EP1856382A1 - Reduced-emissions combustion utilizing multiple-component metallic combustion catalyst and lightly catalyzed diesel oxidation catalyst - Google Patents
Reduced-emissions combustion utilizing multiple-component metallic combustion catalyst and lightly catalyzed diesel oxidation catalystInfo
- Publication number
- EP1856382A1 EP1856382A1 EP06718826A EP06718826A EP1856382A1 EP 1856382 A1 EP1856382 A1 EP 1856382A1 EP 06718826 A EP06718826 A EP 06718826A EP 06718826 A EP06718826 A EP 06718826A EP 1856382 A1 EP1856382 A1 EP 1856382A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- emissions
- fuel
- ppm
- diesel
- 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.)
- Withdrawn
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- 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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- F02M27/00—Apparatus for treating combustion-air, fuel, or fuel-air mixture, by catalysts, electric means, magnetism, rays, sound waves, or the like
- F02M27/02—Apparatus for treating combustion-air, fuel, or fuel-air mixture, by catalysts, electric means, magnetism, rays, sound waves, or the like by catalysts
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- C10L1/1241—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof metal carbonyls
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- F01N2430/00—Influencing exhaust purification, e.g. starting of catalytic reaction, filter regeneration, or the like, by controlling engine operating characteristics
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Definitions
- the invention concerns a new process for to reduce emission of pollutants of the type generated by incomplete combustion, e.g., particulates, unburned hydrocarbons and carbon monoxide, while avoiding increasing the production OfNO 2 .
- Diesel engines have a number of important advantages over engines of the Otto type. Among them are fuel economy, ease of repair and long life. From the standpoint of emissions, however, they present problems more severe than their spark-ignition counterparts. Emission problems relate to particulate matter (PM), nitrogen oxides (NO x ), unburned hydrocarbons (HC) and carbon monoxide (CO). NO x is a term used to describe various chemical species of nitrogen oxides, including nitrogen monoxide (NO) and nitrogen dioxide (NO 2 ), among others. NO is of concern because it is believed to undergo a process known as photo-chemical smog formation, through a series of reactions in the presence of sunlight and hydrocarbons, and is significant contributor to acid rain.
- PM particulate matter
- NO x nitrogen oxides
- HC unburned hydrocarbons
- CO carbon monoxide
- NO x is a term used to describe various chemical species of nitrogen oxides, including nitrogen monoxide (NO) and nitrogen dioxide (NO 2 ), among others. NO is of concern because it
- NO 2 on the other hand has a high potential as an oxidant and is a strong lung irritant.
- Particulates (PM) are also connected to respiratory problems. As engine operation modifications are made to reduce particulates and unburned hydrocarbons on diesel engines, the NO x emissions tend to increase.
- 4,902,487 implements this reaction through the use of a heavily catalyzed DOC upstream of an uncatalyzed DPF.
- the heavily catalyzed DOC converts NO present in the exhaust to NO 2 , which oxidizes carbon particulates to help regenerate the filter.
- a conventional ceramic monolith supported catalyst was employed containing approximately 80 gm/ft 3 Pt. Typical loadings of platinum are reportedly 30 to 90 gm/ft 3 of DOC volume. More recently a manufacturer of such devices has introduced a system which utilizes a heavily catalyzed DPF to help with low temperature regeneration. Total precious metal loadings are now reportedly 90 to 120 gm/ft 3 .
- NO 2 is a strong lung irritant and concentrations have been limited in exhaust gas by MSHA and are proposed to be capped at 20% of exhaust nitrogen oxides by CARB.
- MSHA MSHA
- CARB exhaust nitrogen oxides
- the invention provides a method for reducing particulate emissions from a diesel engine while also controlling emissions OfNO 2 as a percent of exhaust total nitrogen oxides, comprising: adding a fuel borne catalyst comprising platinum and cerium and/or iron at a total metal concentration of from 2 to 15 ppm in the fuel to a diesel fuel; and passing exhaust produced by the combustion through a diesel oxidation catalyst having substrate with a precious metal catalyst thereon, the catalyst be present on the substrate in an amount of less than 15 grams per cubic foot of substrate.
- the invention provides improved systems for diesel operation and preferably employs an FBC and an emissions after treatment device comprising a lightly catalyzed diesel oxidation catalyst, DOC, e.g., of conventional or alternative construction.
- DOC lightly catalyzed diesel oxidation catalyst
- the term FBC refers to fuel borne catalyst, which is typically a fuel soluble or suspended composition having a metal component that is released to the combustion chamber in active form during the combustion of the fuel in the diesel engine.
- DOC and FBC will all be explained in greater detail below and are also known to the art as evidenced by the above citations.
- the invention employs an emissions after treatment device treatment comprising a catalyst substrate that can be a DOC alone or with a DPF, the catalyst substrate being lightly catalyzed with precious metal, e.g., a platinum group metal.
- the catalyst loading will be less that the art has seen the need for to convert NO to NO 2 for use as a soot oxidant, preferably having a metal loading of less than 15 gm/ft 3 , e.g., 1 to 15 gm/ft 3 , platinum group metal loading, desirably less than 10 gm/ft 3 , and most preferably 3 to 5 gm/ft 3 .
- Suitable precious metals for catalyzing the DOC are those identified in the Cooper, et ah, patent identified above, and particularly comprises platinum group metal.
- a lightly catalyzed DOC contains less than 15 grams per cubic foot (gm/ft 3 ), e.g., 1 to 15 gm/ft 3 , platinum group metal loading, desirably less than 10 gm/ft 3 , and preferably 3 to 5 gm/ft 3 , used with a platinum and cerium FBC at 0.015-0.5 ppm Pt and 0.5-8 ppm Ce and/or iron. Higher and lower levels of additives may be employed for portions of a treatment or operation cycle. A further discussion of FBC compositions is provided below.
- the improved systems of the invention significantly reduce PM, e.g., by 30 to 50 % in preferred embodiments, e.g., when used with ultra low sulfur diesel fuel and does not increase NO 2 above baseline and has demonstrated the ability to maintain low NO 2 emissions, e.g., to below 20% of total nitrogen oxide species while also minimizing the use of platinum group metals.
- diesel fuels suitable for use in the invention are those which typically comprise a fossil fuel, such as any of the typical petroleum-derived fuels including distillate fuels.
- the diesel fuel can be of any of those formulations disclosed in the above priority patent applications, which are incorporated by reference herein in their entireties.
- 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, No. 1 Diesel fuel, jet fuel, e.g., Jet A, or the like which is similar in boiling point and viscosity to No.
- Diesel fuel, ultra low sulfur diesel fuel (ULSD) 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.
- 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.
- Jet A and Diesel No. 1 are deemed equivalent for applications of the invention, but are covered by different American Society For Testing and Materials (ASTM) specifications.
- the diesel fuels are covered by ASTM D 975, "Standard Specification for Diesel Fuel Oils”. Jet A has the designation of ASTM D 1655, "Standard Specification for Aviation Turbine Fuels”.
- ULSD ultra low sulfur diesel fuel
- ULSD means No. 1 or No. 2 diesel fuels with a sulfur level no higher than 0.0015 percent by weight (15 ppm) and some jurisdictions require a low aromatic hydrocarbon content e.g., less than ten percent by volume.
- the process of the invention employs a fuel-soluble, multi-metal catalyst, i.e., an FBC, preferably comprising fuel-soluble platinum and either cerium or iron or both cerium and 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 and/or iron being from 5 to 10 ppm, e.g., 7.5 ppm, and the platinum being employed at a level of from 0.0005 to 0.5 ppm, e.g., less than 0.15 ppm.
- the treatment regimen can call for the utilizing higher catalyst concentrations initially or at defined intervals or as needed— but not for the whole treatment as has been necessary in the past.
- the cerium and/or iron are preferred at levels of cerium and/or iron being from 2 to 10 ppm, e.g., 3-8 ppm, and the platinum being employed at a level of from 0.05 to 0.5 ppm, e.g., from 0.1 to 0.5ppm, e.g., 0.15 ppm, for typical operations.
- the tests below run at these levels show surprising results in terms emissions utilizing a lightly catalyzed DOC.
- the cerium and/or iron FBC is preferred at concentrations of 1 to 15 ppm cerium and/or iron w/v of fuel, e.g., 4 to 15 ppm.
- a preferred ratio of cerium and/or iron to platinum for the FBC is from 100:1 to 3:1, e.g., more typically will be from 75:1 to 10:1.
- a formulation using 0.15 ppm platinum with 7.5 ppm cerium and/or iron is exemplary.
- An advantage of low levels of catalyst is the reduction in ultra fine particles resulting from metal oxide emissions.
- Data published under the European VERT program show that at high FBC dose rates of 20 ppm, or 100 ppm, cerium the number of ultra fine particles increases dramatically above baseline. However, for a bimetallic used at 0.5/7.5 or 0.25/4 ppm there is no significant increase in the ultra fine particle number. It has been found that at low levels of FBC there is not a separate ultrafine oxide particle peak and metal oxides are contained in the soot over the entire particle size distribution.
- a further advantage of the low dose rates prescribed by the current invention is a reduction in the contribution of metal ash to overall engine emissions.
- particulate emissions are limited to 100,000 ⁇ g/hp-hr (0.1 gram/hp-hr).
- a cerium FBC used at 30 ppm in fuel represents a metal catalyst input loading to the engine of 6000 ⁇ g/hp-hr of metal or roughly 6% of untreated engine emissions. Therefore, low levels of catalyst used in the present invention of less than 8 ppm and preferably 4 ppm as a bimetallic or trimetallic FBC will, for example, contribute only 800 - 1600 ⁇ g/hp-hr of catalyst loading to the engine or 0.8 - 1.6% of baseline soot emissions. This has the advantage of reduced metal ash emissions and reduces the contribution of the FBC to overall particulate mass emissions or loading of metal ash to downstream emission control devices.
- 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 acetylacetonate and/or 2-20 ppm fuel soluble cerium and/or iron composition, e.g., cerium as a soluble compound or suspension, 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.
- cerium III acetylacetonate cerium III napthenate, and cerium octoate
- cerium oleate and other soaps such as stearate, neodecanoate, and other C 6 to C 24 alkanoic acids, and the like.
- the cerium is supplied as cerium hydroxy oleate propionate complex (40% cerium by weight) or a cerium octoate (12% cerium by weight). Preferred levels are toward the lower end of this range.
- iron compounds include ferrocene, ferric and ferrous acetyl- acetonates, iron soaps like octoate and stearate (commercially available as Fe(III) compounds, usually), iron napthenate, iron tallate and other C 6 to C 24 alcanoic acids, iron penta carbonyl Fe(CO) 5 and the like.
- 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. 5,266,083 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, including substituted (e.g., alkyl, aryl, alkyaryl substituted) and unsubstituted acetylacetonates, platinum group metal dibenzylidene acetonates, and fatty acid soaps of tetramine platinum metal complexes, e.g., tetramine platinum oleate.
- substituted e.g., alkyl, aryl, alkyaryl substituted
- unsubstituted acetylacetonates platinum group metal dibenzylidene acetonates
- platinum group metal dibenzylidene acetonates platinum group metal dibenzylidene acetonates
- fatty acid soaps of tetramine platinum metal complexes e.g., tetramine platinum oleate.
- the invention can employ a DOC alone or it can be used with other devices including DPFs, particulate reactors, partial filters or NO x adsorbers can also be used and benefit from reduced engine out emissions of the current invention. See the examples below, for the engine out results and the benefits of the FBC with catalyzed DOC devices to reduce NO 2 and particulate emissions. While not wishing to be bound by any theory, the unexpectedly good results with after treatment devices as well as for engine out emissions, this may be because the platinum is not present in amounts sufficient to produce excessive amounts of NO 2 and yet produces some NO 2 which is sufficient to foster oxidation of the carbon in the particulates in the presence of low levels of cerium and/or iron.
- NO 2 is a strong lung irritant and can be generated in large quantities by traditional use of heavily catalyzed aftertreatment devices such as DOCs, DPFs or combinations.
- the net result of the limited NO 2 production due to low platinum concentrations and the cerium and/or iron being present in low but sufficient amounts is to produce greater than expected reductions in particulates (as well as other species resulting from incomplete oxidation) and at the same time control the amount of NO 2 generated and released.
- the invention has found that high NO 2 production rates are not necessary and, indeed, has found a way to provide emissions less irritating to humans.
- Another unexpected benefit of the FBC used with a lightly catalyzed DOC is the reduction in NO 2 emissions versus baseline. NO 2 emissions are generally increased with traditional heavily catalyzed devices, but are decreased by over 50% with the FBC/DOC combination described in the invention.
- This example presents the results of testing over a single cold and triple hot FTP transient test cycles for the FBC/DOC combination on a 1990 Cummins 8.3 liter 6 CTA, 275 hp medium heavy-duty engine certified to meet 1991 emission standards for NOx and PM.
- the engine was initially run on untreated No. 2D fuel (> 300 ppm Sulfur) with no exhaust aftertreatment DOC installed. Particulate emissions were determined from the average composite at 0.190 gr/hp-hr.
- the DOC was a 9.5" dia. x 6" L 400 cpsi ceramic substrate made by Corning, Inc. and catalyzed with 3 gr/cu ft. of precious metal by Clean Air Systems, Inc. of New Mexico. It was installed in a stainless steel can with conventional inlet and outlet cones.
- the FBC was a platinum/cerium bimetallic used at a dose rate of 0.5 ppm/7.5 ppm.
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US11/038,287 US20050160724A1 (en) | 2002-02-04 | 2005-01-19 | Reduced-emissions combustion utilizing multiple-component metallic combustion catalyst and lightly catalyzed diesel oxidation catalyst |
PCT/US2006/001813 WO2006078762A1 (en) | 2005-01-19 | 2006-01-19 | Reduced-emissions combustion utilizing multiple-component metallic combustion catalyst and lightly catalyzed diesel oxidation catalyst |
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EP1856382A1 true EP1856382A1 (en) | 2007-11-21 |
EP1856382A4 EP1856382A4 (en) | 2011-01-26 |
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EP06718826A Withdrawn EP1856382A4 (en) | 2005-01-19 | 2006-01-19 | Reduced-emissions combustion utilizing multiple-component metallic combustion catalyst and lightly catalyzed diesel oxidation catalyst |
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US (1) | US20050160724A1 (en) |
EP (1) | EP1856382A4 (en) |
JP (1) | JP2008526509A (en) |
KR (1) | KR101010104B1 (en) |
CN (1) | CN101160455B (en) |
AU (1) | AU2006206466A1 (en) |
BR (1) | BRPI0606584A2 (en) |
CA (1) | CA2595303A1 (en) |
HK (1) | HK1114148A1 (en) |
MX (1) | MX2007008820A (en) |
WO (1) | WO2006078762A1 (en) |
ZA (1) | ZA200706581B (en) |
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- 2006-01-19 JP JP2007552247A patent/JP2008526509A/en active Pending
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Also Published As
Publication number | Publication date |
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US20050160724A1 (en) | 2005-07-28 |
KR101010104B1 (en) | 2011-01-24 |
BRPI0606584A2 (en) | 2009-07-07 |
WO2006078762A1 (en) | 2006-07-27 |
JP2008526509A (en) | 2008-07-24 |
EP1856382A4 (en) | 2011-01-26 |
KR20070100365A (en) | 2007-10-10 |
CA2595303A1 (en) | 2006-07-27 |
AU2006206466A1 (en) | 2006-07-27 |
CN101160455B (en) | 2013-03-27 |
CN101160455A (en) | 2008-04-09 |
MX2007008820A (en) | 2007-09-27 |
ZA200706581B (en) | 2008-09-25 |
HK1114148A1 (en) | 2008-10-24 |
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