CA2349846A1 - Catalyzed particulate oxidizer for reducing particulate emissions from a diesel engine and method - Google Patents
Catalyzed particulate oxidizer for reducing particulate emissions from a diesel engine and method Download PDFInfo
- Publication number
- CA2349846A1 CA2349846A1 CA002349846A CA2349846A CA2349846A1 CA 2349846 A1 CA2349846 A1 CA 2349846A1 CA 002349846 A CA002349846 A CA 002349846A CA 2349846 A CA2349846 A CA 2349846A CA 2349846 A1 CA2349846 A1 CA 2349846A1
- Authority
- CA
- Canada
- Prior art keywords
- fuel
- catalyzed
- engine
- exhaust
- platinum
- 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.)
- Abandoned
Links
- 239000007800 oxidant agent Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims description 25
- 239000000446 fuel Substances 0.000 claims abstract description 38
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002485 combustion reaction Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims abstract 3
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract 3
- NRQSLGLSOHKTOA-UHFFFAOYSA-N [Pt+2].C1(=CC=CC=C1)C1=C(CCCCC=C1)C1=CC=CC=C1 Chemical compound [Pt+2].C1(=CC=CC=C1)C1=C(CCCCC=C1)C1=CC=CC=C1 NRQSLGLSOHKTOA-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 125000006502 nitrobenzyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 150000003058 platinum compounds Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 24
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- -1 platinum group metal compound Chemical class 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000002816 fuel additive Substances 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000004071 soot Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001785 cerium compounds Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical class [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
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- OWYFUIUTCBWBIL-UHFFFAOYSA-N 1,1'-biphenyl cycloocta-1,3-diene Chemical compound C1CCC=CC=CC1.C1=CC=CC=C1C1=CC=CC=C1 OWYFUIUTCBWBIL-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000004658 Medicago sativa Species 0.000 description 1
- 235000017587 Medicago sativa ssp. sativa Nutrition 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- FGWBAWJNMYHXMA-UHFFFAOYSA-K cerium(3+);7,7-dimethyloctanoate Chemical compound [Ce+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O FGWBAWJNMYHXMA-UHFFFAOYSA-K 0.000 description 1
- BTVVNGIPFPKDHO-UHFFFAOYSA-K cerium(3+);octadecanoate Chemical compound [Ce+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O BTVVNGIPFPKDHO-UHFFFAOYSA-K 0.000 description 1
- 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 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 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
- 238000004821 distillation Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 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
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003444 succinic acids Chemical class 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 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
- F01N3/02—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
- F01N3/029—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 by adding non-fuel substances to exhaust
-
- 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
-
- 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
-
- 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
- F01N2250/00—Combinations of different methods of purification
- F01N2250/02—Combinations of different methods of purification filtering and catalytic conversion
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Exhaust Gas After Treatment (AREA)
- Exhaust-Gas Circulating Devices (AREA)
- Electrical Control Of Air Or Fuel Supplied To Internal-Combustion Engine (AREA)
- Filtering Of Dispersed Particles In Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Operation of a diesel engine with low particulate emissions is achieved through the use of a catalyzed particulate oxidizer (14) designed to cause a large number of impacts of particulates with catalyzed surfaces. The catalyz ed particulate oxidizer (14) can be precatalyzed or uncatalyzed initially, but catalyzed during use by a catalyst fed prior to or after combustion in the engine. Preferably, the fuel will contain a catalytic additive (29), such as diphenyl cyclooctadiene platinum (II) or platinum acetylacetonate and/or a fuel soluble organo-metallic compound of cerium, iron, copper or manganese. Alternatively, the platinum group metal or other catalytic compound can be added to the exhaust or combustion air. The catalyzed particulate oxidizer h as a plurality of parallel plates having catalyzed undulating surfaces provided to create a large number of contact points for the particulates in the exhau st gas.
Description
DESCRIPTION
CATALYZED PARTICULATE OXIDIZER
FOR REDUCING PARTICULATE EMISSIONS
FROM A DIESEL ENGINE AND METHOD
Technical Field The invention relates to methods that permit a diesel engine to operate efficiently with low particulate emissions.
Particulate emissions, e.g., PM 10 and PM 2.5, particularly from diesel engines, are considered health risks by a growing number of regulatory and health organizations. A number of technologies exist for controlling NOx and to control diesel particulates. However, to date there is no technology available to reduce diesel particulate emissions to less than 0.1 g/bhp-Hr while also controlling NOx and not creating servicing and reliability problems or requiring ultra-low sulfur (less than 50 ppm) fuel.
Background Art Diesel engines provide advantages in fuel economy and are favored for this reason. However, there is a tradeoff between economy on the one hand, which favors complete combustion, and emissions of NOx, produced in large quantities under these conditions. Moreover, there is a tradeoff between NOx and particuiates and hydrocarbon (HC) emissions. There is no known technology that is available to take full advantage of diesel ' WO 00/30739 PCT/US99/27779 economy without suffering a penalty in terms of increased particulate and/or NOx emissions, When primary measures (actions that affect the combustion process itself) are taken to reduce NOx in diesel engines, fuel economy is usually reduced and particulate emissions are increased. On the other hand, combustion conditions selected to reduce pollution from particulates and obtain good fuel economy, tend to increase NOX.
Among the current strategies to lower NOx emissions, exhaust gas recirculation (EGR) seems to be a good candidate, but with it, increases in particulates - in addition to fuel economy - will be major technical challenges. Injection timing retard (ITR), like EGR, can also be used to reduce NOx but results in increased fuel consumption and increases particulate emissions.
The use of particulate traps for diesel engines has become common due to an inherent trade-off between NOx and particulates - when actions are taken to reduce one, the other increases. Conceptually, the use of a trap could permit NOx to be reduced to a great extent by techniques such as exhaust gas recirculation, engine timing adjustments, or other known technologies. However, the capture of particulates in a trap can be a problem due to loss in engine efficiency when the pressure drop across the trap becomes too high, Moreover, trap regeneration by burning the particulates can cause physical damage to fihe trap and requires the use of catalyst coatings, fuel additives or supplemental heaters to assist regeneration. Low sulfur fuel is also required for most catalyzed systems.
Pressure drops across pass-through catalytic oxidizers are much lower, but these devices are less effective at particulate removal. Also, these devices work best when the particulates are relatively wet with fluid hydrocarbons and do not work as effectively with dryer particulates of the type produced by engines operating with exhaust gas recirculation (EGR) employed for NOx reduction. Generally, they reduce only the soluble organic fraction (SOF) fraction and are, therefore, limited to only 10 to 50%
reductions.
A hybrid type of mechanism has be disclosed in PCT publication WO
97/232268, to Van Hardeveld, et al. That device is catalyzed to enable the particulates trapped to burn, but employs what is termed a turbulent flow precipitator to knock the particulates out of the exhaust stream for capture, collection and burning. This would tend to increase pressure drop much as the particulate filter. However, as with catalyzed traps, the burning cannot occur at low temperatures. When ignition of the particulates does occur, it can cause structural damage to the apparatus. The problems can be most severe where the engine is operated for long periods at low load.
Another problem with all precatalyzed devices, including traps and pass through oxidizers, is that they tend to lose activity too rapidly in the presence of sulfur. This will continue to be a problem for diesel engines far into the future because diesel fuel contains significant sulfur. In U. S.
Patent No. 5,501,714, Valentine and Peter-Hoblyn disclose that the problem can be corrected for pass-through catalytic oxidizers, but this does not solve the basic problems with that technology already noted. And, in PCT publication WO 97/04045, Peter-Hoblyn, Valentine, Sprague and Epperly disclose that platinum alone or with cerium, copper or iron fuel additives could significantly reduce the balance point of a particulate trap. However, low-load conditions may still not be high enough to control back pressure and prevent excessive heat during regeneration. Also, Jelles, Makkee, Moulijn, Acres and Peter-Hoblyn reported at 22"° CIMAC Congress in Copenhagen, Tuesday, May 19, 1998, that platinum/cerium fuel additives in combination with a catalyzed ceramic filter removed high levels of soot at lower ' WO 00/30739 PCT/US99/27779 temperatures than catalyzed filters or additives alone, Even with the enhanced performance of this system at low temperatures, the filter still suffers from inherently high back pressure and did not oxidize at temperatures below about 350°C.
Current technology does not provide an adequate solution to the problem of diesel particulates, especially for engines operated under conditions necessary to minimize NOX emissions. Oxidizers are not effective at removing particulates because they principally reduce the SOF; and while traps are effective at collecting particulates the are troubled with inherent regeneration and durability problems and high back pressures.
Disclosure of Invention It is an object of the invention to provide a method and apparatus, which provide significant particulate reductions.
It is an object of the invention to provide a method and apparatus, which provide significant, long-term particulate reductions and do so with a minimum of maintenance.
It is another object of the invention to provide a method and apparatus that enable optimizing operation of a diesel for reducing particulates, e.g" to less than 0.1 g/bhp-Hr, while dealing with NOx reduction through use of engine changes such as EGR and iTR.
It is another object of the invention to provide a method and apparatus for enabling simultaneous reduction of particulates and NOx from a diesel engine.
' WO 00/30739 PCT/US99/27779 It is another object of the invention to provide a method and apparatus that eliminate the poor removal efficiency normally associated with pass-through catalytic oxidizers, It is another object of the invention to provide a method and apparatus that eliminate the fuel economy penalty normally associated with a diesel particulate trap.
It is yet another, and more specific object of the invention to provide a method and apparatus, which provide significant, long-term particulate reductions, e.g., to less than 0,1 g/bhp-Hr, while simultaneously dealing with NOX reduction through the use of exhaust gas recirculation and/or ITR.
These and other objects are achieved by the present invention, which provides an improved method and apparatus for operating a diesel engine with low particulate emissions, The method of the invention comprises: equipping a diesel engine with a catalyzed particulate oxidizer having an inlet, an outlet, an enlarged central chamber and a plurality of parallel plates within the chamber, the plates having catalyzed, undulating surfaces provided to create large number of points of contact for particulates in exhaust; operating the diesel engine under conditions that create an exhaust containing particulates;
and passing the exhaust through the catalyzed particulate oxidizer.
The catalyzed particulate oxidizer is also claimed.
Preferably, the fuel will contain a fuel-soluble organo-platinum group metal compound, e,g., comprising a platinum group metal selected from the group consisting of platinum, palladium, rhodium and mixtures of two or more of these. In an alternative embodiment, an effective platinum group metal compound can be added to the exhaust gases before the trap or combustion air, In an alternative, cerium, iron, copper, manganese or combinations of any of these with platinum can be used to reduce engine out particulate loading, including both the soluble and carbon soot fractions of the soot prior to the oxidizer. The resulting metal activated soot will also promote enhanced oxidation when it contacts the catalyzed surfaces.
In another preferred aspect of the invention, the engine is operated with exhaust gas recirculation and/or injection timing retard.
Description of the Drawings The invention will be better understood and its advantages will be more apparent when the following detailed description is read in light of the accompanying drawings, wherein:
Figure 1 is a schematic representation of a diesel engine with an exhaust system including a catalyzed particulate oxidizer in accord with the invention;
Figure 2 is a schematic representation of a catalyzed particulate oxidizer in accord with the invention;
Figure 3 is an enlarged, cut-away schematic representation of a portion of a catalyzed particulate oxidizer in accord with the invention; and Figure 4 is a schematic representation of a diesel engine operating with exhaust gas recircufation and an exhaust system including a catalyzed particulate oxidizer in accord with the invention.
Detailed Description of a Preferred Embodiment The term "Diesel eragine" is meant to include all compression-ignition engines, for both mobile (including marine) and stationary power plants and of the two-stroke per cycle, four-stroke per cycle and rotary types.
The term "hydrocarbon fuel" is meant to include all of those liquid and gaseous fuels prepared from "distillate fuels" or "petroleum". The term "distillate fuel" means all of those products prepared by the distillation of petroleum or petroleum fractions and residues. The term " petroleum" is meant in its usual sense to include all of those materials regardless of source normally included within the meaning of the term, including hydrocarbon materials, regardless of viscosity, that are recovered from fossil fuels.
The term "diesel fuel" includes "distillate fuels" including diesel fuels meeting the ASTM definition for diesel fuels or others even though they are not wholly comprised of distillates and can comprise alcohols, ethers, organo-vitro compounds and the like (e.g., methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane). Also contemplated, are emulsions and liquid fuels derived from vegetable or mineral sources such as corn, alfalfa, shale, and coal. These fuels may also contain other additives known to those skilled in the art, including dyes, cetane improvers, anti-oxidants such as 2,6-di-tertiary-butyl-4-rnethyiphenol, corrosion inhibitors, rust inhibitors such as alkylated succinic acids and anhydrides, bacteriostatic agents, gum inhibitors, metal deactivators, upper cylinder lubricants, antiicing agents and the like.
Reference to Figure 1 shows a diesel engine 10 fed fuel from a tank 11.
The fuel is preferably catalyzed with a platinum group metal compound or one or more other catalyst compounds, such as cerium, iron or manganese.
These latter material can be used alone or with a platinum group metal catalyst.
Exhaust from the engine will pass through exhaust pipe 12, carrying catalytic metals released from the fuel additive catalyst compositions of cerium, and preferably also platinum, to a catalyzed particulate oxidizer (CPO) 14, The CPO can be catalyzed either as installed or by building up a catalyst deposit by operating the engine with a platinum group metal fuel additive.
The CPO of the invention is schematically shown in longitudinal cross-section in Figure 2. The CPO 14 is shown as having an inlet 1 b, an outlet 18 and an enlarged central chamber 20. Within the chamber 20 are a plurality of essentially parallel plates 22 with catalyzed, undulating surtaces provided to create large number of points of contact for particulates in exhaust which enters at 16 and exits at 18. The plates will preferably be made of a ceramic, a silica-alumina composition such as cordierite, silicon carbide, glass or metal fibers, porous glass or metal substrates, or the like. or a suitable metal such as alloys of the type used in automotive exhaust systems. Among the suitable catalysts, are those known to be useful for catalyzing traps and pass-through catalytic oxidizers. Prominent among these are platinum group metals such as platinum, palladium and rhodium. The oxidizer may or may not be precoated with an alumina washcoat to provide high surface area prior to catalyzing. It is an advantage of the invention that the washcoat is not required.
Reference to Figure 3 schematically shows a section of a CPO
enlarged to illustrate the dynamics of the process. Channels 24 are formed between individual plates 22. The channels are sufficiently wide to permit the exhaust gases to pass through with minimal pressure drop. The exact configuration of the channels will vary depending on many design and manufacturing variables. The peaks 2b and the valleys 28 formed in the sheets cause the gases to change direction frequently. The particulates, even though small, have a mass that causes them to impact the walls of the channels formed by the plates while the gases easily turn following the undulations in the plates. The particulates are not collected, but are oxidized at least partially by frequent impact with catalyzed surfaces of the plates 22.
The undulations in the drawings are seen to be of chevron shape, but other suitable shapes, including sinusoidal, flat-topped chevrons, and the like can also be employed. In some embodiments, it will be desired to install the plates in sections along the length of the chamber. For example, the plates could be assembled into 2 to 5 sections, each filling the cross section of the chamber, but extending only a portion of its length. In this case, the sections would be separated by a space of preferably less than 5 inches, e.g, 0.25 to 3 inches.
As noted above, the fuel will preferably also contain a fuel-soluble organo-platinum group metal compound, e.g., of platinum, palladium or rhodium. Among these are platinum group metal compounds selected from the group consisting of platinum acetylacetonate and compounds having the general formula XPtR,R2 wherein X is a ligand containing at least one unsaturated carbon-to-carbon bond with an olefinic, acetylenic or aromatic pi bond configuration and R, and RZ are, independently, benzyl, phenyl, nitrobenzyl or alkyl having 1 to 10 carbons, e. g., Biphenyl cyclooctadiene platinum(ll).
Suitable platinum group metal compounds are disclosed for example in prior U.S. Patent Nos. 4,892,562 and 4,891,050 to Bowers and Sprague, 5,034,020 to Epperly and Sprague, 5,215,652 to Epperly, Sprague, Kelso and Bowers, and 5,266,083 to Peter-Hoblyn, Epperly, Keiso and Sprague, WO
90/07561 to Epperly, Sprague, Kelso and Bowers, and U. S. Patent Application Serial No. 08/597,517, filed January 31, 1996, by Peter-Hoblyn, Valentine and Sprague, hereby incorporated by reference. Where the application permits, a blend of these compounds can be used with one or more other platinum group metal compounds such as soaps, acetyl acetonates, alcoholates, p-diketonates, and sulfonates, e.g., of the type which will be described in more detail below.
The platinum group metal compound suitable for use as a fuel or gas-borne additive and/or other catalyst additive material, can be added in any manner effective for its intended purpose, such as by adding it to the fuel in bulk storage, to the fuel in a tank associated with the engine, or by continuous or intermittent addition, such as by a suitable metering device, e.g., 27 from tank 29 in Figure 1, into: the fuel line leading to the engine or the fuel return line from the engine, or in the form of a vapor, gas or aerosol into the air intake, the exhaust gases before the CPO, exhaust gases after the CPO but before recirculation to the engine, or a mixing chamber or equivalent means wherein the exhaust gases are mixed with incoming air.
When employed, platinum group metal catalyst compositions are preferably employed at concenfirations of less than 1 part by weight of platinum group metal per million parts by volume fuel (ppm), When used for the purpose of catalyzing an uncatalyzed CPO (or one that has become inactive), it is possible to higher doses, e.g., from 1 to 25 (or greater) ppm, to effect a rapid deposit of catalyst in the CPO. For the purposes of this descrip-tion, all "parts per million" figures are on a weight to volume basis, i.e., grams/million cubic centimeters (which can also be expressed as milligrams/liter), and percentages are given by weight, unless otherwise indicated, Auxiliary catalysts (named so because they are preferably used with a platinum group metal composition, but can be used without such) are employed at levels effective for their intended purpose, preferably at levels of from 1 to 200 ppm of the fuel utilized, e.g., 5 to 60 ppm.
Among the auxiliary catalytic materials are organometaliic salts of manganese, magnesium, calcium, iron, copper, cerium, sodium, lithium and potassium, which can be employed at suitable levels, e.g., from about 1 to about 100 ppm and preferably 20 to 60 ppm of the catalyst metal in combination with the platinum group metal catalyst in diesel fuels. Among these are the alcoholates, sulfonates, beta-diketonates and soaps, e.g., selected from the group consisting of stearates, paimitates, laurates, tallates, naptl~anates, other fatty acid soaps, and mixtures of two or more of these, of copper, calcium, magnesium, manganese, iron, cerium, sodium, lithium and potassium compounds as are known as fuel soluble and useful fuel additives.
Among preferred cerium compounds are: cerium III acetylacetonate, and various cerium soaps such as cerium III napthanate, cerium octoate, cerium stearate, cerium neodecanoate, and the like. Many cerium compounds are trivalent compounds meeting the formula: Ce(OOCR)3, wherein R = hydrocarbon, preferably C2 to C22, and including aliphatic, alicyclic, aryl and alkylaryl. The dosage level will be at a level of from about 1 to 100 ppm cerium per million parts of fuel (mg per liter), and preferably in the range of from about 5 to 30 ppm, preferably less than 20 ppm. This level can be reduced significantly over what is currently employed in the art by using the cerium in combination with a platinum-catalyzed particulate trap.
Reference can be made to the aforementioned WO 97/04045 for a detailed listing, incorporated herein by reference, of other representative auxiliary catalyst compositions.
Reference to Figure 4 shows, schematically, a diesel engine 10 operating with exhaust gas recirculation and an exhaust system including a catalyzed particulate oxidizer 14 in accord with the invention. During EGR
operation, combustion air from intake 13 (at high or low pressure, heated or cooled) and exhaust gases from line 32 (separated from the main exhaust gas stream 34) are mixed and fed to one or more cylinders of engine 10 (e.g., either diesel or lean-burn gasoline). The proportion of exhaust gases recirculated to the engine for forming a combustion air mixture will be effective to lower the 'production of NOx by the engine utilizing the combustion air mixture as compared to combustion air not containing exhaust gases. Typically, from about 0 to about 30% can be recircuiated.
The combustion air mixture is typically compressed prior to introduction into engine cylinders) wherein it is further compressed, causing heating. The appropriate fuel is injected into the cylinders following compression. The fuel is then combusted with the combustion air mixture to produce exhaust gases that are discharged through exhaust stream 34. The cycle just described is repeated continuously as the engine continues to run in the EGR mode. EGR lowers the combustion temperature and oxygen to the combustion chamber and reduces the amount of NOx produced, but as has been observed, it increases production of particulates and unburned hydrocarbons - again, the compromise between NOx and complete combustion.
Downstream of exhaust stream 34 is a CPO unitl4. The CPO is effective within a temperature window of from about 150 to about 650°
C, depending on the catalyst. During engine operation giving rise to these temperatures, the exhaust temperature is maintained at the temperatures most preferred for the CPO. At these temperatures, NOx conversion by EGR
is practical, and the EGR system is therefore operated. At other times, ITR
can be used alone or in conjunction with EGR to reduce NOx.
Figure 4 also illustrates a control system of a type useful to maintoin the proper operation of EGR and CPO units. The controller 36 can, if desired, measure any of a number of parameters to assure optimum NOX reduction and particulate oxidation. The temperature of the exhaust (sensor means 38) is one parameter of importance. Engine load is another key parameter (sensor means 40), and this or like factor can be monitored to determine the amount of NOx being generated and the need for NOX reduction by EGR or engine timing changes (r5ot shown).
The sensing means provided for sensing operating parameters indicative of conditions effective for NOx reduction, sense the appropriate operating parameter and generate an operation signal representative thereof. The controller 36 provides control means for comparing one or more operation signals to appropriate reference values) and determines if NOx reduction can be effectively operated. The controller then generates appropriate control signals representative of the result of the comparison.
Means-are provided to be responsive to the control signals for operating the EGR unit (and/or engine timing changes), as called for by the controller.
Figure 1 shows, as representative of these latter means, valve 42.
The EGR unit and/or engine timing adjustments can be controlled, in response to a feed-forward controller in response to a number of measured parameters, including: engine load as represented by various mechanical or electronic measures such as fuel flow, tack or pulse width, engine speed, intake air temperature; barometric pressure; intake air humidity; exhaust gas temperature and/or other parameters effective for particular engines. In addition, to the extent that sensors are available, trim or feed back control can be provided based on residual gas species following the CPO, e.g., the level of NOx, HC or CO. If desired, feedback control can be employed to trim the system in response to specific gas species, or any other measurable engine or exhaust gas property.
The above description is for the purpose of teaching the person of ordinary skill in the art how to practice the present invention, and it is not intended to detail all of those obvious modifications and variations of it which will become apparent to the skilled worker upon reading this description. It is intended, however, that all such modifications and variations be included within the scope of the present invention which is defined by the following claims.
CATALYZED PARTICULATE OXIDIZER
FOR REDUCING PARTICULATE EMISSIONS
FROM A DIESEL ENGINE AND METHOD
Technical Field The invention relates to methods that permit a diesel engine to operate efficiently with low particulate emissions.
Particulate emissions, e.g., PM 10 and PM 2.5, particularly from diesel engines, are considered health risks by a growing number of regulatory and health organizations. A number of technologies exist for controlling NOx and to control diesel particulates. However, to date there is no technology available to reduce diesel particulate emissions to less than 0.1 g/bhp-Hr while also controlling NOx and not creating servicing and reliability problems or requiring ultra-low sulfur (less than 50 ppm) fuel.
Background Art Diesel engines provide advantages in fuel economy and are favored for this reason. However, there is a tradeoff between economy on the one hand, which favors complete combustion, and emissions of NOx, produced in large quantities under these conditions. Moreover, there is a tradeoff between NOx and particuiates and hydrocarbon (HC) emissions. There is no known technology that is available to take full advantage of diesel ' WO 00/30739 PCT/US99/27779 economy without suffering a penalty in terms of increased particulate and/or NOx emissions, When primary measures (actions that affect the combustion process itself) are taken to reduce NOx in diesel engines, fuel economy is usually reduced and particulate emissions are increased. On the other hand, combustion conditions selected to reduce pollution from particulates and obtain good fuel economy, tend to increase NOX.
Among the current strategies to lower NOx emissions, exhaust gas recirculation (EGR) seems to be a good candidate, but with it, increases in particulates - in addition to fuel economy - will be major technical challenges. Injection timing retard (ITR), like EGR, can also be used to reduce NOx but results in increased fuel consumption and increases particulate emissions.
The use of particulate traps for diesel engines has become common due to an inherent trade-off between NOx and particulates - when actions are taken to reduce one, the other increases. Conceptually, the use of a trap could permit NOx to be reduced to a great extent by techniques such as exhaust gas recirculation, engine timing adjustments, or other known technologies. However, the capture of particulates in a trap can be a problem due to loss in engine efficiency when the pressure drop across the trap becomes too high, Moreover, trap regeneration by burning the particulates can cause physical damage to fihe trap and requires the use of catalyst coatings, fuel additives or supplemental heaters to assist regeneration. Low sulfur fuel is also required for most catalyzed systems.
Pressure drops across pass-through catalytic oxidizers are much lower, but these devices are less effective at particulate removal. Also, these devices work best when the particulates are relatively wet with fluid hydrocarbons and do not work as effectively with dryer particulates of the type produced by engines operating with exhaust gas recirculation (EGR) employed for NOx reduction. Generally, they reduce only the soluble organic fraction (SOF) fraction and are, therefore, limited to only 10 to 50%
reductions.
A hybrid type of mechanism has be disclosed in PCT publication WO
97/232268, to Van Hardeveld, et al. That device is catalyzed to enable the particulates trapped to burn, but employs what is termed a turbulent flow precipitator to knock the particulates out of the exhaust stream for capture, collection and burning. This would tend to increase pressure drop much as the particulate filter. However, as with catalyzed traps, the burning cannot occur at low temperatures. When ignition of the particulates does occur, it can cause structural damage to the apparatus. The problems can be most severe where the engine is operated for long periods at low load.
Another problem with all precatalyzed devices, including traps and pass through oxidizers, is that they tend to lose activity too rapidly in the presence of sulfur. This will continue to be a problem for diesel engines far into the future because diesel fuel contains significant sulfur. In U. S.
Patent No. 5,501,714, Valentine and Peter-Hoblyn disclose that the problem can be corrected for pass-through catalytic oxidizers, but this does not solve the basic problems with that technology already noted. And, in PCT publication WO 97/04045, Peter-Hoblyn, Valentine, Sprague and Epperly disclose that platinum alone or with cerium, copper or iron fuel additives could significantly reduce the balance point of a particulate trap. However, low-load conditions may still not be high enough to control back pressure and prevent excessive heat during regeneration. Also, Jelles, Makkee, Moulijn, Acres and Peter-Hoblyn reported at 22"° CIMAC Congress in Copenhagen, Tuesday, May 19, 1998, that platinum/cerium fuel additives in combination with a catalyzed ceramic filter removed high levels of soot at lower ' WO 00/30739 PCT/US99/27779 temperatures than catalyzed filters or additives alone, Even with the enhanced performance of this system at low temperatures, the filter still suffers from inherently high back pressure and did not oxidize at temperatures below about 350°C.
Current technology does not provide an adequate solution to the problem of diesel particulates, especially for engines operated under conditions necessary to minimize NOX emissions. Oxidizers are not effective at removing particulates because they principally reduce the SOF; and while traps are effective at collecting particulates the are troubled with inherent regeneration and durability problems and high back pressures.
Disclosure of Invention It is an object of the invention to provide a method and apparatus, which provide significant particulate reductions.
It is an object of the invention to provide a method and apparatus, which provide significant, long-term particulate reductions and do so with a minimum of maintenance.
It is another object of the invention to provide a method and apparatus that enable optimizing operation of a diesel for reducing particulates, e.g" to less than 0.1 g/bhp-Hr, while dealing with NOx reduction through use of engine changes such as EGR and iTR.
It is another object of the invention to provide a method and apparatus for enabling simultaneous reduction of particulates and NOx from a diesel engine.
' WO 00/30739 PCT/US99/27779 It is another object of the invention to provide a method and apparatus that eliminate the poor removal efficiency normally associated with pass-through catalytic oxidizers, It is another object of the invention to provide a method and apparatus that eliminate the fuel economy penalty normally associated with a diesel particulate trap.
It is yet another, and more specific object of the invention to provide a method and apparatus, which provide significant, long-term particulate reductions, e.g., to less than 0,1 g/bhp-Hr, while simultaneously dealing with NOX reduction through the use of exhaust gas recirculation and/or ITR.
These and other objects are achieved by the present invention, which provides an improved method and apparatus for operating a diesel engine with low particulate emissions, The method of the invention comprises: equipping a diesel engine with a catalyzed particulate oxidizer having an inlet, an outlet, an enlarged central chamber and a plurality of parallel plates within the chamber, the plates having catalyzed, undulating surfaces provided to create large number of points of contact for particulates in exhaust; operating the diesel engine under conditions that create an exhaust containing particulates;
and passing the exhaust through the catalyzed particulate oxidizer.
The catalyzed particulate oxidizer is also claimed.
Preferably, the fuel will contain a fuel-soluble organo-platinum group metal compound, e,g., comprising a platinum group metal selected from the group consisting of platinum, palladium, rhodium and mixtures of two or more of these. In an alternative embodiment, an effective platinum group metal compound can be added to the exhaust gases before the trap or combustion air, In an alternative, cerium, iron, copper, manganese or combinations of any of these with platinum can be used to reduce engine out particulate loading, including both the soluble and carbon soot fractions of the soot prior to the oxidizer. The resulting metal activated soot will also promote enhanced oxidation when it contacts the catalyzed surfaces.
In another preferred aspect of the invention, the engine is operated with exhaust gas recirculation and/or injection timing retard.
Description of the Drawings The invention will be better understood and its advantages will be more apparent when the following detailed description is read in light of the accompanying drawings, wherein:
Figure 1 is a schematic representation of a diesel engine with an exhaust system including a catalyzed particulate oxidizer in accord with the invention;
Figure 2 is a schematic representation of a catalyzed particulate oxidizer in accord with the invention;
Figure 3 is an enlarged, cut-away schematic representation of a portion of a catalyzed particulate oxidizer in accord with the invention; and Figure 4 is a schematic representation of a diesel engine operating with exhaust gas recircufation and an exhaust system including a catalyzed particulate oxidizer in accord with the invention.
Detailed Description of a Preferred Embodiment The term "Diesel eragine" is meant to include all compression-ignition engines, for both mobile (including marine) and stationary power plants and of the two-stroke per cycle, four-stroke per cycle and rotary types.
The term "hydrocarbon fuel" is meant to include all of those liquid and gaseous fuels prepared from "distillate fuels" or "petroleum". The term "distillate fuel" means all of those products prepared by the distillation of petroleum or petroleum fractions and residues. The term " petroleum" is meant in its usual sense to include all of those materials regardless of source normally included within the meaning of the term, including hydrocarbon materials, regardless of viscosity, that are recovered from fossil fuels.
The term "diesel fuel" includes "distillate fuels" including diesel fuels meeting the ASTM definition for diesel fuels or others even though they are not wholly comprised of distillates and can comprise alcohols, ethers, organo-vitro compounds and the like (e.g., methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane). Also contemplated, are emulsions and liquid fuels derived from vegetable or mineral sources such as corn, alfalfa, shale, and coal. These fuels may also contain other additives known to those skilled in the art, including dyes, cetane improvers, anti-oxidants such as 2,6-di-tertiary-butyl-4-rnethyiphenol, corrosion inhibitors, rust inhibitors such as alkylated succinic acids and anhydrides, bacteriostatic agents, gum inhibitors, metal deactivators, upper cylinder lubricants, antiicing agents and the like.
Reference to Figure 1 shows a diesel engine 10 fed fuel from a tank 11.
The fuel is preferably catalyzed with a platinum group metal compound or one or more other catalyst compounds, such as cerium, iron or manganese.
These latter material can be used alone or with a platinum group metal catalyst.
Exhaust from the engine will pass through exhaust pipe 12, carrying catalytic metals released from the fuel additive catalyst compositions of cerium, and preferably also platinum, to a catalyzed particulate oxidizer (CPO) 14, The CPO can be catalyzed either as installed or by building up a catalyst deposit by operating the engine with a platinum group metal fuel additive.
The CPO of the invention is schematically shown in longitudinal cross-section in Figure 2. The CPO 14 is shown as having an inlet 1 b, an outlet 18 and an enlarged central chamber 20. Within the chamber 20 are a plurality of essentially parallel plates 22 with catalyzed, undulating surtaces provided to create large number of points of contact for particulates in exhaust which enters at 16 and exits at 18. The plates will preferably be made of a ceramic, a silica-alumina composition such as cordierite, silicon carbide, glass or metal fibers, porous glass or metal substrates, or the like. or a suitable metal such as alloys of the type used in automotive exhaust systems. Among the suitable catalysts, are those known to be useful for catalyzing traps and pass-through catalytic oxidizers. Prominent among these are platinum group metals such as platinum, palladium and rhodium. The oxidizer may or may not be precoated with an alumina washcoat to provide high surface area prior to catalyzing. It is an advantage of the invention that the washcoat is not required.
Reference to Figure 3 schematically shows a section of a CPO
enlarged to illustrate the dynamics of the process. Channels 24 are formed between individual plates 22. The channels are sufficiently wide to permit the exhaust gases to pass through with minimal pressure drop. The exact configuration of the channels will vary depending on many design and manufacturing variables. The peaks 2b and the valleys 28 formed in the sheets cause the gases to change direction frequently. The particulates, even though small, have a mass that causes them to impact the walls of the channels formed by the plates while the gases easily turn following the undulations in the plates. The particulates are not collected, but are oxidized at least partially by frequent impact with catalyzed surfaces of the plates 22.
The undulations in the drawings are seen to be of chevron shape, but other suitable shapes, including sinusoidal, flat-topped chevrons, and the like can also be employed. In some embodiments, it will be desired to install the plates in sections along the length of the chamber. For example, the plates could be assembled into 2 to 5 sections, each filling the cross section of the chamber, but extending only a portion of its length. In this case, the sections would be separated by a space of preferably less than 5 inches, e.g, 0.25 to 3 inches.
As noted above, the fuel will preferably also contain a fuel-soluble organo-platinum group metal compound, e.g., of platinum, palladium or rhodium. Among these are platinum group metal compounds selected from the group consisting of platinum acetylacetonate and compounds having the general formula XPtR,R2 wherein X is a ligand containing at least one unsaturated carbon-to-carbon bond with an olefinic, acetylenic or aromatic pi bond configuration and R, and RZ are, independently, benzyl, phenyl, nitrobenzyl or alkyl having 1 to 10 carbons, e. g., Biphenyl cyclooctadiene platinum(ll).
Suitable platinum group metal compounds are disclosed for example in prior U.S. Patent Nos. 4,892,562 and 4,891,050 to Bowers and Sprague, 5,034,020 to Epperly and Sprague, 5,215,652 to Epperly, Sprague, Kelso and Bowers, and 5,266,083 to Peter-Hoblyn, Epperly, Keiso and Sprague, WO
90/07561 to Epperly, Sprague, Kelso and Bowers, and U. S. Patent Application Serial No. 08/597,517, filed January 31, 1996, by Peter-Hoblyn, Valentine and Sprague, hereby incorporated by reference. Where the application permits, a blend of these compounds can be used with one or more other platinum group metal compounds such as soaps, acetyl acetonates, alcoholates, p-diketonates, and sulfonates, e.g., of the type which will be described in more detail below.
The platinum group metal compound suitable for use as a fuel or gas-borne additive and/or other catalyst additive material, can be added in any manner effective for its intended purpose, such as by adding it to the fuel in bulk storage, to the fuel in a tank associated with the engine, or by continuous or intermittent addition, such as by a suitable metering device, e.g., 27 from tank 29 in Figure 1, into: the fuel line leading to the engine or the fuel return line from the engine, or in the form of a vapor, gas or aerosol into the air intake, the exhaust gases before the CPO, exhaust gases after the CPO but before recirculation to the engine, or a mixing chamber or equivalent means wherein the exhaust gases are mixed with incoming air.
When employed, platinum group metal catalyst compositions are preferably employed at concenfirations of less than 1 part by weight of platinum group metal per million parts by volume fuel (ppm), When used for the purpose of catalyzing an uncatalyzed CPO (or one that has become inactive), it is possible to higher doses, e.g., from 1 to 25 (or greater) ppm, to effect a rapid deposit of catalyst in the CPO. For the purposes of this descrip-tion, all "parts per million" figures are on a weight to volume basis, i.e., grams/million cubic centimeters (which can also be expressed as milligrams/liter), and percentages are given by weight, unless otherwise indicated, Auxiliary catalysts (named so because they are preferably used with a platinum group metal composition, but can be used without such) are employed at levels effective for their intended purpose, preferably at levels of from 1 to 200 ppm of the fuel utilized, e.g., 5 to 60 ppm.
Among the auxiliary catalytic materials are organometaliic salts of manganese, magnesium, calcium, iron, copper, cerium, sodium, lithium and potassium, which can be employed at suitable levels, e.g., from about 1 to about 100 ppm and preferably 20 to 60 ppm of the catalyst metal in combination with the platinum group metal catalyst in diesel fuels. Among these are the alcoholates, sulfonates, beta-diketonates and soaps, e.g., selected from the group consisting of stearates, paimitates, laurates, tallates, naptl~anates, other fatty acid soaps, and mixtures of two or more of these, of copper, calcium, magnesium, manganese, iron, cerium, sodium, lithium and potassium compounds as are known as fuel soluble and useful fuel additives.
Among preferred cerium compounds are: cerium III acetylacetonate, and various cerium soaps such as cerium III napthanate, cerium octoate, cerium stearate, cerium neodecanoate, and the like. Many cerium compounds are trivalent compounds meeting the formula: Ce(OOCR)3, wherein R = hydrocarbon, preferably C2 to C22, and including aliphatic, alicyclic, aryl and alkylaryl. The dosage level will be at a level of from about 1 to 100 ppm cerium per million parts of fuel (mg per liter), and preferably in the range of from about 5 to 30 ppm, preferably less than 20 ppm. This level can be reduced significantly over what is currently employed in the art by using the cerium in combination with a platinum-catalyzed particulate trap.
Reference can be made to the aforementioned WO 97/04045 for a detailed listing, incorporated herein by reference, of other representative auxiliary catalyst compositions.
Reference to Figure 4 shows, schematically, a diesel engine 10 operating with exhaust gas recirculation and an exhaust system including a catalyzed particulate oxidizer 14 in accord with the invention. During EGR
operation, combustion air from intake 13 (at high or low pressure, heated or cooled) and exhaust gases from line 32 (separated from the main exhaust gas stream 34) are mixed and fed to one or more cylinders of engine 10 (e.g., either diesel or lean-burn gasoline). The proportion of exhaust gases recirculated to the engine for forming a combustion air mixture will be effective to lower the 'production of NOx by the engine utilizing the combustion air mixture as compared to combustion air not containing exhaust gases. Typically, from about 0 to about 30% can be recircuiated.
The combustion air mixture is typically compressed prior to introduction into engine cylinders) wherein it is further compressed, causing heating. The appropriate fuel is injected into the cylinders following compression. The fuel is then combusted with the combustion air mixture to produce exhaust gases that are discharged through exhaust stream 34. The cycle just described is repeated continuously as the engine continues to run in the EGR mode. EGR lowers the combustion temperature and oxygen to the combustion chamber and reduces the amount of NOx produced, but as has been observed, it increases production of particulates and unburned hydrocarbons - again, the compromise between NOx and complete combustion.
Downstream of exhaust stream 34 is a CPO unitl4. The CPO is effective within a temperature window of from about 150 to about 650°
C, depending on the catalyst. During engine operation giving rise to these temperatures, the exhaust temperature is maintained at the temperatures most preferred for the CPO. At these temperatures, NOx conversion by EGR
is practical, and the EGR system is therefore operated. At other times, ITR
can be used alone or in conjunction with EGR to reduce NOx.
Figure 4 also illustrates a control system of a type useful to maintoin the proper operation of EGR and CPO units. The controller 36 can, if desired, measure any of a number of parameters to assure optimum NOX reduction and particulate oxidation. The temperature of the exhaust (sensor means 38) is one parameter of importance. Engine load is another key parameter (sensor means 40), and this or like factor can be monitored to determine the amount of NOx being generated and the need for NOX reduction by EGR or engine timing changes (r5ot shown).
The sensing means provided for sensing operating parameters indicative of conditions effective for NOx reduction, sense the appropriate operating parameter and generate an operation signal representative thereof. The controller 36 provides control means for comparing one or more operation signals to appropriate reference values) and determines if NOx reduction can be effectively operated. The controller then generates appropriate control signals representative of the result of the comparison.
Means-are provided to be responsive to the control signals for operating the EGR unit (and/or engine timing changes), as called for by the controller.
Figure 1 shows, as representative of these latter means, valve 42.
The EGR unit and/or engine timing adjustments can be controlled, in response to a feed-forward controller in response to a number of measured parameters, including: engine load as represented by various mechanical or electronic measures such as fuel flow, tack or pulse width, engine speed, intake air temperature; barometric pressure; intake air humidity; exhaust gas temperature and/or other parameters effective for particular engines. In addition, to the extent that sensors are available, trim or feed back control can be provided based on residual gas species following the CPO, e.g., the level of NOx, HC or CO. If desired, feedback control can be employed to trim the system in response to specific gas species, or any other measurable engine or exhaust gas property.
The above description is for the purpose of teaching the person of ordinary skill in the art how to practice the present invention, and it is not intended to detail all of those obvious modifications and variations of it which will become apparent to the skilled worker upon reading this description. It is intended, however, that all such modifications and variations be included within the scope of the present invention which is defined by the following claims.
Claims (12)
1. A method for operating a diesel engine with low particulate emissions, comprising;
equipping a diesel engine with a catalyzed particulate oxidizer having an inlet, an outlet, era enlarged central chamber and a plurality of parallel plates within the chamber, the plates having catalyzed, undulating surfaces provided to create large number of points of contact for particulates in exhaust;
operating the diesel engine by burning fuel under conditions that create an exhaust containing particulates; and passing the exhaust through the catalyzed particulate oxidizer from an inlet to an outlet and transverse to lines drawn parallel to undulations in the undulating surfaces.
equipping a diesel engine with a catalyzed particulate oxidizer having an inlet, an outlet, era enlarged central chamber and a plurality of parallel plates within the chamber, the plates having catalyzed, undulating surfaces provided to create large number of points of contact for particulates in exhaust;
operating the diesel engine by burning fuel under conditions that create an exhaust containing particulates; and passing the exhaust through the catalyzed particulate oxidizer from an inlet to an outlet and transverse to lines drawn parallel to undulations in the undulating surfaces.
2. A method according to claim 1, wherein the fuel contains a fuel-soluble organo-platinum group metal compound.
3. A method according to claim 1, wherein the fuel contains a fuel-soluble organo-metallic compound of cerium, iron, copper or manganese.
4. A method according to claim 1, wherein the fuel contains a fuel-soluble organo-platinum group metal compound and contains a fuel-soluble organo-metallic compound of cerium, iron, copper or manganese.
5. A method according to claim 2, wherein the fuel-soluble organo-platinum group metal compound is one selected from the group consisting of platinum, palladium or rhodium acetylacetonate and compounds having the general formula XPtR1R2 wherein X is a ligand containing at least one unsaturated carbon-to-carbon bond with an olefinic, acetylenic or aromatic pi bond configuration and R1 and R2 are, independently, benzyl, phenyl, nitrobenzyl or alkyl having 1 to 10 carbons, e.g., diphenyl cyclooctadiene platinum(II).
6. A method according to claim 1 wherein, a platinum compound is added to the exhaust or combustion air.
7. A method according to claim 1 wherein, the catalyzed particulate oxidizer is precatalyzed with platinum.
8. A method according to claim 1 wherein, the catalyzed particulate oxidizer is catalyzed by deposition of a platinum group metal from an additive blanded with the fuel.
9. A method according to claim 1 wherein, the engine is operated with exhaust gas recirculation to reduce NO x.
10. A method according to claim 1 wherein, the engine is operated with engine timing retard to reduce NO x.
11. A method according to claim 1 wherein, the engine is operated with exhaust gas recirculation and/or engine timing retard to reduce NO x.
12. A catalyzed particulate oxidizer having an inlet, an outlet, an enlarged central chamber and a plurality of parallel plates within the chamber, the plates having catalysed, undulating surfaces provided to create large number of points of contact for particulates in exhaust as the exhaust passes from the inlet to the outlet in a direction transverse to lines drawn parallel to undulations in the undulating surfaces.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11014898P | 1998-11-24 | 1998-11-24 | |
US60/110,148 | 1998-11-24 | ||
PCT/US1999/027779 WO2000030739A1 (en) | 1998-11-24 | 1999-11-23 | Catalyzed particulate oxidizer for reducing particulate emissions from a diesel engine and method |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2349846A1 true CA2349846A1 (en) | 2000-06-02 |
Family
ID=22331465
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002349846A Abandoned CA2349846A1 (en) | 1998-11-24 | 1999-11-23 | Catalyzed particulate oxidizer for reducing particulate emissions from a diesel engine and method |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP1163043A4 (en) |
JP (1) | JP2002530578A (en) |
CN (1) | CN1328481A (en) |
AU (1) | AU1632900A (en) |
CA (1) | CA2349846A1 (en) |
HK (1) | HK1042266A1 (en) |
WO (1) | WO2000030739A1 (en) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050164139A1 (en) * | 2002-02-04 | 2005-07-28 | Valentine James M. | Reduced-emissions combustion utilizing multiple-component metallic combustion catalyst and lightly catalyzed diesel particulate filter |
US20050160724A1 (en) * | 2002-02-04 | 2005-07-28 | Valentine James M. | Reduced-emissions combustion utilizing multiple-component metallic combustion catalyst and lightly catalyzed diesel oxidation catalyst |
US20040074140A1 (en) * | 2002-10-16 | 2004-04-22 | Guinther Gregory H. | Method of enhancing the operation of a diesel fuel combustion after treatment system |
US6892531B2 (en) * | 2003-04-02 | 2005-05-17 | Julius J. Rim | System for and methods of operating diesel engines to reduce harmful exhaust emissions and to improve engine lubrication |
US7332001B2 (en) * | 2003-10-02 | 2008-02-19 | Afton Chemical Corporation | Method of enhancing the operation of diesel fuel combustion systems |
JP2009156071A (en) * | 2007-12-25 | 2009-07-16 | Mitsubishi Motors Corp | Exhaust emission control device for internal combustion engine |
US9511350B2 (en) | 2013-05-10 | 2016-12-06 | Clean Diesel Technologies, Inc. (Cdti) | ZPGM Diesel Oxidation Catalysts and methods of making and using same |
US9511355B2 (en) | 2013-11-26 | 2016-12-06 | Clean Diesel Technologies, Inc. (Cdti) | System and methods for using synergized PGM as a three-way catalyst |
US20140274662A1 (en) | 2013-03-15 | 2014-09-18 | Cdti | Systems and Methods for Variations of ZPGM Oxidation Catalysts Compositions |
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 |
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 |
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 |
US10287938B2 (en) * | 2015-06-15 | 2019-05-14 | Ford Global Technologies, Llc | System and methods for reducing particulate matter emissions |
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 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4891050A (en) * | 1985-11-08 | 1990-01-02 | Fuel Tech, Inc. | Gasoline additives and gasoline containing soluble platinum group metal compounds and use in internal combustion engines |
US4725411A (en) * | 1985-11-12 | 1988-02-16 | W. R. Grace & Co. | Device for physical and/or chemical treatment of fluids |
US4869738A (en) * | 1987-08-26 | 1989-09-26 | W. R. Grace & Co.-Conn. | Particulate trap |
US4942020A (en) * | 1988-06-27 | 1990-07-17 | W.R. Grace & Co.-Conn. | Converter for removing pollutants from a gas stream |
US5501714A (en) * | 1988-12-28 | 1996-03-26 | Platinum Plus, Inc. | Operation of diesel engines with reduced particulate emission by utilization of platinum group metal fuel additive and pass-through catalytic oxidizer |
JPH0440240A (en) * | 1990-06-05 | 1992-02-10 | Nissan Motor Co Ltd | Metal honeycomb catalyst |
JPH04110022A (en) * | 1990-08-30 | 1992-04-10 | Sakai Chem Ind Co Ltd | Particulate oxidation catalyst filter |
CA2227141A1 (en) * | 1995-07-18 | 1997-02-06 | Clean Diesel Technologies, Inc. | Methods for reducing harmful emissions from a diesel engine |
-
1999
- 1999-11-23 CA CA002349846A patent/CA2349846A1/en not_active Abandoned
- 1999-11-23 CN CN99813663A patent/CN1328481A/en active Pending
- 1999-11-23 EP EP99959082A patent/EP1163043A4/en not_active Withdrawn
- 1999-11-23 WO PCT/US1999/027779 patent/WO2000030739A1/en not_active Application Discontinuation
- 1999-11-23 AU AU16329/00A patent/AU1632900A/en not_active Abandoned
- 1999-11-23 JP JP2000583616A patent/JP2002530578A/en active Pending
-
2002
- 2002-05-22 HK HK02103838.8A patent/HK1042266A1/en unknown
Also Published As
Publication number | Publication date |
---|---|
WO2000030739A1 (en) | 2000-06-02 |
AU1632900A (en) | 2000-06-13 |
EP1163043A4 (en) | 2003-02-12 |
JP2002530578A (en) | 2002-09-17 |
EP1163043A1 (en) | 2001-12-19 |
CN1328481A (en) | 2001-12-26 |
HK1042266A1 (en) | 2002-08-09 |
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