-01-14 | Cdti Advanced Materials, Inc. | Application of synergized-PGM with ultra-low PGM loadings as close-coupled three-way catalysts for internal combustion engines |
US9861964B1 (en) | 2016-12-13 | 2018-01-09 | Clean Diesel Technologies, Inc. | Enhanced catalytic activity at the stoichiometric condition of zero-PGM catalysts for TWC applications |
US10265684B2 (en) | 2017-05-04 | 2019-04-23 | Cdti Advanced Materials, Inc. | Highly active and thermally stable coated gasoline particulate filters |
CN112156749A (en) * | 2020-08-17 | 2021-01-01 | 周悦先 | Preparation method of composite adsorption material of waste gas filtering device |
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